Emerging Technologies in Environmental Science ...

International Conference on

Emerging Technologies in Environmental Science and Engineering

www.excelpublish.com

International Conference on


26–28 October, 2009

Editors

Razaullah Khan Izharul Haq Farooqi Farrukh Basheer

Organised by

Department of Civil Engineering

Z.H. College of Engineering and Technology Aligarh Muslim University Aligarh, U.P., India

In Collaboration with

The University of Toledo OHIO, U.S.A.

EXCEL INDIA PUBLISHERS New Delhi

First Impression: 2009

© A.M.U., Aligarh


ISBN: 978-93-80043-40-1

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DISCLAIMER

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DEPARTMENT OF CIVIL ENGINEERING Zakir Husain College of Engineering & Technology ALIGARH MUSLIM UNIVERSITY ALIGARH-202002 [INDIA]

Prof. Razaullah Khan

Invitation from the Chairman On behalf of organizing committee, I extend to you a warm welcome and cordially invite you to the International conference on Emerging Technologies in Environmental Science and Engineering 26th -28th Oct 2009. The technical committee is inviting recognized national and international leaders to anchor each theme, and it seeks additional platform speakers, and poster presenters to complement the invited speakers. By gathering leading experts and practitioners from environmental fields, this conference will be very enriching experience, with fruitful exchanges of new interdisciplinary ideas, opinions and approaches. I would also like to thank the Dean College of Engineering, University of Toledo, Ohio, USA for co-sponsoring the event. I encourage your participation, and welcome you to Department of Civil Engineering, A.M.U., Aligarh

Prof. Razaullah Khan Chairman

October 6, 2009

Dear Conference Participants: On behalf of our College of Engineering at The University of Toledo, I welcome you to the 2009 International Conference on Emerging Technologies in Environmental Science and Engineering. This international conference brings together professionals from different countries to showcase and share ideas and serves as a global platform where the brightest minds from around the globe can gather to address new challenges facing our society and develop pragmatic solutions for sustainable development. I would like to extend a special welcome to the student attendees. This is a wonderful opportunity for you to meet and network with accomplished professionals in your field. I am pleased that the University of Toledo is a sponsor of this conference. The College of Engineering at the University of Toledo has been an active contributor to research and education in the areas of energy and environment since the 1970s and is committed to graduate leaders in the environmental field. Thank you for being here. It is my hope that you enjoy the conference, both professionally and personally. Let me also take this opportunity to invite all of you to visit us at the University of Toledo College of Engineering. Sincerely,

Nagi G. Naganathan, Ph.D. Professor & Dean

FACULTY OF ENGINEERING & TECHNOLOGY

ALIGARH MUSLIM UNIVERSITY, ALIGARH-202002, INDIA

DEAN

October 15, 2009

Professor Md. Hamiuddin

Message from the Dean’s Desk I appreciate the students and teachers of Civil Engineering Department under dynamic leadership of Professor Razaullah Khan to organize an International Conference on “Emerging Technologies in Environmental Science and Engineering” on 26th to 28th October, 2009. In fact, stock taking of existing technologies on the impact of the environmental degradation and turbulence in the balance of nature needs immediate attention of Technocrats. Competitive consumption of natural resources has resulted into pollution of soil, water and air - the three essential ingredients of life on globe. It is forecast that the globe would become inhabitable by the end of the century. While Green Revolution in Agriculture started in the second half of 20th Century solved the hunger and famine problem of Asia and Africa, its excessive use has resulted into degradation of soil and water. Similarly over- enthusiastic use of minerals resources and fossils fuels like coal, petrol and gas is resulting into depletion of such resources and is compelling the society to use alternative resources of fuels and materials. All these alternatives, if successful, can solve problems partly, creating newer and acute problems. The development in science and technology in isolation, has sometimes resulted into everincreasing problems of ecological imbalance manifest in the form of disease like HIV/AIDs, swine and other flues, psychiatric problem like family breakdown, drug addiction, exploitation, terrorism, genocide etc. If one considers history of human being then Nomadic society cared about physical needs (food, cloth and shelter), Agriculture Society focused on social needs, Industrial Society on comfort in both the above and knowledge society concentration on mental need. There is a fourth human need i.e spiritual of living in harmony with nature. A synergy has to be maintained i.e all human needs are interdependent. In Japan, there are hundreds of farm based on, “Do – nothing farming or One – straw Revolution” base on experiments carried out by Masami Fukuoka in Shikoku of Southern Japan in 1960’s, which consists of no ploughing, no chemical fertilizers, no or

little irrigation and no weeding. Success of Toyota to replace American Giant Auto Industry occupying No.1 global position amongst Auto manufacturers is stated to be due to an eco-friendly, participative, “LEAN MANUFACTURING” developed by Taiko Ohno in 1980’s. These days, Lean Manufacturing, Lean Service Management, Lean/Green Marketing are being adopted by the so-called Global Companies of Europe and America. About 25 years ago, phenomena of Reverse Migration (i.e from cities to country side) started in some countries of Western Europe and price of land for house in villages become exorbitant. However, there is global awakening towards living in harmony with nature and technological community has a major role to play to combat environmental problem as dictated by governmental policies to harness renewable sources of energy like solar, wind, water waves. “World has still enough to meet the needs of the people but enough to meet the greed” – a statement of Gandhi is becoming more relevant. Perhaps, relevance of Gandhism or religious teaching acquires greater significance in the dangerous and explosive situation of man’s ambition to conquer the nature by its destruction which shall lead to destruction of humanity itself. Thus, holistic technologies have to be developed and one has to return to God or nature for its complex and synergistic healing effect which is impossible for man to understand and solve. A beginning has already started and is evident by ever-increasing use of naturo-pathy, yoga, cariopractice, herbal medicines, meditation, reduction of arms, minimum use of the, “so called” modern equipments and devices. I wish all the participants of this conference to have a meaningful deliberation and to arrive at the conclusion such that future conference on this theme should take view of philosophers and humanists with a request to ignore our inadequacies in arrangements for their comfortable stay.

Professor Md. Hamiuddin (Dean)

Z.H. COLLEGE OF ENGINEERING & TECHNOLOGY ALIGARH MUSLIM UNIVERSITY, ALIGARH-202002, INDIA

Prof. Muslim Taj Ahmed, Ph.D.

Telephone No.: (0571) 700042 (O)

Senior Member IEEE (USA) Fellow, IETE (India)

Int. 1902. 1902 Telephone No.: (0571) 701144 (R) E-mail: [email protected]

Prof. M.T. Ahmad

MESSAGE I am pleased to know that the Department of Civil Engineering of Zakir Husain College of Engineering and Technology is organizing an International Conference on, “Emerging Technologies In environmental science and Engineering “in conjunction with University of Toledo, USA .It is hesitating that conference is already gained popularity and its technical committee has been receiving a large number of papers for oral and poster presentations. The conference is expected to be attend ed by eminent personalities from academics and industry. . I am sure it will generate exchange of innovative ideas and present new findings, which will help in the dissemination of knowledge in the contemporary area of Environmental science and engineering. As Principal of the college, I take this opportunity in congratulating the organizers and whishing the conference a grand success.

Prof. M.T. Ahmad Principal

Preface This CD is prepared for the 2009 International Conference on Emerging Technologies in Environmental Science and Engineering. The papers cover air, water, land, and waste areas. The topics include waste water, water quality, global warming, noise, air pollution, toxic waste, and sustainable technologies for environmental protection. The contents of the CD showcase different ideas for solving environmental problems. We would like to thank all the authors who contributed from different countries their knowledge and experience during the conference. The International Advisory Committee, the National Advisory Committee, and the Technical Committee aided us in the development of technical program. We want to recognize the support provided by – Excel India Publishers in the development of the CD. We feel it is of the utmost importance to recognize the excellent ongoing support from the Chairman of the Department of Civil Engineering Z.H. College of Engineering and Technology, Aligarh Muslim University and the College of Engineering, University of Toledo whose support made the organization of this conference possible. The support of the faculty members of the department is highly appreciated. We hope that this CD will provide an excellent compilation of the presented papers for your professional development and of course a productive and stimulating material for your students. We would like to thank the research scholars of the department of civil engineering for the constant help in the compilation of the papers

Izharul Haq Farooqi Ph.D., Aligarh Muslim University

Ashok Kumar Ph.D., University of Toledo

Organising Committee Chief Patron Prof. P.K. Abdul Azis

Vice Chancellor, A.M.U.

Patrons Prof. Hamiuddin Prof. M.T. Ahmed

Dean, F/O Engg.& Tech.AMU Principal, ZHCET,AMU

Conveners Prof. Razaullah Khan Prof. Ashok Kumar

Professor & Chairman, Department of Civil Engineering, A.M.U. Professor & Chair, Department of Civil Engineering, University of Toledo, OHIO, U.S.A.

Organizing Secretary Dr. Izharul Haq Farooqi

Associate Professor

International Advisory Committee Syed R. Qasim

Professor Emeritus, Department of Civil Engineering, The University of Texas at Arlington Professor and Chair, Memorial University of Newfoundland, Canada Delft University of Technology, The Netherlands Michigan State University, U.S.A. Durban University of Technology, South Africa Mersky, Widener University, USA University of Petronas, Malaysia P.E., Department of Defence University of New Orleans, USA

Prof. Tahir Husain Prof. M. Van Loosdrecht Dr. S.A. Hashsham Prof. Faizal Bux Dr. Ronald L Dr. M.H. Isa Dr. Sardar Q. Hassan Dr. B. Kura

National Advisory Committee Prof. R.H. Siddiqui Prof. P.A. Saini Prof. Vinod Tare Prof. Shyam R. Asolekar Prof. Indu Mehrotra Dr. Soumyen Guha Dr. A.K. Mittal Dr. Mohd. Jawed

Retired Professor, AMU Retired professor, AMU I.I.T., Kanpur Professor and Chair, CESE, I.I.T., Mumbai I.I.T., Roorkee I.I.T., Kanpur I.I.T., Delhi I.I.T., Guwahati

Technical Committee Prof. Mohd. Jamil Prof. V.P. Mital Prof. M.M.Ashhar (Convener) Prof. S.S. Shah Prof. Husain Abbas Prof. Naseem Ahmad

Dr. Sohail Ayyub Mr. Nadeem Khalil, Mr. Arshad Hussain, Mr. E. Radha Krishnan, USA Dr. Krishna Nand, USA

Research Scholars Team Mr. Farrukh Basheer Mr. Brajesh Chauhan Ms. Sheeba Khan

Mr. Ahmad Ashfaqe Ms. Saima Badar Mr. Devendra Singh

Faculty Members of the Department of Civil Engineering Professors Prof. Razaullah Khan, Chairman Prof. V.P. Mital Prof. Mohd. Jamil Prof. M.M. Ashhar Prof. Salahudding Shah Prof. Hussain Abbas Prof. Nasim Ahmad Khan

Prof. Sarfaraz Ali Ansari Prof. Mohd. Arif Porf. Mohd. Muzammil Prof. Abdul Baqi Prof. Shakeel Ahmad Prof. Amjad Masood Prof. Mohd. Athar

Associate Professors Mr. Farrukh Ghani Mr. Sajid Ali Khan Mr. Syed Ashraf Ali Dr. Tazyeen Ahmad Dr. Talib mansoor Ms. Tabassum Naqvi Dr. Arshad Umar Dr. Izharul Haq Farooqi Dr. M. Shamsuddin Jafri Dr. Mubin beg

Dr. Fareed Mahdi Mr. Hasan Irteza Dr. Sabih Akhtar Mr. Asif Ali Siddiqui Dr. Iqbal Khalil Khan Dr. Mehboob Anwar Khan Dr. Javed Alam Dr. Malik Shoeb Ahmad Dr. Suhail Ayyub Dr. Rehan Ahmad Khan

Assistant Professor Mr. Nadeem Khalil Khan

Dr. Mohd. Masroor Alam

Wastewater Treatment

International Conference on Emerging Technologies in Environmental Science and Engineering October 26-28, 2009 Aligarh Muslim University, Aligarh, India

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ADSORPTION OF HEAVY METALS AND METALLOIDS ON ORGANOCLAYS Binoy Sarkar*, Yunfei Xi, Mallavarapu Megharaj, GSR Krishnamurti and Ravi Naidu CERAR-Centre for Environmental Risk Assessment and Remediation University of South Australia, Mawson Lakes, SA 5095, Australia CRC CARE-Cooperative Research Centre for Contamination Assessment and Remediation of the Environment, PO Box 486, Salisbury South, SA 5106, Australia *E-mail: [email protected] Telephone: +618 83026293, Fax: +618 83023057

ABSTRACT Naturally occurring clay materials can be modified organically by quaternary ammonium cations resulting into clay products commonly known as organoclays. Such organic modification alters the nature of clay from hydrophilic to hydrophobic, imparting enhanced interaction of the clay products towards pollutants in the environment. Organoclays possess unique sorption behaviour towards hydrophobic organic contaminants in soil and water. These materials can also be used to remediate ionic contaminants such as heavy metals and metalloids. The objective of the present study is to synthesise organoclay and organoclay mixtures efficient to adsorb both heavy metal cations and metalloid anions. Trivalent chromium cation (Cr3+) and hexavalent chromium anion (Cr2O72-) have been selected as the model contaminants from the two above mentioned groups. Results show that modification of bentonite to the extent of double the cation exchange capacity of the clay with cationic surfactant, such as hexadecyltrimethylammonium bromide (HD), remarkably improve its Cr2O72adsorption capacity. Similarly, modification of the bentonite with anionic surfactant, such as sodium dodecyl sulphate (SD), at the same dosage improves its adsorption capacity towards trivalent chromium (Cr3+). When these two organoclays are physically mixed in equal proportions (1:1), the resultant organoclay mixture efficiently adsorb Cr3+ and Cr2O72- simultaneously. The sorption isotherms of Cr3+ by the organoclays and organoclay mixtures could be fitted well with Langmuir model, whereas the sorption isotherms of Cr2O72- fitted well with Freundlich model. Keywords: Organoclay, heavy metals and metalloids, adsorption

1. INTRODUCTION Pollution occurring in the terrestrial environment from various sources is an increasing concern for human beings all over the world. Many resources have been directed towards development of technologies to remediate contaminants causing pollution in soil and water environment. However, there still exist many contaminated sites in sensitive locations due to either prohibitive cost of remediation or lack of technology capable to clean up the environment to levels required by the regulators. So, further attention should be focused on development of remediation materials and technologies that are less expensive but most efficient in performance. In the recent years, several physical, chemical and biological processes have been evolved for the remediation of contaminated soil and water. Among them, sorption is proven to be an effective and attractive mechanism. In this context, the use of clay materials has received considerable attention. Natural materials such as clays are profitably effective to immobilise toxic environmental contaminants due to their inexpensive availability, environmental stability and high adsorptive and ion exchange properties. Additionally, clay materials can potentially be modified using a variety of chemical/physical treatments to achieve the desired surface properties for best immobilisation of

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contaminants. Naturally occurring clay materials can be modified organically by quaternary ammonium cations resulting into clay products commonly known as organoclays. Such organic modification alters the nature of clay from hydrophilic to hydrophobic, imparting enhanced interaction of the clay products towards pollutants in the environment (Boyd et al. 1988; Xi et al. 2004). Numerous studies suggest that organoclays possess unique sorption behaviour towards hydrophobic organic contaminants in soil and water (Boyd et al. 1988; Xi et al. 2004; 2005; Xu and Zhu 2009). Few studies also indicate that these materials can be used to remediate ionic contaminants such as heavy metals and metalloids (Sullivan et al. 2003; Tillman et al. 2004; Oyanedel-Craver et al. 2007; Stathi et al. 2007). However, reports describing interaction of heavy metals and metalloids with organoclays are scanty in literature. Normally, the naturally occurring clays are not efficient sorbents for anionic metalloids because of their intrinsic negative charge. Although very little amount of anion sorption can take place with natural clays through physical sorption, anion exchange or electrostatic binding mechanisms, it is neither significant in terms of sorption quantity nor binding strength. So, in order to immobilise anions like chromate and arsenate effectively by these materials, their surface has to be modified so as to possess enough positively charged sites that can bind with the anions. In addition, another possible mechanism can be affected when the weakly held counter ions of the modifying surfactants in organoclays get replaced with more strongly held adsorbate counter ions. It has been observed that the clay products after organic modification may obtain those favourable surface properties for holding anions (Krishna et al. 2001). At the same time, organoclays may adsorb heavy metal cations by chemisorption with silanol and aluminol groups at the clay edge when their exchange sites are not fully occupied by the modifying cationic surfactant (Oyanedel-Craver and Smith 2006). Some researchers have also suggested that organoclays synthesised from anionic organic surfactant are efficient in adsorbing heavy metal cations (Lin and Juang 2002). However, it is difficult to achieve equally high sorption efficiencies for both heavy metal cations and metalloid anions by a single organoclay sorbent. So, development of sorbent material or material mixture, which has similar affinities towards both heavy metal cations and metalloid anions, is of utmost importance in order to remediate waste effluent containing both kinds of these contaminants. For example, effluents from industries such as alloys and steel manufacturing, metal finishing, electroplating, leather tanning, or pigments synthesis and dying frequently contain both cationic trivalent (Cr3+) and anionic hexavalent (Cr2O72-) chromium. Chromium is a common contaminant in groundwater and soil, particularly in industrial areas and it is listed among 126 priority pollutants by the US EPA (Keith and Telliard 1979). Chromium is also listed among the 25 hazardous substances thought to pose the most significant potential threat to human health at priority superfund sites (USDHHS 1987). Among different forms of chromium, Cr2O72- is the most toxic species with known carcinogenicity and high mobility, whereas Cr3+ is considered less mobile and hence less available to biological systems. However, Cr3+ can also be toxic when present at very high concentrations. So, there exists a need to develop suitable remediation materials for both the forms of chromium present in the terrestrial environment. The present paper discusses the synthesis of bentonite based organoclays and organoclay mixture and investigates their adsorption behaviour towards trivalent (Cr3+) and hexavalent (Cr2O72-) chromium in aqueous environment. Information generated in this study will be helpful to design organoclay based sorbent materials for the treatment of waste effluents containing other heavy metals and metalloids as well.

2. METHODS 2.1 Materials and Reagents The bentonite clay (QB) used in this study is from Queensland, Australia. The cation exchange capacity (CEC) of this clay is 66.7 cmol (p+) kg-1 as determined by ammonia electrode method (Borden and Giese 2001). The two surfactants selected for this study are


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hexadecyltrimethylammonium bromide (C19H42NBr, FW: 364.45, purity 99%, denoted as HD) and sodium dodecyl sulphate (C12H25SO4Na, FW: 288.38, purity 99%, denoted as SD) as supplied by Sigma–Aldrich.

2.2 Synthesis of Organoclays Organoclays were synthesised using hydrothermal cation exchange reaction (Frost et al. 2008). In short, clarifying surfactant solution was obtained by adding certain amount of surfactants into hot deionized water (MilliQ® water system). Then known amount of bentonite was added into that solution and the mixture was stirred gently on a magnetic stirrer cum heater avoiding yield of excess spume. The mixture was stirred for 2 hours and the temperature was maintained at 80°C. The water/clay mass ratio was 10:1. Organoclays synthesised from HD were washed free of bromide as determined by negative AgNO3 test. SD organoclays were also washed four times with deionized water to remove superficially attached surfactants from the clay products. All organoclays were dried in oven at 60°C, ground in agate mortar and stored in a vacuum desiccator for future use. Five different organoclay and organoclay mixture were synthesised in the present study, namely 2 CEC HD bentonite (QB-2HD), 2 CEC SD bentonite (QB-2SD), equal proportion (1:1) mixture of 2 CEC HD bentonite and 2 CEC SD bentonite (QB-2HD+2SD), equal proportion (1:1) mixture of 1 CEC HD bentonite and 1 CEC SD bentonite (QB-1HD+1SD) and equal proportion (1:1) mixture of 0.5 CEC HD bentonite and 0.5 CEC SD bentonite (QB-0.5HD+0.5SD). Individual organoclay was synthesised first with surfactant loading corresponding to 50% (0.5 CEC), 100% (1 CEC) and 200% (2 CEC) of the bentonite clay and then they were mixed homogeneously to obtain the organoclay mixtures.

2.3 Adsorption of Cr3+ and Cr2O72- onto Organoclays and Organoclay Mixtures Due to the reliability and simplicity of the method, batch experiments were conducted to evaluate the adsorption of Cr3+ and Cr2O72- onto the synthesised organoclays and organoclay mixtures. In a typical procedure, 0.05 g sorbent material was added into 10 mL aqueous solutions containing various concentrations of Cr3+ and Cr2O72-. The mixture was agitated on an end over end shaker for 24 hour at room temperature (23±1°C). Following agitation, the mixtures were centrifuged at 4000 rpm for 30 minutes (Multifuge 3 S-R, Hevaeus, Kendo Laboratory Products, Germany). Then, chromium concentration in the clear supernatants were analysed by ICP-OES (PerkimElmer Optima 5300V). The amount of sorbate removed from the aqueous solution was calculated by the following equation: qe = V(Ci – Ce)/(M x 1000)……………………..(1) where, qe is the amount of sorbate removed from the liquid phase (mM g-1), Ci is the initial liquid phase concentration of the sorbate (mM L-1), Ce is the equilibrium liquid phase concentration of the sorbate (mM L-1), V is the volume of liquid phase (mL) and M is the mass of the sorbent (g). Adsorption isotherms were developed and the data were fitted into Freundlich and Langmuir models.

3. RESULTS AND DISCUSSION 3.1 Adsorption of Cr3+ and Cr2O72- onto Organoclays The adsorption data show that bentonite modified by hexadecyltrimethylammonium (HD), which is a cationic surfactant, possesses very high adsorption capacity for hexavalent chromium oxyanion (Cr2O72-), whereas bentonite modified by sodium dodecyl sulphate (SD) exhibit better adsorption performance for trivalent cation of chromium (Cr3+). In both the cases the extent of modification of the bentonite clay is equivalent to double the CEC of the clay. But cationic surfactant modified bentonite is not efficient sorbent for Cr3+ and anionic surfactant modified bentonite is unable to adsorb Cr2O72-

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efficiently (Figure 1a & b). It is probably due to the repulsion of cationic HD and anionic SD molecule towards Cr3+ and Cr2O72-, respectively. Modification of bentonite by HD improves the adsorption of Cr2O72- several folds onto the organoclay as compared to the unmodified natural bentonite (Figure 1a & f). Also, there is an improvement of Cr3+ adsorption onto SD modified organoclay as compared to the unmodified bentonite (Figure 1b & f, Table 2). Normally, naturally occurring clays including bentonite are not efficient sorbents for anionic metalloids because of their intrinsic negative charge. But, after organic modification, the natural clays obtain favourable surface properties such as excess positive charges for holding anions. On the other hand, natural bentonite can adsorb heavy metal cations by cation exchange reaction or by chemisorption with silanol and aluminol groups at the clay edge. Such adsorption capacity is considerably improved when surface of natural bentonite is modified with anionic organic surfactant which provides excess negative charge on the clay surface. a) QB-2HD

b) QB-2SD

60 50 ) g 40 M30 m (e q 20 10

1 -

Trivalent Cr Hexavalent Cr

0 0

0.5

1

40 35 ) 30 1 g 25 M20 m ( 15 e q 10 5 0

1.5


0

0.5

Ce (mM L-1 )

1

1.5

2

Ce (mM L-1)

d) QB-1HD+1SD

c) QB-2HD+2SD 50

25 20 ) g 15 M m ( 10 e q 5

40 ) g 30 M m ( 20 e q 10

1 -

1 -



0

0 0

1

2

0

3

1

2

e) QB-0.5HD+0.5SD


0.5

1 Ce (mM L-1)

4

f) QB

40 35 ) 30 1 g 25 M20 m ( 15 e q 10 5 0 0

3

Ce (mM L-1)

Ce (mM L-1)

1.5

2

35 30 ) 25 1 g 20 M m ( 15 e q 10 5 0


0

0.5

1

1.5

Ce (mM L-1 )

Figure 1: Isothermal plots for adsorption of trivalent (Cr3+) and hexavalent (Cr2O72-) chromium onto organoclays and organoclay mixtures. (Ce is the equilibrium liquid phase concentration of sorbate in mM L-1 and qe is the amount of sorbate in mM g-1 removed from the liquid phase onto the sorbent)

3.2 Adsorption of Cr3+ and Cr2O72- onto Organoclay Mixtures The present study shows that organic modifications of bentonite clay with a particular surfactant can only facilitate adsorption of either one of the two forms of chromium. This result is in agreement with previous reports (Lin and Juang 2002; Oyanedel-Craver and Smith 2006; Oyanedel-Craver et al. 2007). However, the main objective of the present study is to develop a sorbent material that performs


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equally well for adsorption of both trivalent and hexavalent chromium. In order to obtain such a sorbent material, the synthesised organoclays, that individually demonstrate best performance for Cr3+ and Cr2O72-, were physically mixed together and organoclay mixtures were prepared. Those organoclay mixtures were tested for adsorption of Cr3+ and Cr2O72-. The results show that an organoclay sorbent obtained by mixing QB-2HD and QB-2SD in equal proportion (1:1) is very much efficient to adsorb both the cationic and anionic forms of chromium from aqueous medium (Figure 1c). However, similar proportion mixtures of 1CEC and 0.5CEC modified organobentonites synthesised from HD and SD is only able to adsorb Cr3+, but not Cr2O72- efficiently (Figure 1d & e). It should be noted that adsorption of cationic and anionic forms of chromium on to QB-2HD+2SD is lower than the respective organoclay when used individually for adsorbing either Cr3+ or Cr2O72-. In the present study, 0.05 g sorbent material was used for adsorption of Cr3+ or Cr2O72- from 10 mL aqueous solutions of the respective contaminants in all the cases. This is why the sorbent to solution ratio for a particular sorption site, either cationic or anionic, is reduced by 50% for a 1:1 organoclay mixture as compared to an individual organoclay and therefore the adsorption capacity for individual contaminant is reduced. However, this problem might be overcome by increasing application rate of the organoclay mixture during adsorption of Cr3+ and Cr2O72-. Moreover, the main advantage of the organoclay mixture is that it could be used to remediate both Cr3+ and Cr2O72- simultaneously using a single sorbent material. In order to achieve simultaneous adsorption of Cr3+ and Cr2O72-, the maximum adsorption performance of the individual organoclay is getting little compromised. This organoclay mixed sorbent could be effective in adsorbing other heavy metals such as copper, zinc, iron, lead, etc. and metalloids such as arsenite, arsenate, selenite, selenate, etc.

3.3 Isothermal Models for Adsorption of Cr3+ and Cr2O72- onto Organoclay and Organoclay Mixtures The Freundlich and Langmuir isotherm parameters for the adsorption of trivalent and hexavalent chromium onto organoclays and organoclay mixtures are shown in Table 1 and 2, respectively. It has been observed that the adsorption of Cr3+ onto these sorbents is generally better explained by Langmuir isothermal model (Table 2). Langmuir adsorption model assumes that the adsorbent surface has only homogeneous sorption sites having constant bonding energy (Langmuir 1918). This model actually explains saturated monolayer adsorption without any transmigration of the adsorbate molecules on the sorbent surface. Since Cr3+ sorption data fit better to this model, it is evident that organic modification by SD makes the clay surface more homogeneous and thus, improves adsorption. On the other hand, adsorption data of Cr2O72- fit well into Freundlich isothermal model. It implies that physical rather than chemical adsorption is the dominant process when these sorbents are used for adsorbing hexavalent chromium (Khenifi et al. 2007). The maximum adsorption capacities of Cr3+ and Cr2O72- onto various sorbents tested in this study were calculated from Langmuir isotherm model and listed in Table 2. It is found that the adsorption capacity of QB-2HD+2SD towards Cr2O72- is as high as 35.7 mM g-1, whereas that towards Cr3+ is 15 mM g-1 sorbent. Table 1: Freundlich isotherm parameters for adsorption of Cr3+ and Cr2O72- onto organoclays and organoclay mixtures (n and KF are the Freundlich constants related respectively to adsorption intensity and adsorption capacity) Cr3+ Sample QB-2HD QB-2SD QB-2HD+2SD QB-1HD+1SD QB-0.5HD+0.5SD QB

n -17.51 -34.84 -12.06 -7.34 -4.57 -169.49

Kf (L g-1) 4.3 22.0 11.9 21.9 10.3 20.4

Cr2O72r2 0.2038 0.0163 0.1001 0.0692 0.3443 0.0004

n 1.86 1.11 1.33 1.09 1.02 0.84

Kf (L g-1) 58.3 2.7 12.3 2.3 1.8 3.1

r2 0.9846 0.9782 0.9035 0.9947 0.9886 0.9908

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Table 2: Langmuir isotherm parameters for adsorption of Cr3+ and Cr2O72- onto organoclays and organoclay mixtures (qm is the maximum adsorption capacity of adsorbate by the adsorbent (mM g-1) and KL is the Langmuir adsorption constant (L mM-1) related to the free energy of adsorption) Sample QB-2HD QB-2SD QB-2HD+2SD QB-1HD+1SD QB-0.5HD+0.5SD QB

qm (mM g-1) 4.25 36.23 15.08 42.37 33.67 31.45

Cr3+ KL (L mM-1) -37.4 92.0 7.5 47.2 594 3974

r2 0.9951 0.9989 0.9399 0.9861 0.9988 0.9987

qm (mM g-1) 49.02 20.37 35.71 33.33 -208 -6.50

Cr2O72KL (L mM-1) 6.0 0.22 0.55 0.08 -0.009 -0.33

r2 0.9380 0.0143 0.9399 0.6803 0.0033 0.7293

4. CONCLUSION This study concludes that bentonite can effectively be modified by hexadecyltrimethylammonium bromide (HD) for adsorbing hexavalent chromium (Cr2O72-) from aqueous solution. Similarly, modification of the same clay with anionic surfactant such as sodium dodecyl sulphate (SD) improves its adsorption capacity towards trivalent chromium (Cr3+). When these two organoclays are physically mixed in equal proportions (1:1), the resultant organoclay mixture efficiently adsorb Cr3+ and Cr2O72simultaneously. The sorption isotherms of Cr3+ by the organoclays and organoclay mixtures could be fitted well using Langmuir model, whereas the sorption isotherms of Cr2O72- could be fitted to Freundlich model. This study can be helpful for developing remediation technology for removing cationic heavy metals and anionic metalloids from various industrial waste waters by using a single sorbent material. These sorbents can also be used for in situ immobilisation of other heavy metals and metalloids in contaminated soils and sediments.

ACKNOWLEDGEMENTS The authors would like to acknowledge the financial and infrastructural support of the Cooperative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE) and the Centre for Environmental Risk Assessment and Remediation (CERAR), University of South Australia. Help with ICP-OES analysis by Dr Mohammad Mahmudur Rahman is gratefully acknowledged.

5. REFERENCES Borden, D, Giese, RF, 2001, Baseline studies of the clay minerals society source clays: Cation exchange capacity measurements by the ammonia-electrode method, Clays and Clay Minerals, 49, p444-445. Boyd, SA, Shaobai, S, Lee, JF, Mortland, MM, 1988, Pentachlorophenol sorption by organo-clays, Clays and Clay Minerals, 36, p125-130. Frost, RL, Zhoua, Q, He, H, Xi, Y, 2008, An infrared study of adsorption of para-nitrophenol on mono-, di- and tri-alkyl surfactant intercalated organoclays, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 69, p239-244. Keith, L, Telliard, W, 1979, ES&T Special Report: Priority pollutants: I-a perspective view, Environmental Science and Technology, 13, p416-423.


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Khenifi, A, Bouberka, Z, Sekrane, F, Kameche, M, Derriche, Z, 2007, Adsorption study of an industrial dye by an organic clay, Adsorption, 13, p149-158. Krishna, BS, Murty, DSR, Jai Prakash, BS, 2001, Surfactant-modified clay as adsorbent for chromate, Applied Clay Science, 20, p65-71. Langmuir, I, 1918, The adsorption of gases on plane surfaces of glass, mica and platinum, Journal of the American Chemical Society, 40, p1361-1403. Lin, S-H, Juang, R-S, 2002, Heavy metal removal from water by sorption using surfactant-modified montmorillonite, Journal of Hazardous Materials, 92, p315-326. Oyanedel-Craver, VA, Fuller, M, Smith, JA, 2007, Simultaneous sorption of benzene and heavy metals onto two organoclays, Journal of Colloid and Interface Science, 309, p485–492. Oyanedel-Craver, VA, Smith, JA, 2006, Effect of quaternary ammonium cation loading and pH on heavy metal sorption to Ca bentonite and two organobentonites, Journal of Hazardous Materials, 137, p1102-1114. Stathi, P, Litina, K, Gournis, D, Giannopoulos, TS, Deligiannakis, Y, 2007, Physicochemical study of novel organoclays as heavy metal ion adsorbents for environmental remediation, Journal of Colloid and Interface Science, 316, p298–309. Sullivan, EJ, Bowman, RS, Legiec, IA, 2003, Sorption of arsenic from soil-washing leachate by surfactant-modified zeolite, Journal of Environmental Quality, 32, p2387-2391. Tillman, FD, Bartelt-Hunt, SL, Smith, JA, Alther, GR, 2004, Evaluation of an organoclay, an organoclay-anthracite blend, clinoptilolite, and hydroxy-apatite as sorbents for heavy metal removal from water, Bulletin of Environmental Contamination and Toxicology, 72, p1134-1141. United States Department of Health and Human Services and United States Environmental Protection Agency, 1987, Notice of the first priority list of hazardous substances that will be the subject of toxicological profiles, Federal Register, 52, p12866-12874. Xi, Y, Ding, Z, He, H, Frost, RL, 2004, Structure of organoclays—an X-ray diffraction and thermogravimetric analysis study, Journal of Colloid and Interface Science, 277, p116-120. Xi, Y, Frost, RL, He, H, Kloprogge, T, Bostrom, T, 2005, Modification of Wyoming montmorillonite surfaces using a cationic surfactant, Langmuir, 21, p8675-8680. Xu, L, Zhu, L, 2009, Structures of OTMA- and DODMA-bentonite and their sorption characteristics towards organic compounds, Journal of Colloid and Interface Science, 331, p8-14.

10


BIOSORPTION OF Cu2+ BY IMMOBILIZED BIOMASS OF ARTHROBACTER sp.: BATCH AND FIXED BED COLUMN STUDY Preeti Srivastava* S.H.Hasan Water Pollution Research Laboratory, Department of Applied Chemistry, Institute of Technology, Banaras Hindu University ,Varanasi- 221005, U.P., INDIA

*Corresponding Author Email: [email protected] Mobile No.: +91-9794883900 Abstract

The ability of free and polysulphone immobilized biomass of Arthrobacter sp. to remove Cu2+ ions from aqueous solution studied in batch and continuous system. The Langmuir and Freundlich isotherm models applied to the data. Langmuir isotherm model was found to fit the sorption data indicating that sorption was monolayer and uptake capacity (Qo) was 175.87 and 158.7 mg/g for free and immobilized biomass respectively at pH 5.0 and 30oC temperature, which was also confirmed by high correlation coefficient, low RMSE and low Chi square value. Kinetic study was carried out with pseudo first order reaction and pseudo second order reaction equations and it was found that Cu2+ uptake process followed the pseudo second order rate expression. The diffusivity of Cu2+ on immobilized beads was increases (0.402 X 10-4 to 0.435 X 10-4 cm2/s) with increasing concentration from 50 to 150 mg/L. The maximum percentage Cu2+ removal (89.56%) and uptake (32.64 mg/g) was found at 3.5 mL/min and 20 cm bed height. In addition to this Bed Depth Service Time (BDST) model was in a good agreement with the experimental data with high correlation coefficient (>0.995). Furthermore, sorption and desorption studies were also carried out which showed that polysulphone immobilized biomass could be reused up to six sorption-desorption cycle. Keywords:Biosorption; Copper; Arthrobacter sp.; Kinetics; Shrinking Core Model (SCM);

Bed Depth Service Time (BDST) Model. 1. Introduction A worldwide environmental problem is the contamination of aqueous environments by heavy metals. Copper usually occurs in nature as oxides and sulphides. In acidic environments, free aqueous Cu2+ dominates. At pH 6.0 to 8.0, the predominant species are Cu2+, Cu(OH)2, CuHCO3+, CuCO3, and CuOH+, while at pH>10, the major species are Cu(OH)3- (Bodek et al., 1998). Mining waste and acid mine drainage contribute significant quantities of dissolved copper to effluent streams. Fertilizer manufacturing, petroleum refining, paints and pigments, electroplating of electrical equipments etc. are other sources of copper in aqueous system. Chronic copper poisoning causes neurological abnormalities and corneal opacity (ATSDR, 1990). The conventional technologies for the removal of heavy metals from wastewater require high capital cost, investment and running cost (ATSDR, 1990; Bodek et al., 1998). Therefore, the search for new treatment technologies has focused on biosorption. It have many advantages including low capital and operating costs, rapid kinetics adsorption and desorption and no sludge generation (U.S. EPA, 1987; Volesky, 2001;). Various microorganisms were capable of removing toxic heavy metals, precious metals, base heavy metals and radionuclides from wastewater (Atkinson, 1998; Vijayaraghavan and Yun, 2008; Wang et al 2009). The sorption capacity obtained from a batch experiment is useful in providing the fundamental information regarding effectiveness of metal biosorbents system. However, this data may not be useful to most treatment systems because batch operations are not likely to


11

be employed in industries. Hence, there is need to perform column biosorption experiments. Packed and fluidized bed column possesses inherent advantages such as efficient utilization of the sorbent, better quality of effluent, possible sorbent regeneration and easy scale up procedure (Singh et al., 2005; Mata et al. 2009). In the present investigation, Arthrobacter sp. a gram positive bacteria was used in free and immobilized form to remove Cu 2+ from aqueous solution in batch as well as continuous system. The kinetic and isotherm studies of the process carried out. The effects of column parameters have also been studied. In addition to this, Shrinking Core Model (SCM) and Bed Depth Service Time (BDST) model applied on the experimental data. Furthermore, sorptiondesorption experiments were also carried out for successive cycles. 2 Materials and Methods 2.1

Isolation and identification of microorganism

The strain used in this study was isolated from the pond situated in Banaras Hindu University Campus, Varanasi, India. The isolation of this strain was done by standard isolation methods (streak plate methods). This isolate was purified by repeated isolation and subculturing on a nutrient enrichment medium (nutrient agar medium). A pure colony of the strain was identified presumptively based on the following features: colony morphology, cell morphology, Gram-staining reaction and catalase test. 2.3 Preparation of microorganism for biosorption Arthrobacter sp. was cultivated aerobically in 250 mL conical flasks containing sterile nutrient broth containing beef extract 10 g/L, NaCl 5g/L and peptone 20 g/L on a rotary shaker at 30 °C, 150 rpm for 48 hours. The initial pH of the culture was adjusted from 7.0 to 7.5 using 0.1 N NaOH / 0.1 N HCl. The growing cells from culture broth were separated from liquid by centrifugation (REMI 24) at 5000 rpm for 10 min and were washed several times with double distilled water. The wet cell biomass was then dried for 24 h at 60 oC in an oven. The dried cells were powdered in uniform size. The powdered biomass was immobilized and the immobilized biomass was used in the column study. 2.4 Immobilization of biomass Immobilization of the biomass followed the procedures used by Paknikar and Puranik (Puranik and Paknikar,1999). Thus, 100 mL of N, N-dimethylformamide (Qualigens chemical) solution was added into a mixture consisting of 7 g of powdered pre-treated biomass and 7 g of polysulfone (E. Merck India Ltd. Mumbai, India). After continuous stirring of mixture in a magnetic shaker, uniform slurry of biomass was formed. The slurry was then added to a glass beaker containing distilled water in a dropwise manner using a syringe (5 mL). Beads were cured by stirring in distilled water for 8 h. After curing, the beads were air dried at room temperature for 2-3 days. 2.5

Batch sorption experiment

Metal stock solutions for sorption were prepared in double distilled water with analytical grade salts of Cu(NO3)2.3H2O (E. Merck, India Ltd. Mumbai, India). The stock solution (1000 mg/L) was diluted with double distilled water in order to prepare the desired concentrations. Biosorption experiments were performed in conical flasks previously rinsed with HNO3 in order to remove any metal that remained unadsorbed on the glass wall. Preweighted free and immobilized biomass added to each flask and was agitated on the shaker at 150 rpm until the equilibrium reached. The biomass was separated by filtration. Then metal content in the filtrate determined by AAS( UNICAM 929, USA) at 324.8 nm.

12


The detection limit of the said instrument was 10-3 mg/L. The amount of metal ion adsorbed per unit biomass was obtained by using the following equation: qe =

(C o - C e ) xV m

(1)

where qe is the amount of metal ion adsorbed onto the unit mass of the adsorbent (mg/g), Co and Ce are the initial and final equilibrium concentrations (mg /L), V is the volume (L) and m is the mass of biosorbent (g). All the experiments were conducted in triplicates. 2.6

Dynamic Cu2+ sorption studies in a packed bed column

Continuous fixed bed column studies were performed in column. The column is designed with an i.d. 2 cm and length 40 cm. Since the ratio of the column diameter to particle diameter is high, the effects of channeling are negligible. In the column, stainless steel mesh was kept at the bottom as well as at the top of the column to retain the immobilized Arthrobacter sp. beads in the column followed by glass wool. A 3 cm high layer of glass beads was placed at the column base for providing a uniform inlet flow of the metal solution into the column. The metal solution was pumped in an upward direction through the column by peristaltic pump (Miclins pp 10) at a known flow rate. The treated metal solution was collected from the top with same flow rate of feed stream at pre-determined time intervals. All the experiments were performed at room temperature (30°C) and atmospheric pressure (760 mm) at desired pH. 2.11 Column data Analysis To analyze the dynamic Cu2+ removal in up-flow fixed bed column breakthrough curves (Ct/C0 vs. time) were drawn and the data was evaluated with the help of following equations as previously used by (Vijayaraghvan et al. 2008): Effluent volume (14) V eff = Q .t tot The total amount of metal fed to the column (X; mg): C o Qt tot X = 1000 The total percentage removal of metal ion by the column: q Total Re moval % = tot x100 X The length of mass transfer zone (zm): t Zm = Z (1 − b ) t tot

(16)

(17)

(18)

The Cu2+ desorbed (md) can be calculated from the area below the desorption curve (outlet Cu2+ concentration vs. time) multiplied by the flow rate. The desorption efficiency can be calculated from M Desorption Efficiency (%) = d X 100 M ad 2.12 Bed Depth Service Time Model (BDST) The BDST model works well and provides useful modeling equations for the changes of the system parameters (Han et al., 2007). A modified form of the BDST equation is: N Z C 1 t= o − ln( o − 1) (19) Co u k a Co Ct


13

Where, Ct and Co is the effluent and initial metal concentration (mg/L), u is the influent linear velocity (cm/min), No is bed sorption capacity (mg/L), ka is bed rate constant (L/mgh), t is the time and Z the bed height of the column (cm). 3 Results and discussion 3.1 Identification of bacterium Based on electron-microscopy observation, this strain (Arthrobacter sp.) was irregular rodshaped and 0.95–2.0 µm in size. The cell colony is yellow to white in color. This particular bacterium is aerobic in nature it never grows in anaerobic condition. This bacterium is grampositive bacteria. Catalase reaction test is positive. 3.2 Effect of pH

Metal sorption by Arthrobacter sp. was a pH dependent phenomenon as shown in Fig.1. Cu 2+ sorption by free biomass and immobilized biomass is increase by 7.9 to 42.12 mg/g and 4 to 39.5 mg/g respectively at 50 mg/L of initial Cu 2+ concentrations with increase in pH from 2.0 to 5.0.. Metal sorption declined after attaining the maxima at pH 5.0 for both free and immobilized biomass. The reduced sorption of the Cu2+ metal at higher pH may be due to their precipitation, which reduces the concentration of free metal ions in the solutions (Kratochvil and Volesky, 1998). 3.3 Biosorption isotherm

The linear expression of the Langmuir model (Langmuir 1918) and Freundlich model (Freundlich 1906) is given by Eq. (3) Ce/qe =1/bQo+1/Qo Ce (3) ln qe = ln KF + 1/n ln Ce (4) Where Ce is the equilibrium metal concentration (mg/L) and qe is the amount of metal biosorbed on the biosorbent (mg/g). Qo and b are Langmuir constants related to saturated monolayer biosorption and binding of sorption system respectively, KF and n are Freundlich constants related to biosorption capacity (mg/g) and biosorption intensity. In addition to the correlation coefficient (r2), the residual root mean square error (RMSE) and Chi-square (χ2) values were also evaluated for better fit of model. RMSE =

(

1 m ∑ qe − qe m N − p i =1

χ2= ∑ (q e − q em ) 2 / q em

)

2

(5) (6)

where qe is the observation from batch experiment, qem is the measured value from the isotherm for corresponding qe, N is the number of observation in the experimental design, and p is the number of parameters to be determined. Smaller values of RMSE and χ2 and high values of correlation indicate a better fit of model (Tsai and Juang, 2000; Ho and Ofomaja, 2005). The Freundlich and Langmuir isotherm parameter calculated from slope and intercept of there respective plot and correlation coefficient along with RMSE and Chi-square (χ2) values were calculated and presented in Table.1. The higher correlation coefficient and smaller RMSE & χ2 value demonstrate that Langmuir model was adequately fitted to data in the concentration range 50 to 250 mg/L (Fig. 2) than the Freundlich isotherm. The monolayer biosorption capacities Qo were 175.87 and 158.73 mg/g for free and immobilized biomass respectively. These results indicate that immobilized biomass has lower uptake capacity than the free biomass. This variation could be due to the native biomass in contact with the metal

14


ions, under conditions of moderate agitation, has its binding sites freely exposed to the sorbate. However, in immobilized systems, the sorbent particles entrapped and retained at the interior may not have accessibility to the metal ions. (Bai and Abraham, 2003) 3.4

Kinetic modeling

In order to investigate the mechanism of biosorption two models have been used at different initial metal concentrations. 2.9.1. Lagergren model

This was the first equation for the sorption of liquid/solid system based on solid capacity (Singh et al., 2005). This model may be represented as log (q e - q t ) = log (q e ) - k 1 /2.303 t

(8)

where qt = is the amount of solute on the surface of the biosorbent at time t (mg/g) k1 is the equilibrium rate constant of pseudo first order biosorption (1/min). k1 is calculated by the slope of log (qe – qt) against time (min) plots. 2.9.2. Ho model

This model is expressed as (Ho, 2006).

t / qt = 1 / k 2 qe 2 + 1 / qe t

(10)

h = k2 qe2 Where qe is sorption capacity (mg/g), k2 is the equilibrium rate constant for pseudo second order biosorption (g/mg/min) and h is the initial sorption rate (mg/g min). The equation constants can be determined from the slope and intercept of plot of t/qt against t. Effects of contact time with initial Cu2+ concentration (50-150mg/L) on sorption of Cu2+ by free and immobilized biomass were also studied (Figure not given). The amount of Cu2+ adsorbed increased with increase in contact time and reached equilibrium after 45 min for the Cu2+ concentrations used (50 to 150mg/L) in this study. The equilibrium time is independent of initial Cu2+ concentration. In order to predict the sorption kinetics of Cu2+, Lagergren first order and Ho pseudo second order model were utilized to investigate the mechanism of biosorption. The value of correlation coefficient r2 for the pseudo-second-order adsorption model is relatively higher (> 0.997 and > 0.999 for free and immobilized biomass respectively) than the values of r2 for the pseudo-first-order model (>0.954 and > 0.968 for free and immobilized biomass respectively) (Table 2). Therefore, it was concluded that the pseudo-second-order adsorption model is more suitable to describe the adsorption kinetics of Cu2+ over bacterial biomass. Table 1 Langmuir and Freundlich isotherm constants for Cu2+sorption

Biomass

Langmuir Isotherm Q b r2 RMSE χ2 (mg/g) (L/mg) Free biomass 175.87 0.043 0.998 1.58 1.042 Immobilized Biomass 158.7 0.030 0.998 1.09 1.282 o

kF

Freundlich Isotherm 1/n r2 RMSE

2.96

0.451 0.989

1.159 0.459 0.979

3.53

χ2 1.32

3.95 0.853


15

Table 2 Kinetic parameters (pseudo first and pseudo second order sorption rate constant) for Cu2+sorption at different initial Cu2+concentrations

Lagergren model Ho Model (Pseudo Second order) k1 r2 k2x10-2 qe h r2 Initial Cu2+ Concentration (mg/L) (1/min) (g/mg min) (mg/g) (mg/gmin) Free biomass 50 0.073 0.982 0.0023 140.84 0.46 0.999 100 0.093 0.987 0.0040 147.05 0.86 0.998 150 0.112 0.954 0.0055 163.93 1.45 0.997 Immobilized biomass 50 0.041 0.984 0.34 45.75 7.2 0.999 100 0.042 0.974 0.15 84.74 11.42 0.999 150 0.043 0.968 0.12 109.89 14.61 0.999 k1= Pseudo first order rate constant (1/min.), k2 = pseudo second order rate constant (g/mg/min), h = initial sorption rate (mg/g min) 3.5

Shrinking core model

Many investigators have calculated the diffusivities of heavy metals in immobilized beads using the Shrinking Core Model (SCM) (Veglio and Beolchini,1997). This model was applied to fluid-particle chemical reactions by Levenspiel. In case of a process controlled by the diffusion of metal ions through the liquid film (film diffusion control), the extent of the sorption process as a function of time will be given by the following expression: X = 3 D / δ RC α

(11)

Consequently, if the film diffusion is controlling, a plot of X versus α yields a straight line relationship. If the process iscontrolled by the diffusion through reacted shell (particle diffusion control), the model is represented by the following expression: F ( X ) = 1 − 3 (1 − X ) 2 / 3 + 2 (1 − X ) = 6 D / R 2 C o α

(12)

Consequently, in case of particle diffusion control, a plot of function F(X) versus α will gave a straight line relationship and the diffusivity in the immobilized beads could be obtained from the slope of such a plot as follows: D = ( Slope ) C o R 2 / 6

(13)

Where, X (extent of reaction) = [Co – C] / [Co - Ceq], α =

∫

t

o

Cdt , Co is the initial Cu2+

Concentration (mg/L), Co is the average metal binding site density of the immobilized biomass (mg/L), C is the final concentration (mg/L), Ceq is the concentration of metal ion at equilibrium (mg/L), D is the diffusion coefficient (cm2/s) and R is the radius of bead (cm). Table 3 Shrinking core model parameters

Initial Cu2+concentration (mg/L) 50 100 150

Slope (L/mg-min)

Co (mg/cm3)

Diffusivity (D) (cm2/s)

5.0X10-4 2.7X10-4 2.0X10-4

0.79 1.46 1.83

0.435X10-4 0.417X10-4 0.402X10-4

16


The diffusivity of Cu2+ on immobilized beads were increases with increasing concentration from 50 -150 mg/L in the range of 0.402 X 10-4 to 0.435 X 10-4 cm2/s respectively. The results were presented in Table.3. A good fit was found in the case of controlling intraparticle diffusion. 3.6

Continuous studies

The breakthrough curve were obtained for Cu2+ onto immobilized biomass at different bed heights (10, 15, 20 cm) at three constant flow rates (3.5 mL/min, 7.0 mL/min and 10 mL/min) at 50 mg/L metal concentration and 30 °C temperature. In order to yield different bed height, 6.9 g, 10.35 g and 14 g of immobilized biomass were added into the column to produce bed heights of 10, 15 and 20 cm respectively. The breakthrough curves (Ct/Co vs. time) was shown in Fig. 3. The total sorbed Cu2+, breakthrough time, exhaustion time, percent removal and uptake capacity were calculated from the breakthrough curves and presented in Table 4. Result indicates that the breakthrough time, exhaustion time, uptake capacity, percentage removal and volume treated were increased with the rise in bed height from 10 to 20 cm at all Table 4 Column data parameter for sorption of Cu2+ at different flow rate and bed height

Parameter Flow rate 3.5ml/min 7.0ml/min 10ml/min

Co (mg/L)

Z (cm)

Uptake (mg/g)

tb (h)

ttot (h)

∆t (h)

dC/dt (mg/lh)

Veff (l)

% Metal Removal

50 50 50 50 50 50 50 50 50

10 15 20 10 15 20 10 15 20

32.29 32.45 32.64 30.17 31.83 31.95 21.98 21.90 22.56

14.5 21 28.6 9.2 13.8 18.5 4.5 6.5 8.9

29.8 39.5 48.6 18.5 26.2 33.5 9.62 13.6 17.4

15.3 18.5 20.0 9.3 12.4 15.0 5.12 7.1 8.5

3.13 2.59 2.4 5.16 3.87 3.2 9.37 6.76 5.64

6,258 8,295 10,206 7,770 11,004 14,070 5,772 8,160 10,440

71.21 81.00 89.56 53.59 59.89 63.59 52.56 55.67 60.53

the studied flow rate. When the bed depth is reduced, axial dispersion phenomenon predominate in the mass transfer and reduce the diffusion of metallic ions. The solute (metallic ions) has not enough time to diffuse into the whole adsorbent mass. Consequently, an important reduction in the volume treated at breakthrough point was observed. Moreover, an increase in the bed adsorption capacity was noticed at the breakthrough point with the increase in the bed height. This in adsorption capacity with that in the bed height can be due to the increase in the specific surface of the adsorbent, which supplies more fixation binding sites. Then it follows that a delayed breakthrough of the pollutant leads to as increase in the volume of the solution treated. The increase in adsorption with that in bed depth was due to an increase in the adsorbent doses in larger bed, which provides greater service area (or adsorption sites) ( Vijayaraghavan and Yun 2008). Whereas the effect of flow rate on Cu2+ sorption was studied by varying the flow rate from 3.5, 7.0., 10.0 mL/min, the bed height and Cu2+ concentration were held constant at 10, 15, 20 cm and 50 mg/L respectively. The plot of effluent metal concentration versus time at different flow rates were shown in Fig.3. The total sorbed metal ion, breakthrough time, exhaustion times, percentage Cu2+ removal and uptake capacity are presented in Table 4. As the flow rate increases, the breakthrough curve becomes steeper and reduces the metal uptake capacity and percentage removal. This is due to decrease in the residence time of the Cu2+ metal ion within the bed at higher flow rates. One other reason is that if intraparticle mass


17

transfer controls the process, a slower flow rate favors, and if external mass transfer controls the process, a higher flow rate decreases the film resistance (Vijayaraghavan et al., 2004). The plots of service time (tb) against bed height at different flow rates were linear with high correlation coefficient (>0.995) indicating the validity of the BDST model for the present system (Table 5).The sorption capacity of bed per unit bed volume (No) and rate constant (ka) were calculated from the slope and intercept of the BDST plot respectively. As the flow rate was increased, the value of rate constant ka and the adsorption capacity of the bed per unit bed volume increased. The BDST model constants can be helpful to scale up the process for other flow rates without further experimental run. Table 5 Bed Depth Service Time model constants

Flow rate (mL/min)

Inlet metal Slope Intercept No ka concentration (mg/L) (L/mgh) (mg/L) 3.5 1.115 50 1.41 0.217 81.59 0.056 7.0 2.230 50 0.93 0.117 111.45 0.389 10 3.185 50 0.44 0.040 127.2 1.55 u = linear velocity, No = bed sorption capacity (mg/L), ka = bed rate constant (L/mgh) 3.7

u (cm/h)

r2 0.997 0.995 0.999

Regeneration and Reuse of biosorbent

The column regeneration studies were carried out up to six sorption and desorption cycles. The column packed with 14g (bed height 20 cm) of immobilized biomass and flow rate was adjusted to 3.5mL/min. The breakthrough curve for all sorption cycles presented in Fig 4. The breakthrough curve was somewhat fattened as the cycle progressed. The breakthrough time, exhaustion time, total metal removal, and metal uptake capacity were presented in Table 6. The breakthrough time decreased from 28.6 to 19.46 h as the cycle extended, while the exhaustion time was increased from 48.6 to 51.23 h. The Cu2+ uptake capacity and percentage removal was highest for only first cycle; thereafter, it slightly decreases in the forthcoming cycle. This was due to previous elution processes, which affect the biomass binding sites. The desorption curves obtained for all cycles are presented in Fig. 5, and data is presented in Table 6. The desorption curves observed in all the cycles exhibited a similar trend; a sharp increase in the beginning followed by a gradual decrease. The flow rate in the desorption process was maintained at 7 mL/min to avoid over contact of the desorbing agent with the biosorbent. The elution efficiency was greater than 98.02% in all the six desorption cycles. In cycle 1 at 1 h, 521.10 mg Cu/L was present and this value was not reached in any of the other cycles. The total volume of Cu2+ bearing solution (50 mg/L) treated during this regeneration study was around 61.3956 liter in six cycles and total volume of 0.1N HCl utilized for desorption process was nearly 14.490 L which corresponds to approximately 13.619 days of continuous operation. HCl is the most efficient and inexpensive desorbent for Cu2+ metal ion desorption in this study. 4.0 Conclusion

Free and immobilized biomass of Arthrobacter sp. was successfully utilized for the removal of copper both in batch as well as in continuous system. Langmuir isotherm model fitted well to the sorption data indicating that sorption was monolayer and uptake capacity (Qo) of biomass was 175.87 mg/g and 158.7 mg/g for the free and immobilized biomass respectively Table 6 Sorption process parameters for six sorption-desorption cycle

18


cycle

Uptake tb te Z Zm Veff Time for Elution Total metal capacity (h) (h) (cm) (cm) (mL) Elution efficiency removal mg/g (h) (%) (%) 1 32.64 28.6 48.6 20 8.23 10206 6.5 99.85 89.56 2 31.52 27.91 48.14 20 8.41 10109 6.2 99.95 87.32 3 30.81 26.52 48.05 20 8.96 10009 5.9 99.61 85.52 4 29.74 23.10 46.66 20 10.10 9798 5.7 99.52 85.08 5 31.11 22.15 49.68 20 11.10 10432 5.3 99.10 83.52 6 31.50 19.46 51.23 20 12.4 10758 4.9 98.02 82.00 Z= bed height (cm), Zm = Length of mass transfer zone (cm), Veff = volume effluent (mL)

Amount of Copper adsorbed (mg/g)

160

1.2 Free Biomass (50mg/L)

140

Free biomass (250 mg/L)

1

Immobilized biomass (50 mg/L)

120

immobilized biomass (250 mg/L)

0.8

Ce/qe

100 80 60

0.6

0.4 Free biomass

40

immobilized biomass

0.2

20

0

0 0

1

2

3

4

5

6

7

0

8

20

40

60

80

100

120

140

Ce(mg/L)

pH

Fig. 1 Effect of pH of Cu2+ removal: Initial Cu2+ concentration = 50 and 250 mg/L. Vertical bars shows the standard deviation Fig. 2 Langmuir isotherm plot for Cu2+ removal: concentration = 50- 250 mg/L, pH = 5.0 InitialCu2+

of three replicates

1.2

1

Ct/Co(mg/l)

0.8 3.5ml/min flow rate 10 cm bed height 7.0ml/minflow rate 10 cm bed height 10ml/min flow rate 10 cm bed height 3.5mL/min flow rate 15 cm bed height 7 mL/min flow rate15cm bed height 10 mL/min flow rate, 15 cm bed height 3.5 mL/min flow rate, 20cm bed height'" 7 mL/min, 20 cm bed height 10mL/min flow rate, 20cm bed height

0.6

0.4

0.2

50 mg/L initial Copper Concentration

Metal concentration (mg/l)

1.2

1

0.8

0.6

cycle 1 cycle 2 cycle 3 cycle 4 cycle 5 cycle 6

0.4

0.2

0

0 0

10

20

30

40

50

60

0

10

20

30

40

50

60

Time (hours)

Time(min.)

Fig. 3 Breakthrough curves (Ct/Co vs time) at different flow rate and bed height. Vertical bars shows the standard deviation of three replicates

Fig.4 Breakthrough curves for Cu2+ sorption onto immobilized biomass during six sorption- desorption cycle at 3.5 mL/min flow rate, 50 mg/L Cu2+concentration and 20 cm bed height. Vertical bars shows the standard deviation of three replicates


19

Metal concentration(mg/l)

600

500

cycle 1 cycle 2 cycle 3 cycle 4 cycle 5 cycle 6

400

300

200

100

0 0

1

2

3

4

5

6

7

Time (hours)

Fig. 5 Elution curve for desorption of Cu2+ during six sorption-desorption cycle at 7.0 mL/min flow rate 50mg/L Cu2+concentration, 0.1N HCl desorbing agent. Vertical bars shows the standard deviation of three replicates

at pH 5.0 and 30o C temp..The maximum % Cu2+ removal (89.56 %) and uptake capacity (32.64 mg/g) was obtained at 3.5 mL/min and 20 cm bed height. The BDST was successfully utilized and the model constants can be helpful to scale up the process for other flow rates without further experimental run. The sorption performances were evaluated in six sorptiondesorption cycles. A loss of sorption performance was observed as the cycle progressed, which was equally indicated by decrease in metal uptake capacity and decline in percentage removal at the end of sixth cycle. References

Atkinson, B.W., Bux, F., Kasan, H.C., 1998. Consideration for application of biosorption technology ATSDR (Agency for toxic substances and toxic substances and disease registry), toxicological profile for copper, prepared by sugarcane Research Corporation for ATSDR, U.S. Public health. Service under contract 88-0608-2,1990 ATSDR/TP-90-08. Bai, R.S., Abraham, T.E., 2003. Studies on chromium (VI) adsorption-desorption using immobilsed fungal biomass. Bioresour. Technol. 87, 17-26. Bodek, I., Lyman, W.J., Reehl, W.F., Roswnblatt, D.H., 1998. Environmental inorganic chemistry: Properties, Process estimation Methods, Pergamon, New York.

Freundlich, H., Adsorption in solution. Phys. Chem. Soc. 1906, 40(), 1361–1368. Han, R., Wang, Y., Yu, W., Zou, W., Shi, J., Liu, H., 2007. Biosorption of methylene blue from aqueous solution by rice husk in a fixed bed column. J. Hazard. Mater. 141, 713-718. Ho, Y.S., 2006. Review of second order models for adsorptions systems. J.Hazard Mater. B136, 681689. Ho, Y.S., Ofomaja, A.E., 2005. Kinetics and thermodynamics of lead sorption on palm kernel fiber from aqueous solution. Process Biochem. 40, 3455-3461. Kratochvil, D., Volesky, B., 1998. Advances in heavy metal biosorption. Trend.Biotechnol. 16, 291300.

Langmuir, I. Journal of the American Chemical Society, 40 (1918) 1361–1368 Mata, Y.N., Blázquez, M.L., Ballester, A., González, F., Muñoz, J.A. 2008. Optimization of the continuous biosorption of copper with sugar-beet pectin gels. J. Environ Manage, In Press Puranik, P.R., Paknikar, K.M., 1999. Biosorption of lead, cadmium and zinc by Citrobacter strain MCM B-181: Characterizations studies. Biotechnol. Progr. 15, 228-237. Singh, K.K., Rastogi, R., Hasan, S.H., 2005. Removal of Cr(VI) from waste water using rice bran. J. Colloid. Interf. Sci. 190, 61-68. to remediate metal contaminated industrial effluents Water SA 24, 129-135. Tsai, S.C., Juang, K.W., 2000. Comparison of linear and nonlinear forms of isotherm model for strontium sorption on a sodium bentonite. J. Radioanal. Nucl. Ch. 243, 741-746.

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U.S. EPA, Drinking water criteria document for copper, prepared by the office of Health and Environmental Health assessment, environmental criteria and assessment office, Cincinnati OH, for the office of drinking water, Washington, D.C, ECAO- CIN-1987. pp. 417.

Veglio, F., Beolchini, F., 1997. Removal of metal by biosorption. Hydrometallurgy 44, 301316. Vijayaraghavan, K., Jegan, J., Palanivelu, K., Velan, M., 2004. Removal of nickel (II) ions from aqueous solutions using crab shell particle in packed bed up-flow column J. Hazard. Mater. B113, 223-231. Vijayaraghavan, K., Yun, Y.S. 2008. Polysulfone-immobilized Corynebacterium glutamicum: A biosorbent for Reactive black 5 from aqueous solution in an up-flow packed column. Chem. Eng. J, 145, 44-49 Volesky, B., 2001. Detoxification of metal bearing effluents: Biosorption for next century. Hydrometallurgy 59, 203-216.


21

WINKLER’S METHOD OF DO DETERMINATION MODIFIED FOR SMALL SAMPLE VOLUME Amritanshu Shriwastav & Purnendu Bose Environmental Engineering & Management Programme, Department of Civil Engineering, Indian Institute of Technology Kanpur, India-208016 Email: [email protected]; [email protected]

ABSTRACT The main drawback of modified Winkler’s method of dissolved oxygen determination, despite its accuracy, is the large sample volume required which necessitates search for alternative methods when sample volume is limited. Many methods have been developed to deal with this issue viz. colorimetric, gas chromatography etc. but they have the problems of either accuracy, cost or analysis time. Also most of them are calibrated against Winkler’s method. A new modification is proposed in Winkler’s method to deal with sample size of 1 mL. No significant difference was observed between the results of standard & proposed methods (P = 0.05). Also proposed method has advantages over standard one that the analysis time as well as the cost of analysis is substantially reduced. Key Words: Winkler’s method, dissolved oxygen

INTRODUCTION Various methods for dissolved oxygen determination in water have been developed. Modified Winkler’s method (Method No. 4500-O C; Standard Methods, APHA, 1998) has been concluded to be accurate and reliable (Caritt and Carpenter, 1966), although requirements of large sample volume and time consumed are its main drawbacks (Pal and Das, 1988). Alternatively colorimetric methods to deal with limited sample volume have been developed but are expensive in nature due to required complexing reagents like gold sol (Pal et al., 1991). Gas chromatography is also a viable option for DO determination but is time consuming and expensive. Also various polarographic and optical sensors are now available but require frequent calibration against Winkler’s method due to variable response to temperature and pressure (Hydes et al., 2009; Markfort and Hondzo, 2009). The accuracy and reliability of Winkler’s method makes it indispensable and benchmark for DO determination. To overcome the limitation of large sample volume requirement in Winkler’s method, a modification is proposed in the existing method to deal with as low sample size as 1 mL. The philosophy behind the modification is to provide an insulating layer between water sample & the atmosphere so that no oxygen transfer is possible between the two. The desired properties in insulating reagent are low relative density, water immiscibility & negligible oxygen dissolution capacity. Also provision of such an insulating layer has advantage over glass bottles where zero headspace is necessary for accuracy. Another advantage is that the whole existing Winkler’s method can be shrunk to very small sample size (in this case 1 mL) by reducing the amount of required reagents by same ratio without actually affecting the accuracy or the reliability of original method. Again with such small sample size there are some inherent difficulties & additional precautions which if taken care of would give comparable results to Winkler’s method. n-Hexane has low relative density (0.7) and is immiscible in water. Also Dias et al. (2003) calculated the mole fraction solubility of oxygen in n-hexane to be around 0.002. Hence it is selected as insulating layer reagent in this modification. Its volatility does not interfere with reliability of the method as the total time for analysis is substantially reduced (~ 10 min.). A number of samples were

22


analyzed by Winkler as well as proposed methods & their results compared by t-tests. No significant differences were observed between the results of two methods (P = 0.05).

MATERIALS & METHODS All reagents used were laboratory grade and all solutions were made in distilled water. n-Hexane used was HPLC grade. MnSO4 & alkali-azide-iodide solutions were made as per standard method (APHA, 1998). DO of a water sample was first determined using standard Winkler’s method with 300 mL sample. In the proposed method, first 0.1 mL n-hexane was put in 16 mL glass vial so that a hexane layer forms. Then 1 mL water sample was taken in a pipette, which already contained 1 mL of hexane to avoid any contact of water sample with air, and put below the hexane layer in the vial. This step is the most crucial & important one as most errors are prone to occur here. One needs to spend minimum time possible after taking the sample out & putting it below hexane in the vial. Then 5 µL MnSO4 & 5 µL alkali-azide-iodide solutions were added respectively into the water sample below hexane layer with the help of micro syringe. Precipitate forms within 2-3 minutes. 0.1 mL of conc. H2SO4 was added into the sample below hexane after 3 minutes of precipitation to dissolve it. Exact 1 mL of dissolved solution was taken from below the hexane layer using micro syringe & titrated in a 50 mL beaker with 0.00625M Na2S2O3 by 250 µL micro syringe using starch as indicator. In this case 1 mL of titrant corresponds to 50 mg/L DO in the sample. Table 1 gives details about reagents & their required amounts in both methods.

Table 1: Comparison of Reagents Required in Both Methods S.No.

Quantity

Reagent

Strength

Winkler

Proposed

Winkler

Proposed

--As per Standard method As per Standard method 0.025M

--As per Standard method As per Standard method 0.00625M

1. 2.

Water sample MnSO4

300 mL 1 mL

1 mL 5 µL

3.

Alkali-azide-iodide

1 mL

5 µL

4.

Na2S2O3

---

---

5.

Starch

1-2 drops

1-2 drops

As per Standard method

As per Standard method

6.

n-Hexane

Not used

1.1 mL

---

---

RESULTS & DISCUSSION A number of different water samples were analyzed for their DO content by both methods. Results of these experiments are listed in table 2. The normal distribution of experiment results in both methods is evident by coefficient of variance (CoV) values being substantially lower than limiting value of 0.5. CoV of proposed method are comparatively on the higher side suggesting a wider distribution of data. It can be explained as analysis in 1 mL of sample requires more precautions to avoid the external influence of oxygen. Also the level of accuracy required in transferring the exact amount of reagents and samples is more because of small sample size. But this difference in CoV values does not signify the differences in DO results. For the comparison of obtained results by both methods, hypothesis testing was done using student’s two tailed unpaired t-test for a probability value (P-value) of 5%, with null hypothesis being no


23

difference in means. The resulting P-values of the tests in all cases suggest for the acceptance of null hypothesis. The significance is that results in both methods are statistically same.

Table 2: DO Determined in Both Methods DO by Winkler’s method (mg/L) Sample No.

DO by Proposed method (mg/L) Coefficient of Variance

P-value for 2 tailed unpaired t-test

0.38

0.19

0.085

1.15

0.26

0.23

0.061

20

1.78

0.35

0.20

0.664

0.04

9

3.94

1.09

0.28

0.068

0.09

0.06

10

1.4

0.27

0.19

0.21

4.23

0.33

0.08

10

3.98

0.34

0.09

0.106

10

1.98

0.20

0.10

10

2.13

0.32

0.15

0.239

9

8.66

0.29

0.03

9

8.44

0.39

0.05

0.212

No. of Replicates

Mean

Std. Dev.

Coefficient of Variance

No. of Mean Std. Dev. Replicates

1.

20

2.12

0.26

0.12

20

1.94

2.

20

1.02

0.14

0.14

20

3.

20

1.74

0.21

0.12

4.

5

4.72

0.19

5.

10

1.52

6.

10

7. 8.

Figure 1 gives a comparison between the mean results of both the methods. No trend of over or under prediction is observed. Although in sample four under prediction by proposed method is evident, this may be due to less number of samples analyzed. For sufficient replicates, results by both methods are equal. No such trend in DO values for the whole range found in natural water samples makes the proposed method biasfree towards DO content of the sample.

Fig.1: Comparison of Mean DO Results by Both Methods

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The distribution of DO results for all replicates of the samples by proposed method around mean DO value by Winkler’s method are given in figure 2. In all cases these values bracket the actual DO content as represented by mean DO of Winkler’s method. This again reflects evidence of no trend of under or over estimation in comparison to Winkler’s method.

Fig.2: Distribution of all DO Values by Proposed Method The major advantage of the proposed method, as stated earlier, is the requirement of very small sample size (1 mL) which was a major drawback in Winkler’s method. As an insulating layer is provided in the form of n-hexane it makes the glass bottles with zero headspace unnecessary. This cuts on the cost of the analysis substantially without actually compromising with the accuracy and reliability. Reduction in the amount of other reagents is also cost effective. n-Hexane is the only extra reagent used but the small amount does not add much to the overall cost which is drastically less in comparison to Winkler’s method. The total time for analysis is another factor in favour of proposed method. The normal time taken in Winkler’s method is around 30-45 minutes while that in proposed method hardly exceeds 10 minutes for an experienced analyst. The small sample size also requires some additional precautions and care during the analysis. Major chances of errors are during the handling of the sample. Any contact with air will change the DO content in the sample and show up as erroneous results. Second important thing is to transfer exact amount of sample and reagents as with 1 mL sample an error of ±0.1 mL will result in 10% error in DO results which is significant. Titration with micro syringe also requires special attention. The minimum detection limit of this method depends on the micro syringe capacity. In this case micro syringe used was of 250 µL capacity with a least count of 5 µL. This corresponds to 0.25 mg/L DO with 0.00625M Na2S2O3 titrant which is acceptable for most of the samples. This can be lowered by using either lower strength Na2S2O3 or micro syringe with lesser least count.


25

CONCLUSION A modification is proposed in Winkler’s method to deal with small sample size of 1 mL. An insulating layer of n-hexane is introduced as the main modification. The amounts of other reagents required are reduced in the same ratio as sample volume. Whole of the procedure of Winkler’s method is carried out below the hexane layer which ensures the true sample DO representation in the results. The time required in precipitate formation is substantially reduced to 2-3 minutes from 20-30 minutes which is a major time saving step in the analysis. Also careful sample handling and titration give statistically identical results by proposed and existing Winkler’s method. It makes the proposed method an attractive alternative in terms of reduced cost of analysis and saving in analysis time. The accuracy and reliability also remain high as in original method.

REFERENCES Carritt, D.E., Carpenter, J.H., 1966. Comparison and Evaluation of Currently Employed Modifications of the Winkler Method for Determining Dissolved Oxygen in Sea Water; a NASCO Report. Journal of Marine Research, 24, pp. 286–318. Dias, A. M. A., Bonifacio, R. P., Marrucho, I. M., Padua, A. A. H., Gomes, M. F.C., 2003. Solubility of Oxygen in n-hexane and in n-perfluorohexane. Experimental Determination and Prediction by Molecular Simulation. Physical Chemistry Chemical Physics, 5, pp. 543–549. Hydes, D.J., Hartman, M.C., Kaiser, J., Campbell, J.M., 2009. Measurement of Dissolved Oxygen using Optodes in a FerryBox System. Estuarine, Coastal and Shelf Science, 83, pp. 485–490. Markfort, C.D., Hondzo, M., 2009. Dissolved Oxygen Measurements in Aquatic Environments: The effects of Changing Temperature and Pressure on Three Sensor Technologies. Journal of Environmental Quality, 38, pp. 1766–1774. Pal, T., Das, P.K., 1988. Spectrophotometric Determination of Dissolved Oxygen in Water Through the Formation of an Argentocyanide Complex With Silver Sol. Analyst, 113, pp. 1601–1603. Pal, T., Jana, N.R., Das, P.K., 1991. Spectrophotometric Determination of Dissolved Oxygen in Water by the Formation of a Dicyanoaurate (I) Complex with Gold Sol. Analyst, 116, pp. 321–322. Standard Methods, 1998. American Public Health Association, 20th Edition, pp. 4-131–4-133.

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POTENTIAL USE OF NANOTECHNOLOGY IN WASTEWATER TREATMENT Dr. K. SUKUMARAN PRINCIPAL King College of Technology Namakkal – 637020 [T.N] e-mail: [email protected]

ABSTRACT

The increasing demand for fresh water and its inadequate availability forces to go for re -cycle and reuse of treated wastewater for many applications like agriculture, industrial needs, civi c amenities, etc. The population explosion and the related needs of humans in terms of products, f ood, societal purpose, irrigation, etc., enhance the demand for of treated water. Nanotechnologies being an emerging and enabling technology, its applications are used in variety of areas including treatment of water and wastewater. Use of nanotechnology in wastewater treatment is very effective as it reacts and attacks the particles at molecular level and hence safer, cost effective, energy efficient and mitigates the harmful viruses, pathogens, bacteria, etc. It is also effective in the treatment of indu strial wastes with contaminants such as mercury, arsenic and perchlorate. The various emerging methods of nanotechnology in the treatment of wastewater are overviewed in this paper. Some of the prominent methods viz., Solar nano -photocatalytic treatment, use of nanostructured silica, fullerences as pollution tracers, chemically modified nonporous ceramic, nanomembranes, nanoporous zeolites, carbon aerosol, etc., are briefed in highlighting the significance and advantages offered by nanowaste water treatment. Discussion and conclusions are elicited in emphasizing the importance of nanotechnology applications in wastewater treatment to minimize freshwater stress and scarcity the world is going to face for its future needs and wants. Keywords: Nanofiltration Membranes, Nanocatalysts, Nanomesh, Carbon Aerogel, Nanowire Mesh, Nanopolymers.

1. INTRODUCTION

Nanotechnology is the art, science and engineering for manipulating materials or matter at the 1 to 100 nm scale. It involves design, synthesis, manipulation, characterization and exploitation of materials and devices with structures at nm scale. The manufacturing of tiny and minuscule particles and materials by nanotechnology could be an innovative technique which is applied in water and wastewater treatment. It is forecasted that by 2014, fifteen percent of all goods manufactured globally will be using nanotechnology. Nanotechnology is a multidisciplinary science and technology including the aspects of chemistry, physics, material science, engineering, tech nology, etc., involving the specialists or experts including chemists, physicists, biologist, medical doctors, engineers and computer scientists. Nanotechnology is an enabling technology that could potentially lead to co st-effective and high performance water and wastewater treatment systems. It has the potential for performance to generate technically and environmentally appropriate solutions to water/wastewater treatment compared to the practiced conventional methods. Apart from treatment of water/waste water, it has scope for instant and continuous monitoring of quality of treatment and offer pollution less clean technologies for better conversion of materials and elimination of waste generation. The precautions a nd challenges are to be taken care before nanomaterials could be successfully used on large scale in water/wastewater treatment that include safety evaluation, large scale production facilities, safe disposal of wastes and


energy efficiency. According to the U.S. Environmental Protection Agency r eport on emerging nanotechnologies, “EPA and Nanotechnology oversight for the 21 st century” that more than 450 manufacturers identified nanotechnology related products in the commercial market and greater than 600 raw materials, intermediate components and industrial equipments items are used by nano manufacturers. Hence, the future treatment methods of wastewater using nanotechnology makes it a most preferred method treatment compared to the conventional methods in terms of cost effectiveness, elimination heavy metals, biological contamination and harmful chemicals.

2. SIGNIFICANCE OF NANOTECHNOLOGY

Nanoparticles are expected to improve products used in biomedical, electronic s, consumer products and environment products and environmental applications . Nanoparticles are being researched and developed to improve drug delivery in the body, create smaller and more efficient electronic components enhance the properties of materials to render more services with extended durability and to remove contaminants from industrial wastewater. Research has proved that nanoparticles synthetically manufactured , behave very differently than similar particles of greater size and some can be further modified by attaching specific molecules on them to enhance their properties. There are two major types of nanoparticles that are environmental and engineered / manufactured. Environmental nanoparticles are formed naturally by chemical and biological process es in the environment. These environmental nanoparticles are mainly metal o xides and metal sulfides commonly found as minerals. Engineered nanoparticles are those particles that have been synthetically manufactured, which are of four types . (i) (ii) (iii) (iv)

carbon-based nanoparticles metal-based nanoparticles dendrimers nanoparticles composites nanoparticles

2.1 Carbon – based nanoparticles These are fullerenes (spherical in shape) and nanotubes (cylindrical in shape) are two popular engineered nanoparticles being researched. Fullerenes are pure carbon, cagelike molecular composed of at least 20 atoms of carbon and the word fullerenes mean carbon -60(C60) molecule. C 60 and C70 are two of the most common and easy to produce fullerenes.

2.2 Metal-based Nanoparticles These are nanoparticles of metal -oxides, quantum dots, nano -gold and nano-silver are being studied for their ability to bind with other molecules and catalyze chemical reactions. Metal-based nanoparticles properties being once they enter the environment, they could release their metal which may be toxic to organisms. Quantum dots ar e closely packed semiconductor crystal comprised of hundreds or thousands of atoms, and whose size is the order of a few nanometers to a few hundred nanometers. Variation in size of quantum dots changes their optical properties.

2.3 Dendrimers These are constructed from pieces of different nanomolecules called nanopolymers. Dendrimers is a large molecule comprised of many smaller ones (monomers) linked together. Similar to quantum dots, smaller molecules can be attached to dendrimers surfaces, which enable these dendrimers to perform specific chemical functions.

27

28


2.4 Composites These are the final class of engineered nanoparticles and are mixtures of nanoparticles or nanoparticles attached to larger, bulk materials.

3. WASTEWATER TREATMENT PROCESS A typical wastewater is a collection of residential, commercial and industrial waste discharged and flows through sewers to the treatment plant by gravity flow or pumped ( if required ) to the wastewater treatment. The stages of treatment of wastewater star ts with screening to remove larger waste particles or a grit and then taken to primary clarifiers where solids allowed to sink to the bottom. After the presettlement, biological reactor uses bacterial organisms to reduce the waste to CO2 and water with the addition of compressed air into the basin. The wastewater from the reactor is passed to secondary clarifiers, where biological colonies formed and settled to the floor of the basins. Supernatant or liquid at the top of clarifier is directed to filtration and disinfection. The disinfected water is discharged to surface waterbody or to land irrigation. The slurry or sludge of the clarifiers is pumped either to primary clarifier for recycling or to a digester for stabilization and then subjected to dewatering for final disposal. Dewatering of sludge is done mechanically or by drying in open -air beds and the dried solid wastes transported to a landfill or used as a mature.

4.

STABILITY OF NANOPARTICLES IN WATER

The stability of nanoparticles in water depends upon their chemical structure , water pH and temperature. Carbon-based nanoparticles such as C 60 form negatively charged colloids, soluble in water from 0.000000001 mg / l to 100 mg /l (Fortner et al.). In water, the C60 undergoes a transformation due to high solubility, whereby aggregates are formed (diameter 5 -500 mm) and outer carbon molecules become oxidized thus making the molecule more water soluble. The pH of water has influence on the diameter of C 60 aggregates. Generally particle size is decreased to 50% as water pH increased from 3.8 to 10.3 as shown in Table 1 (Fortner et al.).

Table 1 Variation in Particle Diameter of C 60 Aggregates Based on Water pH Water pH 3.8 5.0 7.0 9.0 10.3

Average Particle Diameter of C60(nm) 118 92 92 91 60

Investigations shows that C 60 aggregates are stable in waters with ionic strength similar to that of ground water and surface water up to 15 weeks. Also it has been proved that these carbon based components can be chemically altered during manufacturing in an effort to increase their water soluability (10,000 to 1, 00,000 mg / l). The solubility of quantum dots with modified surfaces has also been found to be dependent on chemical structure and water pH but also the presence of specific minerals in water. Zhan g et al. studied the soluability of quantum dots having sulphur and acid groups attached (Zhang Y, Chen Y et al.) Results from their study indicated their ‘functionalized’ quantum dots readily bonded with potassium, calcium, manganese, aluminium each under certain water pH conditions. More specifically, particles aggregated and formed floes below pH3 in the presence of monovalent cations, but at about pH5 these suspensions were clear. Interestingly, Zhang et al. also found the functional groups attached to the quantum dots prevented aggregation (Zhang Y, Chen Y et al.). No studies were found investigating the water stability of dendrimers and composites;


however it can be predicted that these molecules would act similarly to carbon -based and metal-based nanoparticles under similar conditions.

5. SORPTION OR BINDING

Research shows that carbon -based nanoparticles sorb to materials commonly used in wastewater systems. It has been reported that fullerences can sorbs to natural organic matter. Organic mater ials are commonly found in domestic wastewater in the form of suspended and dissolved solids, consumer products and debris could sorbs nanoparticles (Duncan CK et al). The C60 is sorbed to plastic, Teflon and any plastic or gasket materials exposed to nan oparticles could contain nanoparticle residue. Fullerences have the potential to sorb to organic contaminants such as naphthalene. Due to their binding potential, metal-based nanoparticles have been used to assist in removing heavy metals from wastewater, specifically, maghemite nano -particles at 10 nm diameter, found to be effective at binding chromium (VI), copper (II) and nickel (III) (Hu J, Chen G and Lo IMC) . Complexion of nanoparticles with metals is found to be pH dependent. Maximum maghemite nanopa rticles binding and heavy metal removal of chromium (VI) was obtained at pH less than 4, while copper (II) and nickel (III) were removed most effectively at pH6 and pH8 respectively. It has also been found that maghemite nanoparticles were effective at b inding with chromium, vanadium, lead and arsenic from wastewater (Yavuz C.T et al.). Four different semiconductor industries ´ wastewater slurries processing with turbidity from 100 -1000 NTU and pH 6.8-8.6 by coagulation combined with flocculation, sedimen tation and filtration has been studied by Carrerra et al. (Cheng MR, Lee DJ Lai JY). Coagulants examined were aluminum sulphate, ferric sulphate, chitosan, polyacrylamide and an anionic polymer. Results show that 45% of the copper was initially bound to p articles and that most of the copper was removed by gravity settling (60-70%). It was reported that nanoparticles containing copper (II) ions were also removed during coagulation and filtration. Nanoparticle removal by coagulation using polyaluminium chlo ride (PACl) and thermal treatment were studied by Chang et al. (Cheng MR, Lee DJ, Lai JY) . Wastewater from a secondary treatment works of a high-tech industrial park containing silica based nanoparticles and CaF 2 was investigated. The size of the wastewater sample particles was segregated into four groups, 30 mm, 1-4 mm, 2-5 nm and 30-300 nm. Experiments revealed that silica -based nanoparticles were not sufficiently removed by coagulation under the test conditions; but increasing the temperature to 65 0C resulted in nanoparticle agglomeration and improved water quality. Subsequent studies by Chang et al. reported that silica based nanoparticles of 1 -5 nm effectively coagulated using a PACl dose of 2.08 mg / l as Al. Electrocoagulation of nanoparticles has been attempted, but it is not a standard conventional wastewater treatment process. It is commonly used to treat industrial wastewaters from semi conductor manufacturing operations. Nanoparticules typically in the wastewater are SiO 2, Al2O 3 or CeO 2 (Den W, Haung C, Ke HC). Reduction in turbidity was the only measure of treatment effectiveness used in this study and no work to characterize the size of nanoparticles on treated water was done. Zhang et al. reported that divalent cations such as manganese and calcium not only affected quantum dot water soluability, but also resulted in these nanoparticles aggregating into 2 µm flocs and being removed by settling up to 70 % by mass from tap water [b]. These investigations also indicate that coagulation using alum produced marginally better results (80 % removal of mass). Filtration using a 0.45 µm filter achieved 85 % reduction in nanoparticle mass regardless of coagulated or not coagulated.

29

30


5. NANOMEMBRANCE TREATMENT / FILTRATION OR REVERSE OSMOSIS

Membrane is a thin semi-permeable film that enables removal of certain components from solution of liquid phase by affecting it as a selective barrier for transfer of suspended and dissolved substances. The passage of substance through membrane depends on physica l and chemical properties of the substance, pore dimensions and electric and chemical properties of membrane. The membrane serves as a functional barrier to transfer of dissolved substances whose permeability depends of physical and chemical interactions between membrane and dissolved substances. Removal of nanoparticles from the wastewater could be done with nanofiltration or reverse osmosis. These membranes possess the capacity of removing very small suspend or dissolved particles from water because of their small pore size. This process needs high energy input , moderate cost equipment maintenance and replacement. Membrane filtration is highly effective in comparison to many other treatment process like flocculation, settling and conventional treatment sy stem. The various membrane processes is as shown in Table 2. Table 2 – Characteristics of Various Membrane Process of Wastewater Treatment

Sl. No

1

2

Membrane Process

Pressure (bar)

Pore Size

Separation Capability

Reverse Osmosis

S3 (1258.5±34.50 - 551.5±23.60 µg g-1). Since the trend are much change on the S2 and S1, on the basic of the metal contents in the bedrock, the inherited levels of Cd and Pb in sediment are likely to be anomalous near mineralization depending on the nature of weathering and other environmental factors (Pitchel et al., 1999). Pb translocation from the sediment to roots was, on average, very low. There is usually no mobility of Pb from roots to shoots and stems due to barriers or lack of transport mechanisms (Zdenka & Mateja, 2009). It was found that the concentrations of Fe in sediment in three stations are higher than Scirpus mucronatus in the following order S1>S2>S3 (715884±112.06 - 280650±78.90 µg g-1). Plant uptake of Fe becomes more important when the trace element concentrations in the surrounding environment are high. Given their higher Fe concentrations in sediment, it was concluded that most of the Fe are translocation from roots to stems on the plant. Sediment was affect directly by the abundant reed bed. The Fe uptake sediment was relatively high in the AMD effluent and there was high adsorption of Fe on stems as well. Most of the metal uptake by plant tissue is by absorption to anionic sites in the cell walls and the metals do not enter the living plant. It makes wetland plants could have heavy metal concentration in their tissues up to 200000 times that of the surrounding environment (Sheoran, 2006). Allan (1995) reported that plants that grow near heavy metal contaminated areas showed a high degree of heavy metal tolerance. However, close to the discharge point at the S1, the metal contents show strong enrichment due to primary dispersion effects. Pyrite, sphalerite, anglesite and muscovite settled out of the mine water in form of detritical-enriched sediment. It is because of the Fe complexity process by two ways that is precipitation and dissolution of the bedrock (Daniel & Richard, 2005; Eva & Maria, 2005; Reeves & Brooks, 1983; Mishra et al., 2008; Lobinski & Marczenko, 1996). The lower pH environment can be responsible for some free Fe enrichment in AMD. In abundant reed bed, the free Fe (iron oxides) values are considerably lower and can be related to rock weathering and soil formation processes. Besides that, higher concentrations of Fe were found at the S1 than S3 of the abandoned reed bed effluent with sediment. One reason could be that the sediment consists of relatively particles and the water can infiltrate the substrate and in turn cause the sedimentation of the metal (Johanna & Maria, 2008). Zn in sediment show a descending order of trend from S1>S2>S3 which is 194.67±1.83 478.33±3.67 µg g-1. The accumulation of Zn in plants are strongly affected by the concentration of Zn in soil sediments (An et al., 2006). Sediment in AMD are not toxic to plants since the highest in concentration in S1 showing the value of 478.33 µg g-1. It is generally considered the total concentration of Zn between 70 mg kg-1 and 400 mg kg-1 in soil sediment is toxic to plants (An et al., 2006). In the three stations, the concentration of Zn in roots and stems of Scirpus mucronatus and sediments are different between each and others. It is because the Zn occurs in environment mainly in oxidation +2 state, Zn remain as free ions especially in low pH values, free Zn ions are deposited and adsorped by the soil sediments resulting the enrichment of Zn in sediments (Ademoyero & Gan, 1994).

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International Conference on Emerging Technologies in Environmental Science and Engineering October 26–28, 2009 Aligarh Muslim University, Aligarh, India

CONCLUSION The distribution of cadmium, zinc, lead and iron in the roots, stems of Scirpus mucronatus and sediment in S1, S2 and S3 in AMD were determined in this study. Heavy metals accumulated were different in each station but follow the sequence of Fe>Zn>Pb>Cd. Lead, zinc and iron in sediment is higher concentration than Scirpus mucronatus. The distributions of heavy metals in roots were higher compare to stems except cadmium in all the three stations. The uptake of heavy metals from sediment into the stems and roots of Scirpus mucronatus were probably depend on the metals availability in sediment.

REFERENCES Ademoyero, A. A. & Gan, K. N. 1994. Toxicology Profile for Zinc. U.S Department of Health and Human Services. Public Health Services, Agency for Toxic Substances and Diseases Registry. Allan, R. J. 1995. Impact of mining activities on the terrestrial and aquatic environment with emphasis on mitigation and remedial measures. Heavy Metals problems and solution, Springer-Verlag Berlin. pg 119. An Zi-Zhuang, Huang Ze-Chun, Lei Mei, Liao Xiao-Yong, Zheng Yuan-Ming & Chen Tong-Bin. 2005. Zinc Tolerance and Accumulation in Pteris vittata L. and its Potential for Phytoremediation of Zn- and Ascontaminated Soil. Chemosphere 62. Page 796-802. Azizli, M. K., Tan, C. Y. & Birrel, J. 1994. Technical note design of the Lohan tailings dam, Mamut Copper Mine Sdn. Bhd., Malaysia. Journal of Mineral Engineering 8(6), pg 705-712. Basic, N., Salamin, N., Keller, C., Galland, N., & Besnard, G. 2006. Cadmium hyperaccumulation and genetic differentiation of Thlaspi caerulescens populations. Biochemical Systematics and Ecology 34(9), pp 667– 677. Cunningham, S. D., Berti, W. R. & Huang, J. W. 1995. Manipulating metabolism, phytoremediation of contaminated soils. Elsevier Science Ltd. pg. 393. Deng, H., Ye, Z. H. & Wong, M. H. 2003. Accumulation of lead, zinc, copper and cadmium by 12 wetland plant species thriving in metal-contaminated sites in China. Journal of Environmental Pollution 132, pg 29-40. Daniel, L., & Richard, M., 2005. Origin of high manganese concentrations in coal mine drainage, eastern Tennessee. Geochemical Exploration 86, pp 143–163. Eva, S. & Maria Greger. 2005. Effects of different wetland plant species on fresh unweathered sulphidic mine tailings. Plant and Soil 7, pp 251–261. Fedius, E. & Erdei, L. 2002. Physiological And Biochemical Aspects Of Cadmium Toxicity And Protective Mechanisms Induced In Phragmites Australis and Typha Latifolia. Journal of Plant Physiology 159, pp. 265–271. Ghosh, M. & Singh, S. P. 2005. A Review On Phytoremediation of Heavy Metals and Utilization of Its Byproducts. Applied Ecology and Environment Research 3 (1). Page 1-18. Jayaweera, M. W., Kasturiarachchi, J. C., Kularatne, R. K. A. & Wijeyekoon, S. L. J. 2008. Contribution of water hyacinth (Eichhornia crassipes (Mart.) Solms) grown under different nutrient conditions to Feremoval mechanisms in constructed wetlands. Environmental Management 87, pp 450-460. Johanna, N. & Maria G. 2008. A field study of constructed wetlands for preventing and treating acid mine drainage. Ecological Engineering (ECOENG-1401), pp 1-13. Karpiscak, M. M., Whiteaker, L. R., Artiola, J. F., & Foster, K. E. 2001. Nutrient and heavy metal uptake and storage in constructed wetland systems in Arizona. Water Science and Technology 44 (11), pp 455–462. Kumar, N. J. I., Soni, H., Kumar, R. N. & Bhatt, I. 2008. Macrophytes in Phytoremediation of Heavy Metal Contaminated Water and Sediments in Pariyej Community Reserve, Gujarat, India. Turkish Journal of Fisheries and Aquatic Sciences 8, pg. 193-200. Lim, W. H., Kho, B. L., Tay, T. H. & Low, W. L. 1998. Plants Of Putrajaya Wetlands. Agriquest Sdn Bhd. Malaysia. Lobinski, R. & Marczenko, Z. 1996. Comprehensive Analytical Chemistry: Spectrochemical Trace Analysis For Metals And Metalloids. Wilson & Wilson’s. Mishra, V.K., Upadhyaya, A.R., Pandey, S.K. & Tripathi, B.D. 2007. Heavy Metal Pollution Induced Due To Coal Mining Effluent On Surrounding Aquatic Ecosystem And Its Management Due Through Naturally Occurring Aquatic Macrophytes, Bioresource Technology. 99, pp. 930–936. Monica, L. N. & Paul, J. K. 2005. Weeds of Rain Fed Lowland Rice Fields of Laos & Cambodia. Unpublished MSc thesis, University of Leiden.


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National Mapping Malaysia. 2006. Kundasang Map 1: 50 000. The Director of National Mapping Malaysia. The Deparment of Survey and Mapping Malaysia. Series DNMM 5201 Edition 1-PPNM Sheet 22, Sabah, Kota Kinabalu. Pentreath, R. J. 1994. Mining and its Environmental Impact. Issues in Environmental Science and Technologies. Royal Society of Chemistry, R.E. & Harrison pg 121. Pitchel, J., Kuroiwa, K., & Sawyer, H. T. 1999. Distribution of Pb, Cd and Ba in soils and plants of two contaminated soils. Environmental Pollution, 4 (110), pp 171–178. Reeves, R.D., & Brooks, R. R. 1983. Hyperaccumulation of lead and zinc by two metallophytes from mining areas of Central Europe. Environmental Pollution 31, pp 277–285. Salt, D.E., Smith, R.D., & Raskin, I. 1998. Phytoremediation. Annual Review Plant Physiology. Plant Molecular Biology. 49; Page 643-668 Shankers, A.K., Cervantes, C., Losa-Tavera, H., & Avdainayagam, S. 2005. Chromium toxicity in plants. Environmental Science 31, pp 739–753. Sheoran., A.S. 2006. Performance of Three Aquatic Plant Species in Bench-scale Acid Mine Drainage Wetland Test Cells. Mine Water and the Environment 25, pp 23–36. Zdenka M. & Mateja G. 2009. Trace element accumulation and distribution in four aquatic macrophytes. Chemosphere 74, pp 642–647.

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ISOLATION, CHARACTERIZATION AND REMOVAL CAPACITIES OF PB2+ RESISTANT BACTERIA FROM ACID MINE DRAINAGE. Naida Haruliza Harun1, Piakong Mohd. Tuah2 and Rubia Idris3 School of Science and Technology, Universiti Malaysia Sabah, Locked bag 2073, 88999, Kota Kinabalu, Sabah. email: [email protected], [email protected], [email protected] Abstract Ten Pb2+ resistant bacteria had been isolated from rhizospheric sample at ex-Mamut copper mine drainage using direct and enrichment technique on nutrient and Ramsay agar at 30 °C. Five of the strains were Gram positive rod, 3 were Gram negative rod and two Gram positive cocci. The removal capacities (RC) of these strains towards Pb2+ were determined after incubated for 48 hours in Pb2+ modified broth. RC of these strains ranged between 1.18 – 12.48 mg g-1, the highest Pb2+ RC was shown by strain NMeHI-Cr2 (B. cereus 1). This was followed by NMeHI-Cr1 (B. anthracis) and NMeS2-W1 (B. cereus 2) with the RC of 10.152 and 8.808 mgg-1 respectively. The result of this study indicates the possibility of these strains to enhance the bioremediation of Pb2+ contaminated wastewater. Keywords: isolation, removal capacity, Pb+2 resistant bacteria, acid mine drainage

1. INTRODUCTION Heavy metals contamination in the aquatic environment is a serious pollution. It can bring health hazard to all level of organisms through accumulation in food chain magnification (Miretzsky et al., 2004). Heavy metals can not be degraded biologically or chemically hence its persistence in the environment indefinitely. Proper clean-up for heavy metals contamination can be achieved by concentrating the metal ions in a form that could be extracted conveniently or be properly disposed. Phytoremediation defined the use of the plants to remove, absorbed and accumulate contaminants from the environment had been explored to combat heavy metals pollution. It had proven to aid in metals removal through plants uptake and accumulation at lab scale and field trials at a cheaper cost, thus providing economic alternative to remediate our environment. The success of phytoremediation may not only depend on the plant itself but also on the interaction of the plant roots with bacteria and the concentration of heavy metals in the soil (Ying Ma et al., 2007). Recently, works had been focused on the role of rhizospheric bacteria to facilitate the uptake of metals ions by plants and enhance the efficiency of phytoremediation. Microorganisms such as bacteria possesses surfaces that can interact with metal ions in soil and water, its cells have a high ratio of surface area to volume which enables bacteria to have strong capacity of

adsorbing and immobilizing metal ions (Beveridge and Schultze, 2005). Furthermore, this organisms are able to discrete various organic compounds such as organic acids, carbohydrates and enzymes that may be beneficial to host plants (Huang et al., 2002). In this study, Pb2+ tolerant bacterial strains were isolated from water and rhizosperic samples taken from a disused mining site. These isolates were characterized through and their removal capacities of Pb2+ were


determined. Selected bacterial strains with high removal capacity were identified using the apiweb database.

2. MATERIALS AND METHODS 2.1 Isolation of Pb Tolerant Strains. Pb2+ tolerant bacterial strains were isolated through direct and enrichment techniques from water and rhizosperic samples collected at Mamut copper mine in Ranau, west coast of Sabah. The samples were serially diluted, spread on nutrient and Ramsay agar medium and incubated at 30 °C for 48 h. Purified colonies were then incubated on nutrient and Ramsay broth amended with 25 mgl-1 of Pb2+ (1000 mgl-1 stock solution, Merck) and gradually taken to higher concentration of Pb2+ (25 – 100 mgl-1) to differentiate Pb2+ tolerant strains.

2.2 Characterization for Bacteria. The characteristic of the isolated colonies was established by microscopic observation and physiological properties of the colony in pure culture. Colony morphology characteristics which include configuration, colour, margin and elevation of the isolates were examined from 24 h culture on agar plates under a stereo microscope. The strains were Gram-stained and examined using bright-field microscope.

2.3 Removal Capacity (RC) of Isolates. Pb2+ removal capacity (RC) of each bacterial strain was determined as described by So et al., (2003). The bacterial cells were incubated in nutrient and Ramsay Pb-modified broth with 25 mgl-1 of Pb2+ at 30 °C for 2 days. The bacterial cells were harvested through centrifugation at 10 000 g for 15 min at 4 °C, then bacterial pellets were dried at 105 °C until constant weight and digested with 10 ml of concentrated HNO3 in block digester. The concentrations of Pb2+ in digested solutions were determined using atomic absorption spectrometer (AAS, Perkin Elmer).

2.4 Identification of Bacterial Strain. Selected Pb2+ tolerant strains with high Pb2+ removal capacities were identified using Analytical Profile Index (API) according to its cellular morphology. Fresh culture of selected strains were inoculated in CHB & Staph medium, then incubated in 50 CHB, 20 staph and 20 E strips at 30 °C for 24 – 48 h. Results were recorded and data were analyzed using apiweb identification software.

RESULT AND DISCUSSION. 10 bacterial strains isolated from rhizospheric and water samples collected at Mamut copper mine had shown the ability to tolerate and grow in Pb2+ amended broth up to 100 mgl-1. 5 strains were Gram positive rods, 3 were Gram negative rods and 2 Gram positive cocci (Table 1).

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Table 1 Characterization of Pb2+ tolerant strains isolated from rhizosperic and water samples incubated on nutrient and Ramsay agar. Strain NMdS1-Cr1

Colony morphology colour configuration Cream L-form

margin Lobate

elevation Flat

Gram staining +VE

Cellular morphology rod

Identification (apiweb) B.

subtilis/

amyloliquefaciens

NMeS2-W1

White

Round

Wavy

Raised

+VE

rod

NMeS2-W2

White

Round

Smooth

Raised

-VE

rod

NMeS3-Cr1

Cream

Round

Smooth

Convex

+VE

cocci

NMdS3-Cr3

Cream

L-form

Irregular

Raised

+VE

rod

Bacillus cereus 2 Bacillus pumilus Staphylococcus xylosus B.

subtilis/

amyloliquefaciens

NMeHI-Cr1

Cream

L-form

Ciliate

Raised

+VE

rod

NMdHI-W1

Cream

Round

Smooth

Raised

-VE

rod

NMdHI-Cr2

Cream

Ciliate

Raised

+VE

rod

RMeS2-Cr2

Cream

Round radiatemargin Concentric

Smooth

Umbonate

-VE

rod

RMdHI-P

Pink

Round

Wooly

Raised

+VE

cocci

Bacillus anthracis Aeromonas hydrophila Bacillus cereus 1 Moerella wisconsensis Staphylococus capitis

The removal capacities (RC) of these strains towards Pb2+ were determined after being incubated for 48 hours in Pb2+ modified nutrient and Ramsay broth. RC of these strains ranged between 1.18 – 12.48 mg g-1, the highest Pb2+ RC was shown by strain NMeHI-Cr2 (Table 2). This was followed by NMeHI-Cr1 and NMeS2-W1 with the RC of 10.15 and 8.81 mg g-1 respectively. These strains are Gram positive (rod) and Gram positive bacteria are particularly suitable for metal binding as the result of interactions between metal ions and the negatively charged microbes surface (Bitton, 1994).

Table 2 Pb2+ removal capacity of isolated Pb2+ tolerant bacterial strains Bacterial strains Bacterial cell mass Pb2+ removed by RC (mg Pb2+ g-1 bacterial cells (mg) bacterial cells) (DW, g) NMdS1-Cr1 0.0031 0.0037 1.22 NMeS2-W1 0.0013 0.011 8.81 NMeS2-W2 0.0013 0.0077 5.91 NMeS3-Cr1 0.0107 0.0126 1.18 NMeS3-Cr3 0.0042 0.0096 2.30 NMeHI-Cr1 0.0013 0.0127 10.15 NMeHI-Cr2 0.0020 0.0249 12.48 NMeH1-W1 0.0023 0.00544 2.37 RMeS2-Cr2 0.0030 0.0116 3.88 RMdHI-P 0.0020 0.0117 3.91

Bacterial strains with high metal ions removal capacities could help with the removal of metal contamination from wastewater. This is agreeable to So et al., (2003) who reported that


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inoculation of strain CU-1 with 10.62 mgg-1 of Cu+2 removal capacity (RC) enhanced the Cu2+ RC of Eichornia crassipes roots that were exposed to Cu contamination. Colonization of strain in the roots area with high RC was likely to enhance plants RC due to the increased of metal ions adsorbed by the cell of the strains. Alteration of the microbial community of the rhizosphere by increasing the population of beneficial bacteria can increase the feasibility and efficiency of phytoremediation (O’Connell et al., 1996). Identification by apiweb database recognized strain NMeHI-Cr2 as Bacillus cereus 1, NMeHI-Cr1 and NMeS2-W1 as Bacillus anthracis and Bacillus cereus 2 respectively. The colony of these strains were shown in Figure 1.

a

b

c

Figure 1 Colony of strains (a) NMeS2-W1, (b) NMeHI-Cr1 and (c) NMeHI-Cr2 Several strains of Pseudomonas and Bacillus were shown to increase the amount of Cd2+ accumulated by Brassica juncea seedlings (Jiang, 2006). Some bacteria are also capable of reducing the toxicity of metal ions to plants and some bacteria such as B. megaterium and B. mucilaginosus can increase the bioavalability of heavy metals (Wu et al., 2006). Symbiotic interaction between plants and rhizospheric bacteria promotes growth to host plant by producing phytohormones, sidespores and solubilizing minerals (Zaidi et al., 2006).

CONCLUSION The ability of high removal capacity bacterial strains can be applied to increase the efficiency of plant-based wastewater treatment systems. Effective phytoremediation depends mainly on the plant itself and the interaction of its roots with microbial community. Therefore, improvement of the interaction between plant and beneficial rhizospheric microbes can enhance the role of plants to remove heavy metal pollutants and are considered to be an important component of phytoremediation technology.

REFERENCES Beveridge, T.J., and Schutze-Lam, S., 1995. Detection of anionic sitee on bacterial walls, their ability to bind toxic heavy metals and form sedimentable flocs and their contribution to mineralization. In: Allen, H.E., Huang, C.P., Bailey, G.W. (Eds), metal Speciation and Contamination in Soil. CRC Press, Boca Raton, pp 183-205. Bitton, G., 1994. Wastewater Microbiology. Wiley-Liss,Inc., New York pp 301-303. Miretzky, P., Saralegui, A. & Cirelli, A.F., 2004. Aquatic macrophytes potential for the simultaneous removal of heavy metals (Buenos Aires, Argentina). Chemosphere 57 pp 9971005.

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O’Connell, K.P., Goodman, R.M., and Handelsman, J., 1996. Engineering the rhizosphere expressing a bias. Trends in Biotechnology 236 pp 83-88. So. L.M., chu, L.M., and Wong, P.K., 2003. Microbial ehancement of Cu2+ removal capacity of Eichhornia crassipes (Mart.). Chemosphere 52 pp 1499-1503. Wu, S.C., Luo, Y.M., Cheung, K.C., and Wong, M.H., 2006. Influence of bacteria on Pb and Zn speciation, mobility and bioavailibility in soil : A laboratory study. Environmrntal Pollution 144 pp 765-773. Ying, M., Rajkumar, M., and Freitas, H., 2009. Inoculation of plant growth promoting bacterium Achromobacter xylosoxidans strain Ax10 for the improvement of copper phytoextraction by Brassica juncea. Journal of Environmental Management 90 pp 831-837. Zaidi. S., Usmani. S., Singh. B.R., and Musarrat. J., 2006. Significance of Bacillus subtilis strain SJ-101 as a bioinoculant for concurrent plant growth promotion and nickel accumulation in Brassica juncea. Chemosphere 64 pp 991-997.


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EFFECT OF ACID MINE DRAINAGE ON METAL CONTENT OF SEAWEEDS IN AMLWCH, NORTH WALES, U.K. R. N. Jadeja* Department of Chemistry, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara, India Lesley Batty School of Geography, Earth and Environment Science, University of Birmingham, Birmingham, U.K.

ABSTRACT The bioaccumulation ability of five species of green, brown and red seaweeds namely Fucus Serratus, Fucus vesiculosus, Pelvetia canaliculata, Entromorpha instetanalis and Furcellaria lumbricalis have been studied in the vicinity of acid mine drainage affected area. The algal tissue concentration of Cu, Al, Fe, Mn and Zn in these seaweeds was determined by Inductive Coupled Plasma Atomic Emission Spectrometry (ICP-AES). These metals were also estimated in the seawater to compute the concentration factors for the metals in studied seaweeds. The bio-sequestering capacity of different seaweed to different metals and their suitability for bioremediation under the influence of acid mine drainage is discussed.

* Corresponding author, Email: [email protected] Keywords: acid mine drainage, Seaweeds, metal content, ICP-AES, pollution 1. INTRODUCTION Wales (United Kingdom) is particularly rich in mineral resources, the type and distribution of which are related to the complex geologic and tectonic history. Parys Mountain, about two miles south of Amlwch in Anglesey (Fig.1), has been the site of sporadic copper extraction from Roman times although it was not until the late 18th and early 19th centuries that major works were carried out.

Figure 1 Map showing the study area At this point Parys became Europe’s premier copper mine exporting 3040 tons/ year of copper together with minor amounts of lead and zinc ore. The ore was originally mined from shafts but was replaced by opencast mining until 1920 when all hard rock mining had ceased. Rain, snowmelt and

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groundwater now percolate through the abandoned mine tunnels, producing an acidic solution of dissolved metals known as acid mine drainage (AMD) (Price et al. 1995), also referred to as acid rock drainage. In 1989, it was estimated that ca.19,300 km of streams and rivers, and ca. 72,000 ha of lakes and reservoirs worldwide had been seriously damaged by mine effluents, although the true scale of the environmental pollution caused by mine water discharges is difficult to assess accurately. Such waters typically pose an additional risk to the environment by the fact that they often contain elevated concentrations of metals (iron, aluminium and manganese, and possibly other heavy metals) and metalloids (of which arsenic is generally of greatest concern). It is difficult to accurately measure the extent to which water bodies are directly impacted by mine waters, but estimates have suggested that in the UK around 700 km of watercourses are affected (Jarvis and Younger 2000), and Neymeyer et al. (2007) have recently documented migration of a major plume of polluted mine water in a public supply aquifer. In addition to the effect that mine discharges have on water bodies as a potential resource, they have been shown to have a significant effect upon riverine ecosystems, causing changes in communities and a reduction in diversity (Armitage and Blackburn, 1985; Malmqvist and Hoffsten 1999). The abandoned mine and the processing grounds around it are a source of toxic levels of metal contamination due to AMD. One of the major pathways through which material is transported to the oceans is riverine input. During this process, part of the material being transported will be modified in the estuarine mixing zone. As a result, estuaries are usually referred to as filters of river-derived signals. The estuarine water of study site Amlwch is contaminated with AMD of abandoned mines. Many species of seaweeds grows luxuriantly in this area. The most common and diverse group in the aquatic environment are the algae. These organisms come in a variety of sizes and shapes, and occur in some of the most extreme environments on earth (Brock et al. 1984). Algae grow in a wide spectrum of water qualities, from alkaline environments to acidic mine drainage waste waters. Algae can be divided into a number of groups, functionally, taxonomically, and ecologically. Algae and other aquatic plants are known to actively pump metals across their cell membranes. This requires an energy source, and is therefore usually coupled to photosynthesis and temperature. Since large numbers of metals in the environment are essential nutrients, it is not surprising that many metals are actively pumped into algal cells. The problem arises when the external metal concentrations far exceed cell requirements. We have previously reported the metal accumulation in marine alga in the vicinity of area polluted with soda ash industry effluent (Jadeja and Tewari 2007). The aim of the present study is to examine the metal content and metal accumulation capacity of the selected seaweeds under the influence of AMD of abandoned copper mines.

2. MATERIALS AND METHODS The samples of Pelvetia canaliculata, Fucus vesiculosus, Furcellaria lumbricalis, Fucus Serratus and Entromorpha instetanalis (Fig.2) were manually collected from the habitat near the Amlwch port (Fig.1) during the lowest low water tide of April 2008.

Pelvetia canaliculata

Fucus vesiculosus

Furcellaria lumbricalis

Fucus Serratus Entromorpha instetanalis Figure 2 Seaweeds used in the present study


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Sample collection, treatment and analytical procedures is quite analogues to those reported recently by us (Jadeja and Tewari 2007, 2008, 2009). The whole plants were cut above holdfast before collection. The seaweeds (fresh weight 2 kg) of same age and good health were collected randomly from the intertidal belt. Each sample of seaweed was washed thoroughly three times with filtered seawater to remove dirt and other attached material and then they were rapidly rinsed in deionized water to remove adhere seawater. The samples were brought to the shore laboratory and spread on clean polythene sheet under shade and left for drying. The plants and animal epiphytes and other material attached to the plants were physically hand picked before drying. The dried material was packed in polythene bags and they were dried in air forced oven at 60oC till constant weight. These samples were pulverized and sieved through 60 µM mesh sieve out of which 100 g pulverized samples were again dried at 60oC and stored in desiccators for metal analysis. About 1 g (dry wt) of the pulverized sample of each species of seaweed was digested in microwave oven after 12 h of pre mineralization with 8 mL of ultra pure concentrated HNO3 Merck Suprapur (Darmstadt, Germany). The solutions were filtered through Whatmann type 589/2 filters and diluted accurately to 25 mL volume with ultra pure deionized water. Such solutions were then analyzed for metal content by inductively coupled plasma atomic emission spectrometry (ICP-AES) model LABTAM 8440 Plasmalab at Sophisticated Analytical Instrument Facility, Indian Institute of Technology, Mumbai, India. Limits of detection from procedural blanks were 0.054 g l-1 for Cu, 0.068 g l-1 for Fe, 0.016 g l-1 for Mn, 0.02 g l-1 for Zn and 0.065 g l-1 for Al. Surface seawater samples were collected from the sub tidal water in front of sampling station during the course of the study. The seawater samples were collected from the same place from where the seaweeds were collected and then homogenized by mixing. Samples were filtered through acidcleaned 0.45 µm membrane filters, stored in 1000 mL polypropylene bottles and frozen after the addition of nitric acid to adjust the pH between 4 and 5. The concentration of Cu, Fe, Mn and Zn in the seawater was determined by atomic absorption spectrophotometry (AAS) using Perkin Elmer AAnalyst 600 model. The minimum detection limit for each element was 1.5 g/L for Cu, 5 g/L for Fe, 1.5 g/L for Mn and 1.5 g/L for Zn, respectively. All chemicals used in sample treatments were of ultrapure grade. Ultrapure water (Milli-Q System, Millipore) was used for all solutions. All glassware was cleaned prior to use by soaking in 10% HNO3 for 24 h and rinsed with Milli-Q water. The standard solutions of metals were prepared from stock standard solution of ultrapure grade supplied by Merck.

3. RESULTS AND DISCUSSION The bio metal concentrations in various seaweed tissues under the influence of the AMD are depicted in Table 1. Different algae exhibit different affinities towards different metals, which in turn depend on the chemical structure of the biosorbent (Hamdy 2000). Also, metal concentrations vary in different portions of the plant, being generally higher in the older parts of the algae and lower in fast growing tips, as the older parts of the plants are exposed to the ambient concentration of element for a longer time than younger parts (Farias et al. 2002). In this study, only whole organisms were analyzed in order to obtain information about the mean concentration of trace metals in algae. Table 1. Bioaccumulation of metals in various seaweed tissues Seaweed / metal content in ug/gm Cu Al Fucus Serratus 158.3(10) 800.0(50) Fucus vesiculosus 200.0(15) 2458.3(103) Pelvetia canaliculata 58.3(4) 1758.3(87) Entromorpha instetanalis 33.3(3) 3850.0(173) Furcellaria lumbricalis 58.3(7) 225.0(27) Figures in parentheses are standard error (n = 3).

Fe 441.6(18) 1333.3(48) 1033.3(56) 4166.7(148) 208.3(45)

Mn 216.7(22) 450.0(23) 100.0(22) 208.3(16) 66.7(18)

Zn 1183.3(87) 750.0(32) 358.3(17) 475.0(37) 200.0(31)

The highest tissue concentration of copper and manganese were found in sub tidal alga F. vesiculosus, whereas that of iron and aluminum in E. instetanalis. However, the zinc content in the tissue was

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found highest incase of F. Serratus. This shows that different seaweeds have different affinity and mechanism to accumulate the different metal ions. The results suggest that the concentrations of different metals in the macroalgae are determined by two factors, the dissolved phase concentrations of the metals as well as their relative concentrations. Evidently, the uptake and/or sequestration pathways are mechanistically linked in order to account for these observations. There have been many previous studies of metal content in Fucus spp., although most have examined habitats in Europe and fucoid algae other than F. gardneri. Riget et al. (1995) found 1.3±3.3 ppm Cu in dry weight of F. vesiculosus in unpolluted water in Greenland. Other studies in Europe have found up to 20 ppm Cu in dry weight of Fucus spp. in what are referred to as unpolluted waters (Foster 1976; Bryan 1983; Ho, 1984). Bryan (1983) also examined the metal content in Fucus spp. in the mine water-polluted Fal Estuary and found 293 ppm Cu in dry weight. While dissolved Cu in seawater does not necessarily reflect the amount of bioavailable Cu at a given site or time (Gledhill et al. 1997), it does provide a useful tracer of how much AMD is present in a given sample of water; the amount of AMD in water should be proportional to the concentration of dissolved Cu. Additionally, we focused on the distribution of Cu, rather than other aspects of the AMD such as Zn, Fe and acidity, because (1) Zn is typically an order of magnitude less toxic to algae than Cu (Hargreaves and Whitton 1976; Munda and Hudnik 1986), and (2) the buffering capacity of seawater appears to overwhelm the acidity of the drainage except in the immediate vicinity of the Creek mouth (Grout et al. 1998). However, any effects of AMD on biota cannot be attributed to any one component; these effects are likely caused by the cumulative effects of several parts of the effluent. The least concentration of copper was found in E. intestinalis. Enteromorpha spp. have been found to be more tolerant of copper than other algae (Correa et al.1996), and copper-polluted areas have been found to be dominated by E. intestinalis (Castilla 1996). Chlorophytes have been shown to be highly resistant to environmental stress, showing tolerance of copper, with optimum growth rates in the presence of elevated copper levels, and tolerance of a wide range of pH (Blackwell and Gilmour 1991). The Enteromorpha used in the present study are amongst the most commonly used genus in the biomonitoring of trace metal pollution. Different species of algae of the genera Enteromorpha have been used as bioindicators of contamination in different parts of the world (Buo-Olayan and Subrahmanyam 1996, Brown et al. 1999, Villares et al. 2002). Concentration factors (CF) were calculated for each metal and seaweed as the ratio of the mean metal concentration in the seaweed and its mean concentration in the seawater collected from the same place. Mathematically, CF = Cs / Csw Where Cs = mean metal concentration in the seaweed Csw = mean metal concentration in the seawater collected from the sampling point The influence of AMD on concentration factor (CF) of different species of seaweeds for different metal ions is depicted in Table 2. Ii is obvious that the concentration of heavy metals in marine algal species is several orders of magnitude higher than the concentration of the same metals in seawater (Donat and Dryden 2001). The wide range of metal concentrations in different algal species reflects the importance of biochemical factors in affecting the relative tendency of different tissues to concentrate pollutants. Such biochemical or physiological differences may also play a major role in causing certain species to concentrate pollutants to much higher levels than other organisms, regardless of the relative position of the species in the aquatic food chain (Millward and Turner 2001). Additionally, the marine plants including algal plants are important in marine biogeochemical cycles not only because they are able to concentrate large quantities of elements (relative to seawater), but also because they can transport them in a variety of ways. These include: detritus sink and decomposition of organic matter in the sediments; direct release through plant tissue-water exchange, and part of aquatic food chain (Millward and Turner 2001). The results are similar to that of bio concentrations of metals in the seaweeds i.e. the highest CF for copper and manganese were found in brown alga F. vesiculosus while that of iron in green alga E. instetanalis.


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Table 2 Concentration factors (CFs) for various metals Seaweed / concentration factors

Cu

Fe

Mn

Fucus Serratus Fucus vesiculosus Pelvetia canaliculata Entromorpha instetanalis Furcellaria lumbricalis

33.7 42.5 12.4 7.1 12.4

18.3 55.3 42.8 172.9 8.6

10.4 21.7 4.8 10.0 3.2

Zn 25.4 16.1 7.7 10.2 4.3

The CFs for Al is not shown in this table as it was not possible to determine the Al concentration in the seawater sample. The values for CF in different seaweeds for different metals showed different trends of variation. The trend in F. Serratus was Cu > Zn > Fe > Mn while in F. vesiculosus it was Fe > Cu > Mn > Zn. Similarly the trend for F. lumbricalis was Fe > Cu > Zn > Mn, while that for P. canaliculata it was Cu > Fe > Mn > Zn. The similar trend for E. instetanalis was Fe > Zn > Mn > Cu. Many biological communities and organisms (i.e. periphyton, macroinvertebrates, and fish) are commonly employed as biomonitors. Filamentous algae are regarded as useful biological monitors of metal accumulation levels (Stokes 1979, Whitton et al. 1981). However, there has been limited investigation into the use of other measurements of macroalgal assemblages to assess the impact of various anthropogenic inputs. Most work conducted in this arena has concentrated on the use of other algal groups such as the diatoms and scaled chrysophytes (Pan et al. 1996, Lotter et al. 1997, Stewart et al. 1999). Beyond cursory observations, little work has been carried out using macroalgae as a bioassesment tool of aquatic systems after the reclamation of surface mines (Bennett 1969). Our data suggest that the metal content in macroalgae maybe a useful indicator of the biologically available fraction of metals in seawater.

4. ACKNOWLEDGMENTS This work was partially supported by British Ecological Society, London.

5. REFERENCES Armitage, P.D., Blackburn, J.H., 1985, Chironomidae in a Pennine stream receivingmine drainage and organic enrichment, Hydrobiologia, 121, p65–72. Bennett, H.D., 1969, Algae in relation to mine water, Castanea, 34, p306–328. Blackwell, J.R., Gilmour, D.J., 1991. Stress tolerance of the tidal pool chlorophyte, Chlorococcum submarinum. British Phycology Journal, 26, p141–147. Buo-Olayan A.H., Subrahmanyam M.N.V., 1996, Heavy metals in marine algae of the Kuwait coast. Bull Environ Contam Toxicol, 57, p816–823. Brown M.T., Hodgkinson W.M., Hurd C.L., 1999, Spatial and temporal variations in the copper and zinc concentrations of two green seaweeds from Otago Harbour, New Zealand. Mar Environ Res, 47, p175–184 Bryan, G.W., 1983, Brown seaweed, Fucus vesiculosus, and the gastropod, Littorina littoralis, as indicators of trace-metal availability in estuaries. Sci. Total Env., 28, p91-104. Brock, T.D., Smith, D.W., Madigan, M.T., 1984, Biology of Microorganisms, fourth ed. PrenticeHall, Englewood Cliffs, NJ.

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Castilla, J.C., 1996, Copper mine tailing disposal in northern Chile rocky shores: Enteromorpha compressa (Chlorophyta) as a sentinel species. Environmental Monitoring and Assessment, 40, p171– 184. Correa, J.A., Gonzalez, P., Sanchez, P., Munoz, J., Orellana, M.C., 1996, Copper–algae interactions: inheritance or adaptation?, Environmental Monitoring and Assessment, 40, p41–54. Donat J., Dryden C., 2001, Transition metals and heavy metal speciation. In: Steele J, Thorpe S, Turekian K (eds) Encyclopedia of ocean sciences. Academic, Elsevier Science, New York, p3027– 3035 Farıás S., Pe´rez-Arisnabarreta S., Vodopivez C., Smichowski P., 2002, Levels of essential and potentially toxic trace metals in Antarctic macro algae. Spectrochimica Acta Part B, 57, p2133–2140. Foster, P., 1976, Concentrations and concentration factors of heavy metals in brown algae. Environ. Poll., 10, p45-53. Gledhill, M., Nimmo, M., Hill, S.J., 1997, The toxicity of copper (II) species to marine algae, with particular reference to macroalgae. Journal of Phycology, 33, p2–11. Grout, J.A., Levings, C.D., Piercey, G.E., Mossop, B., 1999, Biological data from near Britannia mine and in Howe Sound, British Columbia, during 1997–1998. Canadian Data Report of Fisheries and Aquatic Sciences #1055 Hamdy A.A., 2000, Biosorption of heavy metals by marine algae. Curr Microbiol ,41, p232–238. Hargreaves, J.W., Whitton, B.A., 1976, Effect of pH on tolerance of Hormidium rivulare to zinc and copper, Oecologia, 26, p235–243. Ho, Y.B., 1984, Zn and Cu concentrations in Ascophyllum nodosum and Fucus vesiculosus (Phaeophyta, Fucales) after transplantation to an estuary contaminated with mine waters, Conserv. Recycl., 7, p329-337. Jadeja R.N., Tewari A., 2007, Effect of soda ash industry effluent on bioaccumulation of metals by seaweeds of coastal region of Gujarat, India, J. Hazard. Mater., 147, p148-154. Jadeja R.N., Tewari A., 2008, Effect of soda ash industry effluent on protein content of two green seaweeds, J. Hazard. Mater., 151, p559-561. Jadeja R.N., Tewari A., 2009, Effect of soda ash industry effluent on agarophytes, alginophytes and carragenophyte of west coast of India, J. Hazard. Mater., 162, p498-502. Jarvis A.P., Younger P.L.. 2000, Broadening the scope of mine water environmental impact assessment. Environ Impact Asses., 20, p85–96. Lotter, A.F., Birks, H.J.B., Hofmann, W., Marchetto, A., 1997, Modern diatom, cladocera, chironomid, and chrysophyte cyst assemblages as quantitative indicators for the reconstruction of past environmental conditions in the Alps. I. Climate. J. Paleolimno. 18, p395–420. Malmqvist B, Hoffsten P.O., 1999, Influence of drainage from old mine deposits on benthic macroinvertebrate communities in central Swedish streams. Water Res., 33, p2415–23. Millward G.E., Turner A., 2001, Metal pollution. In: Steele J, Thorpe S, Turekian K (eds) Encyclopedia of ocean sciences. Academic, Elsevier Science, New York, p 1730–1737


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Munda, I.M., Hudnik, V., 1986, Growth response of Fucus vesiculosus to heavy metals, singly and in dual combinations, as related to accumulation. Botanica Marina, 29, p401–412. Neymeyer A, Williams R.T., Younger P.L., 2007, Migration of polluted mine water in a public supply aquifer, Q J Eng Geol Hydroge., 40, p75–78 Pan, Y., Stevenson, R.J., Hill, B.H., Herlihy, A.T., Collins, G.B., 1996, Using diatoms as indicators of ecological conditions in lotic systems: a regional assessment. J. North Am. Benthol. Soc., 15, p481– 495. Price, W.A., Schwab, T., Hutt, N., 1995, A reconnaissance study of acid mine drainage at the Britannia mine. British Columbia Ministry of Energy, Mines and Petroleum Resources, Victoria, Canada. Riget, F., Johansen, P., Asmund, G., 1995, Natural seasonal variation of cadmium, copper, lead and zinc in brown seaweed (Fucus vesiculosus), Mar. Pollut. Bull., 30, p409-413. Stewart, P.M., Butcher, J.T., Gerovac, P.J., 1999, Diatom (Bacillariophyta) community response to water quality and land use, Nat. Areas J., 19, p155–165. Stokes, P.M., 1979, Copper accumulation in freshwater biota. In: Nriagu, J.O. (Ed.), Copper in the Environment. Part 1. Ecological Cycling. Wiley/Interscience, New York, p360–381. Villares R., Puente X., Carballeira A., 2002, Seasonal variation and background levels of heavy metals in two green seaweeds. Environ Pollut., 119, p79–90 Whitton, B.A., Diaz, B.M., 1981, Influence of environmental factors on photosynthetic species composition in highly acidic waters. In: Verhandlungen Internationalen Vereinigung für Theoretische und Angewandte Limnologie, 21, p1456–1465.

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INTERACTION BETWEEN RAINFALL, GROUNDWATER TABLE AND WATER QUALITY IN THIRUVANNAMALI DISTRICT R.Raja1 G.Gopinath1 J.Harikrishanan1 C.Prabhu1 J.Chandrasekar1 E.Arunkumardeepan1 1) Adhiparasakthi Engineering College Melmaruvathur 603 319 Kanchepuram District Tamil Nadu 2)

E.Pasumalaidevan2 Executive Engineer Water Resources Office Tramani, Chennai Tamil Nadu ABSTRACT Thiuvannamali district has been carved out as separate district in 1989 as a result of bifurcation of Vellore district of Tamil Nadu. The study area is bounded between Vellore district in the West and Villupuram district in the South and Kanchepuram district in the East of Thiruvannamali district and the district consists of Thiruvannamali, Chengam, Polur, Cheyyar, Vandavasi, Arani with a geographical area of 6312.05Km2. The entire geographic area consists of sedimentary rock and the hard rock. There is no perennial river and potential aquifer in the study area; hence water resources are surface water bodies and ground water resources from the weathered rocky aquifer for the Drinking, Agriculture, and the Industrial activities. The study mainly aims to understand interaction between rainfall, groundwater table and water quality in Thiruvannamali district. The secondary data have been collected from Water Resources Office, Taramani, Chennai for rainfall data between 1989 and 2004, groundwater table, and water quality parameter such as EC, TDS, Ca, Mg, Fe, NH3, NO2, NO3, SO4 and PO4 between 1999 and 2004. The study follows decrease in water quality with decrease in rainfall has been observed. Keywords: Potential aquifer, weathered rocky aquifer, groundwater table, water quality

INTRODUCTION Water is indeed a precious and scarce commodity today. It is necessary that conservation of water to the extent possible by using less water and by protecting and enhancing our water resources. All over India, There is a severe crisis in groundwater resources for quantity as well as quality in resources-poor households in rural areas owing shallow wells are losing their access to water and availability of water for small towns and areas on urban fringes is also declining. Thus groundwater is the largest sources of fresh water on the planet excluding the polar icecaps and glaciers. The amount of ground water within 800m from the ground surface is over 30 times the amount in all fresh water lakes and reservoirs, and about 3000times the amount in stream channels, at any one time. At present nearly one fifth of all the water used in the world is obtained from the ground water resources. Agriculture is the greatest user of water accounting for 80% of all consumption. It takes, roughly speaking, 1000 tons of water to grow one ton of grain and 2000tons to grow one of rice. Animal husbandry and fisheries all require abundant water. About 15% of world’s cropland is irrigated area in India is 60 million hectares of which about 40% is from ground water. The average annual rainfall of India is around 114 cm. Based on this Dr. K. L. Rao has estimated that the total annual rainfall over the entire country is in the order of 370 M ha-m of water and one third of this lost in evaporation, of the remaining 247 M ha-m of water, 167 M ha –m goes as runoff and the rest of the 80 M Ha-m goes as subsoil water. Out of this 80 M ha-m of subsoil water that seeps down annually into


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the soil, about 43 M ha-m gets absorbed in the top layer, thereby contributing to the soil moisture, the balance of 37 M ha-m is the contribution to the groundwater from the rainfall. The average annual groundwater recharge from rainfall and seepage from canals and irrigation systems is the order of 67M ha-m of which 40% i.e. 27 M ha-m is extractable economically. The figure given by the Dr.K.L Rao shows that the about 14M ha-m of water is available for feature use. The rabid urbanization and increase in population forces the drastic change in land use pattern and change in climatic condition over the longer the period, hence the distribution of rainfall over the basin records lower than average value in some basin and higher than average value in some basin against the average annual rainfall with the time and space. The urbanization reduces the run off time immediately produces the run off and reach the ocean immediately, this leads to reduction in percolation of the water in to the soil there by reduction in groundwater potential is takes places.

OBJECTIVE OF THE STUDY From the above it clear that the amount of water resources available in the globe remains the same and there is always steady increase in groundwater for the various demand such as drinking , irrigation, industrial and other recreational purpose. Where as the groundwater potential is reducing due to because of the urbanization and the quality water depends upon the quality of recharging basin and the exploitation of the groundwater resources. Hence this study aims address “Interaction between Rainfall, Groundwater Table and Water Quality in Thiruvannamali District” By collecting the secondary data from Water Resources Office, Taramani, Chennai

1) Rainfall data for the years 1989 to 2004. 2) Groundwater table for the years 1999 to 2004 3) Water quality parameter such as EC, TDS, Ca, Mg, Fe, NH3, NO2, NO3, SO4 and PO4 between 1999 and 2004.

STUDY AREA Vellore district in the north, Dharmapuri district and Vellore district in the west and Villupuram in the south and Kanchepuram district in the east bound Thiruvannamali district shown in Figure -1. The district lies between 12˚00’0”, and 12˚08’40”, north latitude and 78˚06’1” and 79˚07’3” east longitude shown in Figure-1. The general geographical information of the district is of small hills and flatted area. Ponnaiyar River and Vellar are flowing in the district and they will be dry during the summer season. Thiruvannamali district consists of six taluks, namely 1) Thiruvannamali 2) Chengam, 3) Polur 4) Cheyyar, 5)Vanadvasi, 6) Arani. The total geographical area of the district is 6312.05 Sq.Km divided into 18 Blocks.

ENVIRONMENTAL STATUS OF THE DISTRICT AGRICULTURE AND HORTICULTURE Cultivation is the mainstay of the people of the district and the rural economy centers. When monsoons occur normally, while paddy is the main food grain produce in the district, groundnut is the important commercial crop. The three agricultural seasons are “Swaranavari” (May to September), Samba (August to February), and Navarai (December to May) and all are suited for paddy cultivation.

Land utilization

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The geographical area of the district was 6312.05Sq.Km in 1996-97. Cropped area accounts for 55.39% of the total area. Forest lands cover about 24.29% of the total land. A significant portion of the land falls under the category of “non available for cultivation’ and ‘fallow lands’. About 3.82% fall under the category of uncultivated land.

CONSUMPTION OF FERTILIZERS AND PESTICIDES About 29000 metric tones of chemical fertilizers were used in 1995-96 including 3.57% of chemical fertilizers in the district, followed by pesticides in 1995-96. Moreover, 26,500 tones of urea were used in the district.

SOIL TYPES Thin red soil and deep red soil are the predominant soil types in this district accounting for 86% followed by clayey soil for 8.31% and rest of the soil is gravelly soil.

RESULT AND DISCUSION The district consists of six blocks in which 57 places are identified as sampling location to monitor the water quality of the district and maintained by the department. The rainfall data is collected for the years 1989 to 2004 and the water quality parameters for 1999 to 2004.

ELECTRICAL CONDUCTIVITY (EC) AND TOTAL DISSOLVED SOLIDS (TDS) CONDUCTIVITY (EC) Conductivity of a water sample is a measure of ability of the sample to carry electric current. Several factors influence conductivity influence conductivity-amongst them are temperature, ionic mobilities, and ionic valencies, but over all concentration of ions present in water that influences conductivity the most and it is the indicator of dissolved ions present in any water sample. The present study observed the conductivity 190µS-3000µS.

TOTAL DISSOLVED SOLIDS (TDS) The material is left as a solid residue upon evaporation of the water and constituent a part of total solid. The TDS represents the presence of various salts in the water in the dissolved form. In this study the range concentrations between 135 to 2310ppm. The range of TDS value is lower than the WHO recommended value of 500ppm and slightly higher than the recommended concentration of WHO recommended maximum permissible limit of 1500ppm. The variation of the concentrations may be due unsaturated water that comes in contact with the existing soil and the rock and dissolves the material.

SULPHATE (SO4) Sulpahte is the major nutrient for the plant, and it is essential for the plant growth. The presence sulphate in groundwater is due the presence gypsum in the soil formation and the use of gypsum based agrochemical may produce the run-off followed by the groundwater contribution. The sulphate readily reacts with the Ca and Mg present in the formation. The concentrations of sulphate observed in the study area are 70.56ppm to 76.07ppm with an average value of 72.1ppm. The range of concentration and the average concentration is well below the WHO recommended concentration of 200ppm and well below


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maximum permissible concentration of 400ppm. The value shows the degree of weathering varying from location to location over the district and the agrochemical usage in the agriculture activity. Figure-2 shows that the decrease in trend of Groundwater table and sulphate has started from the year 2002 onwards and the observed ground water table of 10.07m for the same year.

AMMONIA (NH3, NO2 & NO3) Ammonia is a chemical made by both man and nature. The amount of ammonia produced every year by man is very small compared to that produced by nature every year. However, when ammonia is found at a level that may cause concern, it is usually produced either directly or indirectly by man. Ammonia easily dissolves in water. In wells, rivers, lakes, and wet soils, the ammonium form is most common. Ammonia is very important to animal and human life. It is found in water, soil, and air, and is a source of muchneeded nitrogen for plants and animals. Most of the ammonia in the environment comes from the natural breakdown of manure and dead plants and animals. Eighty percent of all man-made ammonia is used as fertilizer the value of ammonia ranging between 0.01ppm to 0.21ppm with an average value of 0.09ppm, the values are very less and it is free from the objectionable odor in the groundwater. The value NO3 ranging between 17.93ppm to 23.42ppm with an average value of 20.3ppm, the values are within the range WHO recommended maximum permissible concentration of 5-500ppm. Nitrification is defined as the biological oxidation of ammonium-nitrogen to nitrate (Larry W. Canter ). Nitrification takes place in two stages as (NH+4 --> NO2) and (NO2Æ NO3). The ammonium oxidation of nitrite can be written as NO-2+11/2 O2-Æ NO-2+2H++H2O Nitrite oxidation to nitrate can be written as (Larry W. Canter) NO-2+1/2O2ÆNO-3 Combining reaction yields NH+4+2O2ÆNO-3+2H++H2O

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The variation of NH3 is as same as SO4 and it is not shown in the figure. The Figure-3 maximum value of NO3 is observed as 23.42ppm in the year 2003 and the lowest groundwater table of 13.38m is observed in the same year.

PHOSPHROUS (PO4) Phosphrous appears exclusively as phosphate in aquatic environments. Phosphate is a constituent of soils and is used extensively in fertilizers to replace and supplement natural quantities on agricultural lands. Phosphate is also a constituent of animal waste and may become incorporated into the soil in grazing and feeding areas. Infiltration by runoff may become major sources to groundwater. The concentration of PO4 ranges in this study varies between 0.2ppm to 0.43ppm with an average value of 0.33ppm. Generally the presence of PO4 in the groundwater is very minimal and this study also reveals the same trend of sulphate is observed and it is not shown in figure.

CALCIUM (Ca) AND MAGNESIUM (Mg) Calcium and magnesium are considered to be two ions with similar behavior. Several compounds in groundwater reflect the mineral composition of the bedrock or the soil. It is observed that the concentration of calcium ranging between 41ppm to 360ppm in the study area. The range of concentration well below the WHO recommended concentration of 75ppm and above the WHO recommended maximum permissible concentration of 200ppm. The range of Magnesium concentration shown figure-4 varies from 32.18ppm to 39.23ppm, with an average concentration of 35.0ppm. The range concentration


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well below the WHO recommended concentration as 50ppm and the WHO recommended maximum permissible concentration 150ppm. The variation of concentrations of calcium and Magnesium shows the degree of weathering formation varies from location to location in the study area.

IRON (Fe) All metals are to some extent in water. While excessive amounts of any metal may cause health hazard, iron is non toxic metal. The most common non toxic metals are highly reactive with other element. Significant quantities of iron will usually be found only in systems devoid of oxygen such as groundwater, which can cause colour and taste problem. The iron present in the study is ranging from 0.09ppm to 0.13ppm with an average concentration of 0.12ppm. The range of concentration and the average observed in the study area is less than the WHO recommended concentration as 0.3ppm and reveals that the water is free from staining of clothes and good taste for drinking.

RAINFALL AND GROUND WATER TABLE The rainfall recorded in the study area varies between 352mm (1989) to 1426mm (1996) with an average rainfall of 1074.7mm over a period of 1989 to 2004. The years 1989, 92, 99, and 2002 are declared as the drought year; the years 1990, 91, 93, 94, 95, 97, 98, 2000 and 2003 are declared as normal rainfall and in the year 1996 and 2004 received excess rainfall. The highest groundwater table observed as 4.32m in the year 2000 during pre monsoon period and 7.33m in the year 2004 during post monsoon period. The maximum low groundwater table observed 11.29m and 13.38m in the year 2003 both for the pre monsoon as well as post monsoon period. The groundwater resources in the study are the shallow open shallow well. There is no perennial aquifer or Perennial River in Thiruvannamali district, the yield of waters in the wells are through the weathered formation and the quality of groundwater depends on the degree of weathering of the base rock in the study area, the contribution of run off into groundwater may contain agrochemicals, deposition of soils and debris by wind. The recession trend of rainfall is observed from 2000 onwards and reached a maximum drought in the year 2002 with a 0.6m of rainfall followed by an increase in trend of 1.04m of rainfall in the year 2003. The observed groundwater table and groundwater quality is decreases with decrease in rainfall and rebuild up of groundwater table and increase groundwater quality with increase in rainfall is observed.

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References 1. Central Pollution Control Board,’ Ground Water Quality in Problems Areas’ Status Report Part 1pp.14-27. 2. Geological Survey of India, Public Works Department, Chennai. 3. Government of Tamilnadu, Public Work Department, Water resources Organization, ‘State Frame Work Water Resources Plan Palar River basin’pp.10-20. 4. The Director of Environmental, Government of Tamilnadu, Chennai- ‘Environmental Profile of Thiruvannamali District’ Final Report Background, Resources, Infrastructures pp.3-11. 5. Abbasi. ’Environmental Pollution and its Control’Gogent International.pp.438 6. Larry W.Canter, ‘Nitrogen in groundwater Lewis publishes, CRC Press 1997.


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QUANTITATIVE MONITORING OF UNDERGROUND DRINKING WATER QUALITY Gaurav Kumar Rastogi* and D.K. Sinha** *Department of Applied Science, Sunder Deep Engineering College, Ghaziabad-201001(U.P.) Mob.09711117477 Email:[email protected] **Reader &Head, Department of Chemistry, KG.K. (P.G.) College, Moradabad-244001 (U.P.) Mob.09412580987 Email:[email protected]

ABSTRACT With rapid growing population and improved living standards, the pressure on water resources is increasing day-by-day. To meet the rising demand, it is imperative to recognize the quality of fresh water resources. Water is a universal solvent and it dissolves the minerals from the rocks in which it is stored and thus chemical and physical parameters of a particular area will be changed. The quality of groundwater shows a marked change with seasonal change specially rainfall. The quality of groundwater is the resultant of all the pressure and reaction that act on the water from the movement, it condenses in the atmosphere to the time and it is discharged by an underground source. Water-borne diseases and water-caused health problems are mostly due to inadequate and incompetent management of water resources. The present study is aimed to monitor the underground drinking water quality at Moradabad and the effect of rainfall on water quality quantitatively at Moradabad. For these five different underground water samples of India Mark II hand pumps of different places was collected and analysed for eighteen water quality parameters for pre-monsoon and post monsoon period following standard methods of sampling and estimation. Water quality indices (W.Q.I.) for five different sites for two seasons have been calculated with the help of quantitative data of all estimated eighteen parameters. Underground drinking water was found to be severely polluted at four sites and moderately polluted at one site for the pre-monsoon as well as after onset of monsoon. The quality of underground water showed improvement after the onset of monsoon markedly at two sites of study. Residents exposed to polluted sites are prone to health hazards of polluted drinking water and water quality management is urgently needed in the area of study. The results on the basis of calculated values of W.Q.I. are similar to the results of individual parameters. Hence, quantitative monitor of water quality with the help of W.Q.I. is an effective tool. Keywords: Water quality index, Drinking water, Quality rating, Unit weight.

1. INTRODUCTION Water also known as ‘blue gold’ is the life for all living beings, yet over one billion people across the world are deprived of safe drinking water. The situation is grim especially in developing countries, as the lack of clean drinking water denices the most essential of all fundamental rights, the right to life. The underground drinking water contamination is sometimes of geogenic origin and mostly it is due different kinds of anthropogenic activities of human beings. Underground drinking water is gradually accumulating pollutants since industrial revolution started. It has been observed that any type of treatment would not be successful to protect the earth from pollution (Khan et al. 2005). A problem solved in one part of the environment may become a new problem in another part. So, the only alternative is that we must curtail pollution closer to its point of origin so that it is not transferred from place to place.


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Water quality index (WQI) is regarded as one of the most effective way to communicate water quality (Mahapatra 2005, Pradhan et al. 2001, Tripathy 2005). In a number of nationwide studies, water quality of different natural resources has been assessed on the basis of calculated water quality indices (Sinha 1994, Sinha 2006). The data obtained through quantitative analysis and WHO water quality standards (W.H.O. 1971) are used for calculating water quality indices. The objective of calculating WQI and comparing with the standards is to assess underground drinking water quality at Moradabad. Moradabad is a ‘B’ class city of western Uttar Pradesh having urban population more than 38 lakhs. Moradabad is situated at the bank of Ram Ganga river and its altitude from the sea level is about 670 feet. It is extended from Himalaya in north to Chambal river in south. It is at 28°20', 29°15'N and 78°4', 79°E. District Bijnor and Nanital are in the north, Rampur in the east, Ganga river in the west and district Budaun is in the north of district Moradabad. Moradabad has seen rapid industrialization and population growth during the last few decades. The major industries are brassware, steelware, paper mills, sugar mills, crushers, dye factories and a number of associated ancillaries. Most of these industries and different kinds of human activities are playing their roles in multiplying the level of water contamination.

2. MATERIAL AND METHOD Five different underground drinking water sites at Moradabad were selected in order to study the physicochemical characteristics of water samples (Merck 1974). Commonly used hand pump water sites at five different public places specifically government offices were selected. A brief description of sites is presented in Table 1. The samples were collected and analysed following the standard methods and procedures (APHA 1998).World-widely accepted standards prescribed by WHO are used for calculating water quality indices . Eighteen different water quality parameters were estimated. The parameters are pH, conductivity, turbidity, dissolved oxygen, biological oxygen demand, chemical oxygen demand, total hardness, calcium, magnesium, and chloride, total solid, total dissolved solid, alkalinity, iron, fluoride, sulphate, zinc and free CO2.

Table 1 : Details of sampling locations Sl. No.

No. and Name of site

Location of site

Type of hand pump

1.

I, Bus Station

2 km east-north to site no II

India Mark II

Only source

Water becomes turbid on standing

2.

II,District Court

I km south to collectorate

India Mark II

Only source

Water turns yellowish on standing

3.

III, MDA Office

3 km west to site no II

India Mark II

Only source

Neat and clear water

4.

IV, Telephone 2.0 km west to sit no India Mark II II Exchange

Only source

Yellowish water

5.

V, Town Hall

Only source

Water becomes turbid on standing

1.0 km east to site no II

India Mark II

Type of source

Apparent water quality

The WQI of underground drinking water samples were calculated by the methods proposed by Horton (Horton 1965) and modified by Tiwari and Mishra (Tiwari 1985). According to the roles of various parameters on the basis of importance and incidence on the overall quality of drinking water, the rating scales

352


are fixed in terms of ideals values of different physico-chemical parameters. Even if, they are present, they might not be the ruling factor. Hence, they were assigned zero values. For calculating WQI following four equations are used: 1. Quality rating, Qn = 100 [(Vn – Vi) / (Vs – Vi)] Vn = actual amount of nth parameter

Where,

Vi = the ideal value of this parameter Vi = 0, except for pH and D.O. Vi = 7.0 for pH; Vi = 14.6 mg/lit for D.O. Vs = recommended WHO standard of corresponding parameter. 2.

Unit weight (Wn) for various parameters is inversely proportional to the recommended standard (Sn) for the corresponding parameter. Wn = K / Sn Where,

Sn = world - widely accepted drinking water quality standard prescribed by WHO K = constant n=18

∑Wn = 1, considered here n=1

(SI) n =

(Q n)Wn

3.

Sub indices,

4.

The overall WQI is calculated by taking geometric mean of these sub indices. n=18

WQI =

n=18

π (SI)n = n=1

π (Qn)Wn n=1

OR n=18

WQI =

antilog10 [ ∑Wnlog10Qn] n=1

To include, the collective role of various physico-chemical parameters on the over all quality of drinking water, quality status is assigned on the basis of calculated values of water quality indices. On the basis of a number of water pollution studies following assumptions are made with reference to assess the extent of contamination or the quality of drinking water. The assumptions are: WQI < 50: fit for human consumption; WQI < 80: moderately contaminated; WQI > 80: excessively contaminated; WQI > 100: severely contaminated.


353

3. RESULTS AND DISCUSSION The physico-chemical parameters with their W.H.O. Standards and unit weights (Wn) assigned with the help of equation no. 2 are listed in Table 2. Site-wise and parameter-wise estimated values (Vn) and calculated quality rating (Qn) are presented in Table 3. Site-wise calculated values of WQI are given in Table 4. Sitewise variation of WQI is depicted in Figure 1.On the basis of data presented in Table no.4 and Figure 1 the observed range of W.Q.I. for pre-monsoon season is 73-258 and for onset of monsoon it is 52-235. The water with the value of W.Q.I. less than 80 is assumed to be moderately polluted hence, the water of site no. III is moderately polluted for both the seasons; however, to some extent the water quality shows some improvement after the onset of monsoon. The underground water quality at all other sites for both the season are severely polluted and should not be consumed for drinking and other purposes. Ground water quality at these sites also shows some improvement during the onset of monsoon.

Table 2 : Parameter-wise W.H.O. standards and their assigned unit weights Sl. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Parameter pH value Conductivity ( S/cm) Turbidity (NTU) Dissolved Oxygen (ppm) Biological Oxygen Demand (ppm) Chemical Oxygen Demand (ppm) Total Hardness (ppm) Calcium (ppm) Magnesium(ppm) Chloride (ppm) Total Solids (ppm) Total Dissolved Solids (ppm) Iron (ppm) Alkalinity (ppm) Flouride (ppm) Sulphate (ppm) Zinc (ppm) Free co2 (ppm)

W.H.O. Standard

Assigned Unit Weight (Wn)

7 - 8.5 (8.0) 0.300 5.0 5.0 6.0 10.0 100 100 30 200 500 500 0.5 100 1.0 500 5.0 10.0

0.016669 0.444503 0.026670 0.026670 0.022225 0.013335 0.001334 0.001334 0.004446 0.000667 0.000267 0.000267 0.266702 0.001334 0.133351 0.000267 0.026670 0.013335

4. CONCLUSIONS On the basis of above exhaustive discussion it may be concluded that the underground water of study area is highly polluted and unfit for domestic and commercial uses as well. The water quality shows some improvement after the onset of monsoon but of no use. The management in terms of underground water quality is urgently needed in study area. The comparison of values of estimated parameters with drinking water standards reveals the same results .Hence, quantitative monitoring of underground water quality with the helps of W.Q.I. is once again proved to be fruitful.

354


Table 3 : Parameter- wise and site-wise estimated actual value (Vn) and calculated quality rating (Qn) Site No. I Sl.No.

Parameter

1

pH value

2

Conductivity ( S/cm) Turbidity (NTU)

3 4

8

Dissolved Oxygen (ppm) Biological Oxygen Demand (ppm) Chemical Oxygen Demand (ppm) Total Hardness (ppm) Calcium (ppm)

9

Magnesium(ppm)

10

Chloride (ppm)

11

Total Solids (ppm)

12 13

Total Dissolved Solids (ppm) Iron (ppm)

14

Alkalinity (ppm)

15

Flouride (ppm)

16

Sulphate (ppm)

17

Zinc (ppm)

18

Free co2 (ppm)

5 6 7

Pre-monsoon

Site No. II

Onset of monsoon

Pre-monsoon

Site No. III

Onset of monsoon

Pre-monsoon

Onset of monsoon

Vn

Qn

Vn

Qn

Vn

Qn

Vn

Qn

Vn

Qn

Vn

Qn

7.26

26

7.03

3

7.21

21

7.02

2

7.76

76

7.37

37

1.14

380

1.13

376.66

1.50

500

1.45

483.83

0.44

146.67

0.42

140

20

400

25

500

14

280

16

320

1

20

2

40

2.40

127.08

1.80

133.33

3.40

116.67

2

131.25

1.70

134.37

0.80

143.75

10

166.67

16

266.72

18

300.06

20

333.4

8

133.36

6

100.02

60

600

60

600

60

600

60

600

100

1000

112.

1120

320

320

310

310

408

408

412

412

140

140

120

120

89.6

89.6

92.8

92.8

88

88

120

120

40

40

38.4

38.4

23.34

77.80

18.96

63.20

45.7

152.33

27.23

90.77

9.72

32.40

5.83

19.43

52

26

64

32

86

43

90

45

24

12

28

14

400

80

460

92

500

100

525

105

216

43.2

244

48.8

380

76

442

88.4

470

94

490

98

180

36

230

46

1.2

240

1.5

300

1.10

220

1.23

246

0.14

28

0.10

20

388

388

350

350

430

430

390

390

208

208

145

145

1.07

107

0.64

64

1.25

125

0.84

84

0.50

50

0.11

11

80

16

50

10

110

22

80

16

50

10

25

5

0.40

8

2

40

0.20

4

0.20

4

0.70

14

0.30

6

40

400

42

420

44

440

50

500

18

180

20

200


355

Table 3 : Cont. Site No. IV Sl.No.

Parameter

1

pH value

2

Conductivity ( S/cm) Turbidity (NTU)

3 4

8

Dissolved Oxygen (ppm) Biological Oxygen Demand (ppm) Chemical Oxygen Demand (ppm) Total Hardness (ppm) Calcium (ppm)

9

Magnesium(ppm)

10

Chloride (ppm)

11

Total Solids (ppm)

12 13

Total Dissolved Solids (ppm) Iron (ppm)

14

Alkalinity (ppm)

15

Flouride (ppm)

16

Sulphate (ppm)

17

Zinc (ppm)

18

Free co2 (ppm)

5 6 7

Pre-monsoon

Site No. V

Onset of monsoon

Onset of monsoon

Pre-monsoon

Vn

Qn

Vn

Qn

Vn

Qn

Vn

Qn

7.30

30

7.42

42

7.48

48

7.07

7

1.12

373.33

0.42

140

1.16

386.67

1.20

400

10

200

3

60

12

240

22

440

2.10

130.21

0.80

143.75

2.80

122.92

1.80

133.33

14

233.38

6

100.02

26

266.67

16

266.72

50

500

96

960

58

580

64

640

320

320

270

270

300

300

296

296

65.6

65.6

56

56

51.20

51.20

80

80

37.92

126.40

31.60

105.33

41.81

139.37

23.33

77.77

48

24

28

14

64

32

70

35

292

58

300

60

450

90

490

98

270

54

270

54

435

87

455

91

0.30

60

0.20

40

1.10

220

1.26

252

390

390

250

250

396

396

360

360

0.67

67

0.04

4

1.07

107

0.46

46

80

16

50

10

80

16

80

16

0.40

8

0.20

4

0.10

2

0.40

8

30

300

32

320

38

380

42

420

356


Table 4: Site-wise calculated values of water quality index

Water Quality Index (WQI)

Sl. no.

Site no. & Name

Pre-monsoon

1

I, Bus Station

234

Onset of monsoon 235

2

II, District Court

258

241

3 4

III, MDA Office IV, Telephone Exchange

73 148

52 56

5

V, Town Hall

222

214

WQI < 50 : Fit for human consumption ; WQI < 80 : Moderately contaminated WQI > 80 : Excessively contaminated ; WQI > 100 : Severely contaminated

Site-wise and season wise variation of W.Q.I. 300 250 W.Q.I.

200 150 100 50 0 I

II

III

IV

V

Site no.

Figure1: Site-wise and season wise variation of W.Q.I.

5. REFERENCES 1. APHA, AWWA, WPCF, 1998, Standard Methods for Examination of Water and Wastewater, Washington, D.C. 2005, U.S.A. 19th ed. 2. Horton, R.K., 1965, A index number system for rating water quality, J. Water Poll, Cont. Fed. , 37, p300.


357

3. Khan, N., Mathur, A. and Mathur , R. , 2005, A study on drinking water quality in Lashkar(Gwalior) , Indian J. Env. Prot., 25(3), p222-224. 4. Mahaptra , M.K. and Mishra , H.S. , 2005, Ground water pollution in Subarampur and Nuapada district of Orissa , Poll.Res. , 24(4) , p863-865 . 5. Merck , E. , 1974, Testing of Water , Dermstadt , Federal Republic of Germany . 6. Pradhan , S.K. , Patnaik , D. and Rout , S.P. ,2001, Ground water quality index for ground water around a phosphatic fertilizer plant , Indian J. Env. Prot. , 21(4) , p355-358 . 7. Sinha , D.K. and Saxena , R. , 2006, Statistical assessment of underground drinking water contamination and effect of monsoon at Hasanpur , J.P. Nagar (Uttar Pradesh , India ) , Journal of Environ. Science & Engg. , 48(3) , p157-164 . 8. Sinha , D.K. and Srivastava , A.K. , 1994, Water quality index of river Sai at Rae Bareli for pre-monsoon period and after the onset of monsoon , Indian J. Env. Prot . , 14(5), p340-345 . 9. Tiwari , T.N. and Mishra , M. , 1985, A preliminary assignment of water quality index of major Indian rivers , Indian J. Env. Prot. 5(4), p276-279. 10. Tiwari , T. N. , Das , S.C. and Bose , P.K. , 1986, Weighed geometric water quality index for river Jhelum in Kashmir , Journal M.A.C.T. , 19 , p33-41 . 11. W.H.O., 1971, International Standards for Drinking Water, World Health Organization, Geneva.

358


Assessment of underground water quality of Atrauli town in Aligarh district, U.P. (India) Mohammad Anwar Khwaja* Devendra Singh** Prof. M.M.Ashhar*** The study was conducted to assess the physico-chemical quality of under ground water at Atrauli town in Aligarh district, Uttar Pradesh. Sampling was done as per Standard methods.Samples were collected from fourteen deep bore wells located at different parts of the town. Wells were selected for the sample collection randomly. Analysis was carried out for pH, TDS, total hardness, alkalinity, chloride, iron, nitrate, fluorides, sulphates, turbidity etc. the data revealed that at twelve locations alkalinity, at five locations TDS and total hardness and at three locations Iron is higher than permissible limit of Indian standard drinking water specifications. It was found that some effective measures are required for water quality management in this region. The present study reports the results of physio-chemical analysis of groundwater samples, which were collected from different parts of the town. Key words: water quality, physico-chemical parameters, ground water, rain water harvesting.

Introduction Ground water is an important source of drinking water supply in many regions. The ground water is also used for many domestic and economic purposes such as irrigation and industrial activities. Due to urbanization, industrialization and population increase, the demand for water increased tremendously, which creates a critical stress on ground water, most especially in the dry season when water from other source are not readily available. The ground water levels continue to decline due to over exploitation of the resources induces degradation of underground water quality. Ground water contains various minerals, often salts in solution. Presence of Carbonates and bicarbonates of multivalent metallic cations causes hardness in water. Determination of physico-chemical characteristics of ground water is essential for assessing the suitability of water for various purposes like drinking, domestic, industrial and irrigation. The ground water quality primarily governed by the extent and composition of dissolved solids.

Study area The study concentrates on Atrauli town of Aligarh district, western Uttar Pradesh. It is one of the two municipal boards of Aligarh district. This town is around 30 Km North West of Aligarh district headquarter, which is 130 Km south east of Delhi. It is located at 28o2’0” north latitude and 780 17’ 0” east longitude, has an average elevation of 136 meters. As per 2001 India censes, Atrauli had a population of 43,843. This town is an agriculture based area and famous for milk dairies. Climate of the town is hot and dry. The coldest months of the year are December to February. The hottest months of the year are May and June. The temperature of the town lies between 20 to 480 Celsius. The annual rainfall of the town lies between 60cm to 100cm in the month of mid June to mid September. * Water works engineer, municipal board, Atrauli (Aligarh) Email: [email protected] ** Research Associate, Department of civil engineering, A.M.U. Aligarh. *** Professor, Environmental Engg. Section. Department of civil engineering, A.M.U. Aligarh.


359

Material and methods Fourteen sites at Atrauli town were selected in order to study the physico-chemical characteristics of underground water samples. The depth s of all these sources studies ranged between 65 to 80 meter. These samples were collected as per the standard methods prescribed for sampling. The grab sampling method was chosen for collection of the samples, which reflects composition of water at the source at the sampling time and place. Before filling, rinse sample bottle two or three times with the water being collected. The water samples were subjected to analysis within 24 hours of collection for the physico-chemical parameters. Total 14 water quality parameters viz. pH, total dissolved solids, alkalinity, iron, nitrate, fluorides, chlorides, turbidity, sulfates, and total hardness. The parameters were analyzed in the laboratory using standard methods 16th edition (APHA, 1995).

Results and discussion The results obtained were evaluated in accordance with the standards prescribed under Indian Standard Drinking water specification IS: 10500:1991 of Bureau of Indian Standards. The physical and chemical characteristics of underground water are tabulated in table 1 & 2. Physical characteristics The water samples collected from sampling station S1 to S14 showed unobjectionable taste and odor. The water samples found colorless. The turbidity for all the samples is below the prescribed limit 5.0 NTU BIS accepted Standards. The highest value of turbidity is 0.7 NTU at sampling station S14. Turbidity in water is causes the degradation in the clarity in water due to presence of particles such as silt, clay and other forms of living and non living materials found in water. Electrical conductivity values in all 14 samples under study ranged between 549 to 1200 micro-mho. Electrical conductivity depends on the amount of dissolved solids in the water. pH of the ground water samples with in the town is with in the acceptable limits 6.5-8.5 prescribed by BIS. A direct relationship between human health and pH of drinking water is impossible to ascertain, because the pH is closely associated with other aspects of water quality.3 It was also unable to establish any significant correlation between the incidence of diseases and pH4.

360


Table no. 1 Physical characteristics of under ground water Sampling

Parameters

Location

Station number

pH

Elect.

6.5-

Cond.

8.5

m.m.

Taste

Odour

Colour

agreeable unobjectionable

Turbidity in (5.0 NTU)

S1

Company bagh

7.64

1200

sweet

odourless

colorless

0.1

S2

Kherapatan

7.43

1000

sweet

odourless

colorless

0.2

S3

Nagaichpara

7.90

1200

sweet

odourless

colorless

0.2

S4

Thsheel

8.08

838.4

sweet

odourless

colorless

0.7

compound S5

Bahadur nagar

8.09

811.6

sweet

odourless

colorless

0.4

S6

Basua mandir road

7.75

1467

sweet

odourless

colorless

0.1

S7

Janakpur

7.50

591

sweet

odourless

colorless

0.2

S8

Takia nazza shah

8.00

831.1

sweet

odourless

colorless

0.1

S9

Pakki garhi

7.50

1200

sweet

odourless

colorless

0.2

S10

Bhoodh nagarya

8.00

706.2

sweet

odourless

colorless

0.1

S11

Madoli

7.75

846.1

sweet

odourless

colorless

0.1

S12

Khurja adda

8.00

756.7

sweet

odourless

colorless

0.1

S13

Vaishpara

7.75

549.1

sweet

odourless

colorless

0.2

S14

Shivaji nagar

7.25

1128

sweet

odourless

colorless

0.2

Chemical characteristics

The total hardness of the water samples of station no S1 to S5 ,S7, S8, S10 and S13 falls with in the permissible limits of BIS 300 mg/l. The total hardness of water samples collected from station no S6, S9, S11, S12 and S14 found above permissible limit. Hard water is useful in the growth of children, if within the permissible limit. Cater & Knox (1986) observed a correlation between hardness of water to kidney & heart problems. Hardness of water causes disadvantages in domestic uses by producing poor lathering with soap, deterioration of cloths, scale forming and skin irritation.


361

Table no. 2 Chemical characteristics of under ground water Parameters

Sampling Stations

Total

Total

Dissolved Hardness

Alkalinity Chloride Iron

Nitrate Fluorides Sulphates

as Caco3

Solids

as Caco3

Specification as

500

300

200

250

0.30

45

1.0

200

per BIS

mg/l

mg/l

mg/l

mg/l

mg/l

mg/l

mg/l

mg/l

S1

600

250

184

60

0.22

11.35

0.5

34.63

S2

500

244

194

64

0.23

11.64

0.5

30.74

S3

600

286

228

85

0.07

0.90

0.4

24.33

S4

419.5

290

292

87

0.06

0.33

0.8

36.57

S5

405.7

276

284

88

0.06

6.83

0.8

38.30

S6

733

484

380

178

0.3

6.64

0.35

48.00

S7

295.5

190

266

22

0.3

0.88

0.65

14.40

S8

415.5

266

306

55

0.35

4.87

0.45

19.20

S9

600.1

436

268

159

0.3

6.64

0.4

28.80

S10

353.2

280

250

44

0.25

3.54

0.45

19.20

S11

422.8

310

246

71

0.3

7.53

0.6

28.80

S12

378.7

342

312

78

0.35

3.08

0.45

52.80

S13

274.5

288

298

31

0.4

2.65

0.5

48.00

S14

563.7

480

232

202

0.3

3.54

0.5

48.00

10500:1991

Total dissolved solids (TDS) concentration of the water samples of station no S2, S4, S5, S7, S8, S10 to S13 falls with in the permissible limits of BIS 500 mg/l. The total hardness of water samples collected from S1, S3, S6, S9, S14 found 563.7 to 733 mg/l which are above permissible limit. TDS in water are contributed by inorganic salts and small amount of organic matter which influences the taste of water. WHO has prescribed the limit of TDS as below 1000 mg/l. The TDS values in the present study varies from 274 to 733 mg/l. Water with high TDS are of inferior palatability and may induce an unfavorable physiological reaction in the transient consumers and gastrointestinal irritation.

362


Nitrate concentration in all 14 samples varies from 0.33 to 11.64 mg/l. The desirable limit of nitrate for drinking water is 45 mg/l as per BIS standards for drinking water. Hence the nitrate concentration of all water samples studied is with in the standard limits. The fluoride value ranged from 0.35 to 0.80 mg/l. Fluoride is an important criterion for ground water quality with an acceptable limit of 1.0 mg/l as per BIS standards. Sulphates concentration in all the samples varies from 14.40 to 52.80 mg/l. This is under prescribed limit of 200 mg/l as per BIS standards. The occurrence of chloride in ground water is attributed to dissolution of chlorite rocks and sewage discharges5. It also reaches the ground water through the leaches from the percolated surface water over the land when cow dung heaps and such other organic waste abound in near vicinity6. In the present study, chlorides content of under ground water ranged from 31 to 202 mg/l, with higher values of chloride occurring in sampling stations S6 (178), S9 (159)and S14 (202mg/l) .Thus the chloride levels observed in all the samples with in the permissible limit of 250 mg/l as per BIS standards. Iron concentrations varied from 0.06 to 0.40 mg/l. Higher values of Iron occurred in Sampling stations S8 (0.35), S12 (0.35), S13 (0.40 mg/l). The maximum limit of iron in drinking water is 0.30 mg/l as per BIS standards. The higher values may be due to rust in casing/delivery pipes of wells. The alkalinity varied between 184 and 380 mg/l. The alkalinity concentration is higher at 12 sampling stations except S1 and S2. The permissible value of alkalinity is 200 mg/l as per BIS standards. Large amount of alkalinity imparts a bitter taste to water. Excess alkalinity in water is harmful for irrigation, which leads to soil damage and reduce crop yields.

Conclusions The present study of under ground water samples reveals that nearly all water samples are suitable for drinking purpose in terms of physico-chemical characteristics. The physico-chemical parameters investigated did not indicate presence of any pollutant in water samples. TDS, alkalinity and total hardness values are in higher sides. This indicates over exploitation of ground water resource. Augmenting the ground water resources by recharging the ground water aquifers through rain water harvesting and thus reducing the high concentration of the chemical parameters is a very important measure. Public awareness programmes should be initiated to create a sense of awareness in them to save water around their habitants.


363

References 1. Standard methods for the examination of water and wastewater, sixteenth edition. APHA, American public health association , Washington D.C., USA (1995) 2. BIS, Indian Standard drinking water specification, Manak Bhawan, New Delhi, 10500 (1991) 3. WHO, guidelines for drinking water quality, vol 3rd, Geneva (1984). 4. Taylor,F.B. the case study for water worn infectious hepatitis, American journal of public health,56,2093(1966). 5. Pettyjohn, W.A., water quality in a stressed environment,(Minnesofa, Burgess Pub. Company) 1972. 6. Sharma, B.K, Sharma, L.LDhurve, V.S. Assessment of hand pumps waters in three tribal dominated districts of Southern Rajasthan, India.

364


INTERNATIONAL CONFERENCE ON EMERGING TECHNOLOGY IN ENVIRONMENT SCIENCE & ENGINEERING Place: Department of Civil Engineering Z. H. College of Engineering and Technology, A.M.U. Aligarh, U.P. October 26th to 28th, 2009 Theme: Ground Water Pollution

Water is a very important part of environment, and now it has also become polluted as the whole environment of our planet. The amount of freshwater on Earth represents a small percentage of the total water available. The freshwater in groundwater, rivers and lakes is our primary source of drinking water. Half of the citizens in the United States depend on groundwater as their source of drinking water; the remainder relies on surface water as their drinking water source. You may have been surprised to learn that groundwater and surface water make up such a small percentage of the Earth’s total supply. It becomes very apparent then how important it is to protect these water sources since they are available in a limited quantity and since our existence depends on them. Ground water pollution problem is an accute problem in India. Many people are destroying their lives by drinking the floride full water in various parts of India and abroad. Not only floride but also many other different types of chemicals which have been mingled in our available drinking water. A larg number of population in U.P. depend on ground water. Our country is a country which has ample sources of water. The three border line are surrounded by sea and the Himalayan areas in north are covered by snow. ‘Water is life’ has been a very popular slogan in India, but our people are suffering horrible water crisis. Rivers, ponds, old lakes, and wells have become polluted and most of them are going to be dry in a very fast speed. Water crisis has taken the traditional water sources in its grip and ground water is also not untouched from it. In many places of our country either ground water is in a narrow condition or it is going to be polluted speedily. During Independence period where the availability of water for per human being was 5100 cube metre, now has become only 1750 cube metre. It is very unfortunate that there have been no appropriate rules and regulation made for the disciplinary use of groundwater sources.


Now groundwater has reached on an ending stage due to its blind use and exploitation. The states like Maharashtra and M.P. in India where some years before groundwater level was available at 50 to 100 feet below the ground has now gone 500 to 600 feet below the ground. During the green revolution irrigation by tubewell was promoted, rapidly and the earth mother has suffered many holes on her chest. To provide water for a big number of generations in our country the government has preferred hand pumps in many villages till many years in her agendas. Unfortunately those hand pumps have because totally dry, become by using ground water which scientific solution were needed they were never put into practice. The condition which was required for the dribbling of rain water into earth in no more at present. Hundreds of ponds of our country are now closed. The government has no clear scheme for the revival of the old dry lakes. The water from these ponds used to dribble into the earth and this was the reason that the level of ground water was maintained. The big residential schemes have been made by cutting the jungle which resulted the soil cut off and the rain water has going to be waste. In urban areas maximum number of roads and open lands are made cemented and the rain water can not reach into the ground. The government is also unable to perform her duty properly because it has no accomplishment remained yet. Water harvesting system has been noticed very later at the time of making of houses and multistory buildings of housing societies. Only metro cities have started thinking about water harvesting system now. Not only to fulfill the necessities of citizen and agriculture but for the industrial development also ground water was exploited speedily and is being exploited continuously to up till now. Since the strategy of pure drinking water and cold drinking water has developed in our country, the condition has become all the more horrible and worst. Selling of water is a big occupation. The government gets millions of revenue from these occupations. Therefore the government does not care about the processing of water of these companies. The companies which make cold drinking water allow there chemical full dirty water to dribble into the ground and this is the main reason that the ground water of those area becomes much polluted and it is very harmful for the fertilizing power of the particular land of the surrounded area. Central Ground Water Board has also recognized the area of 4 lacks hectare of our country for the rescue of groundwater, where the recycling of wells and ponds are being continue. In Rajasthan, Maharashtra and Madhya Pradesh along with many other places where ground water level is going below in the speed of 1 to 1.50 metre every year, there for the filling of rain water, ground water board is planning to grow move and more trees. For the

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active participation and contribution of local people there is running a public awareness expedition, because in the absence of community feeling, it can be very difficult and damaging for the human beings, to save the water of their own earth. Today the condition has become such that many villages requires immediate acquisition. In this kind of situation local people should take an application of their old acquisition and they should effort for crop cycle, proper manner of irrigation and protection of trees, so that the coming generation will not be accused to live a life without water. It is a good news that In a month from now stealing water or wasting, it will be an expensive proposition for the capital’s citizens. The Delhi High Court has appointed three special magistrates with powers to impose penalty for misusing water or stealing it. The government of Haryana is committed to provide safe potable water supply to all the people living in the villages and towns of the state. In order to solve the problem of scarcity of drinking waster in 503 villages of district Mewat work on phase-I of Mewat project costing Rs. 425 crore was taken up by the present state government in April 2005. As many as 335 villages out of total 503 villages of Mewat district have already been provided with safe drinking water under this project. The remaining 168 villages will be augmented by the end of September 2009. IN Chandigarh, all difficult villages of Ferozpur, Bhathinds, Faridkot, Mansa and Mukstar districts and a definite stretch of the Majha region of Punjab that are faced with the problem of salinity in ground water would be provided reverse osmosis (RO) or ultrafiltration plants within 21 months to provide ultra-clean potable water. Some Natural Solution To protect and clean ground water and our environment there are soma natural solution and one of them is rain garden. A rain garden is a garden of native shrubs, perennials and flowers planted in a small depression, which is generally formed on a natural slope. It is designed to temporarily hold and soak in rain water run off that flows from roofs, driveways, patios or lawns. Rain gardens are effective in removing up to 90% of nutrients and chemicals and up to 80% of sediments from the rainwater runoff. Compared to a conventional lawn, rain gardens allow for 30% more water to soak into the ground. A rain garden is not a water garden. Nor is it a pond or a wetland. Conversely, a rain garden it is dry most of the time. It typically holds water only during and following a rainfall event. Because rain gardens will drain within 12-48 hours, they prevent the breeding of mosquitoes. Every time it rains, water runs off impermeable surfaces, such as roofs or driveways, collecting pollutants such as particles of dirt, fertilizer, chemicals, oil, garbage, and bacteria


along the way. The pollutant-laden water enters storm drains untreated and flows directly to nearby streams and ponds. The US EPA estimates the pollutants carried by rainwater runoff account for 70% of all water pollution. Rain gardens collected rainwater runoff, allowing the water to be filtered by vegetation and percolate into the soil recharging groundwater aquifers. These processes filter out pollutants. In the design of a rain garden, typically six to twelve inches of soil is remove and altered with tillage, compost and sand to increase water infiltration. The type of alteration to the soil depends on the current soil type, so it is a good idea to obtain a soil test. Rain gardens are generally constructed on the downside of a slope on your property and collect rainwater runoff from the lawn, roof and/or the driveway. Once water collects in the rain garden, infiltration may take up to 48 hours after a major rainfall. Also, rain gardens incorporate native vegetation; therefore, no fertilizer is needed and after the first year, maintenance is usually minimal. What Benefits do Rain Gardens: Improves water quality by filtering out pollutants. Aesthetically pleasing. Preserves native vegetation. Provides localized stormwater and flood control. Attracts beneficial birds, butterflies and insects. Easy to maintain after establishment. References: Dainik Jagran, 31 July, 2009. The Hindu, 20 August, 2009. The Hindu, 21 August, 2009. http://www.groundwater.org/ta/raingardes.html http://www.groundwater.org/kc/activity6.html From:

Dr. Juhi Shukla Senior Lecturer & Head in Painting Dept. Prayag Mahila Vidyapeeth Degree College Allahabad Resi. : 304, Barsana Apartment, Madhokunj, Katra, Allahabad Tel.: 0532-2250032, Mob.: 9411082387, e-mail: [email protected]

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Environmental Impact Assessment


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Heavy Metals and Trace Elements Content in Human Milk Fractions Robert STAWARZ, Grzegorz FORMICKI, Anna WYRZYKOWSKA Magdalena CZAJKOWSKA, Ewa BARTO-SŁUSZKIEWICZ Pedagogical University, Krakow, Poland Peter MASSANYI, Norbert LUKAC, Slovak University of Agriculture, Nitra, Slovak Republic

ABSTRACT The purpose of this study was to determine the concentration and distribution of xenobiotic heavy metals such as mercury (Hg), lead (Pb), cadmium (Cd), and trace elements: zinc (Zn), and copper (Cu) in foremilk available at the beginning of a feeding and hindmilk available later. Hindmilk was divided into two fractions: first - at the beginning, and second – at the end of its outflow. Mature milk was taken from 11 nursing adult women, with low environmental metals exposure. Milk samples were collected through seven consecutive days in the morning and in the evening. The total number of 462 samples (n=462) were collected and analyzed. Statistical tests have shown that the content of xenobiotic metals in investigated milk fractions was invariable both in the morning and evening milk samples, and that one of the most stable and lowest in foremilk and hindmilk were mercury contents (p=0.990). The most changeable were cadmium contents in consecutive fractions of the morning milk samples (0.576), and among biogenic elements – copper contents (p=0.361). Although most changes of metal levels in milk fractions were not statistically significant, the calculated correlation coefficients showed that xenobiotic elements have significant impact on biogenic elements status in human milk. Keywords: zinc, copper, lead, cadmium, mercury, breast milk

1. INTRODUCTION The interest in breast feeding is still high: the benefits of breast feeding infants have been emphasized by medical and psychological studies. Therefore, it is clear why the concern over the excretion of toxic metals, drugs and other environmental chemicals into breast milk keeps up. The milk-making cells in breasts produce only one type of milk, but the composition of the milk that is removed varies both according to how long the milk has been collecting in the ducts, and how much of the breast is drained at the moment. Generally, the composition of human milk is of great importance because the xenobiotic substances and elements absorbed by the mother may pass via the milk to the infant organism (Jensen, Slorach, 1991). Occurrence of chemical residues in human breast milk is determined not only by the fact of their presence in food, water and air, but also by their properties. Cellular barriers between blood plasma and mammary gland cells are readily cleared by small lipophilic organic molecules which concentrate in the fat globules. Most metals in breast milk occur in trace levels. They were found both in inorganic and organic compounds, but not associated with milk fat. The investigations of milk samples taken from women living in different regions of the world indicate that levels both trace and xenobiotic metals are very diversified (Dorea, 2000a, 2000b; Froković at al. 1997; Honda et al. 2003) and change in the course of lactation (Stawarz et al. 2007a), and in relation to breast feeding women’s age (Stawarz et al. 2007b).

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The presence of xenobiotics such as cadmium and lead in breast milk is well documented. Both these elements are not regular constituent metals in mammalian tissues. They are absorbed in the gastrointestinal and respiratory systems, and loaded into milk (Hallen et al. 1995; Manton et al. 2003). In our times, mercury and its compounds are a significant threat to human health, particularly to pregnant women, women of childbearing age, developing fetuses, and breast-fed infants (Chien et al. 2006). Some studies have shown that diet is the primary pathway of human exposure to methylmercury (MeHg), and the most endangered group constitute people consuming high fish food (Oskarsson et al. 1995). It is probable that milk, as a source of mercury, may be a serious source of risk for a developing infant. The trace elements status may change when the toxic metals are present – they may also disrupt some phases of bio-metals assimilation. Human milk monitoring brings interesting data about the presence and mobility of trace elements and xenobiotics in organisms. Milk, as a fluid easy to collect, reflects not only condition of mineral economy of the organism but also is the way of excretion. Therefore, the analysis of human milk content reflects potential problems with the environment in which women live, and possible hazard for infants (Stawarz, 2009). The aim of this study was to determine the concentration and distribution of xenobiotic heavy metals such as mercury (Hg), lead (Pb), cadmium (Cd), and trace elements: zinc (Zn), and copper (Cu) in foremilk available at the beginning of a feeding and hindmilk, and to assess the potential health risk to infants of breast milk xenobiotic elements in urban mothers. 2. MATERIAL AND METHODS Eleven women aged 28-31 were selected for the experiment. The subjects were all Polish and lived in Krakow (Southern Polnad, Malopolska Province). Seven of them were mothers of their first and four of their second baby. Collecting milk samples started on the second postpartum month (mature milk). All women had sufficient breast milk to provide samples during feeding their babies. Milk samples were taken from eleven women through seven consecutive days, two times a day at 7:00 a.m., and at 7:00 p.m. There were no significant differences in nutritional status and health management practices between the participants of the experiment. Informed consent for this study was obtained from all the women in the appropriate manner. Information about potential environmental exposure to heavy metals such as mercury (Hg) cadmium (Cd) and lead (Pb), diet and smoking habit were obtained via a questionnaire filled out by the subjects themselves. Milk samples were extracted with the use of a manual breast pump. Before the collection of samples, the women washed their hands well with soap and water and also sterilized the breast pumps (Butte et al., 1984). The procedures of milk samples collection were prepared in the way enabling to obtain the three milk fractions. In this experiment the “milk fraction” term means samples obtained in definite time of milk leakage from a mammary gland. The first fraction constitutes the milk leaking at the beginning of a feeding action through the first two minutes, at the moment when the breast is very full. These samples were usually collected by the time the mothers began feeding. The women skimmed a little amount of milk with the breast pumps. This procedure allowed to collect the foremilk – named the first fraction (I) – the thin, watery milk that the baby obtains at the beginning of a feeding. Next, women fed normally, and after 10 minutes the feeding was stopped in order to skim with manual breast pumps another milk portion. That way the hindmilk was collected. In our experiment we decided to divide the hindmilk in two fractions. The milk samples collected after 10 minutes of feeding constitute the second fraction (II). The samples collected at the end of the feeding process – often after a baby stopped sucking at the breast and mother had to skim the residues of milk – constitute the third fraction of milk (III). Milk was swirled in a container and 5 mL were taken into polypropylene tubes and were kept frozen at –20°C until all the samples were collected. The total number of 462 samples (n=462) were collected and analyzed. The milk samples were mineralized in separate mineralization tubes by adding 3 mL HNO3-HClO4 (4:1) mixture and heating at 120°C for 65 min in a thermostat-controlled digestion block. After


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cooling the resulting solution was diluted to 10 mL with demineralized water. The mercury content was measured by cold vapor atomic absorption (CVAAS) method. The cadmium and lead contents in all milk samples were measured by the voltammetric method (ASV) with CGMDE working electrode. Zinc and copper concentrations were measured by flame absorption spectrophotometry (FAAS) method. All element concentrations are expressed on wet-weight basis in mg•L-1. The distribution of investigated elements in milk and urine was checked with Shapiro-Wilk test for normality at p 1.5 mg/l I causes fluorosis thereby requiring critical evaluation of the means and treatment technologies to be adopted. Adoption of treatment method varies with socio-cultural, geoenvironmental and techno-economic conditions. Keywords Fluoride, Fluorspar, Fluorosis, Defluoridation, Activated alumina

INTRODUCTION Fluorine is found in the form of fluorides and exists in almost all the soils, comprising approximately 0.08 percent of the earth’s crust. Common fluoride producing compounds are sellaiteMgF2, Villianmite- NaF, fluorspar - CaF2, cryolite - Na3AlF6 , fluorapatite - 3Ca3(PO4)3F2 . In water, fluorspar contributes the highest percentage of fluoride by weight (Rao, 2003; Saxena et al., 2003). Fluoride concentration in groundwater depends on various hydro-geological factors and chemical characteristics in addition to the porosity & acidity of soil and rocks and thus, it may range from less than 1 mg/l to 35 mg/l or at times even higher. In this paper a review, based on literature survey, of the available technologies for fluoride removal and their feasibility analyses has been presented to enable the researchers and entrepreneurs to develop appropriate and cost effective technologies for defluoridation.

DISTRIBUTION IN WATER AND HEALTH EFFECTS Fluoride is usually found in all waters at varying concentrations. Seawater contains about 1mg F/l while river and surface/lake waters less than 0.3 mg F/ l. In ground water, fluoride depends upon the nature of the rocks, weathering and leaching of fluoride-bearing minerals in alkaline environment and level of calcium in aquifers. Its concentration increases in ground waters with the cation exchange of sodium for calcium (Edmunds, 1996). There is a negative correlation between fluoride and calcium concentrations while a positive correlation between fluoride and bicarbonate concentrations in groundwater (Bulusu et al., 1980; Meenakshi et al., 2006). High fluoride waters in large and extensive geographical belts in many regions are correlated with dissolution of fluorite, apatite and topaz from the local bedrock and associated with sediments of marine origin in mountainous areas, volcanic rocks, granitic and gneissic rocks. Excessive fluoride concentrations have been reported of groundwaters in more than 25 developed and developing countries including India where 19 states are facing serious health hazards of fluorosis involving tens of million populations (Mehta, 2007). Probably, the highest fluoride concentration in the world ever reported was about 2800 mg/L in the rift Lake Nakuru, Keniya(Kloos, H. et al.,1999). Drinking-water is the major single contributor of fluoride intake (75-80% of daily intake) and its consumption increases with increase in temperature, humidity and physical activity etc. (Murray, 1986, Haikel, 1986, Chand, 1998). Other sources of additional fluoride intake are food, industrial exposure, drugs, cosmetics, etc (Meenakshi et al., 2006). In fact, fluoride in minute quantity is an essential component for normal mineralization of bones and formation of dental enamel. A guideline value of 1.5 mg F/L is recommended by WHO for

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minimizing dental fluorosis (WHO 1996; 2004). Further, WHO concluded that mottling of teeth (i.e. dental fluorosis) is associated with prolonged consumption of high fluoride water i.e. above 1.5 mg/ l and crippling skeletal fluorosis when it exceeds 10 mg/ l affecting children as well as adults equally. Normally, the degree of dental fluorosis varying from teeth mottling or becoming chalky white in Children less than nine years of age depends upon the exposure of fluoride level beyond 2 mg F/L (Choubisa et al., 1974). Apart from dental and skeletal fluorosis, excessive consumption of fluoride may also lead to nonskeletal fluorosis. It is also responsible for alterations in the functional mechanisms of liver, kidney, digestive system, respiratory system, excretory system, central nervous system and reproductive system, destruction of about 60 enzymes (Susheela 1991, Sharma et al, 2004).

REVIEW OF REMOVAL TECHNIQUES Low–cost technologies rely on precipitation/ flocculation or adsorption/ion-exchange processes. The common methods used for the removal of fluoride can be divided broadly in the following four categories:

Precipitation: This process involves addition of chemicals, suitable grade, formation of fluoride precipitates and removed as sludge. Based on this process (a combination of aluminum sulphate and lime) popularly known as ‘Nalgonda technique’is probably the most established method. This method can be used at a domestic scale (in buckets) and community scale as well. It has moderate removal efficiency, costs and materials required are easily available (Bulusu et al., 1979). In the Netherlands, a new type of contact precipitator was developed (Giesen, 1998). It is a fluidized-bed type crystallizer also called a pellet reactor. In the reactor fluoride is removed from the water producing calcium fluoride pellets with a diameter of 1 mm. The major advantages of this unit are the compact installation, reusable calcium fluoride pellets with a high-purity and extremely low water content. The total costs are typically arrived about 1/4th of the costs for conventional precipitation method. However, for treating high fluoride waters below 1 mg/l fluoride, a second technique is necessary (for example I.E). Defluoridation using batch electrocoagulation/electroflotation (EC/EF) was carried out in two reactors for comparison purpose: a stirred tank reactor (STR) close to a conventional EC cell and an external-loop airlift reactor (ELAR) for EC. The respective influences of current density, initial concentration and initial pH on the efficiency of defluoridation were investigated. The same trends were observed in both reactors, but the efficiency was higher in the STR initially and gave similar results after 15 min of operation. The influence of the initial pH was explained using the analyses of sludge composition and residual soluble aluminum species in the effluents. It was found related to the prevailing mechanisms of defluoridation. Fluoride removal and sludge reduction were both favoured by an initial pH around 4 requiring pH adjustment. Finally, electric energy consumption was similar in both reactors at current density < 12 mA/cm2, but mixing and complete flotation of the pollutants were achieved without additional mechanical power in the ELAR. It was performed using only the overall liquid recirculation induced by H2 micro-bubbles generated by water electrolysis, making subsequent treatments easier to carry out (Essadki A.H., et al., 2009). A process named ARCIS-UNR was developed for fluoride removal from groundwater by means of coagulation with polyaluminium chloride (PACl) and double filtration. The study was conducted in two phases. Statistic analysis over first phase results indicated that only pH has relevant effects on fluoride removal. The main conclusions of the second phase were: a) from adsorption experiment, the results fit Freundlich isotherm. b) Optimum pH conditions of the feed water were around neutral value, in order to obtain residual fluoride and aluminum below permissible values (Ingallinella, 2000). Fluoride removal increases as pH diminishes and final F< 1.5 mg/l may be obtained for PACl doses of 100 mg/l at pH = 6.0 with fluoride removal efficiency of 32%.


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Adsorption and Ion-Exchange (IE): This process involves the passage of water through a contact bed where fluoride is removed by ion exchange or surface chemical reaction with the solid bed matrix. The media exhausted is regenerated or refilled. Presently, number of the adsorbents i.e. activated alumina (Al2O3), carbon, bone charcoal and synthetic ion exchange resins are in use. Activated alumina (AA), grains prepared to have a sorptive surface, is commonly used defluoridation material for POE (point-of-entry) and POU (point-of-use) as disposable filters. AA is generally specific for fluoride and is not affected by the common other competing sulfate, nitrate, or chloride anions present in the feed water. The saturated alumina is need to be regenerated by using caustic soda (NaOH- 4%) and sulfuric acid (2%) rinse procedure. AA Filters together with carbon cartridge are popular, since AA alone does little for water except remove fluoride. AA cartridges have certain advantages and limitations being short effective lifespan, relatively expensive, does not improve the taste nor remove other chemical contaminants like pesticides (http://purewaterproductsllc.com/ fluorideinwater.htm). Batch sorption kinetic studies employing AA were conducted to remove fluorides from water. It was observed to be dependent on various system parameters like contact time, pH, dose and ionic environment. AA was found effective in removal of fluoride and the data also denotes that an increase in pH, alkalinity, carbonates and calcium resulted in a decrease in sorption capacity. The presence of chloride, sulphate, potassium, sodium and magnesium has marginal influence on sorption capacity. Savinelli and Black, 1958, concluded that the removal of fluoride from water by AA is possibly exchange sorption. Balusu et al. (1988) investigated the effectiveness of AA for defluoridation and concluded that it depends on above stated parameters and TDS, ionic environment - presence of mono and/or bivalent anions and cations, physico-chemical properties of AA and regeneration procedures. Draw flow column studies found AA as a practical option by removing fluoride from an initial fluoride concentration of 5.0 mg/l to permissible limits of < 1.0 mg F/l. The candles of domestic water filters filled with AA in the hollow portion was investigated and found to be effective. Further, regeneration studies (cyclic adsorption – desorption studies) indicated that the used AA may be regenerated offsetting the overall cost of fluoride removal (Srimurali M. 2008). The ability of the alum-impregnated activated alumina (AIAA) has been investigated for removal of fluoride water by adsorption in batch experiments. The efficacy of AIAA to remove fluoride is found to be 99% at pH 6.5, contact time for 3 h, dose of 8 g/l, (for 50 ml of sample water with 20 mg F/l). Energy-dispersive analysis of X-ray shows that the uptake of fluoride at the AIAA/water interface is due to only surface precipitation. The desorption study reveals that this adsorbent can be regenerated following a simple base–acid rinsing procedure, however, re-impregnation of the regenerated adsorbent (rinsed residue) is needed for further defluoridation process (Tripathy 2006). Further, a new technique using the combination of an AA column and an electrochemical system was investigated for fluoride removal from synthetic solution after optimizing the process under various experimental parameters (i.e. volumetric flow, temperature, pH, initial fluoride concentration and hardness). The comparison of the performance of the current AA and the electrosorption system, the latter was proved to be more efficient i.e. the performance increased by about 60% by combo of AA & electrochemical processes ( Lounici H et al. 1997). Nagendra Rao(2004) investigated defluoridation by adsorption onto Gamma Alumina (GA), the purest form of Alumina, and reported a removal of 98% at optimum test conditions in upflow fixedbed continuous flow columns. However, GA is costly and difficult to prepare. Bone charcoal (BC) was investigated for the feasibility and cost-effectiveness. BC based column adsorption experiments indicated that fluoride removal is dependent on flow rate and bed height. Based on the batch tests with natural tourmaline and active alumina as the reference adsorbents, BC

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has demonstrated a higher fluoride adsorption capacity which enhances with increase in fluoride concentration (Wei Ma 2008). Adsorption and exchange were responsible mechanism for fluoride reduction. pH was kept below 6.5 to suppress any ion competition. A study was conducted in Tanzania for optimization and application of the regenerated BC media to remove fluoride from water,------------ regeneration temperature, BC dosage & duration, contact time and particle size. Results indicated that the highest fluoride removal and adsorption capacity were 70.64% and 0.75mgF/gm of BC regenerated at 500OC respectively. In this study the optimum burning duration was found to be 120 min, which resulted in residual fluoride that varied from a maximum value of 17.43 mg/l for 2 min contact time to a minimum value of 8.53 mg/l for 180 min. contact time. It was further observed that the smallest size of regenerated BC media (0.5–1.0mm diameter) had the highest defluoridation capacity (DC), with residual fluoride which varied from 17.82 mg/l at 2 min contact time to 11.26 mg/l at 120 min contact time. In terms of dosage of the regenerated BC media, optimum dosage was found at 25 gm of media (grain size of 0.50–1.0mm) and a removal capacity of 0.55 mgF/gm media. Column filter experiments indicated that regenerated media is capable of removing fluoride from water within permissible limit (Kaseva, M.E. 2006). Batch adsorption studies were undertaken to assess the suitability of commercially available activated charcoal for removal of fluoride. The effects of some major parameters of adsorption, viz. pH, and dose of adsorbent, rate of stirring, contact time and initial adsorbate concentration on fluoride removal efficiency were studied and optimized. Accordingly, the optimum sorbent dose was found to be 2.0 g/100 ml with 120 minutes equilibrium time and resulted in enhanced adsorption (94% of max. F. removal) at pH 2. (Tembhurkar AR, 2006). Ion exchange involves the exchange of undesirable ions present in water with the innocuous species. The process uses either natural or synthetic resins of two basic types, i.e. cation and anion. It is possible to get complete demineralization by using a mixed bed resin combination of anion and cation exchange resins Ram Gopal et al.(1985). The product water needs to be blended with raw water to get desired quality. The cost of plant is high for removal of single contaminant but one-half to one-fourth of the cost of a RO unit. A study was carried out for the ion exchange of metal ions (Al3+, La3+ and ZrO2+) on modified zeolites using batch method to evaluate the fluoride sorption characteristics of the sorbents. Natural zeolite samples ( R > F > B = S > E > H; Zn – H > S > E > B > O > R > F; Fe – R > B > F > > O > S > E > H; Cd – H > B > R > E > O > F > S; Pb – R > O > H > F > B > E > S and Ni – H > F > R > O > E > B > S. The total percentage of spermatozoa abnormalities differed according to species: F (7.76%) – H (41.6%). Further analysis detected these high/medium* correlations – stallions: Fe – Cd, Fe – Pb, Fe – Ni, Cd – Pb, Cu – FT, Zn – TN, Zn – FT, Fe – TN, Fe – FB, Cd – SF, Pb – TN, Pb – SF; bulls: Fe – Zn, Ni – SF; rams: Cd – Pb, Cu – Ni, Ni – SF, Cu – SF, Fe – FT; boars*: Cu – Pb, Cd – Ni, Pb – Ni, Cd – SF, Fe – SH, Fe – LH, Zn – BF, Ni – SF, Zn – FT, Cd – BF, Pb – OP, Ni – OP, Cu – TN; foxes: Cu – Pb, Cu – OP, Zn – BF, Fe – RC, Cd – SF, Cd – RC; rabbits: Zn – TN; man*: Cu – Pb, Ni – Fe, Pb – FB, Fe – OP, Cd – LH [flagellum torso (FT), total number of pathological spermatozoa (TN), flagellum ball (FB), separated flagellum (SF), small head (SH), large head (LH), broken flagellum (BF), other pathological spermatozoa (OP), retention of cytoplasmic drop (RC)]. Keywords: Environmental contaminants, toxicity, reproduction, spermatozoa, fertility.

1. INTRODUCTION Some metals are essential for life, others have unknown biological functions, either favorable or toxic, and some others have the potential to produce disease. Those causing toxicity are the ones, which accumulate in the body through the food chain, water, and air (Ikeda et al. 1996). Essential trace elements are components of many important enzymes. Zinc and copper are involved in carbohydrate or lipid metabolism an in immune functions (Bires et al. 1997). Copper has a multilateral function in the organism – is important in iron absorption, effects the haemopoiesis and activates ferments. Zinc deficiency results in disorders of testes development and course of spermatogenesis (Cigankova et al. 1998). Lead is a heavy metal distributed into environment, natural and antropogenic sources. It has unknown essential role in organism and its accumulation in tissues may cause several health hazards including neurotoxicity, hematotoxicity and reproductive disturbances (Rodmilans et al. 1996). Abnormal spermatozoa chromatin structure is not related to blood lead concentration, but some indications of deterioration of spermatozoa chromatin was found in men with the highest

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concentrations of lead within spermatozoa (Bonde et al. 2002). Exposure to cadmium, via air and food, leads to renal tubular dysfunction. Cadmium has various effects on reproduction, causing follicular atresia in ovary, edematization of uterus as well as degenerative alterations in testes (Massanyi and Uhrin 1996, 1997, Toman and Massanyi 2002, Massanyi et al. 2002). High quantity of nickel is known to be injurious for animal and human health. Its effects on various aspects of reproduction have been described. Animal studies may include that nickel reaches the testis, seminal vesicle and prostate gland and there is similar report of adverse effect on spermatozoa (Forgacs et al. 2001, Pandey and Srivastava 2000). The data reporting the metal concentration are mainly related to human semen (Telisman et al. 2000, Huang et al. 2001) and less in animal (stallion, bull, coypu) semen (Mertin et al. 1998, Dhami et al. 2001, Danek 2002). Generally, studies reporting effects of various metals on spermatoza in non–toxic environment that may influence individual susceptibility to adverse effects are lacking. The purpose of this study was to determinate copper, zinc, iron, cadmium, lead and nickel concentration in the semen of various animals and men, to find possible correlations and to evaluate the relation of these elements to the spermatozoa quality (occurrence of pathological spermatozoa). To minimise the differences between formats of different papers, and thus to provide a professional appearance to the conference proceedings, these editorial instructions need to be followed closely. This paper itself has been formatted according to the instructions and may be used as a model.

2. MATERIAL AND METHODS All semen was from adult bulls (n=200), rams (n=100), boars (n=20), stallions (n=10), foxes (n=10) and men (n=47). Semen was processed at the animal breeding station and Centre for Assisted Reproduction to frozen–thawed pellets (bulls, rams, foxes), frozen–thawed tubes (stallions) and in natural status (boars, men). Semen samples (at least 1 mL) were stored at –20°C and subsequently mineralized in the laboratory. All material of each sample was placed in separate mineralization tubes and mineralized by adding of 2 mL HNO3–HClO4 (4:1) mixture and heating it at 120°C for 65 minutes in a thermostat–controlled digestion block. The resulting solution was diluted to 10 mL with demineralizated water. Metal contents (cadmium and lead) were determined by the voltametric method (ASV) by EA9C potentiostat model equipped with working CGMDE electrode and AgCl2, and platinum electrodes. Concentrations of iron, nickel, copper and zinc were measured by flame absorption spectrophotometry method with Cole Parmer 200 A model. All elements concentrations are expressed in mg/kg (Stawarz et al. 2007, Kolesarova et al. 2008). For analysis of pathological spermatozoa, histological samples fixed with Hancock's solution and stained with Giemsa were prepared. All slides were analyzed at the magnification 500x (Massanyi et al. 2000). For each sample at least 1000 spermatozoa were evaluated and the percentage of pathological spermatozoa was recorded according to the table of pathological spermatozoa. These pathological changes were classified: separated flagellum, knob twisted flagellum, flagellum torso, flagellum ball, broken flagellum, retention of cytoplasmic drop, and other pathological spermatozoa. The mean ± S.D. values for each sample were calculated. Data from analyzed samples were statistically evaluated using Students t–test. To determine the significance between total number of pathological spermatozoa and trace elements level two-way analysis of variance (ANOVA) and correlation using PC software GraphPad ver. 3.01.

3. RESULTS 3.1 Metal Content The analysis of copper in semen showed that the concentration is higher in rams in comparison with bulls, boars, stallions and men. In comparison with foxes the concentration is very similar. In the studied animals we can report that the semen concentration of copper is the highest in rams and foxes and lower in bulls, boars, stallions and men (Table 1). Boar and men semen is typical with higher zinc concentration in comparison with stallion, bull as well as ram semen. The lowest level of zinc was


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recorded in fox semen. In iron we found that the concentration of this element in semen is similar in rams, bulls and foxes. Lower values were found in boar, stallion and men semen (Table 1). Concentration of cadmium in the semen of all studied animals is very similar (0.05 – 0.13 mg/kg). Any significant differences were found (Table 2). The highest lead concentration was found in human semen. Lower level of lead is reported in rams, foxes, bulls, stallions and boars. In nickel, we have found higher level of this element in human, fox and ram semen in comparison with boars. The concentration of nickel in the semen of stallions and bulls is between these values (Table 2). Table 1 Concentration of copper, zinc and iron in the semen Parameters Copper (mg/kg) Zinc (mg/kg) Mean ± SD Mean ± SD Bulls (n=200) 1.64±0.21 83.15±61.61 Rams (n=100) 2.49±0.18 60.46±35.37 Boars (n=20) 1.64±0.28 171.74±65.72 Stallions (n=10) 0.86±0.10 86.20±45.88 Foxes (n=10) 2.16±0.53 13.09±5.22 Men (n=47) 0.28±0.06 153.93±67.08

Iron (mg/kg) Mean ± SD 38.04±22.07 40.32±10.81 16.14±10.35 12.68±9.09 33.16±24.36 2.59±0.21

Table 2 Concentration of cadmium, lead and nickel in the semen Cadmium (mg/kg) Lead (mg/kg) Nickel (mg/kg) Mean ± SD Mean ± SD Mean ± SD Bull (n=200) 0.10±0.14 0.06±0.04 0.12±0.07 Rams (n=100) 0.12±0.12 0.35±0.68 0.31±0.19 Boars (n=20) 0.05±0.04 0.02±0.03 0.06±0.08 Stallions (n=10) 0.09±0.11 0.05±0.05 0.20±0.24 Foxes (n=10) 0.07±0.05 0.08±0.06 0.36±0.24 Men (n=47) 0.13±0.15 1.49±0.40 0.40±0.07

3.2 Spermatozoa Analysis In stallions the total percentage of pathological spermatozoa was 17.09±3.66%. From this total number 4.93% had knob twisted flagellum, 4.71% separated flagellum, 1.60% flagellum torso, 0.87% broken flagellum, 0.78% retention of the cytoplasmic drop, 0.74 acrosomal changes, 0.67% large heads, 0.51% small heads, 0.34% flagellum ball, and 1.94% forms other of pathological changes. In bull semen we found 11.79±4.88% of pathological spermatozoa, with the dominancy of separated flagellum, flagellum torso and knob twisted flagellum. Higher occurrence of pathological spermatozoa is in ram semen (17.17±3.76%) in comparison will the semen of bulls. Separated flagellum, flagellum torso and knob twisted flagellum are the most frequent forms of pathological spermatozoa. The total percentage of pathological spermatozoa in boars was 9.82±1.47%. From this total number 3.18% had a separated flagellum, 2.26% knob twisted flagellum, 0.88% flagellum torso, 0.85% flagellum ball, 0.42% broken flagellum 0.23% retention of the cytoplasmic drop, 0.14% small heads, 0.03% large heads and 1.83 % forms other of pathological changes (teratoid spermatozoa; a spiral twisted flagellum; deformation of the mitochondrial part; acrosomal changes; others). In foxes the total percentage of pathological spermatozoa was 7.76±1.33%. From this total number 3.22% had knob twisted flagellum, 1.99% separated flagellum, 0.33% broken flagellum, 0.30% flagellum torso, 0.30% flagellum ball, 0.28% retention of the cytoplasmic drop, 0.21% acrosomal changes, 0.09% large heads, 0.01% small heads, and 1.02% forms other of pathological changes. In men the total number of pathological spermatozoa was 9776 (41.6±9.80%). From this number had a broken flagellum 15.43%, 7.09% flagellum torso, 4.29% separated flagellum, 2.94% small heads, 2.89% a retention of cytoplasmic drop, 2.63% were other pathological spermatozoa, 2.29% large heads, 2.03% acrosomal changes, 2.00% knob twisted flagellum and 0.80% flagellum ball.

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3.3 Metal and Spermatozoa Quality Correlations Correlation analysis detected these high/medium* correlations – stallions: Fe – Cd, Fe – Pb, Fe – Ni, Cd – Pb, Cu – FT, Zn – TN, Zn – FT, Fe – TN, Fe – FB, Cd – SF, Pb – TN, Pb – SF; bulls: Fe – Zn, Ni – SF; rams: Cd – Pb, Cu – Ni, Ni – SF, Cu – SF, Fe – FT; boars*: Cu – Pb, Cd – Ni, Pb – Ni, Cd – SF, Fe – SH, Fe – LH, Zn – BF, Ni – SF, Zn – FT, Cd – BF, Pb – OP, Ni – OP, Cu – TN; foxes: Cu – Pb, Cu – OP, Zn – BF, Fe – RC, Cd – SF, Cd – RC; rabbits: Zn – TN; man*: Cu – Pb, Ni – Fe, Pb – FB, Fe – OP, Cd – LH [flagellum torso (FT), total number of pathological spermatozoa (TN), flagellum ball (FB), separated flagellum (SF), small head (SH), large head (LH), broken flagellum (BF), other pathological spermatozoa (OP), retention of cytoplasmic drop (RC)]

4. DISCUSSION It has been reported that many metals have negative effects on the reproduction in animals as well as humans (Blottner et al. 1999, Gaur et al. 2000). In the study of 107 fertile and 103 subfertile male blood and semen specimens the concentrations of calcium, magnesium, zinc, and copper in blood and seminal plasma were not different between the subfertile and fertile group. Weak correlations were demonstrated between blood plasma zinc concentrations and sperm count, sperm motility and abnormal sperm morphology. Zinc concentrations in seminal plasma correlated weakly with sperm count and copper concentrations in blood plasma with motility (Wong et al. 2001). Our analyses showed that the relatively high concentration of zinc is typical for men and boar semen in comparison with other males. In relation to zinc the main alteration cause the status of hypozincaemia. The zinc deficiency cause degenerative changes in spermatogenic cells after meiosis, their depletion and cumulation in the lumen of seminiferous tubuli. The increased occurrence of malformed spermatids indicates to an impaired course of spermatogenesis. It has been stated that zinc is an indispensable element for a normal course of spermatogenesis (Cigankova et al. 1998). It has been reported that the concentration of copper in semen is 0.28 – 2.49 mg/kg. It has been reported the copper has a toxic effect on the seminiferous epithelium (Gamcik et al. 1990). In the toxic phase of disease, the germinative epithelium was first damaged. Parenteral administration of iron to swine is a common practice in a pig industry to prevent and to threat anaemia. Besides being a hemopoetic factor, iron plays an important role in modulating the functions of many cells in the body. Iron deficiency has been shown to reduce the activity of ironcontaining and iron–dependent enzymes. In FeSO4/ascorbate–incubated samples, the activities of antioxidant enzymes, superoxid dismutase, glutathione peroxidase and glutathione reductase were decreased while lipid peroxidation increased as compared to the control spermatozoa samples (Murugan et al. 2002). Cadmium accumulates mainly in the kidney and liver, but it has various effects on male as well as female reproductive organs. Previous studies report that a low cadmium dose (40 µg/mL natrium citrate) does not significantly decreases spermatozoa motility over a lenght of time, progressively decreases motility and decreases the percentage of spermatozoa with the highest motility. When comparing the four different cadmium doses (0.02; 0.1; 0.2 and 2.0 mg CdCl2/ml), it was found that the progressive motility, path velocity and straightness were most affected in the group with the highest cadmium concentration (Massanyi et al. 1996). The level of lead in semen in our study was the highest in human samples. The toxic effect of lead on gonadotropin binding (lower affinity) has been reported in rats (Combs 1997). With regard to the lead intoxication, hypoplasia of the Leydig cells producing testosterone in atrophic testes was recorded. In the study of male reproductive toxicity of inorganic lead at current European exposure levels have been found an adverse effects of lead on sperm concentration and susceptibility to acid induced denaturation of sperm chromatin (Bonde et al. 2002). In nickel, we report relatively low levels in semen (0.12 – 0.40 mg/kg) but a dose–related depression in stimulated testosterone production of mouse Leydig cells in culture following either in vivo or in vitro nickel treatment at a dose that does not induce any general toxic or significant cytotoxic action has been reported. The data of the time-course study indicate that the effect of nickel on testosterone


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production is both time and concentration dependent and not due to cytotoxicity (Forgacs et al. 2001, Pandey and Srivastava 2000).

5. CONCLUSIONS When evaluating reproductive effects of a certain metal on human males, one must take into account possible influences of concomitant exposures to other toxic and essential metals; these may act additively, synergistically, or antagonistically. Generally, our results suggest that there are very significant differences in the concentration of studied elements in animal semen which might directly effects the spermatozoa quality.

6. ACKNOWLEDGEMENT This was supported by VEGA Scientific Grant 1/0696/08 and APVV Project 0299–06.

7. REFERENCES Bires, J, Bartko, P, Huska, M, Biresova, M, 1997, Distribution of risk elements in the organism of sheep after industrial intoxication with zinc, Spectroscopy Letters, 30, p1263-1277. Blottner, S, Frolich, K, Roedlants, H, Streich, J, Tataruch, F, 1999, Influence of environmental cadmium on testicular proliferation in roe deer, Reproductive Toxicology, 13, p261-267. Bonde, JP, Joffe, M, Apostoli, P, Dale, A, Kiss, P, Spano, M, 2002, Sperm count and chromatin structure in men exposed to inorganic lead: lowest adverse effect levels, Journal of Occupational and Environmental Medicine, 59, p234-242. Cigankova, V, Mesaros, P, Bires, J, Ledecky, V, Ciganek, J, Tomajkova, E, 1998, The morphological structure of the testis in stallions with zinc deficiency, Slovak Veterinary Journal, 23, p97-100. Combs, DW, 1997, Male contraception, Annual Reports in Medicinal Chemistry, 32, p191-200. Danek, J, 2002, Role of zinc in stallions, Medycyna Weterynaryjna, 58, p840-844. Dhami, AJ, Shelke, VB, Patel, KP, Paradva, JP, Kavani, FS, 2001, Trace minerals profile of blood and seminal plasma of breeding bulls, Indian Journal of Animal Sciences, 71, p761-763. Forgacs, Z, Nemethy, Z, Revesz, C, Lazar, P, 2001, Specific amino acids moderate the effects of Ni2+ on the testosterone production of mouse Leydig cells in vitro, Journal of Toxicology and Environmental Health, A62, p349-358. Gamcik, P, Bires, J, Vrzgula, L, Mesaros, P, 1990, Effect of experimental intoxication with copper from industrial emission on reproductive ability in rams, Reproduction in Domestic Animals, 25, p235-241. Gaur, M, Pruthi, V, Prasad, R, Pereira, BMJ, 2000, Inductively coupled plasma emission spectroscopic and flame photometric analysis of goat epididymal fluid, Asian Journal of Andrology, 2, p288-292. Huang, YL, Tseng, WC, Lin, TH, 2001, In vitro effects of metal ions (Fe2+, Mn2+, Pb2+) on sperm motility and lipid peroxidation in human semen, Journal of Toxicology and Environmental Health, A62, p259-267. Ikeda, M, Zhang, ZW, Moon, CS, Imai, Y, Watanabe, T, Shibo, S, Ma, WC, Lee, CC, Guo, YLL, 1996, Background exposure of general population to cadmium and lead in Tainan City, Taiwan, Archives of Environmental Contamination and Toxicology, 30, p121-126. Kolesarova, A, Slamecka, J, Jurcik, R, Tataruch, F, Lukac, N, Kovacik, J, Capcarova, M, Valent, M, Massanyi, P, 2008, Environmental levels of cadmium, lead and mercury in brown hares and their relation to blood metabolic parameters, Journal of Environmental Science and Health, A43, p646-650. Massanyi, P, Uhrin, V, 1996, Histological changes in the ovaries of rabbits after an administration of cadmium, Reproduction in Domestic Animals, 31, p629-632. Massanyi, P, Lukac, N, Trandzik, J, 1996, In vitro inhibition of the motility of bovine spermatozoa by cadmium chloride, Journal of Environmental Science and Health, A31, p1865-1879.

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Massanyi, P, Uhrin, V, 1997, Histological changes in the uterus of rabbits after an administration of cadmium. Journal of Environmental Science and Health, A32, p1459-1466. Massanyi, P, Trandzik, J, Lukac, N, Strapak, P, Kovacik, J, Toman, R, 2000, The contamination of bovine semen with cadmium, copper, lead, and zinc and its relation to the quality of spermatozoa used for insemination, Folia Veterinaria, 44, p150-153. Massanyi, P, Kiss, Z, Toman, R, Bardos, L, 2002, Effect of acute cadmium exposure on testicular tissue and testicular retinoid and beta-carotene content, Hungarian Veterinary Journal, 124, p688-692. Mertin, D, Suvegova, K, Szeleszczuk, O, Flak, P, Polacikova, M, 1998, Content of some mineral elements in coypu semen, Czech Journal of Animal Science, 43, p459-463. Murugan, MA, Gangadharan, B, Mathur, PP, 2002, Antioxxidative effect of fullerenol on goat epididymal spermatozoa, Asian Journal of Andrology, 4, p149-152. Pandey, R, Srivastava, SP, 2000, Spermatotoxic effects of nickel in mice, Bulletin on Environmental Contamination and Toxicology, 64, p161-167. Rodmilans, M, Torra, M, To-Figueras, J, Corbella, J, Lopez, B, Sanchez, C, 1996, Effects of reduction of petrol lead on blood lead levels of the population of Barcelona, Bulletin of Environmental Contamination and Toxicology, 56, p717-721. Telisman, S, Cvitkovic, P, Jurasovic, J, Pizent, A, Gavella, M, Rocic, B, 2000, Semen quality and reproductive endocrine function in relation to biomakers of lead, cadmium, zinc, and copper in men. Environmental Health Perspectives, 108, p45-53. Stawarz, R, Formicki, G, Massanyi, P, 2007, Daily fluctuations and distribution of xenobiotics, nutritional and biogenic elements in human milk in Southern Poland, Journal of Environmental Science and Health, A42, p1169–1175. Toman, R, Massanyi, P, 2002, Changes in the testis and epididymis of rabbits after an intraperitoneal and peroral administration of cadmium, Trace Elements and Electrolytes, 19, p114-117. Wong, WY, Flik, G, Groenen, PMW, Swinkels, DW, Thomas, CM, Copius-Peereboom, JH, Merkus, HM, Steegers-Theunissen, RPM, 2001, The impact of calcium, magnesium, zinc, and copper in blood and seminal plasma on semen parameters in men, Reproductive Toxicology, 15, p131-136.


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ENVIRONMENTAL IMPACT ASSESSMENT FOR BUDGET HOTEL IN LANGKAWI, MALAYSIA Firuza Begham Mustafa, Department of Geography, University of Malaya, Malaysia. [email protected] Nather Khan Ibrahim, Ecotone Environmental Management Ptd. Ltd., Malaysia. [email protected]

ABSTRACT The island of Langkawi in Malaysia is a popular destination for local and international holidaymakers. In continuing the tourism development in Langkawi, the Tune Hotels Ptd. Ltd. planned to build a low cost budget hotel in Langkawi. An Environmental Impact Assessment (EIA) study is a mandatory requirement under the Environmental Quality (Prescribed Activities) (Environmental Impact Assessment) Order 1987 for the project prior to the commencement of the project. Under the legislation meant to protect and conserve the environment, approval for the proposed project is only granted upon the Preliminary EIA study being completed and approved by the Director General of the Department of Environment (DOE), Malaysia. The Project Proponent has engaged Ecotone Environmental Management Ptd. Ltd. to conduct a Preliminary EIA study and provide an assessment of potential impacts of the proposed project activity is likely to have on the environment and to propose appropriate mitigation measures to minimise or nullify the significant potential impacts, in accordance with the guidelines issued by the Department of Environment, Malaysia. This paper discusses briefly the Preliminary EIA carried out for the budget hotel project in Langkawi island of Kedah State in Malaysia. Keywords: Environmental Impact Assessment, Environmental Quality, Environmental Monitoring, Environmental Auditing, Langkawi.

1.0

INTRODUCTION

The island of Langkawi has always been a popular destination for local and international holidaymakers. In continuing the tourism development in Langkawi, Tune Hotels Ptd. Ltd. planned to build a budget hotel called the “Tune Hotel” at Lot 2085 consisting of 1.638 acres in Pantai Tengah, Langkawi. The primary advantage in developing the budget hotel at this location is that it will enhance the tourism industry in Langkawi as a premier tourist destination with the end result of creating an enduring economic sector to diversify Malaysia’s economy and reduce its reliance on resource based economy.

2.0

THE GOVERNMENT REQUIREMENT

It has been the Malaysian Government’s commitment to ensure that a balanced approach in its efforts in promoting socio-economic development and the management of natural resources and environmental quality. Emphasis has been stressed on the needs of environmental consideration for inclusion as a required factor in decision making at the planning stage for all major development projects. In recognizing the need to adopt a comprehensive legislation in the management of environment, the Malaysian Government implemented the Environmental Quality Act of 1974. However, this act had little jurisdiction over forestry operations, land clearing and development, agricultural activities and mining, all of which have contributed towards the degradation of the

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environment. As a result, the Environmental Quality Act of 1974 had to be amended in 1985, gazetted on 9th January 1986 and finally implemented on 1 April 1988. This amendment calls for Environmental Impact Assessment reports to be prepared for various prescribed activities developed by the Department of Environment (DOE) of Malaysia. The amendment contains provisions for the incorporation of measures to prevent, reduce or control adverse environmental impacts during the design, construction and operation stages of the project. The proposed development budget hotel project is classified as a Prescribed Activity under Section 34A of the Environmental Quality (Prescribed Activities) (Environmental Impact Assessment) Order of 1987. Hence, an Environmental Impact Assessment is legally mandatory for the proposed project. A completed EIA report therefore, is required to submit to the Director-General of DOE for evaluation and approval prior to commencement of the project.

3.0

PROCEDURE AND METHODS

The EIA study will begin with a scoping meeting with relevant project management team to identify the major components of the project and data availability regarding the project details. A site reconnaissance survey will be conducted to assess the existing environment, including general land use, economic activities around the area, natural resources, sensitivity of the project to local communities, benefit of the project, etc. The Terms of Reference (TOR) of EIA study will be discussed with the project team such that any areas of ambiguity, which may have existed prior to the initiation of the project. Subsequently, the baseline environmental parameters like the air quality, noise, vibration and water quality will be monitored at selected locations in and around 3 km radius of the proposed project site, which may be influenced by the project development. Secondary information that is available from various sources could be of importance for the proposed project, like data from Malaysian Meteorological Services Department, local structure plans and other published documents will be obtained to cover other essential elements in the study. At the same time, the project description detailing the various activities, conceptual or final development plan and construction schedule will be sought from the client. Then, the project activities will be superimposed over the existing environment to predict the significant impacts that likely to occur. This will include quantitative and qualitative description of the changes to the natural environmental settings. The consultant shall refer these changes with those standards and guidelines established by the DOE or other agencies for compliance. Based on this assessment, environmental safeguards or mitigating measures for both the construction and operational phases of the project will be developed to minimize the potential impacts. These will be developed in close association with project engineering team. The EIA study report prepared will clearly outline the nature and details of the proposed project, existing baseline data, the environmental mitigation and management strategies to be adopted and the likely environmental and economic implications due to the project.

4.0

CONDUCTING ENVIRONMENTAL IMPACT ASSESSMENT

4.1

Statement of Needs

The islands of Langkawi is a major tourist hub in Malaysia. Tourist arrivals in Langkawi recorded approximately 2.24 million tourists (1.52 domestic tourists and 713,874 foreign tourists) in 2006 as compared to 1.06 million in 1999. To provide an opportunity to further promote growth in the tourism industry, the project proponent has proposed the development of the budget hotel at Pantai Tengah in Langkawi in the state of Kedah Darul Aman. The primary advantage in developing the budget hotel at this location will enhance tourism industry in Langkawi as a premier tourist destination with the end result of creating an enduring economic sector to diversify Malaysia’s economy and reduce its reliance on resource based economy. The area is also identified for tourism development in the Langkawi Structure Plan and several hotels and resorts are already there at the proposed project site.


4.2

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The Project Description

The concept of budget hotel as an affordable accommodation provider without compromising the comfort standard is extended into a resort setting of Langkawi. It is located across from the main road and just next to the existing hotels. The rooms shall over look the beach or swimming pool amidst manicured lawns inter dispersed with swaying palms. This idea of the boutique hotel is essentially designed with a unique central core which interconnects the two wings on the east and south side. The core is further enhanced by a void to bring light into the main point of arrival acts as a visual and physical anchor for this hotel. Located within are the main administration and front of house areas at the ground floor of the centre core. The naturally ventilated lobby has a tropical setting overlooking the idyllic garden and pool. Visually the facade is dynamic in a way that the balconies are angled to capture the sunlight and provide a distinct feature to the outlook of the building especially on the northern face as one approach the main entrance of the centre core. The facade is further enhanced on the circular face of the core with horizontal fins and expanded metal cladding giving the overall hotel a trendy, fun and active outlook in line with the image of the Tunes Hotel brand as a dynamic holiday establishment for all. Layouts of the rooms are arranged with the wings wrapping the pool for the guests to face and take advantage of the pool view and overlook the retail areas. Other guest rooms are outward looking with open air balconies to capture the fresh sea breeze and sunlight further enhancing the experience of relaxation in the ‘sun and sea’. The cleverly organized rooms are packed with the essential amenities for travellers whether they are a single, double or family unit who can book for the available adjoining rooms. The retail outlets are designed to be physically separated from the hotel complex in terms of operation and management. The hotel mainly practices an open concept with free access for the guests and also external patrons to make use of the retail food and beverage outlets. Each outlet shall be operated separately by various providers with typical Malaysian cuisine, grab and go sandwich bars and more formal dining.

4.3

Project Options

Though the project options are limited in terms of site selection and technological options, however, with the intention of assessing the most appropriate option(s) for the development of the proposed budget hotel project, the criteria such as (a) Environmental acceptability; (b) Social and economic value in terms of employment, social impacts and contribution to the economy; (c) Land use compatibility and (d) Relevance to Government policies and development strategies for the area, are identified and followed.

4.3.1

Site selection and suitability

With reference to the above criteria, the project site was judged to be suitable for the construction of the hotel. The site is currently an open, levelled, and grassy field, which ensures minimal land clearing activities. The project site is owned by the project proponent. Furthermore, the project site is situated along the popular Pantai Tengah area surrounded by several hotels, resorts and tourism related activities, ensuring land use compatibility with its neighbours. Tourism has become a major industry in Langkawi, and as such, the hotel will further expand the tourism industry in Langkawi, in line with the local development strategy for the area.

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Figure 1: Project Location and Baseline Monitoring Stations 4.3.2

Hotel development options

The concept of budget hotel as an affordable accommodation provider without compromising the comfort standard is extended into a resort setting of Langkawi. It is located across from the main road and just next to the existing Lanai Beach Resort and Holiday Villa hotels. The project concept is based on the “5-star living experience with a 1-star price”. The hotel will have amenities such as a swimming pool as well as commercial and retail spaces. Tourist can expect to have high quality living experience without paying a hefty bill for it. The main idea is to provide quality but cheap accommodations to help promote tourism in Langkawi.

4.3.3

No project option

To ignore the development of the proposed project will have an impact on the tourist development, generally in Malaysia and particularly in Langkawi. This would be incompatible with the State government’s objective to further enhance the economic status of this part Kedah state. The ‘No Build’ option would probably result in the following negative impacts (a) Deny tourists important and necessary infrastructures (b) Restriction of additional revenue through which the state authorities could derive and further expand their economic base (c) Inhibit potential avenues for additional investment and employment opportunities and associated spin-off opportunities (d) Adversely affect the high potential of the overall tourism industry in Langkawi.

4.4

Baseline Study for Existing Environment


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The proposed project site covers an area of approximately 1.638 acres. The project site is currently an undeveloped green field area. There is no prior development on the site. It is basically a grassy field with some vegetation on its borders. In the north is a Federal Rest House; while on the south is a secondary forest with a pond which is covered with aquatic vegetation. Bordering the east is Jalan Teluk Baru which runs north, parallel to Pantai Tengah. West side there is the Lanai Beach Resort and the beautiful beach. The topography of the site is generally flat and gently sloping down to the west towards the shoreline (Pantai Tengah). The project site is located approximately 1 meter to 3 meter above the mean sea level. The geology of the proposed project site and immediate surroundings is characterised by the Singa Formation. The lithology of the formation is comprised of dark coloured shale and siltstone. This type of material is widely distributed in the south-western part of the Langkawi islands. At the proposed project site, metamorphosed shale and siltstone is observed. The weathering rock has provided a significant layer of soil which supports thick and healthy vegetation. The tides along the island of Langkawi are of the semi-diurnal type (twice daily), where there are two tidal cycles with one high tide and one low tide each day. The tidal levels are extracted from the Tide Prediction Table for 2009 for two standard ports at Teluk Ewa and Kuah. From the table, tides along the Pantai Tengah coastline ranged between 0.53 ACD to 3.56 ACD. The deepwater wave statistics show that more than 70% of the waves are less than 1.75m and waves higher than 2.5m accounts for only 1%. Wave heights between 1.75 m and 2.75m has about 5% occurrence while the mean wave period is between 5 to 8 seconds. The water quality monitoring is essential part of the environmental assessment and therefore, monitoring stations are established within 3 km radius of the project site and approximately 100 meters from the coastline. The marine water quality sampling and testing was carried out at both high and low tide. A total of 8 water samples were collected from the 4 stations. At all stations, samples were analyzed for all 23 parameters specified in Standard B under the Environmental Quality (Sewage and Industrial Effluent) Regulations, 1979 plus E. coli, dissolved oxygen, turbidity and salinity. Marine water data thus obtained was compared against the Interim National Marine Water Quality Standards (INMWQS). There is some variation in marine water quality between locations but most of the data are well within INMWQS including the heavy metals. There are some differences between water quality parameters during high and low tides. At the Langkawi Airport Meteorological Station, the mean daily temperature varied from 26.6°C to 29.3°C from 2003 – 2008. The mean monthly rainfall ranged from 151.9 mm to 263.9 mm. The number of rain days a month ranged from none 0 to 27 days. Wind speeds were most prevalent at 0.3 m/s to 3.3 m/s. Maximum wind speed recorded were 8.0 m/s to 10.7 m/s, most common during October. The air pollutants that are relevant and important to the proposed project are Total Suspended Particulate (TSP), Particulate Matter (PM10), Sulphur Dioxide (SO2), and Nitrogen Dioxide (NO2). The TSP and PM10 concentrations monitored at two stations were within the Recommended Malaysian Air Quality Guidelines of 260 μg/m3 and 150 μg/m3, respectively. The TSP levels recorded were 124 and 110 μg/m3, whilst PM10 was 90 - 95 μg/m3. The NO2 and SO2 concentration was not detected at all the stations and far below the DOE recommended limit of 320 µg/m3 and 105 µg/m3. The equivalent noise levels (Leq) monitored from 21st – 23rd November 2008 at the four stations indicates that noise varied from 57.3 to 62.1 dB(A). The noise levels recorded were all within the DOE daytime noise limit of 65 dB (A). Sudden increase in noise level occasionally during the daytime may be due to vehicle movement along the adjacent main road. The background noise for this location is generally high due human voices and sea waves. There is no wetland or freshwater or terrestrial ecosystems of significant importance within 3 km radius of the project site. The marine habitats include the beach front, the intertidal zone and the islands, Pulau Rebak Besar and Kecil at the north of the project area and Pulau Tepur at the south end of the project area. The main consideration on the biological environment would be plankton and the fisheries within Pantai Cenang and Pantai Tengah marine waters. Generally, the shallow marine waters of Langkawi are reasonably rich in plankton and are important for artisanal (traditional) fisheries.

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Report from the “Kajian Kependudukan dan Sosio-ekonomi Pulau Langkawi, 1999” conducted by LADA shows that in 1999 about 50% of the locals in Langkawi earned an average monthly household income raging from RM 500 to RM 1 000 whilst another 28% earned less than RM 500 per month. However, increased participation by some members of the local population in the service and hospitality sector since then has pushed the average monthly household income raging from RM 1 000 to RM 1 500. Kuah recorded an average monthly household income of RM 1 524 whilst, the study area (Mukim Kedawang) recorded mean monthly household income of RM 1 250. The project site is located at Pantai Tengah, which is a well known tourist destination in Langkawi. There is already a multitude of hotels, resorts, restaurants, shops, boutiques and other commercial activities in Pantai Tengah. It has all the necessary infrastructure and utility including roads, water supply, electricity supply and telecommunications. Pantai Tengah is a popular tourist spot and therefore infrastructure development in the area is well established. In Pulau Langkawi, the solid waste management including collection of solid wastes and disposal of solid wastes falls under the jurisdiction of Majlis Perbandaran Langkawi (MPL). This includes both residential and commercial establishments. The collection of solid wastes from various locations is undertaken by waste collection vehicles owned by Majlis Perbandaran Langkawi and also private owners, mainly the hotels. Sewage treatment services in Langkawi are managed by Indah Water Konsortium (IWK). There is a sewage treatment plant located at Jalan Teluk Baru, Pantai Tengah with a design capacity of 10 000 PE. The sewage treatment plant utilises the extended aeration activated sludge system to treat sewage.

4.5

Potential Significant Impacts and Proposed Mitigation Measures

The principal project activities that will be carried out during the construction and operational phases and the expected impacts on the environment due to the development of budget hotel in Langkawi are discussed in detail. The aim is to highlight specific activities that may have an impact on the existing environment so that appropriate mitigation and abatement measures can be instituted. During the construction phase the main environmental impacts expected are increase in noise level and vibration due to construction activities and vehicle movements, soil erosion and sedimentation due to earthwork and land clearing activities, increased traffic and potential accidents due to transportation of construction materials and increase in solid and liquid wastes from the workers camps. During the operation phase of the hotel, the main impacts are increase in sewage and solid waste and its management, increase in traffic and influx of tourists to the area. Several mitigation measures are proposed which are mainly to prevent soil erosion and surface runoff to control suspended solids and nutrient runoff to coastal areas and to minimise noise and vibration due to transportation activities. The mitigation measures proposed during operation phase are mostly to minimise the impacts related to noise, solid and sewage management, traffic and public safety due to increased traffic and tourists.

4.6

Residual Impacts

The residual impacts are defined as potentially significant long-term environmental impacts which remain even after mitigating measures have been introduced. These impacts are considered to be permanent and long-term, which might occur during the construction and operational phases of hotel and are likely to affect the three major environmental components, i.e. physical, biological and human environment. These residual impacts require closer investigation and are managed with well-defined environmental monitoring programme which should be implemented during the construction and operational phases of the project.

4.7

Environmental Management Plan (EMP)

A comprehensive Environmental Management Plan (EMP) for the hotel shall be prepared to effectively manage all potential impacts identified in this report and monitor the project activities and the implementation of mitigation measures at the site during both construction and operational phases


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of the project. This is to ensure environmental objectives are met and all activities relating to the implementation of the project are carried out in an environmentally sustainable manner. The document will provide specific guidelines on steps that need to be performed by the project proponent to ensure that mitigation measures recommended in this report, the EIA approval conditions and any other requirements imposed by the DOE are implemented.

4.8

Project Abandonment

Project abandonment means when the whole project or a part of the project has to be abandoned for specific reasons. Abandonment could happen at any stage of the proposed project. Abandonment during the planning stage would not result in any significant financial losses other than costs incurred for undertaking various studies and planning. Abandoned structures and machinery could be a health hazard to the public and cause negative impacts to the surrounding environment if left exposed, such as soil erosion and surface run-off.

5.0

CONCLUSION

The Preliminary Environmental Impact Assessment study has attempted to identify and assess the environmental impacts with respect to physical, biological and human environment due to the development of Tune Hotel at Pantai Tengah, Langkawi, Kedah. The deductions and interpretations made here are based on the best available information and the studies carried out specifically for the project as outlined in the various chapters of the EIA report.

ACKNOWLEDGMENTS We like to express our sincere thanks to Tune Hotel Sdn. Bhd. for allowing us to publish salient points of the EIA report prepared for their project. Special thanks to Mr. Mark Lankester, Ms. Sharon Ruba and various consultants involved in the EIA study like Dr. Harinder Rai Singh and Mr. Abdul Wahid Ghazali for their support and valuable contributions. REFERENCES Aishah, S., Ahmad Wakid, S., Shah Bahnan, I., Abdul Rahman, K.A., & Nasrodin, S, 2005, Diversity of phytoplankton at Langkawi Island, Malaysia. Malaysian J. Sci, 24: 43 – 55. DOE, 1979, Environmental Quality (Sewage and Industrial Effluents) Regulations 1979, Environmental Quality Act, (1991), International Law Book Services. DOE, 1989, A Handbook of Environmental Impact Assessment Guidelines, Department of Environment, Kuala Lumpur. DOE, 1991, Environmental Quality Report 1991, Proposed Interim Standards for Water Quality for Malaysia, Department of Environment, Kuala Lumpur. DOE, 1991, Interim National Water Quality Standard, In: Environmental Quality Report, Malaysia, Ministry of Science, Technology and the Environment, Department of Environment, Kuala Lumpur. DOE, 1995, The Handbook of Environmental Impact Assessment Guidelines, Department of Environment, Kuala Lumpur.

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EQA, 1974, Environmental Quality Act 1974 (Act.127) Environmental Quality (Prescribed Activities) (Environmental Impact Assessment) Order 1987. EQA, 1974, Environmental Quality Act 1974 (Act.127) Environmental Quality (Sewage and Industrial Effluents) Regulations 1979. Firuza Begham Mustafa, 1995, Evaluation of biological impact for recreational and tourism activity, Project paper, Universiti Kebangsaan Malaysia, Bangi. Majlis Daerah Langkawi, 1999, Langkawi Structure Plan 1985 – 2005, Report on Survey. Ministry of Health, 1997, National Health and Morbidity Survey 1996, Volume 2 General Findings. U.S EPA Intergrated Risk Information system (IRIS). National Center for Environmental Assessment, Washinton, DC. Online. http://www.epa.gov/iris. [accessed 20 Jun 2006]. U.S EPA, 2004, Example Exposure Scenarios. National Center for Environmental Assessment, U.S Environmental Protection Agency, Washington, DC 20460. U.S EPA, 2000, Supplementary Guidance for Conducting Health Risk Assessment of Chemical Mixtures, Risk Assessment Forum, EPA/630/R-00/002.


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ESTIMATION OF HEALTH IMPACT OF ENVIRONMENTAL CONTAMINANTS: HEAVY METALS AND TESTICULAR CHANGES LUKAC Norbert, MASSANYI Peter, KOVACIK Jaroslav, TOMAN Robert, KROCKOVA Jirina, CAPCAROVA Marcela Slovak University of Agriculture, Nitra, Slovak Republic, Robert STAWARZ, Grzegorz FORMICKI Pedagogical University, Krakow, Poland

ABSTRACT Distribution of cadmium, lead, nickel and cobalt as a risk factor of environment, in testis and its effects on the testicular structure in experimental animals were studied. All studied elements were intraperitoneally administered in a single dose. Cadmium (CdCl2) was administered in mice group A/Cd (0.25 mg.kg-1 body weight) and group B/Cd (0.5 mg.kg-1). Rats received lead (PbNO3) in dose 50 mg.kg-1 (group A/Pb), 25 mg.kg-1 (group B/Pb) and 12.5 mg.kg-1 (group C/Pb) of body weight. Nickel (NiCl2) was administered for mice in dose of 20 mg NiCl2 per kg of body weight (group A/Ni), 40 mg NiCl2 per kg b. w. (group B/Ni). Hamsters in group A/Co received cobalt (CoCl2) in dose 20 mg.kg-1 in group B/Co 10 mg.kg-1 and in group C/Co 5 mg.kg-1 CoCl2 /kg body weight. Animals were killed 48 hours after application of observed elements. After a preparation of histological samples the results were compared with control (Ctrl). Micromorphometry found any significant differences in observed histological parameters in cadmium treated animals. Morphometric analysis showed that in all lead-treated groups the relative volume (RV) of seminiferous epithelium was significantly decreased. RV of interstitium was significantly decreased in group C/Pb. The diameter of seminiferous epithelium was significantly decreased in group B/Pb and C/Pb in comparison with control. In both experimental groups with nickel a significant (pDaman forest>Daman agriculture (Figure 5). But the quality class remained same, i.e., Class 3 for all sites except Daman agriculture, which had a quality class of 2/3. To get higher quality class this index requires Proturan (organism) but in our sample these organisms were entirely absent. This may be due to one time sampling result need to be verified to do more intensive sampling in different seasons. A recent study in Ansi Khola Watershed by Rokaya (2008) to assessed soil quality using physico- chemical and biological indicators, showed that the soil quality (QBS-ar) was highest in Forest followed by Khet, Bari and Grazing.

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QBS-ar

80 60 Agriculture

40

Forest 20 0 LAMIDADA

DAMAN

PALUNG

sampling sites Figure 5.QBS-ar at the sampling sites

4. CONCLUSIONS Land use significantly affects the soil physico-chemical and biological properties. This in turn affects the soil quality. Soil quality as determined using QBS-ar was found to be somewhat higher in the forest as compared to agriculture. Soil faunal abundance was found to be the higher in the forest at all three locations except in Daman where agriculture soil had higher faunal abundance. Most of the physico-chemical properties of the soil except bulk density differed significantly with the land use. Among the physical and chemical properties, soil moisture and soil organic carbon appeared to be good indicators of soil quality and positively correlated with biological indices. Further research is required to fully understand the effects of land use changes on the different faunal abundance and diversity and other soil biological indices for the sustainable management of agro ecosystem and conservation of biological diversity.

Acknowledgment Financial and technical support from the NUFU programme of Norway enabling this study is highly acknowledged.

REFERNENCES Bajracharya, R.M., Sitaula, B.K., Sharma,S and Jeng, A, 2007, Soil quality in the Nepalese context – An analytical review, International Journal of Ecology and Environmental Sciences, 33, p143-158. Blake, G.R and Harte, K.H, 1986, Bulk Density, p363–375 In A. Klute, ed. Methods of Soil Analysis Part 1. Physical and Mineralogical Methods-Agronomy Monograph (2nd Edition), American society of agronomy-soil science society of America. Madison,WI. Burton.S., Shah ,P.B and Schreier, H, 1989, Soil degradation from converting forest land into agriculture in the Chitwan district of Nepal, Mountain research and development, 9, p393404. Coleman, D.A., Crossley Jr, D.A and Hendrix, P.F, 2004, Fundamentals of Soil Ecology. 2nd Edition. Elsevier Academic Press, Burlington, USA. Doran, J.W., Leibig, M., Santana, D.P, 1996, Soil health and sustainability, Adv. Agron, 56, p1–56. Gee, G.W and Bauder, J.W, 1986, Particle Size Analysis, p383-411, In A. Klute, ed.Methods of Soil Analysis, Part 1. Physical and Mineralogical Methods-Agronomy Monogram No. 9 (2nd Edition). American Society of Agronomy- Soil Science Society of America, Madison, WI.


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Karlen, D.L., Ditzler, C.A and Andrew, S.S, 2003, Soil quality: why and how? Geoderma, 114, p145-156. Karlen, D.L., Mausbach, M.J., Doran, J.W., Cline, R.G., Harris, R.F and Schuman, G.E, 1997, Soil quality: A concept, definition, and framework for evaluation, Soil Science Society of America Journal, 61, p4-10. Karlen, D.L, 2004, Soil quality as an indicator of sustainable tillage practices, Soil and Tillage research, 78, p129-130. Lal, R, 2000, Soil Management in the Developing Countries, Soil Science, 165, p57-72. Larson, W.E and Pierce, F.J, 1991, Conservation and enhancement of soil quality. Evaluation for Sustainable Land Management in the Developing World, p 175-203. Int. Board for Soil Res. and Management. Bangkok, Thailand. Mc.Lean, 1982, Soil pH and Lime requirement. Methods of Soil analysis. Chemical and Microbiological properties 2nd edition.SSSA Book Ser. 5. SSSA, Madison, WI.USA. Nelson, D.W and Sommers, L.E, 1982, Total Carbon, Organic Carbon and Organic Matter, p. 539-580, In A. L. Page, R. M. Miller and D. R. Keeney, eds. Methods of Soil Analysis Part 2. Chemical and Microbiological Properties, 2nd Ed. American Soc. Agron. Monograph No. 9, ASA-SSSA, Inc., Madison, WI, USA. Parisi, V., Menta, C., Gardi, C., Jacomini, C, 2003, Evaluation of soil quality and Biodiversity in Italy: The biological quality of soil index (QBS) Approach, Proceedings from an OECD Expert Meeting – Rome, Italy, p654. Rokaya.K., Bajracahrya,R. M, 2008, Soil Physical and Biological Parameters as an Indicator of Soil Quality in a Mid Hill Watershed of Nepal,Unpublished M.Sc theses, Kathmandu University, Nepal. Ruf,A., Beck,L., Dreher,P., Hund-Rinke,K.., Rombke,J and Spelda,J , 2003, A biological classification concept for the assessment of soil quality: “biological classification scheme” (BBSK), Agriculture Ecosystems and Environment, 98, p263-271. Scholter, M., Dilly, O and Munch, J.C, 2003, Indicators for evaluating soil quality, Agriculture Ecosystem and Environment, 98, p255-262 Shrestha, B., Sitaula, B.K., Singh, B.R and Bajracharya, R.M, 2004, Soil organic carbon stocks in soil aggregates under different land use system in Nepal, Nutrient Cycling in Agro ecosystems,70, p201-213. Sitaula, B.K., Bajracharya, R.M., Singh, B.R and Solberg, B, 2004, Factors Affecting Organic Carbon Dynamics in Soils of Nepal/Himalayan Region - a Review and Analysis, Nutrient Cycling in Agroecosystems, 70, p215-229. Sturtz, A.V and Christie, B.R, 2003, Rationale for a holistic approach to soil quality and crop health, Soil and Tillage Research, 72, p105-106. Upadhyay, T.P., Sankhayan, P.L and Solberg, B, 2005, A Review of Carbon Sequestration dynamics in the Himalayan Region as a Function of Land-Use Change and Forest/Soil Degradation with Special Reference to Nepal, Agriculture Ecosystems & Environment 105, p449-465. Upadhyay, T.P, 2006, Land-Use Changes and Forest/Soil Degradation Effects on Carbon Sequestration at Watershed Level in Nepal: An Interdisciplinary Systems Analysis Using BioEconomic Modeling, Norwegian University of Life Sciences, Department of Ecology and Natural Resource Management, Ås. Wairiu, M and Lal, R, 2003, Soil organic carbon in relation to cultivation and topsoil removal on sloping lands of Kolombangara, Solomon Island, Soil and tillage research, 70, p19-27. Wardle, D.A., Giller, K.E, 1996, The quest for a contemporary ecological dimension to soil biology, Soil Biology and Biochemistry, 28, p1549-1554.

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INDUSTRIAL EXPOSURE IN EMPLOYEES OF FOUNDRY AT NUNIHAI INDUSTRIAL ESTATE, AGRA Shabana Parveen, R.S. Rawat Department of Zoology, Agra College, Agra E-mail: [email protected] H.N. Sharma Department of Zoology, Dr. B.R. Ambedkar University, Agra E-mail: [email protected]

ABSTRACT Present era is technological era as many things are technologically modified either they are artificial or natural. The proof of technology development is increasing number of gadgets and machines. Technology also brings some problems embedded with it. The main problem is environmental pollution, degradation and human health. Today almost everything contaminated with pollutants. One can avoid everything artificial but occupational exposure is not avoidable and it affects human life directly or indirectly. We know the harms of occupational exposure but there is no way to avoid it. It is mandatory to assess the effects of occupational exposure on health of workers to make guidelines and awareness among those who are unknown of these harms. Government has to make guidelines and regulations for industries to take precautions and management of this type of exposure to their workers. Keeping these points in view the observations were made in workers of foundry industry at Nunihai industrial estate, Agra on the basis of serum urea, creatinine and bilirubin. The values of these parameters have been found to be higher as compared to reference values of scientific laboratories. This indicates the bad working conditions in foundry industry at Nunihai, Agra. It is advisable to aware the workers through discussion and tell them about harm and precautions for safe life.

1. INTRODUCTION The sizeable number of studies made in India by anthropologists, sociologists, psychologists, psychiatrists etc to study the nature if medical profession, structure and function of health organizations and hospitals, doctor-patient relationship, health awareness and social dimensions of health, hygiene and medicine in tribal and rural communities, social aspects and consequences of drug abuse aspects of ethno-medicine, role of traditional health analysis of people towards modern/traditional medicine culture components of disease, economic aspects of treatment and hospitalization etc. all these studies are of recent origins. However, if we take retrospectively, the studies done by scientists in the area of nutrition occupational disease, coal miners, tannery workers, foundry workers, etc provide rich data about the socio-economic aspects of health and disease in the country. Pollutants emitted from foundry work cause so much damage to blood which carries oxygen to the organs of the body; very innocently carries the harmful chemicals and gases to the various organs. Substances have been shown to produce harmful effects on the blood, bone marrow, spleen and lymph nodes, since blood cells are constantly being replenished, with new ones entering the circulation as mature cells are lost the blood system is especially vulnerable to the toxins. However, the information on the effects of foundry emissions on the biochemistry of foundry workers at industrial area Nunihai has not been reported so far. The present investigation will certainly recollect the health problems of workers professionally exposed to these industries as well as the public residing around this area, so as the necessary precautions may be adopted and applied for the safety measures.

2. MATERIALS AND METHODS Present study has been conducted on the workers and staff employed in the iron foundries at Nunihai, Agra. For the present investigation India Casting Co., D-42 Foundry Nagar, Agra has been


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selected which have about 125 employees. The life of the majority of the employees is beset by the problems caused by the direct involvement of the furnace, poverty, illiteracy, disputed life style, unwholesome housing and working conditions, lack of basic sanitation and onset of disease. A small number of employees, however, is well off but the people belonging to this strata may also suffer from the disease which can be aptly related to affluence. The employees under investigation have been distributed in following groups: Group A- Consisting of molders Group B- consisting of ladle men, furnace operators Group C- Consisting of sandmixer, coremaker Group D- Consisting grinding men, shot blast, welder, electrician Group E- Consisting pattern maker, painter, labour, water women, maintenance fitter Group F- Consisting laboratory incharge, mechanical-testing, quality inspector, quality controller, production incharge, dispatch incharge, supervisor, accountant, computer operator, store keeper, marketing manager, gate keeper. Further, on the basis of age the workers of factory have been divided into following groups1. 18-30 years 2. 31-40years 3. 41-50years 4. 51-65years COLLECTION OF BLOOD FOR ANALYSIS The blood samples from the volunteer workers have been collected separately in different vials. Dry sterilized syringes and needles were used to draw the blood from the arms of the workers. Minimum amount of constriction was applied to the arm at the time of drawing of blood. The blood flow was maintained at a slow and steady speed and transferred into vial after removing the needle. The vials used, were kept clean and dry. Separation of plasma or serum was done by slow centrifugation. The serum was also allowed to come out after the clot has firmly contracted. SEPARATION OF SERUM Freshly collected blood was transferred slowly and carefully from the plastic syringe to the sterilized dry centrifuge tube. The tubes were left undisturbed in a slanting position for about 1hour to enable clotting. When the clot retraction started, centrifugation was done at 2500rpm for 30minutes to get rid of suspended red blood corpuscles. Supernatant serum was carefully separated from the clot by a fine glass pipette, transferred into air tight glass vials and stored below 80C until used. However, serum was brought to room temperature before performing biochemical tests. The blood sugar has been calculated by the enzymatic GOD-POD kit method. The blood urea was calculated by DAM kit method. The serum bilirubin was calculated by Malloy and Evelyn method. The serum creatinine was calculated by the alkaline picrate method.

3. RESULTS Results are tabulated in Table-1, Table-2 and Table-3. Table-1: Serum urea (mg/100ml) in various groups of India Casting Co., Agra Group A B C D E F

18-30 29.8 31.0 16.4 29.2 24.9 29.1

31-40 19.1 30.7 28.4 30.8 22.8 19.1

41-50 24.6 39.8 39.1 36.3 31.0 20.0

51-65 39.9 41.5 42.4 38.5 34.4 39.8

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Table-2: Serum creatinine (mg/100ml) in various groups of India Casting Co., Agra Group A B C D E F

18-30 0.6 0.6 0.8 0.8 0.6 0.7

31-40 0.7 0.9 0.7 0.6 0.5 0.6

41-50 0.8 0.6 0.9 0.9 0.5 0.8

51-65 0.4 0.9 1.7 0.8 1.8 0.4

Table-3: Serum bilirubin (mg/100ml) in various groups of India Casting Co., Agra Group A B C D E F

18-30 1.2 0.64 0.74 0.60 0.62 0.46

31-40 0.64 0.60 0.74 0.68 0.84 1.4

41-50 0.51 1.16 0.72 0.45 1.14 0.64

51-65 1.12 0.98 1.8 1.3 1.2 0.78

4. DISCUSSION The metal casting industry has long been considered to be a hazardous occupation characterized by heavy exposure to chemical and physical hazards. Although many changes have occurred in foundry technology and materials, the basic process and these potential hazards remain more or less the same. In fact, metal casting is still a labor-intensive and complex process demanding a great amount of repetitive manipulation and stressful physical and postural loads, off which, are associated with work safety hazards, including musculoskeletal strain, cumulative traumatic and ergonomic injuries due to lowering or moving objects, as well as lifting and carrying tasks. In the present study, an effort has been made on the assessment of some urological parameters viz. urea, creatinine and bilirubin. Serum urea, creatinine and bilirubin level exhibited the variable values depending up on the trades and age groups of the foundry workers. However, values were beyond normal at many places as depicted in respective tables. The present observations have been supported by the findings of Baranowska-Dutkiewicz (1991) who observed industrial and environmental exposure to metals, Colosico et al. (1993) who obtained toxicological and immune findings in workers exposed to pentachorphenol (PCP), Krieger (1995), Carbonell et al. (1995), Xu et al. (1996), Lander and Ronne (1995), Clavel et al. (1996) among pesticide exposed farmers and by Iorrizo et al. (1996) and Parron et al. (1996) among green house sprayers. Serum urea, creatinine and bilirubin level depicts two ends of complete metabolism as they played very important role in determining it. Assessment of these parameters can be used for keeping eye on metabolic system. The above study revealed that the environment of foundry is not upto standards for human health and affect the biological system by unwanted materials which are toxic to human’s vital system. We feel that until the socioeconomic and educational status of these people is improved, the health cannot be improved and this improvement can only be obtained when a change the attitudes and behavior is attempted through the health education drive. One has to efforts for maintaining systematic improvement of working environment for better health of workers.

5. REFERENCES Baranowska-Dutkiewicz, B and Dutkiewicz, T, 1991, Evaluation of simultaneous industrial and environmental exposure to metals, Sci. Total Environ., 101, p149-151. Carbonell, E, Valbuena, A, Xamena, N, Creus, A and Marcos, R, 1995, Temporary variations in chromosomal aberrations in a group of agricultural workers exposed to pesticides, Mutat. Res., 344(3-4), p127-134.


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Clavel, J, Hemon, D, Mandereau, Delemotte, LB, Severin, F, Flandrin, G, 1996, Farming, pesticide use and hair cell leukemia, Scand. J. Work Environ. Health, 22, p285-293. Colosico, C, Maroni, M, Barcellini, W, Meroni, P, Alcini, D, Colombi, A, Cavallo, D, Foa, V, 1993, Toxicological and immune findings in workers exposed to pentachorphenol (PCP), Arch. Environ. Health, 48, p81-88. Iorizzo, L, Bianchi, A, Gamberini, G, Rubino, A, Missere, M, Minak, GJ, Tabanetti, S, Violante, FS, Raffi, GB, 1996, Assessment of human exposure to pesticides in greenhouse and effectiveness of personal protecite devices, Arch. Hig. Rada. Toksikol., 47, p25-33. Krieger, R, 1995, Pesticide exposure assessment, Toxicol. Lett., 82-83, p65-72. Lander, F and Ronne, M, 1995, Frequency of sister chromatids exchange and hematological effects in pesticide exposed green house sprayers, Scand. J. Work Environ. Health, 21(4), p283-288. Parron, T, Hernandez, AF, Pla, A, Villanueva, E, 1996, Clinical and biochemical changes in greenhouse sprayers chronically exposed to pesticides, Hum Exp. Toxicol., 15(12), p957963. Xu, Z, Pan, GW, Liu, LM, Brown, LM, Gaun, DX, Xiu, Q, Sheng, JH, Stone, BJ, Dosemeci, M, Fraumeni, JF, Blot, WJ, 1996, Cancer risks among iron and steel workers in Anshan, China, Part I: proportional mortality ratio analysis, American Journal of Industrial Medicine, 30, p1-6.

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ASSESSMENT OF PHYSICO-CHEMICAL STATUS OF KHANPURA LAKE, AJMER IN RELATION TO ITS IMPACT ON PUBLIC HEALTH Mamta Tiwari* and Alok Chaturvedi**, *Department of Zoology, Govt. College, Ajmer **Department of Chemistry, Govt. College, Ajmer

ABSTRACT

The present investigation was carried out to evaluate the magnitude of physico-chemical parameters of the water of Khanpura Lake, Ajmer and to assess its suitability for human and cattle consumption. The lake receives domestic waste from Khanpura village and its adjoining areas. People living near the lake, use it for irrigation purpose while cattle use the water for drinking and bathing and are frequently suffer from waterborne diseases. The lake water contained high values of TDS, BOD, COD, alkalinity, hardness and chloride, which are beyond safe limits indicating severe degradation of water quality. pH ranges from 7.6-8.9 mg/L, DO from 6.1-10.42 mg/L, BOD from 55-405 mg/L, COD from 72-427 mg/L, Chloride from 152-452 mg/L, Total Alkalinity from 113.25-686.64 mg/L, Total Hardness from 78-401 mg/L, TDS from 180-602 mg/L and Sulphate from 72-120 mg/L. Present finding indicates that the aquatic environment of the Khanpura Lake has undergone extreme degradation. Proper remedial measures should be taken immediately in order to restore it from further deterioration.

Key word: - Physico-Chemical character, Khanpura lake, Ajmer.

Address for correspondence- A/6. D.A.V., college quarters Beawar Road, Ajmer - 305001 *E-mail – [email protected]


INTRODUCTION Pollution of water is responsible for a large number of mortalities and incapacitations in under developed and developing countries. Pollution of water resources has also led to steady decline in fisheries and affected the irrigated cropland. A regular monitoring of water bodies with required number of parameter vis-a vis the quality to water, not only prevents out break of diseases and occurrence of other hazards, but also checks the water from further deterioration. Several studies have been conducted1-8 so far to understand the physico-chemical properties of lakes, ponds and reservoirs during the last decade. Khanpura lake is situated between 260.24’ to 260.25’ north and 740.34’ to 740.39’ east longitude. The water of this lake is used for drinking of cattles and for irrigation. Due to multifold pressure of urbanization, urban sewage waste discharge, agriculture practices, construction of housing colonies, a major part of the Khanpura Lake is greatly affected. The surface flow-water into lake during rainy season and is also carries urban waste and fertilizers from agriculture field.

METHODS & MATERIAL The samples were collected from January to December 08. The overlying waters were collected using a precleaned plastic buckets and were kept in polythene bottles which were disinfected earlier by soaking it with 2% HNO3. BOD, COD, dissolved oxygen and alkalinity was estimated by standard methods9-10. The chemicals used for analysis were all of A.R. grade. The physico-chemical parameter were estimated according to the methods in APHA (1989)9. Expect pH and conductivity all other parameters are exposed in mg/L (Trivedy and Goel, 1986)10.

RESULTS The analyzed physico-chemical characteristics of water samples are summarized in Table-1. Thirteen parameters viz temperatures, transparency, turbidity, DO, BOD, COD, pH, fluoride, chloride, alkalinity, hardness, TDS, sulphate are used. Water temperature varied from 110C to 300C. The variation in temperature in different months of the year followed the seasonal variation in atmospheric temperature. The river registered an alkaline pH ranging from 7.6 to 8.9 throughout the study period. The lowest pH in August can be attributed to the monsoon rains, which cause input of freshwater in the river. Higher pH value in winter months may be due to the consumption of CO2 by the algal population during the process of photosynthesis. The lake water contained high values of dissolved solids that ranged from 180 to 621 mg/L. High values of TDS were due to the addition of sewage with the lake water.

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Potable water should have DO of 7.6 and 7.0 mg/L at 300C and 350C, respectively. It is obtained 3.03 to 10.42 mg/L throughout the study period, BOD in water showed a very critical situation. The values rang from 55 to 405 mg/L and presented seasonal fluctuations. Higher values are obtained in monsoon season and lower values in post monsoon season. COD values are also very high in the lake water which ranged between 70 to 427 mg/L. High values of COD were due to algal biomass and other organic matter. Values of total alkalinity were found to range from 132.12 to 686.64 mg /L. Hardness varied between 78 to 401 mg/L. Hardness in water is caused by cations like calcium and magnesium. Very high amount of sulphate was detected in the lake water. The values were found between 70 to 120 mg/L. Ingestion of water containing high concentration of sulphate may lead to a laxative effect in man. Concentration of chloride was found to be high to the safe limit as prescribed by WHO. The values ranged from 152 to 452 mg/L. High concentration of chloride gives an undesirable taste of water. Fluoride is in permissible limit ranged from 0.24 to 0.61 mg/L. Transparency was observed to be maximum during winter months of January and minimum during September month of rainy season. Turbidity ranged between 24 NTU to 220 NTU.

DISCUSSION On the basis of alkaline nature of water throughout the investigation Khanpura lake may be classified under third category i.e. alkaline water. Decrease in pH in monsoon is probably due to inflow of rainwater, which brings down the level of carbon dioxide and carbonate. This observation agrees with the trends noted on studies conducted in other fresh water bodies (Mathur 1992 11, Sharma 1998 12). The thermal regime of Khanpura lake exhibited a surface maxima during June and minimum during the month of January. Wastewater was clearest in the month of January as indicated by maximum values of transparency and minimum values of turbidity. In the area of investigation maximum TDS were observed in summer months owing to the loss of water due to heat and concentration of salt present in water. Similar results have also been reported by Paka and Narsing Rao (1997)13. Variation in total alkalinity showed significant positive correlation with pH which is consonance to the finding of Sharma (1994)14 and Abraham (2002)15. Hardness observed maximum in summer season and minimum in monsoon season. Hardness reported is the present study is good agreement with Thorat and Sultana (2006)16 and Zambare


(2004)17. Low values of dissolved oxygen during summer season might be explained on the basis that large amount of dissolved oxygen was utilized during the oxidation of organic matter in summer season. The comparison of BOD with dissolved oxygen in the present study indicated that there is an inverse relationship between both parameters. Similar relationship has also been reported by Das (2001)18, Verma (2009)19. It is clear from the present finding that the aquatic environment of the Khanpura lake has undergone extreme degradation. Proper remedial measure should be taken immediately in order to restore it from further deterioration. There must be an alternative waste disposal system away from lake and the disposal of solid and liquid waste must be stopped forth with.

ACKNOWLEDGEMENT

One of the authors Mamta Tiwari is thankful to P.H.E.D. laboratory Ajmer for its assistance in research work.

REFERENCES 1. Salodia P.K. (1995), Hydro biological studies of Tiddem, Udaipur, Ph.D. Thesis, M.D.S. University Ajmer. 2. Dadhich N. and Saxena M.M. (1999), Zooplankton as indicators of Trophic Status of Some Desert Water near Bikaner (Rajasthan), J. of Environ. and Poll. 6(4), 251-254. 3.

Sharma L.L. and Bhardwaj R. (1999). Studies of some Physico-Chemical Characteristics of Sewage Fertilizer Seasonal Lake of Udaipur, J. of Environ. and Poll. 6(4), 255-260.

4. Singh R.V. and Shalini, Kulshrestha (2001). Water Pollution due to Rising Nitrate Level in Same Parts of Jaipur and its Remedies, 8(4), 339-345. 5. Sharma K.C., Hussain, I. Ojha K.G., (2001). Ground Water Quality of An Industrial Town Bhilwara, J. of Environ. and Poll., 8(1), 109-114. 6. Das A.K. (2001), Limnological Studies of Chaurasiawas Lake, Ajmer with Special Reference to Zooplanktonic Population Dynamics, Ph.D. Thesis M.D.S. University, Ajmer. 7. Hussain (2001), Study on the Impact of Industrial and Domestic Water on Ground Water Quality of Bhilwara, Ph.D. Thesis M.D.S. University Ajmer.

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8. Singh R.V., Dhindas S.S., Devendra H.S. and Kulshrestha, Shalini (2003) Studies on Causes and Possible remedies of Water and Soil Population in Sanganer Town of Pink City, Indian J. of Environ. Sci., 7(1), 47-52. 9. APHA (1989), Standard methods for the examination of Water and Wastewater APHA, AWWA and WPCF, Washington D.C. 10. Trivedi R.K.., Goel P.K., (1986)Chemical and Biological Methods for Water Pollution Studies, Karad (India). 11. Mathur M. (1992). Studies on Physico-Chemical Characteristics and Aerobic Bacteria of two Fresh Water Lakes at Ajmer, Ph.D. Thesis M.D.S. University, Ajmer. 12. Sharma K.P., Goel P.K. and Gopal B. (1978), Limnological Studies of Polluted Fresh Water. Physico-Chemical Characteristics, j. Ecol. Environ. Sci., 4, 89-105. 13. Paka, Swarnalatha and Rao Narsing A., (1997). Interrelationship of Physico-Chemical Factors of a Lake J. Environ. Biol., 18(1), 67-72. 14. Sharma K.C. and Sharma R. (1992). Algal Diversity in the Littoral Zone of Polluted Shallow Lake at Ajmer Rajasthan, Inter. J. of Co. and Environ. Sci., 18, 139-146. 15. Abraham Beena T., Bissibose K.S., Henna T.N., (2002). Study of Some PhysicoChemical Parameter and Treatment of Industrial Effluent, J. of Environ. and Poll., 1(2), 213-216. 16. Throat S.R., and Sultana Masarrat (2000). Pollution status of Salim Ali Lake, Aurangabad (M.S.) Poll. Res. 19(2), 307-309. 17. Rajput S.I., Waghlade G.P., Zambare S.P. (2004). A study on Physico-Chemical Characteristics of Water from right canal of Hatnur Reservoir of Jalaon. Maharashtra State. Eco. Environ. D Conc. 10(2), 171-173. 18. Das A., Ph.D. Thesis (2002), M.D.S. University Ajmer. 19. Verma M., Prakash B. (2009), Physico-Chemical Characteristics of Various Lakes in Ajmer, Indian J. of Environ. Sci., 13(1), 75-77.


13 74 55

8.9

10.42

55 70 0.26 152 132.12 172 180 72

7.35 305 328 0.45 228

291.71 92 306 95

Aug

29 48 220

7.9

6.67 405 427 0.48 287

317.87 78 616 102

Jul

29 53 180

7.9

6.24 320 355 0.53 342

487.18 110 621 108

Jun

30 63 138

7.6

6.1 298 335 0.61 452

686.64 401 602 120

May

28 65 94

7.7

3.03 286 315 0.57 328

524.5 351 427 105

Apr

23 68 65

8.3

5.05 238 258 0.42 279

426.8 276 228 93

Mar

20 72 41

83

6.87 207 225 0.37 228

302.16 236 224 82

Feb

15 79 33

8.4

8.15 85 89 0.31 172

224.87 205 186 76

Jan

11 80 24

8.7

9.18 70 76 0.24 165

113.25 190 185 70

Sulphate mg/L

8

T.D.S. mg/L

25 48 215

Total Hardness mg/L

Sep

Total Alkalinity mg/L

213.92 114 252 86

Chloride mg/L

7.67 258 270 0.42 197

Fluoride mg/L

8.2

COD mg/L

23 52 200

BOD mg/L

Oct

DO mg/L

188.75 144 227 79

pH

9.67 106 115 0.35 175

Turbidity NTU

8.3

Transparency, cm

18 60 135

Temperature oC

Nov

Parameter

Months

Monthly variation of water quality of Khanpura Lake Ajmer

Table 1

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Air and Noise Pollution



Theme: Air Pollution and Control “Implementation of Wet Scrubbers for minimizing air pollution at Benara Castings – AGRA” Biographical Notes: 1

Kunal Dwivedi is a 3rd year Mechanical Engineering Student at ANAND ENGINEERING COLLEGE and his area of strength is Production Engineering. 2

Ketan Kapoor is a 3rd year Mechanical Engineering Student at ANAND ENGINEERING COLLEGE and his area of strength is Production Engineering. 3

Aman Sachdeva is an Assistant Professor in Mechanical Engineering Department of Anand Engineering College and his area of strength is Production Engineering

ABSTRACT Atmospheric pollution is considered to be most dangerous pollutant of our ecosystem as it has direct influence over all living and nonliving things and its control by isolation and then cleaning becomes beyond man’s effort unless the pollutants are controlled at the source itself. A diverse variety of pollutants are emitted into the atmosphere by both natural, anthropogenic and industrial activities sources. To control air pollution in casting units of Agra region, wet scrubbing process plays a vital role to remove particulate and gaseous pollutants simultaneously. The objective of this paper is to give cost effective solution to the industry engaged in casting of heavy automobile components. For the same a case study was performed for the specific industry and the results achieved were satisfactory. There are large varieties of wet scrubbers in use, the most important of which are spray towers and chambers, packed and plate columns, impingement type scrubbers, multi-stage bubble column, multi-jet column and the venturi scrubbers. As it is very important to incorporate design changes, modifications to enhance the efficiency of collection of air pollutants, thus authors have given reasonable cost effective solution to the industry for reducing air pollutants to significant level by incorporating the design changes for the selected case. Keywords: Pollutants, Emission Factors, Venturi Scrubber

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1. INTRODUCTION The atmosphere is a complex, dynamic natural gaseous system that is essential to support life on this Earth. As we know that stratospheric ozone depletion due to air pollution has long been recognized as a threat to human health as well as to the Earth's ecosystems. Thus in general air pollution is the introduction of chemicals, particulate matter, or biological materials that cause harm or discomfort to humans or other living organisms, or damages the natural environment, into the atmosphere. An air pollutant is known as a substance in the air that can cause harm to humans and the environment. Pollutants can be in the form of solid particles, liquid droplets, or gases [1]. In addition, they may be natural or manmade. Pollutants can be classified as either primary or secondary. Usually, primary pollutants are substances directly emitted from a process, such as ash from a volcanic eruption, the carbon monoxide gas from a motor vehicle

exhaust or sulfur dioxide released from factories. Whereas secondary pollutants are not emitted directly. Rather, they form in the air when primary pollutants react or interact. It is important to note that some pollutants may be both primary and secondary: that is, they are both emitted directly and formed from other primary pollutants. This paper addresses the challenges to control the air pollutants within the Metal casting units in Agra region. It describes the implementation of wet scrubbers within the polluting units so as to control the pollutants to a significant level. The rest of the paper is organised as follows. The pollutants mostly in air is reviewed in depth in Sec 2. The problem occuring within the metal casting units is described in Sec 3. The proposed methodology is presented in Sec 4. A case study illustrating the application of the proposed methodology is presented in Sec 5. Finally conclusions are drawn in Sec 6.

Figure 1 – State of Art in Minimization of Air pollution through Wet Scrubbers

Minimizing Air Pollution

Factors Incorporated for Implementing Wet Scrubbers Nitrogen Oxides Sondreal et al [17]

Sulphur Oxides

Merrick et al [15]

Proposed in

Particulate Matter

Secondary Pollutants

NONE

NONE

this

paper


2. LITERATURE REVIEW In metal casting units, high temperature ranges to the tune of 850oC is mandatory so as to have the required castings [2]. Hence proper design of the casting units is essential for the minimization of the pollutants. Major primary pollutants produced by the industries include: Sulfur oxides (SOx) - especially sulfur dioxide, which is produced by volcanoes and in various industrial processes. Since coal and petroleum often contain sulfur compounds, their combustion generates sulfur dioxide. Further oxidation of SO2, usually in the presence of a catalyst such as NO2, forms H2SO4, and thus acid rain. This is one of the causes for concern over the environmental impact of the use of these fuels as power sources. Nitrogen oxides (NOx) especially nitrogen dioxide are emitted from high temperature combustion. This reddish-brown toxic gas has a characteristic sharp, biting odor and is one of the most prominent air pollutants. Carbon monoxide - is a colourless, odourless, nonirritating but very poisonous gas. It is a product by incomplete combustion of fuel such as natural gas, coal or wood. Carbon dioxide (CO2) - a greenhouse gas emitted from combustion but is also a gas vital to living organisms. It is a natural gas in the atmosphere. Volatile organic compounds VOCs are an important outdoor

air pollutant. In this field they are often divided into the separate categories of methane (CH4) and non-methane (NMVOCs). Methane is an extremely efficient greenhouse gas which contributes to enhanced global warming. Within the NMVOCs, the aromatic compounds benzene, toluene and xylene are suspected carcinogens and may lead to leukemia through prolonged exposure. 1,3butadiene is another dangerous compound which is often associated with industrial uses. Particulate matter - Particulates, are tiny particles of solid or liquid suspended in a gas. In contrast, aerosol refers to particles and the gas together. Sources of particulate matter can be man made or natural. Human activities, such as the burning of fossil fuels in vehicles, power plants and various industrial processes also generate significant amounts of aerosols. Averaged over the globe, anthropogenic aerosols—those made by human activities— currently account for about 10 percent of the total amount of aerosols in our atmosphere [3,4]. Increased levels of fine particles in the air are linked to health hazards such as heart disease, altered lung function and lung cancer. Ammonia (NH3) - emitted from agricultural processes. It is normally encountered as a gas with a characteristic pungent odor. Ammonia contributes

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significantly to the nutritional needs of terrestrial organisms by serving as a precursor to foodstuffs and fertilizers. Ammonia, either directly or indirectly, is also a building block for the synthesis of many pharmaceuticals. Although in wide use, ammonia is both caustic and hazardous. Secondary pollutants include: Particulate matter formed from gaseous primary pollutants and compounds in photochemical smog .Smog is a kind of air pollution which is a combination of smoke and fog. Classic smog results from large amounts of coal burning in an area caused by a mixture of smoke and sulfur dioxide. Modern smog does not usually come from coal but from vehicular and industrial emissions that are acted on in the atmosphere by sunlight to form secondary pollutants that also combine with the primary emissions to form photochemical smog. Ground level ozone (O3) formed from NOx and VOCs. Ozone (O3) is a key constituent of the troposphere (it is also an important constituent of certain regions of the stratosphere commonly known as the Ozone layer). Photochemical and chemical reactions involving it drive many of the chemical processes that occur in the atmosphere by day and by night. At abnormally high concentrations brought about by human activities (largely the

combustion of fossil fuel), it is a pollutant, and a constituent of smog. Peroxyacetyl nitrate (PAN) similarly formed from combination of NOx and VOCs are pollutants which are hazardous to human health. Persistent organic pollutants (POPs) are organic compounds that are resistant to environmental degradation through chemical, biological, and photolytic processes. Because of this, they have been observed to persist in the environment, to be capable of long-range transport, bioaccumulate in human and animal tissue, biomagnify in food chains, and to have potential significant impacts on human health and the environment.

Emission factors Air pollutant emission factors are representative values that attempt to relate the quantity of a pollutant released to the ambient air with an activity associated with the release of that pollutant. These factors are usually expressed as the weight of pollutant divided by a unit weight, volume, distance, or duration of the activity emitting the pollutant (e.g., kilograms of particulate emitted per megagram of coal burned). Such factors facilitate estimation of emissions from various sources of air pollution [5,6]. In most cases, these factors are simply averages of all available data of acceptable quality, and are generally assumed to be representative of long-term averages.


Control devices The following items are commonly used as pollution control devices by industry or transportation devices. They can either destroy contaminants or remove them from an exhaust stream before it is emitted into the atmosphere. Particulate control o Mechanical collectors (dust cyclones, multicyclones) o

o

Electrostatic precipitators An electrostatic precipitator (ESP), or electrostatic air cleaner is a particulate collection device that removes particles from a flowing gas (such as air) using the force of an induced electrostatic charge. Electrostatic precipitators are highly efficient filtration devices that minimally impede the flow of gases through the device, and can easily remove fine particulate matter such as dust and smoke from the air stream [7,8] Particulate scrubbers – Wet scrubber is a form of pollution control technology. The term describes a variety of devices that use pollutants from a furnace flue gas or from other gas streams. In a wet scrubber, the polluted gas stream is brought into contact with the

scrubbing liquid, by spraying it with the liquid, by forcing it through a pool of liquid, or by some other contact method, so as to remove the pollutants [9-12] Scrubbers o Baffle spray scrubber o Cyclonic spray scrubber o Ejector venturi scrubber o Mechanically aided scrubber o Spray tower o Wet scrubber NOx control o Low NOx burners o Selective catalytic reduction (SCR) o Selective non-catalytic reduction (SNCR) o NOx scrubbers o Exhaust gas recirculation o Catalytic converter (also for VOC control) VOC abatement o Adsorption systems, such as activated carbon o Flares o Thermal oxidizers o Catalytic oxidizers o Biofilters o Absorption (scrubbing) o Cryogenic condensers o Vapor recovery systems Acid Gas/SO2 control o Wet scrubbers o Dry scrubbers o Flue gas desulfurization

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Wet scrubber is a form of pollution control technology. The term describes a variety of devices that remove pollutants from a furnace flue gas or from other gas streams. In a wet scrubber, the polluted gas stream is brought into contact with the scrubbing liquid, by spraying it with the liquid, by forcing it through a pool of liquid, or by some other contact method, so as to remove the pollutants. The design of wet scrubbers or any air pollution control device depends on the industrial process conditions and the nature of the air pollutants involved.

remove dust particles by capturing them in liquid droplets. Wet scrubbers remove pollutant gases by dissolving or absorbing them into the liquid.

Inlet gas characteristics and dust properties (if particles are present) are of primary importance. Scrubbers can be designed to collect particulate matter and/or gaseous pollutants. Wet scrubbers

The classification of wet scrubbers on the basis of pressure drop can be seen according ot Figure 2.

Any droplets that are in the scrubber inlet gas must be separated from the outlet gas stream by means of another device referred to as a mist eliminator or entrainment separator (these terms are interchangeable). Also, the resultant scrubbing liquid must be treated prior to any ultimate discharge or being reused in the plant.

Figure 2 – Classification of Wet Scrubbers on basis of pressure drop WET SCRUBBERS (Classification based on pressure drop)

Low Energy Scrubbers - have pressure drops of less then 12.7cm

Medium Energy Scrubbers - have pressure drops between 12.7cm and 38.1cm

A wet scrubber's ability to collect small particles is often directly proportional to the power input into the scrubber. Low energy devices such as spray towers are used to collect particles larger than 5 micrometers. To obtain high efficiency removal of 1 micrometer (or less) particles generally requires high energy

High Energy Scrubbers - have pressure drops greater than 38.1cm

devices such as venturi scrubbers or augmented devices such as condensation scrubbers. Additionally, a properly designed and operated entrainment separator or mist eliminator is important to achieve high removal efficiencies. The greater the number of liquid droplets that are not captured by the mist


eliminator the higher the potential emission levels. Wet scrubbers that remove gaseous pollutants are referred to as absorbers. Good gas-to-liquid contact is essential to obtain high removal efficiencies in absorbers. A number of wet scrubber designs are used to remove gaseous pollutants, with the packed tower and the plate tower being the most common. If the gas stream contains both particle matter and gases, wet scrubbers are generally the only single air pollution control device that can remove both pollutants. Wet scrubbers can achieve high removal efficiencies for either particles or gases and, in some instances, can achieve a high removal efficiency for both pollutants in the same system. However, in many cases, the best operating conditions for particles collection are the poorest for gas removal. In general, obtaining high simultaneous gas and particulate removal efficiencies requires that one of them be easily collected (i.e., that the gases are very soluble in the liquid or that the particles are large and readily captured) or by the use of a scrubbing reagent such as lime or sodium hydroxide.

3. PROBLEM DESCRIPTION Agra is also renowned for castings of various metals because of the intrinsic property of the sand found around the region. But because of TajMahal, the casting units are always under threat as the air pollution caused during casting of these metal products is huge. Approximately 1000+ casting units (both big and small) are located in the vicinity of Agra region, thus the solution for these units is desired so that both the workers as well as the industries benefit from the solutions on the long term basis. Benara castings is one of the premier casting units in Agra region engaged in casting of various automobile products mainly of cast iron and aluminium alloys. Time and again the air pollution has been a matter of concern for the workers as well as the people living in the area nearby. Thus the authors aim to reduce the air pollution significantly by giving long term solution to the industries. 4. METHODOLOGY For the research authors aims to follow the following methodology for the shortlisted case. These steps can be easily understood according to the following flow chart.

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STAGE 1 Hot flue gases enters the SATURATOR

STAGE 2 Hot gases enters the venturi scrubber

STAGE 3 Gases then enters a second scrubber (A packed bed absorber)

STAGE 4 Treated scrubbing liquid is recycled back to the saturator and is recycled for 4 times

END Fans and ductwork moves the flue gas stream out of the stack Figure 3 – Stages of flow of polluting gases in Venturi Scrubber 5. CASE STUDY Benara Udhyog pvt ltd is a medium scale industry which is engaged in manufacturing of various products for automobile industry of various segments. Time and again the unloading workers within the industry used to complain about the unhealthy work environment and the continuous suffocation during work. So authors selected the aluminium casting unit in that industry to see the results of above proposed methodology.

6. CONCLUSIONS In this paper, a detailed research was carried out with a aim to reduce air pollution to significant levels. For the selected case following points must be adhered so as to reduce air pollution significantly: a. Venturi scrubber must be installed of 0.075 tons capacity. b. It is proposed to keep the scrubber on for at least 40 minutes before the actual polluted gases start emerging


c. Minimum distance of 0.8m must be maintained between the face of the duct and the top of the furnace d. Length of the chimney of the scrubber must be to a height of minimum 27m from the ground level e. Workers are advised to wear proper masks during filling of molten aluminium into the crucible f. Project cost for implementing venturi scrubber for the researched casting unit is 38000/- which is a minute amount of the companys total turnover 7. ACKNOWLEDGEMENTS The authors gratefully acknowledge the support of Benara Udhyog Ltd, AGRA for extending their full support and cooperation for a fruitful discussions with the management and the workers. Authors also extend their thanks to Professor D.R.Somashekar, Director of Anand Engineering College for his continous motivation and valuable guidance without which it would have been difficult to bring out the following research. 8. REFERENCES 1. AWMA, 1992. Air & Waste Management Association, Air Pollution Engineering Manual, Van Nostrand Reinhold, New York.

2.

Avallone, 1996. “Marks’ Standard Handbook for Mechanical Engineers,” edited by Eugene

3. Cooper, 1994. David Cooper and F. Alley, Air Pollution Control: A Design Approach, 2ndEdition, Waveland Press, Prospect Heights, IL, 1994. 4. Corbitt, 1990. Standard Handbook of Environmental Engineering, edited by Robert A. Corbitt, McGraw-Hill, New York, NY, 1990. 5. EC/R, 1996. EC/R, Inc., “Evaluation of Fine Particulate Matter Control Technology: Final Draft,” prepared for U.S. EPA, Integrated Policy and Strategies Group, Durham, NC, September,1996.

6. EPA, 1973. U.S. EPA, “National Emissions Data System Control Device Workbook,” APTD-1570, Research Triangle Park, NC, July, 1973. 7. EPA, 1981. U.S. EPA, Office of Research and Development, “Control Techniques for Particulate Emissions from Stationary Sources – Volume 1,” EPA-450/3-81-005a, Research Triangle Park, NC, September, 1982. 8. EPA, 1982. U.S. EPA, Office of Research and Development, “Control Techniques for Particulate Emissions from Stationary Sources – Volume 1,”

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EPA-450/3-81-005a, Research Triangle Park, NC, September, 1982. 9. EPA, 1991. U.S. EPA, Office of Research and Development, “Control Technologies for Hazardous Air Pollutants,” EPA/625/6-91/014, Washington, D.C., June, 1991. 10. EPA, 1992. U.S. EPA, Office of Air Quality Planning and Standards, “Control Technologies for Volatile Organic Compound Emissions from Stationary Sources,” EPA 453/R-92-018, Research Triangle Park, NC, December, 1992 11. EPA, 1993. U.S. EPA, Office of Air Quality Planning and Standards, “Chromium Emissions from Chromium Electroplating and Chromic Acid Anodizing Operations – Background Information for Proposed Standards,” EPA453/R-93-030a, Research Triangle Park, NC, July,1993. 12. EPA, 1995. U.S. EPA, Office of Air Quality Planning and Standards, “Survey of Control Technologies for Low Concentration Organic Vapor Gas Streams,” EPA-456/R-95003, Research Triangle Park, NC, May. 13. EPA, 1996. U.S. EPA, Office of Air Quality Planning and Standards, “OAQPS Control Cost Manual,” Fifth Edition, EPA 453/B-96-001, Research

Triangle Park, NC, February, 1996. 14. EPA, 1998. U.S. EPA, Office of Air Quality Planning and Standards, “Stationary Source Control Techniques Document for Fine Particulate Matter,” EPA-452/R-97-001, Research Triangle Park, NC, October, 1998. 15. Merrick, 1989. David Merrick and Jan Vernon, “Review of Flue Gas Desulphurization Systems,” Chemistry and Industry, February 6 , 1989. 16. Perry, 1984. “Perry’s Chemical Engineers’ Handbook,” edited by Robert Perry and Don Green, 6th Edition, McGraw-Hill, New York, NY, 1984. 17. Sondreal, 1993. Everett A. Sondreal, “Clean Utilization of Low-Rank Coals for Low-Cost Power Generation,” from “Clean and Efficient Use of Coal: The New Era for Low-Rank Coal,” Organization for Economic CoOperation and Development/International Energy Agency, Paris, France, 1993. 18. Soud, et al., 1993. Hermine N. Soud, Mitsuru Takeshita, and Irene M. Smith, “FGC Systems and Installations for Coal-Fired Plants” from “Desulfurization 3,” Institution of Chemical Engineers, Warwickshire, UK, 1993.


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ESTIMATES OF AEROSOL OPTICAL DEPTH AND THEIR RADIATIVE EFFECTS DURING SUMMER SEASON OVER KHARAGPUR Santhosh.K.R1, Shantanu Kumar Pani2 and S. Verma1, 2 1 Civil Engineering Department 2 Centre for Oceans, Rivers, Atmosphere and Land Sciences Indian Institute of Technology Kharagpur West Bengal, India, 721302

ABSTRACT This work was undertaken to investigate the properties of one of the very important atmospheric components, aerosols which are responsible for the global climate change due to their consequent changes in the atmosphere in different seasons. In the absence of long-term ground-based measurements of aerosol characteristics over the east region of the Indo-Gangetic plain, this work was aimed to evaluate the aerosol optical depth and their radiative effects during the summer period (March'08- May'08) at Kharagpur (22. 3°N, 87. 2°E), located under the vent region of Indo-Gangetic plain. The monthly average of 24 hourly Atmospheric concentrations of the total suspended particulate matter (TSP) during the summer period (March'08- May'08) were estimated to be highest in May (183.28 µg/m3) followed by April (147.72 µg/m3), and March (130.85 µg/m3). The surface mass concentrations were used to calculate the aerosol optical properties using OPAC. The estimated AOD at 550nm and 50% relative humidity matched with the AOD retrieved from satellite observations with MODIS showed the highest values in May (0.68) month followed by March (0.53) and April (0.44). The Angstrom exponent at wavelength of 500/650nm were estimated to be 1.22, 1.12, 1.13 respectively for March, April and May indicating the higher influence from coarser mode particles, such as dust particles, in April compared to March. The estimates of AOD for aerosol component (Insoluble, water soluble, soot, mineral accumulation mode and mineral coarse mode) in OPAC showed the major contribution of AOD were due to the water soluble part of aerosols contributing about 57.8%, 61.5% and 68.9% respectively to the total AOD during March, April and May, followed by mineral accumulation mode and soot. The net radiative forcing (W/m2) calculated were found to be -9.03, -10.33, and -19.81 respectively for March, April and May, showing the decrease in the solar radiation due to aerosols. Keywords: Aerosol, Aerosol optical depth, Angstrom Exponent, Radiative forcing.

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1. INTRODUCTION The earth's weather is maintained by the amount of solar radiation that reaches the earth, the fraction of energy that are absorbed and the fraction of energy that are re radiated back into the atmosphere. Nowadays this radiation balance is deviated due to the rapid changes in the atmospheric composition observed over the past century have been driven largely by increased usage of fossil fuels, intensive farming, industrial activities and biomass burning. Atmospheric aerosols affect Earth’s radiation budget in two different pathways, one is by directly scattering and absorbing the electromagnetic radiation and is called direct effect of aerosols. Aerosol particles can also modify the lifetime and microphysical properties of clouds. Increased concentration of aerosols increases the number concentration of cloud droplets but reduce their size. This leads to an increase in cloud reflectance. Also smaller size droplets have lower precipitation efficiency and hence lifetime of clouds increases. This results in increased global cloud cover. These effects of aerosol are known as indirect effects. Aerosols exist in the atmosphere in a variety of hybrid structures: externally mixed internally mixed, coated particles or most likely a combination of all of the above. The optical properties over Kharagpur region in summer season are calculated using the OPAC (Optical Properties of Aerosols and Clouds) software from the mass concentration of aerosols measured at IIT Kharagpur. A change in radiative fluxes (be it at the surface or the top-of-the atmosphere) due to aerosols is referred to as aerosol radiative forcing and that due to anthropogenic aerosols is referred to as anthropogenic aerosol forcing; and the difference between the two forcing terms is due to natural aerosols (Ramanathan et.al.,2001).

2. MATERIALS AND METHODS A combination of measurement techniques and modelling tools were applied to characterise the aerosols. Aerosol measurements were carried out at Kharagpur (22.3oN, 87.2oE) which lies in the Indo-Gangetic plain. Ground-based measurements include sampling of PM10 and TSP using a High-volume sampler (HVS) which was kept at 12m above the ground level in the roof top of Civil engineering department building, IIT Kharagpur. The optical depth calculations using ground-based measurements at Kharagpur were carried out through assuming an aerosol model using OPAC (Hess et.al., 1998). To best fit the observation and to derive the different microphysical and optical properties, such as aersol optical depths, scattering and extinction coefficients, single scattering albedo, asymmetry factor etc., OPAC model allows the user to define new mixtures of aerosol components. So in an urban aerosol model we used different combinations of aerosol components such as insoluble, water soluble, soot, mineral accumulation mode and mineral coarse mode to best fit the measured AOD spectrum with the observed AOD spectrum from MODIS (Moderate Resolution Imaging Spectroradiometer), the online satellite data. Model derived optical parameters were obtained by varying the number concentration of the particles which was obtained from the measurement of mass concentration at IIT Kharagpur. The number concentration of the individual components were altered until the following constraints were fulfilled (i) Angstrom exponent for the observed and the model estimated AOD spectra for measured season were comparable with each other, (ii) the mean difference between the measured and the observed values was less (approximately ±0.02), (iii) the measured single scattering albedo was matched with the observed value and (iv) the measured mass fraction of black carbon was matched with the observed value in the study site. Further, the radiative forcing calculations were done using the aerosol optical parameters computed from OPAC model.

2.1 Calculation of Radiative forcing: The general equation of net radiative forcing of an aerosol that both scatters and absorbs was first derived by Haywood and Shine in 1995 (Seinfeld and Pandis 2006). ∆F=-0.5F0Ta2 (1-Ac) ωβτ [(1-Rs) 2-2Rs/β ((1/ω)-1)] ∆F is the Radiative forcing F0 is the incident solar flux, W/m2


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Ac is the fraction of surface covered by cloud Ta is the fractional transmittance of the atmosphere Rs is the albedo of underline earth's surface ω is the single-scattering albedo, β is the upscatter fraction of aerosol τ is the optical depth

3. RESULTS AND DISCUSSIONS: The monthly average of 24 hourly Atmospheric concentrations of the total suspended particulate matter (TSP) during the summer period (March'08- May'08) (Figure.1) were estimated to be highest in May (183.28 µg/m3) followed by April (147.72 µg/m3), and March (130.85 µg/m3). It is to be noted that the monthly averaged 24hourly TSP concentration did not exceed the permissible standard of 200 µgm−3 (National Ambient Air Quality) during the measurement period from April 2008 to March 2009.

Figure 1: Monthly Average of TSP values in µg/m3 The AOD estimated from different days of measurements and averaged on monthly basis at 50% RH and at 550 nm was calculated to be higher during the May month (0.68) followed by March (0.53) and April (0.44). The measured aerosol surface mass concentration are distributed into different aerosol components (water soluble, insoluble, soot, mineral accumulated, mineral coarse, sea salt) in the aerosol model are chosen and their mass mixing ratios are defined so that the estimated aerosol optical characteristics matches the available measurements. The estimates of AOD for aerosol component (Insoluble, water soluble, soot, mineral accumulation mode and mineral coarse mode) in OPAC showed the major contribution of AOD were due to the water soluble part of aerosols contributing about 57.8%, 61.5% and 68.9% respectively to the total AOD during March, April and May, followed by mineral accumulation mode and soot which is shown in (Figure2a).The estimated AOD were then matched with the AOD retrieved from satellite observations with MODIS (Figure2b) showed the nearest values to the measured data during summer period at Kharagpur.

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Figure 2a: Percentage contribution of species to AOD estimated in OPAC

0.8 0.7

AOD @550 nm

0.6 0.5 MODIS AOD

0.4

OPAC AOD

0.3 0.2 0.1 0 Mar'08

Apr'08

May'08

Month

Figure 2b: Comparison of OPAC and MODIS observation of AOD at 550nm The Angstrom exponent at wavelength of 500/650nm from OPAC (Figure.3a) were estimated to be 1.22, 1.12, 1.13 as respectively for March, April and May indicating the higher influence from coarser mode particles, such as dust particles, in April and May compared to March.

Angstrom Exponent@500/650nm

1.5 1.22

1.12

1.13

Apr'08

May'08

1

0.5

0 Mar'08

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Figure 3a: Angstrom exponent from OPAC at 500/650 nm


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The single scattering albedo (SSA) estimated in OPAC from different days of measurements and averaged on monthly basis at 50% RH. The result shows the presence of lowest SSA values (0.80) in March followed by April (0.88) and May (0.95) which was shown in the (Figure.3b).The lower SSA in March was due to large influence from soot when compared to April and May which is comparatively less during these months. 0.95

1 0.9

SSA at 50% RH

0.8

0.88 0.8

0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 Mar'08

Apr'08

May'08

Month

Figure 3b: Single scattering Albedo estimated from OPAC The net radiative forcing in W/m2 (Figure.4) calculated were found to be -9.03, -10.33, and -19.81 respectively for March, April, and May, showing the decrease in the solar radiation at the surface of the earth due to aerosols.

Radiarive Forcing in W/m2

0

-5

-10

-9.03

-10.33

-15

-20

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Figure 4: Net radiative forcing (W/m2)

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4. CONCLUSION: The estimates of Aerosol optical depth and their radiative effects during summer season over Kharagpur were carried out and the results showed that the highest AOD (0.68) in May month was due to the contribution of water soluble part of aerosols. The highest Angstrom exponent value in March (1.22) indicates that lower influence of coarse mode particles and higher influence of soot particles. The highest value of SSA (0.95) was in May followed by April (0.88) and March (0.8) due to the lower influence of soot particles in the aerosols. The estimated net radiative effects of aerosols showed negative values indicating the cooling effect due to aerosols. Further work is required to estimate the radiative effects in the various layers of the atmosphere during summer over the region.

5. REFERENCES: “Goddard Earth Sciences Data and Information Services Centre”, http://disc.sci.gsfc.nasa.gov/giovanni. Hess, M., P. Koepke and I. Schult (1998), Optical properties of aerosols and clouds: The software package OPAC, Bull. Am. Meteorol. Soc., 79, 831–844. John H. Seinfeld and Spyros N. Pandis (2006), Atmospheric chemistry and physics. John Wiley and sons inc, A Wiley-interscience publication, second edition., 1077-1100. Ramanathan, V., et al. (2001), Indian Ocean Experiment: An integrated analysis of climate forcing and effects of the great Indo-Asian haze, J. Geophys. Res.,106(D22), 28371-28399.


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ESTIMATES OF AEROSOL OPTICAL DEPTH AND THEIR RADIATIVE EFFECTS DURING WINTER SEASON OVER KHARAGPUR 1

Shantanu Kumar Pani1, Santhosh K.R.2, S. Verma1, 2 Centre for Oceans, Rivers, Atmosphere and Land Sciences 2 Department of Civil Engineering Indian Institute of Technology, Kharagpur West Bengal, India

ABSTRACT Aerosols play an important role in the radiation budget of earth-atmosphere system and affect climate. In the present study Aerosol Optical Depth (AOD) and its Direct Radiative Forcing has been estimated at Kharagpur (22. 3°N, 87. 2°E) a tropical sub-urban continental site of Indo-Gangetic plain during the winter (December'08 to February'09). Atmospheric concentrations of Total Suspended Particle (TSP) were measured during the winter periods by using the High Volume Sampler at the roof top of the Department of Civil Engineering, IIT Kharagpur, approximately 12 meters above the ground level. The monthly average of 24 hourly TSP was found to be the highest in December (200 µg/m3) followed by January (187 µg/m3) and February (112 µg/m3). The surface mass concentrations were used to calculate aerosol optical properties in OPAC (Optical Properties of Aerosol and Clouds) model depth at wave length of 550nm. The estimated AOD at 550nm and 50% relative humidity matched with the AOD retrieved from satellite observations with MODIS showed the higher values in January (0.8) and December (0.78) compared to February (0.53). The angstrom exponent at wavelength of 500/650 nm were estimated to be 1.33, 1.34, 1.35 for Dec 08, Jan 09, Feb 09 respectively indicating the dominance of smaller particles in February. The highest AOD value as estimated in January month is due to larger influence from anthropogenic sources from biomass burning and coal burning. The estimates of AOD for aerosol component (Insoluble, water soluble, soot mineral accumulation mode and mineral coarse mode) in OPAC showed that AOD is dominated by water soluble component during all the months followed by insoluble, soot, mineral accumulation mode and mineral coarse mode. The calculated net radiative forcing for all these months were found to be -6.37 W/m2, -8.46 W/m2, and -6.89 W/m2 respectively. Keywords: Aerosol, Aerosol Optical Depth, Angstrom Exponent, Radiative forcing

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1. INTRODUCTION Atmospheric aerosols consist of particles suspended in the atmosphere with radii ranging from 0.01 to 20 µm. Although they are very small, atmospheric aerosols have multiple and complex effects on climate change, air quality, visibility, and even our health. Aerosols, natural and anthropogenic, affect the climate directly as well as indirectly; though the magnitudes remain uncertain even today (IPCC 2007). The direct effects are due to the absorption and scattering of solar radiation by aerosols leading to changes in the planetary albedo and hence the radiation budget (Charlson et al., 1992). Because of the relatively short lifetime of aerosol particles and their large regional variability, instances of strong localized direct forcing can occur. On a regional scale, it is suggested that aerosols are already affecting surface radiative forcing, atmospheric heating, and precipitation (Ramanathan et al., 2001). The important role played by aerosols with regard to climate and environment is widely recognized. However, large uncertainties in the chemical, physical, and radiative properties of atmospheric aerosols render quantitative assessment of aerosol effects on climate and environment problematic.

2. STUDY AREA The site in the present study is Kharagpur. It is situated at 22.3° N latitude and 87.2° E longitude. Kharagpur has a tropical wet-and-dry climate. The annual mean temperature is 26.8°C. Summers are hot and humid with temperatures and during dry spells the maximum temperatures often exceed 40°C during May and June. Winter tends to last for only about three months, with seasonal lows dipping to 9°C–11°C (between December and February). The highest recorded temperature is 43.9°C and the lowest is 5°C. On an average, May is the hottest month with daily temperatures ranging from a low of 27°C to a maximum of 37°C while January the coldest month has temperatures varying from a low of 12°C to a maximum of 23°C.

3. METHODOLOGY Atmospheric concentrations of Total Suspended Particle (TSP) were measured during the winter periods by using the High Volume Sampler (Envirotech APM 460 BL) at the roof top of the Department of Civil Engineering, IIT Kharagpur, approximately 12 metres above the ground level. The surface mass concentrations were used to calculate aerosol optical properties in OPAC (Optical Properties of Aerosol and Clouds) model depth at wave length of 550nm (Hess et al., 1998). The chief components of the OPAC model are water soluble, insoluble, soot, mineral accumulation mode, mineral coarse mode total aerosol mass concentration, and aerosol size distributions. The concentrations of constituent components are adjusted in such a way that the model estimated spectral optical depths; visibility and angstrom wavelength exponent are consistent with the observations. The net radiative forcing has been calculated by using the following numerical equation ∆F=-0.5F0Ta2 (1-Ac) ωβτ [(1-Rs) 2-2Rs/β ((1/ω)-1)] ∆F is the Radiative forcing; F0 is the incident solar flux, W/m2; Ac is the fraction of surface covered by cloud; Ta is the fractional transmittance of the atmosphere; Rs is the albedo of underline earth's surface; ω is the single-scattering albedo; β is the upscatter fraction of aerosol and τ is the optical depth.


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4. RESULT AND DISCUSSION The monthly average of 24 hourly TSP (Figure 1) was found to be the highest in December (200 µg/m3) followed by January (187 µg/m3) and February (112 µg/m3). The winter is influenced by low winds and low mixing height of pollutants in the atmosphere leading to a longer residence time of pollutants in the atmosphere. It is noted that the TSP values did not exceed the NAAQS permissible standard value 200 µg/m3 during the study period.

Figure 1: Monthly Average of TSP values in µg/m3 Due to the unavailability of seasonal characteristics of aerosol optical properties over Kharagpur from ground-based measurement platforms, the aerosol optical characteristics are estimated in optical properties of aerosols and clouds (OPAC) model [Hess et al., 1998]. Aerosol models are assumed for different seasons based on the measured aerosol surface mass concentration. The measured aerosol surface mass concentration are distributed into different aerosol components (water soluble, insoluble, soot, mineral accumulated, mineral coarse, sea salt) in the aerosol model and their mass mixing ratios are defined so that the estimated aerosol optical characteristics matches the available measurements (Figure 2a ) from satellite observations with MODIS (Moderate Resolution Imaging Spectroradiometer). The estimated AOD (figure 2a) at 550nm and 50% relative humidity from OPAC matched with the AOD (Figure 2b) retrieved from satellite observations with MODIS (Moderate Resolution Imaging Spectroradiometer) showed the highest values in January (0.8) and December (0.78) compared to February (0.53).

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Figure 2a: Percentage contribution of species to AOD estimated in OPAC 0.9 0.8

AOD@550 nm

0.7 0.6 0.5

MODIS AOD

0.4

OPAC AOD

0.3 0.2 0.1 0 Dec'08

Jan'09

Feb'09

Month

Figure 2b: Comparison of OPAC and MODIS observation of AOD at 550nm The angstrom exponent at wavelength (Figure 3a) of 500/650 nm were estimated to be 1.33, 1.34, 1.35 for Dec’08, Jan’09, Feb’09 respectively indicating the dominance of smaller particles in February. The highest AOD value as estimated in January month is due to larger influence from anthropogenic sources from biomass burning and coal burning. The estimates of AOD for aerosol component (Insoluble, water soluble, soot mineral accumulation mode and mineral coarse mode) in OPAC showed that AOD is dominated by water soluble component during all the months followed by insoluble, soot, mineral accumulation mode and mineral coarse mode. The single scattering albedo (Figure 3b) were found to be


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the lowest in December (0.69) followed by January (0.72) and February (0.75) as estimated from OPAC. The result shows that the lowest SSA value in December was due to the large influence from the soot when compared to January and February.

Angstrom Exponent@500/650nm

1.5

1.33

1.34

1.35

Dec'08

Jan'09

Feb'09

1

0.5

0 Month

Figure 3a: Angstrom exponent from OPAC at 500/650 nm

0.8 0.7

0.69

0.75

0.72

SSA at 50% RH

0.6 0.5 0.4 0.3 0.2 0.1 0 Dec'08

Jan'09

Feb'09

Month

Figure 3b: Single scattering Albedo from OPAC

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The calculated net radiative forcing (Figure 4) for December, January and February were found to be -6.37 W/m2, -8.46 W/m2, and -6.89 W/m2 respectively.

Figure 4: Net Radiative forcing (W/m2) 5. CONCLUSION Aerosol chemical and optical characteristics were estimated at Kharagpur during the winter (Dec’08 to Jan’09). Estimated values of AOD were found to be the highest during December and January. The AOD was dominated by water soluble particles in all the months with the highest concentration of soot during December. The single scattering albedo were in the range 0.69 to 0.75 during these months indicating the dominance of absorbing aerosols emitted from the anthropogenic sources. The estimated aerosol surface radiative effects showed the negative forcing during all seasons with its highest value during January. Further work is required to estimate the radiative effects in the various layers of the atmosphere during winter season over the region. . REFERENCES Charlson et al., 1992: Climate forcing by anthropogenic aerosols. Science, 255, 423-430. “Goddard Earth Sciences Data and Information Services Centre”, http://disc.sci.gsfc.nasa.gov/giovanni. Hess et al., (1998), Optical properties of aerosols and clouds: The software package OPAC, Bull. Am. Meteorol. Soc., 79, 831–844. John H. Seinfeld and Spyros N. Pandis (2006), Atmospheric chemistry and physics. John Wiley and sons Inc, A Wiley-interscience publication, second edition. 1077-1100. Ramanathan et al., 2001, Aerosols, climate, and the hydrological cycle, Science 294 (2001), pp. 2119–2124.


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INDUSTRIAL NOISE AND ITS EFFECTS ON WORKERS AHMED HAMEED KALEEL DEPARTMENT OF MECHANICAL ENGINEERING, JAMIA MILLIA ISLAMIA NEW DELHI-110025, Phone: 0091-9911521195, E-mail [email protected]

ZULQUERNAIN MALLICK DEPARTMENT OF MECHANICAL ENGINEERING, JAMIA MILLIA ISLAMIA NEW DELHI-110025, Phone: 0091-011-26981259, E-mail [email protected]

ABSTRCT The problem of noise in the industry inside I.T.O power plant has been examined in this study; and noise measurement and survey studies have been carried out at four high noise level zones (steam turbine, air handling units, coal burners, and circulation pumps) located in this region. A questionnaire was completed by 122 workers during this study in order to determine the physical, physiological, and psycho-social impacts of the noise on workers and to specify what kind of measurements have been taken both by the employers and workers for protection from the effects of noise. It has been specified, during the surveys, that the noise levels detected in all the zones are much above the 80 dB(A) that is specified in the regulations: 65.57 % of the workers in these zones are disturbed from the noise in their workplaces, 50 % of them have complaints about their nervous situations, 28.86 % of these workers are suffering hearing problems although they had not had any periodical hearing tests and they are not using ear protection equipment. Keywords: noise, industrial noise, exposure to noise

1. INTRODUCTION Noise is one of the physical environmental factors affecting our health in today’s world. Noise is generally defined as the unpleasant sounds which disturb the human being physically and physiologically and cause environmental pollution by destroying environmental properties (Melnick 1979). The general effect of noise on the hearing of workers has been a topic of debate among scientists for a number of years (Jansen 1992), (Johnson 1991), and (Alton and Ernest 1990). Regulations limiting noise exposure of industrial workers have been instituted in many places. For example, in the U.S., the Occupational Noise Exposure Regulation states that industrial employers must limit noise exposure of their employees to 90 dB(A)

for one 8-h period (USEPA 1973), (Eleftheriou 2002). This permitted maximum noise exposure dose is similar to the India Standard, which is less than 90 dB(A) for 8 h period (ISO 1990). Exposure to continuous and extensive noise at a level higher than 90 dB(A) may lead to hearing loss. Continuous hearing loss differs from person to person with the level, frequency and duration of the noise exposed (USEPA 1974). Negative effects of noise on human beings are generally of a physiological and psychological nature. Hearing losses are the most common effects among the physiological ones. It is possible to classify the effects of noise on ears in three groups: acoustic trauma, temporary hearing losses and permanent hearing loss (Melamed et al. 2001). Blood pressure increases, heart beat accelerations, appearance of muscle reflexes, sleeping disorders may be considered among the other physiological effects. The

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psychological effects of noise are more common compared to the psychological ones and they can be seen in the forms of annoyance, stress, anger and concentration disorders as well as difficulties in resting and perception (Cheung 2004), (Öhrstron 1989), and (Finegold et al. 1994). A great majority of people working in industry are exposed to noise. Therefore, in this study, the effects of noise on workers beings have been investigated with respect to the level of noise they are exposed to. In this context, measurement and questionnaire studies have been conducted at I.T.O power plant station.

2. MATERIAL AND METHODS 2.1 Industrial noise measurement technique This study has been carried out at four zones (steam turbine, A.H.U, coal burner, circulation pumps). Actual noise levels in these zones have been measured and their maximum and minimum values have been placed in the associated Tables. The noise level was measured with the help of Cirrus sound level meter, model CR:710B ,UK. The instrument is sensitive to sound pressure between 20 to 20000 Hz was used to measure the noise level calibrated by microphone adapter. The range and sensitivity of the instrument is 30 dB(A) to 100 dB(A) for low sound pressure and 60 dB(A) to 130 dB(A) for high sound pressure with accuracy ±3% . Measurements results have been recorded by holding the instrument at a height of 1.5m from ground in living and working environments of the workers in order to determine the noise levels to which the workers are exposed. A 29-question questionnaire has been applied in the context of the study. Purpose of the Questionnaire 1. To learn whether hearing losses in workers originate from any factors other than noise (a hereditary illness, effect of medication, exposure to sudden non-professional sources of noise, etc.) 2. To determine effects and complaints other than permanent hearing loss that may occur due to the noise. 3. To determine rates of using ear protection equipment used to decrease the level of noise

influencing workers at workplaces, and expressing the complaints and positive comments on using them. 4. To determine the factors that is effective on workers exposed to noise. 5. for specifying worker comments on protection from noise.

2.2 Questionnaire studies (surveys) in the industry – A questionnaire has been applied on a oneto-one basis at the I.T.O factory. – The questionnaire forms were distributed during the day shift and collected the next day while it has been done on a one-to-one basis during the night shift. – At the A.H.U zone the questionnaire forms have been distributed during the day and collected at the end of working hours. Questionnaire results were compiled using Minitab statistical program software. The data were evaluated using the χ2 test. Additionally, some important results have been also demonstrated in the associated Tables and Figures.

3. MEASUREMENT AND QUESTIONNAIRE RESULTS 3.1 Noise measurement results As shown in Table 1, the highest noise among these zones was detected at the steam turbine (110 dB(A)) and A.H.U (98 dB(A)) zones. Comparison of these results with the standards taking place in the Noise Control Regulation shows that none of the industries subject to this survey are meeting the associated standards.

3.2 Questionnaire results and evaluation The questionnaire has been applied to 122 workers selected from all the zones. Distribution of the participants has been examined with respect to their ages, servicing periods, educational situations and departments. Distribution of the workers according to their zones is: 21% steam turbine, 19% A.H.U, 29% coal burners, and 31% circulation pumps (Figure1). It has been determined that their distribution with respect to their service periods is: 42% 5-10 years,


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28% 11-15 years, 26% 15-20 years and 4% more than 20 years (Figure 2). Distribution of the workers according to their educational level is: Table 1. Industrial noise measurement results. zone Steam turbine A.H.U Coal burner Circulation pumps

Max(dB(A)) 110 98 90 85

Min(dB(A)) 90 78 70 65

2% literate, 30% primary school, 12% secondary school, 38% high school and 18% university education (Figure 3). Age distribution of the workers is: 23% 20-30 years, 54% 31-40 years and 21% 41-50 years, more than 50 is 2% (Figure 4).

Figure 1. Industrial distribution of workers.

Figure 2. Working period of workers worked in industries.

Figure 3. Education level of workers.

Figure 4. Age distribution of workers.

When the ages, working periods and education levels were compared, it has been specified that the majority of the workers were from service period range of 5-10 years, age range of 31-40 years and are generally high school graduates. The following points have been determined during the studies; In the steam turbines zone, 35% of the workers in the production department are exposed to a noise level of 110 dB(A) while 67% of the workers in the whole factory also were exposed to a noise level much above the standards specified in the Noise Control Regulations. – In the A.H.U zone, 70% of the workers were exposed to a noise level of maximum 98 dB(A) and they are working at the mill department. – At coal burner and circulation pumps zones, the majority of the workers are working in very noisy environments. Looking at the level of disturbances from industrial noise in these zones, 63.11% of the workers (80 participants) have complaints about high level of noise in general. As shown in Table 2, the steam turbine zone among these zones is the one with the highest level of disturbance from noise (maximum of 110 dB(A)). The rate of disturbance was never below 53% in any one of the zones, indicating that the problem of noise exists in all these zones. By examination of the rates of disturbance in the workers depending on their working periods, it has been observed that there is no significant relation between the working periods and the disturbances from noise. As shown also in Table 3, the rate of disturbance from noise among the workers working for 5-

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10 years is 78.44% while this rate is 80% among workers working for more than 21 years. These results are considered to be statistically important, but they are not yet convincing. The workers have been asked about the type of their complaints, and 50% of the 122 workers responding to this question have complained about nervousness. When all the zones are considered individually, it has been specified that maximum level of nervousness complaint was determined at the steam turbine zone having a noise level of 110 dB(A) (42.62%) (see Table 4). Carelessness is the disturbance type with the lowest rate of appearance (4.91%). Looking at Table 2, it is possible to state that

the most significant disturbance caused by noise is nervousness. Examinations made on the type of hearing problems indicate that 28.68% of the workers are generally complaining about illnesses like ringing and leakage in the ears as well as hearing loss (Table 5). Distribution of hearing problems according to zones is 26.9% steam turbine, 20.83% A.H.U, 42.85% coal burner, and 35.13% circulation pumps zones. As seen in these results, the coal burner zone was the one where the highest level of complaints (42.85%) determined with regard to the hearing complaints among the zones at I.T.O power plant.

Table 2. Annoyance levels of industrial workers. zone

yes N 22 15 17 26 80

Circulation pumps Coal burner A.H.U Steam turbine Total X2 = 6.454, D. F = 3, P> 0.05 N*: Working number, D. F*: Degrees of freedom

% 59.45 42.85 70.83 100 65.57

Annoyance from noise No N % 15 40.54 20 57.14 7 29.18 0 0 42 34.42

Total N 37 35 24 26 122

% 30.32 28.68 19.67 21.31 100

Table 3. The relationship between working periods and level of annoyance of workers. Working period(years)

Annoyance of noise at working place No Total % N % N % 78.44 11 21.56 51 42.14 73.50 9 26.50 34 28.09 64.51 11 35.49 31 25.61 20 4 80 5 4.13 71.07 35 28.92 121 100

yes 5-10 11-15 16-20 20-Total X2 = 8.647, D. F = 3, P 0.05). Removal of As was maximum in CaO (499.75µgL-1) and ZnO (326 µgL-1) and exhibiting the following order of variation: ZnO and CaO > MgO and MnO2 > CuO > Fe2O3 > C > Al2O3 (Figure 4). As removal by ZnO and CaO was markedly higher (0.04 – 37.45%) than that of the remaining metal oxides. A sharp As removal trend was registered in ZnO and CaO at 0.5 h and slow thereafter, whereas As removal process showed a slow trend throughout the study period in the remaining metal oxides (Figure 4).

A

T ypes of met al oxide mixed soils C MgO MnO2 Al2O3 Fe2O3 CaO ZnO CuO

200

100

0 0

0.5

3

6

14

72

Pe riod (h)

Figure 4. Effects of seven metal oxides on As removing trend of seven metal oxide impregnated akadama soils employed in the experiment - II. Inset showing the characteristics of As removal efficiency.

4. DISCUSSION In experiment – I, As removal efficiency was maximum (5.30 µgL-1g-1h-1) in S5 exhibiting 38.18, 8.87, 4.08, 8.12 and 2.35 times higher than that of the S1, S2, S3, S4 and S6, respectively, which indicating that S5 types of volcanic soil (akadama soil) may be considered as a efficient As removing agent from water column (Figure 3) among the examined six soil types possibly due to having quartz, anorthite, calcium mordenite as crystalline phase, reduced amount of major constituting elements SiO2 (58.09%) and presence of CuO. Besides these, porosity and surface area are the other major regulating factors in removing As by the adsorption means which is the limitations of the present study. However, akadama soil was used for impregnation of metal oxides in the experiment – II due to highest As removal capacity. Total removal of As by different metal oxides impregnated akadama soils remarkably high and varied from 395.35 to 499.987


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µgL-1 except Al2O3 (363.75 µgL-1), whereas control group showed 385.75 µgL-1. Excepting Al2O3, total As removals were 1.286, 1.280, 1.025, 1.295, 1.30 and 1.20 times greater in MgO, MnO2, Fe2O3 CaO, ZnO and CuO, respectively over the control. Above results of substantial As reduction clearly demonstrated that metal oxides have a potential effect to improve the As removal capacity of soil from the water phase and might be played a significant role for the conservation of aquatic environment from As pollution point of view. Soils play a significant role to remove as well as overcome the toxicity problems of Cd, other heavy metals and various nutrients in the aquatic environment (Bhakta and Munekage 2008) and are also very important pools in the global biogeochemical cycle of Hg, acting both as source and sink (Gillis and Miller 2000). A critical appraisal of the data clearly revealed that maximum As removal efficiency was observed in CaO (6.940 µgL-1g-1h-1) and ZnO (6.944 µgL-1g-1h-1) impregnated soils, whereas second highest As removal capacity were pronounced in the soils mixed with MgO (6.891µgL-1g-1h-1) as well as MnO2 (6.859 µgL-1g-1h1 ). Al2O3 mixed soil showed a lower As removal value (5.052 µgL-1g-1h-1) than that of the control (5.357 µgL1 -1 -1 g h ) (Figure 4). Above results clearly revealed that though 2.5 to 30% As retention capacity of soil was elevated by the incorporation of metal oxides but highest percentage removal of As (29.5 - 30%) was found in CaO and ZnO mixed soils. Therefore, it can be concluded that except Al2O3 remaining six metal oxides showed an affinity to the As which improved the As retention capacity of soils. Apart from that, on the basis of temporal scale of As removal, the rate of As adsorption was maximum in CaO (97%) and ZnO (82%) mixed soils within 0.5 h period, whereas a slow and gradual adsorption rates (24 – 62%) were found in remaining metal oxide mixed soils; which indicating that the As adsorption dynamic of CaO and ZnO was substantially faster over the rest employed oxides. The functional mechanism in removing As by metal oxides impregnated soil is associated with the synergistic adsorption effects of both soil and metal oxide. In addition to that formation of ion complex between metal oxides and As is supposed to be the another driving force for the removal of As. Zeng (2003) proposed that Fe–Si binary oxide complexes improves As removal capacity. Moreover, it may also be suggested that incorporation of metal oxides especially CaO and ZnO in the natural soil/clay for the development of ceramic microfiltration membrane and adsorbent tools in removing As from contaminated water would be a significant approach which improves the mechanical strength of tools in one hand as well as increases the As retention capacity on the other hand. Oxide based inorganic membranes (such as, Al2O3, ZrO2, TiO2 and hyteropolysiloxanes) having high mechanical, chemical and thermal resistance potentially applied in liquid separation, gas separation, pervaporation, membrane reactors, etc. (Larbot et al. 1994, Corriu et al. 2002, Medoukali et al. 1999, Belouatek et al. 2005). According to Bhakta and Munekage (2009), ceramic produced from natural clay and waste materials is used as a potential tool to reclaim aquatic environment. 5. CONCLUSION Present study affords to draw the conclusion that though differential affinity of different metal oxides to As facilitates the differential As withdrawal efficiency of soil but CaO and ZnO mixed soils would be the efficient tool in removing higher percentage (29.5 - 30%) of As from aquatic environment. In this context, furthermore, it should be suggested incorporation of CaO and ZnO for developing the soil/clay based As removal ceramic membrane or adsorbents improves the mechanical strength along with increased removal efficiency and reduced adsorption period.

6. ACKNOWLEDGEMENTS Authors are grateful to Govt. of Japan for sponsoring the JSPS research grant (No. 20380181) to carry out the present study. Dr. Bhakta is also grateful to Kochi University for offering the position of Researcher Faculty. We express our thanks to Dr. Y. Yamamoto for extending his kind support in SEM-EDS analysis.

7. REFERENCES Bailey, S E, Olin, T J, Brica, R M, Adrin, D D, 1999, A review of the potential low cost sorbents for heavy metals, Water Research, 33, p2469–2479. Barron-Zambrano, J, Laborie, S, Vier, Ph, Rakib, M, Durand, G, 2002, Mercury removal from aqueous solutions by complexation–ultrafiltration, Desalination, 144, p201–206. Belouatek, A, Benderdouche, N, Addou, A, Ouagued, A, Bettahar, N, 2005, Preparation of inorganic supports for liquid waste treatment, Journal of Micro Meso Mate, 85, p163-68.

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Bhakta, J N, Munekage, Y, 2008, Role of ecosystem components in Cd removal process of aquatic ecosystem. Ecological Engineering, 32, p274–280. Chemlal, S, Sghyar, M, Rafiq, M, Larbot, A, Cot, L, 2000, Elaboration de membranes de spinelles decobalt CoAl2O4 et de spinelle de manganese MnAl2O4 pour l’ultrafiltration, Ann. Chim. Sci. Mat., 25, p577. Corriu, R, Mehdi, A, Reye, C, Ledon, H, 2002, Mesoporous silicabased organic–inorganic hybrid materials, especially for gas separations, US Patent, 0276991. Cot, L, Guizard, C, Larbot, A, 1989, First international conference on Inorganic membranes, F-Montpellier, ICIM, 5, p44–51. Gillis, A A, Miller, D R, 2000, Some local environmental effects on mercury emission and absorption at a soil surface, Science of the Total Environment, 260(1–3), p191–200. Gupta, S K, Chen, K Y, 1978, Arsenic Removal by Adsorption. Journal of Water Pollution Control Federation, 50(3), p493–506. Hemond, H F, Solo-Gabriele, H M, 2004, Children’s exposure to arsenic from CCA-treated wooden decks and playground structures, Risk Analysis, 24, p51–64. Hsia, T H, Lo, S L, Lin, C F, 1994, Characterization of arsenate adsorption on hydrous iron oxide using chemical and physical methods, Colloids Surf A: Physicochem Eng Aspects, 5, p1–7. Hunsom, M, Pruksathorn, K, Damronglerd, S, Vergnes, H, Duverneuil, P, 2005, Electrochemical treatment of heavy metals (Cu2+, Cr6+, Ni2+) from industrial effluent and modeling of copper reduction, Water Research, 39, p610–616. Jones, B F, Galan, E, 1988, Sepiolite and palygorskite. In: S.W. Bailey (Ed.), Reviews in Mineralogy, Hydrous Phyllosilicates, Mineralogical Society of America, Washington, 19, p631–674. Kentish, S E, Stevens, G W, 2001, Innovations in separations technology for the recycling and re-use of liquid waste streams, Chemical Engineering Journal, 84(2), p149–159. Larbot, A, Alami-younssi, S, Persin, M, Sarrazin, J, Cot, L, 1994, Preparation of a c-alumina nanofiltration membrane, Journal Membr. Sci., 97, p167–173. Li, Y, Zhang, X, Wang, J, 2001, Preparation for ZSM-5 membranes by a two-stage varying-temperature synthesis, Separ. Purif. Tech., 25(1), p459–466. Medoukali, D, Mutin, P H, Vioux, A, 1999, Synthesis and characterization of microporous pillared alphazirconium phosphatebiphenylenebis (phosphonate), Journal Mater. Chem., 9(10), p2553–2557. Messaoudi, L, Larbot, A, Rafiq, M, Cot, L, 1995, Mise au point d’une membrane de microfiltration sur supports tubulaires a base dune argile marocaine, Ind. Ceram. Ver., 12(910), p831–835. Mukasyan, A S, Costello, C, Sherlock, K P, Lafarga, D, Varma, A, 2001, Perovskite membranes by aqueous combustion synthesis: synthesis and properties, Separ. Purif. Tech., 25(1), p117–126. Murphy, B L, Toole, A P, Bergstrom, P D, 1989, Health risk assessment for arsenic contaminated soil, Env. Geochem. Health, 11, p163–169. National Academy of Sciences, 1977, Arsenic-Medical and Biological Effects of Environmental Pollutants, U.S. Government Printing Office, Washington, DC. National Research Council, 1999, Arsenic in Drinking Water, National Academy Press, Washington, DC. Pacheco, S, Tapia, J, Medina, M, Rodriguez, R, 2006, Cadmium ions adsorption in simulated wastewater using structured alumina–silica nanoparticles, Journal Non-Crystalline Solids, 352(52-54), p5475–5481. Pierce, M L, Moore, C B, 1982, Adsorption of arsenite and arsenate on amorphous iron hydroxide, Water Research, 16, p1247–1253. Raven, K P, Jain, A, Loeppert, R H, 1998, Arsenite and arsenate adsorption on ferrihydrite: kinetics, equilibrium, and adsorption envelopes, Environ Sci Technol, 32, p344–349. Sidheswaran, P, Bhat, A N, 1997, Synthesis of sodalitehydrate from clays, Indian J. Chem., 36A, p672–676. Sun, X, Doner, H E, 1998, Adsorption and oxidation of arsenite on goethite, Soil Science, 163(4), p278–287. USEPA, 2001, EPA Implements Standard of 10 ppb, http://www.epa.gov/safewater/arsenic.html. Vergnes, A, Nobili, M, Delord, P, Cipelletti, L, Corriu, R J P, Boury, B, 2003, Auto-organisation in silicabased organic–inorganic gels obtained by sol–gel process, J. of Sol–Gel Science Technol., 26, p621–624. Wilkie, J A, Hering, J G, 1996, Adsorption of Arsenic onto Hydrous Ferric Oxide: effects of adsorbates/adsorbent ratio and co-occurring solutes, Colloids and Surfaces A: Physicochemical Engineering Aspects, 107, p97–110. Zeng, Le, 2003, A method for preparing silica-containing iron(III) oxide adsorbents for arsenic removal, Water Research, 37, p4351–4358. Bhakta, J N, and Munekage, Y, 2009, Ceramic is a Potential Tool to Reclaim Aquatic Environment: A Short Review, Journal of Environmental Protection Science (in press).


569

EFFECT OF TEMPERATURE ON THE FORMATION AND DEGRADATION OF POLYCYCLIC AROMATIC HYDROCARBONS Edward Nixon Pakpahan1,*, Mohamed Hasnain Isa2, Shamsul Rahman Mohamed Kutty2, Amirhossein Malakahmad2 1,*

Student in Civil Engineering Department, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia and Staff of The State of Ministry for the Environment, the Republic of Indonesia ([email protected]; [email protected]) 2 Civil Engineering Department, Universiti Teknologi PETRONAS, 31750 Tronoh, Perak, Malaysia

Abstract - Polyaromatic hydrocarbons (PAHs) are a class of aromatic hydrocarbon compounds which are catagorised as pollutants with carcinogens, and mutagenic characteristics. Scientifically, incomplete combustion and petroleum compounds emission were proven as a major source of PAHs. Thermal degradation of PAHs is one of the methods to destroy the pollutants as well as their hazardous by-products. During thermal treatment process, formation and/or degradation of PAHs is related to their chemical structural stability and rate of degradation. Summarized, PAHs with four or more rings are formed at low-temperature thermal treatment, and only the ones with less than 4 rings are degraded. High-temperature thermal treatment generally forms PAHs with 4 rings or less and degrades 5 rings or more. Due to environmental and human health considerations, thermal treatment of PAHs should be designed to completely degrade or destroy the pollutants as well as their hazardous byproducts. High-temperature thermal treatment and liquid extraction are effective in the treatment of PAHs, but expensive. A cheap alternative treatment method such as optimization of low temperature treatment perhaps combined with catalysis needs to be developed in order to reduce PAHs formation and increase their degradation simultaneously. Keywords - degradation, formation, PAHs, temperature

INTRODUCTION Polycyclic aromatic hydrocarbons (PAHs) are lipophilic, non-polar compounds, consisting of planar and non-planar hydrocarbon geometry bonding with carcinogenic and mutagenic characteristics [1-5]. They often have recalcitrant properties i.e. difficult to biodegrade and will persist in the environment. Petroleum crude oil, coal, processed (combusted) fossil fuel deposits and even smoking contains significant amounts of PAHs [3, 4]. More than 160 PAHs have been characterized in nature, however only sixteen were selected as EPA priority pollutants, as shown in Table 1 [3-5]. The priority PAHs compounds are carbonaceous, sixmembered, non-methylated with less than seven aromatic (benzene) rings. A number of scientific papers that mention the carcinogenic and mutagenic effects of PAHs [6] have been published. Borosky [6] stated that carcinogenicity is initiated by oxidative chemistry, likely that electrophilic PAHs attack DNA by diol epoxide carbocation, which interacts with tissue nucleophiles, and bind covalently [7] giving rise to the alkylation of DNA base. Laali [7] proposed biological oxidation via cationic radical. Both mechanisms can initiate cell damage. Lowe and Silverman [8] stated that carcinogens are classified as genotoxic carcinogen (directly damage DNA) and epigenic carcinogen (do not bind covalently, do not directly damage DNA), isomerization of PAHs partially transforms non-mutagens to mutagens [3, 5].

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TABLE 1. SIXTEEN PAHs IN THE EPA PRIORITY POLLUTANTS LIST PAHs (Rings)

Formula

Naphthalene (2)

C10H8

Acenaphtylene (3)

C12H8

Acenaphthene (3)

C10H10

Fluorene (3)

C13H10

Phenantrene (3)

C13H10

Anthracene (3)

C13H10

Fluoranthene (4)

C16H10

Pyrene (4)

C16H10

Chrysene (4)

C18H12

Benzo(a)anthracene (4)

C18H12

Benzo(b)fluoranhtrene (5)

C20H12

Benzo(k)fluoranthrene (5)

C20H12

Benzo(a)pyrene (5)

C20H12

Indeno(1,2,3-cd)pyrene (6)

C22H12

Benzo(g,h,i)perylene (6)

C22H12

Dibenzo(a,h)anthracene (6)

C22H14

Structure

PAHs carcinogenicity and its structural perspective have been intensely studied by researchers. PAHs with concave region of one carbon atom of epoxide ring and an open inner corner (active diol epoxide) are called PAHs with a ‘bay-region’or ‘fjord-region’ [7, 9] of their moiety structure. They are predicted to be more active than their isomers, and are able to form stable DNA adducts [9]. PAHs with a bay region have increased mutagenic and carcinogenic activities by so called ‘bay-region theory’ [6]. Consequently, structure-activity relationship for PAHs has to be intensively investigated but this review would focuses on selected PAH compounds only, in which heteroatom-containing such as ethers and phenols will not be discussed.


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Controlled thermal process is an effective means for degradation of PAHs [2-5]. This review summarizes and evaluates some empirical results of thermal processes which have been used for PAHs treatment.

TEMPERATURE EFFECT ON PAHs THERMAL TREATMENT PAHs thermal formation The major mechanisms for PAHs formation are pyrolysis or incomplete combustion and pyrosynthesis process [1], [3]. Thus, the formation and transformation of PAHs during thermal treatment process would affects by thermodynamic factors of temperature. During pyrolysis, the macromolecular aromatic compounds are broken into fragments to form small fragments. Through pyrosynthesis process, these small fragments (mainly reactive free radicals), undergo cyclization and aromatization to form polycyclic compounds. Temperature affects intermolecular cyclization among the PAH fragments produced [3]. PAHs formation from hydrocarbons heating/combustion is possible at the temperatures as low as 300oC to 500oC for high molecular weights, also at 1,000oC or more for low molecular weights whenever vapor phase of pyrolysis and partial oxidation proceed readily. Pope et al. [5] elucidated that in spite of structural complexity of PAHs they have significant number of isomers. As the temperature rises, the relative abundance of all PAH isomers in mixture other than the most stable isomer would also increase. Kwon and Castaldi [10] also stated that formation of PAHs occurs either through hydrocarbon addition reactions or by benzene ring combination reactions. Kwon and Castaldi [10], through PAHs formation in thermal degradation of Styrene Butadiene Copolymer (SBR) (in range of 300 to 500°C), showed that the substituted aromatic (PAHs), 2, 3 and 4 rings, reached their maximum concentrations at temperatures of 380, 400 and 450°C respectively. Poutsma [11] mentioned that the condensation of larger PAHs can occur even in the low-temperature regime (~350°C). However, the kinetics of derivative and co-product formation is still unclear. Similarly, Richter et al. [12] confirmed observations by Pope et al. [5] and Kwon and Castaldi [10] through their research on pyrene-contaminated soil and its contributions to PAHs formation, whereby the oxygen-free heating process (at the temperature range of 250 to 1,000oC) showed that all of the treatment temperatures resulted in the formation of volatile PAHs by-products, which contain pyrene. Alfe et al. [13] also reported progressive increase in concentration profiles of PAHs in the pyrolysis region of the lower temperature range. Liu et al. [14] measured the emission of PAHs from the combustion of coals in Fluidized Bed Combustor (FBC); bench-scale at the temperature range of 790900oC with excess air ratio range of 1.13 to 1.34. The results showed that high molecular weight PAHs of 4 and 5 rings were formed at temperature below 850oC, while low molecular weight PAHs of 2 and 3 rings were formed at above 850oC. Lower operating temperatures were studied by Wey et al. [15]. They employed a laboratory-scale fluidized bed reactor for wastes incineration in a temperature range of 600 to 800oC, and found that formation of gas-phase PAHs was increased by inclusion of CaO additive at 600 and 700oC, but then decreased at 800oC. Along with it, the formation of solid-phase of PAHs was effectively suppressed by CaO additive at 600 and 700oC, but it was poor at 800oC.

PAHs thermal degradation Controlled thermal treatment process is an effective means for degradation of PAHs [5]. The technology has been studied for a wide range of temperatures.

Low temperature thermal process Many experiments were done in low ranges of temperature for thermal treatment of PAHs. One example which combined the process with certain thermo-mechano dynamical related factors was conducted by Magoha [16] in the study of operating ball mills to destruct selected PAHs of 3 rings at temperature less than 100oC. Chen and Chen [4] studied the chemical structure stability of the selected PAHs (BaP, BaA, DBahA) at temperatures of 100 and 200oC with varying time, and the results showed that the loss of each PAHs, either in solid orm or in solution, was greatly dependent upon temperature. It would be higher at 200oC compared to 100oC. Kopinke and Remmler [17] conducted a study of low-temperature reactions of hydrocarbon sediments at the optimum temperature of 300oC

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which then evidenced thermo-desorption of PAHs accompanied by their chemical conversion to nonvolatile products (charring); in other words decontamination was achieved.

High temperature thermal process Wheatley and Sadhra [2] conducted high temperature thermal treatment of clinical waste by incineration with an operating temperature range of 800 to 1,000oC, and it was found that low molecular mass PAHs would not be present in bottom ash, but levels of higher molecular mass PAHs (MW: 228 to 252) were abundant in it; and no PAHs were found in fly ash. Combustion of petroleum coke [18] with the first and second stage temperatures of 900oC and 1,200 to 1,300oC resulted in 16 EPA priority PAHs-benzo(a)pyrene (group), as usually expressed in terms of equivalent PAHs, detected below the regulation limit (0.066 mg/Nm3 compared to 0.1 mg/Nm3).

Intermediate temperature thermal process Basic thermodynamic principle of the effect of temperature suggests that high temperature would result in high rate of degradation, because temperature will produce more energy to break bonds in molecules of PAHs [3]. However, using low temperature in combination with other thermodynamic factors, such as pressure might also produce results similar to high temperature treatment. Wey et al. [15] indicated that addition of additive (CaO) in a thermal treatment process caused formation of gas-phase PAHs, which was less than solid-phase PAHs; but the additive (CaO) at a higher temperature could also suppress the emission of gas-phase PAHs but increase the formation of solid-phase PAHs. Magoha [16] also showed by the mechano-chemical experiment that the process does not require high temperature for selected PAHs degradation (destruction). An example of the recent technology of PAHs degradation was demonstrated by Dadhkah and Akgerman [19] through a variation series of small-scale extractions and in situ wet oxidation on aged PAHs polluted-soil. The process used sub-critical water as the removal agent, whereas hydrogen-peroxide (H2O2) as oxidizing agent. The experiments were performed in semi-continuous with residence times of 1 and 2 hours at 250°C, 1000 psig. In all combined extraction and oxidation flow experiments, 16s PAHs in the remaining soil after the experiments were almost undetectable. Based on these results, extraction with hot water in combination with oxidation can be used as a feasible alternative technique for PAHs destruction despite constraints of sophistication equipment system and operating cost.

SUMMARY Besides temperature, an excess amount of air which promotes complete combustion may also be considered for reducing PAHs formation [3, 14]. The highest transformation and/or degradation rate of PAHs is closely related to range of temperature together with their chemical structural stability [3, 4]. Actually, increasing temperature will increase isomerization, but isomerization should be avoided, because there is a possibility of partial transformation of non-mutagen PAHs to mutagens such as pyrene (4 rings) and benzo(e)pyrene (5 rings) to fluoranthene (4 rings) and benzo(a)pyrene (5 rings) respectively [5]. The effect of temperature on the PAHs thermal treatment: formation and degradation is shown in Table 2. In general, operating high-temperature thermal process with or without additive for PAHs degradation is a common technique in spite of its being energy intensive and hence costly. Recent technique of extraction with hot water in combination with oxidation also can be used as a feasible alternative for PAHs degradation despite constraints of sophisticated equipment and operating cost. The system used by Magoha [14] did not require high temperature PAHs degradation, but was only effective for the degradation of certain selected low molecular weight (LMW) PAHs. Indeed, the mechanism of formation and/or degradation is still unclear for all PAHs [9]. But in general, one can conclude that PAHs with four or more rings are formed at low-temperature thermal treatment (≤ 1,000 °C), and only the ones with less than 4 rings are degraded. High-temperature thermal treatment (≥ 1,000 °C) generally forms PAHs with 4 rings or less and degrades 5 rings or more.


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TABLE 2. COMPARISON OF RESULTS ON PAHs THERMAL TREATMENT Selected PAHs Thermal Treatment 3 T ≤ 100oC

300 oC ≤ T ≤ 500 oC

600 oC ≤ T ≤ 1,000 oC

600 oC ≤ T ≤ 1,000 oC

Formation 4 5

thermo-mechano [16] not discussed thermodesorption [17] ● ● polymer degradation [10] ● ● ● fluidized bed, excess air [14] ● ● ● without additive [15] ● ● with additive [15] ●

6

3

Degradation 4 5

●

●

●

●

●

6

not discussed not discussed not discussed not discussed o

Pyrolysis (oxygen-free heating under He) ~1,000 C [12] ● ● ● ● ● T ≥ 1,000 oC

●

o

pyrolysis ~1,100 C [5] ● ●

not discussed o

direct burning (calcination) ~1,300 C [18] ● ● : number of rings of PAHs; ● : presence

●

●

CONCLUSION High-temperature thermal treatment is effective in the treatment of PAHs. However, the treatment cost is very high and it also requires complicated equipment which also has potential operational risks. It is therefore important to develop a novel and cheap alternative treatment method or procedure such as optimization of low temperature treatment (perhaps combined with catalysis or additives) in order to reduce PAHs formation and increase their degradation.

REFERENCES 1. L. Carlsen, P. Lassen, G. Pritzl, M.E. Poulsen, P.A Willumsen, U. Karlson. Fate of polycyclic aromatic hydrocarbons in the environment, NERI Technical Report No. 190. 2. A.D. Wheatley, S. Sadhra. Polycyclic aromatic hydrocarbons in solid residues from waste incineration, Chemosphere 55 (2004) 743-749. 3. P. Sun. Investigation of polycyclic aromatic hydrocarbons (PAHs) on dry flue gas desulphurization (FGD) by-products, The Ohio State University (2004). 4. Y.C. Chen, B.H. Chen. Stability of polycyclic aromatic hydrocarbons during heating, J. of Food and Drug Analysis, Vol. 9, No. 1, 2001, Pages 33-39. 5. C.J. Pope, W.A. Peters, J.B. Howard. Thermodynamic driving forces for PAH isomerization and growth during thermal treatment of polluted soils, Journal of Hazardous Materials B79 (2000) 189-208. 6. G.L. Borosky. Theoretical study related to the carcinogenic activity of polycyclic aromatic hydrocarbon derivatives, J. Org. Chem., 1999, 64 (21), 7738-7744.

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7. K.K. Laali. Stable ion studies of protonation and oxidation of polycyclic arenas, Chem. Rev. 1996, 96 (6), 1873-1906. 8. J.P. Lowe, B.D. Silverman. Predicting carcinogenicity of polycyclic aromatic hydrocarbons, Acc. Chem. Res., 1984, 17 (9), 332-338. 9. R. Benigni. Structure-activity relationship studies of chemical mutagens and carcinogens: mechanistic investigations and prediction approaches, Chem. Rev., 2005, 105 (5), 1767-1800. 10. E. Kwon, M.J. Castaldi. Polycyclic aromatic hydrocarbon (PAH) formation in thermal degradation of styrene butadiene copolymer, Department of Earth and Environmental Engineering-Columbia University-NY 10027. 11. M.L. Poutsma. Free-radical thermolysis and hydrogenolysis of model hydrocarbon relevant to processing of coal, Energy Fuels, 1990, 4 (2), 113-131. 12. H. Richter, V. Risoul, A.L. Lafleur, E.F. Plummer, J.B. Howard, W.A. Peters. Chemical characterization and bioactivity of polycyclic aromatic hydrocarbons from non-oxidative thermal treatment of pyrene-contaminated soil at 250-1,000oC, Environmental Health PerspectivesVolume 108-Number 8-August 2000. 13. M. Alfe, R. Barbella, M. Mallardo, A. Tregrossi, A. Ciajolo. The effect of temperature on the chemical structure of premixed methane flames, 31st Meeting on Combustion-Italian Section of the Combustion Institute. 14. K. Liu, W. Han, W.-P. Pan, J.T. Riley. Polycyclic aromatic hydrocarbon (PAH) emissions from a coal-fired pilot FBC system, J. of Hazardous Materials B84 (2001) 175-188. 15. M.-Y. Wey, .J.-C. Chen, H.-Y. Wu, W.-J. Yu, T.-H. Tsai. Formations and controls of HCl and PAHs by different additives during waste incineration, Fuel 85 (2006) 755-763. 16. H.S. Magoha. Destruction of polycyclic aromatic hydrocarbons (PAH’s) and aliphatic hydrocarbons in soil using ball milling, Auckland University of Technology (2004). 17. F.-D. Kopinke, M. Remmler. Reactions of hydrocarbons during thermodesorption from sediments, Thermochimica Acta 263 (1995) 123-139. 18. A. Bayram, A. Muezzinoglu, R. Seyfioglu. Presence and control of polycyclic aromatic hydrocarbons in petroleum coke drying and calcination plants, Fuel Processing Technology 60 (1999) 111-118. 19. A.A. Dadkhah, A. Akgerman. Hot water extraction with in situ wet oxidation: kinetics of PAHs removal from soil, Journal of Hazardous Materials b 137 (2006) 518-526.


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COMPLETE DEGRADATION OF PENTACHLOROPHENOL IN A LAB SCALE CONTINUOUS FLOW ACTIVATED SLUDGE UNIT Upendra D. Patel1 and Sumathi Suresh2 1

Department of Civil Engineering, S. V. Patel Institute of Technology, Vasad, Dist. Anand – 388306, India, PH (091) 2692 274766, FAX (091) 2692 274540; email: [email protected]

2 Centre for Environmental Science & Engineering, Indian Institute of Technology – Bombay, Powai, Mumbai – 400076, India, PH (091) 22 25767859, email: [email protected]

ABSTRACT More than 90% degradation of 5 to 20 mg/L pentachlorophenol (PCP) was achieved in a lab-scale continuous flow complete-mix activated sludge unit with sucrose as a primary carbon source. Identical PCP removal was also obtained in batch mode. Hydraulic retention time of 3 days and mixed liquor suspended solids (MLVSS) concentration of 1000-1200 mg/L were maintained. Long acclimatization period (~120 days) was required to achieve complete degradation of PCP. During the initial phase of acclimatization, sorption on biomass was found to be the predominant mechanism of PCP removal. However, after ~100 days of acclimatization removal of PCP was found to be due to biodegradation. The acclimatized microbial culture was also capable of removing 2,4,5-, and 2,4,6trichlorophenols in conjunction with PCP. GC-MS analysis of supernatant of settling tank did not reveal the presence of chlorinated metabolites.

KEY WORDS: Pentachlorophenol, Biodegradation, Activated Sludge Process INTRODUCTION PCP is toxic to humans and animals, with major potential effects on the liver, kidney, central nervous system, and immune system (ATSDR, 2001). Proposition 65 of the Office of Environmental Health Hazards, EPA, California, identifies PCP as a carcinogen (Proposition 65, 2005). Other chlorophenols (CPs) are also found to adversely affect human and animal health. PCP was widely used as a woodpreservative; however, such use is now reducing due to health problems associated with it. Pulp bleaching operations using elemental chlorine and chlorine dioxide generates a variety of chlorinated organic compounds; collectively called, AOX (adsorbable organic halides). CPs represent a substantial fraction of AOX compounds. Harmful properties of CPs necessitate the development of simple and less-expensive methods for their remediation. Biodegradation of CPs under aerobic and anaerobic conditions has been studied in detail. Biodegradation processes are economical in comparison to physico-chemical processes and may achieve almost complete removal of many chlorinated compounds. However, they often require very long acclimatization and retention times. Biodegradation, especially under anaerobic conditions, is very sensitive to shock loads. It is also possible that strict anaerobic conditions and specific redox conditions may not be available in field conditions, limiting the scope of field application of anaerobic biodegradation processes. Aerobic pathways (via formation of catechols) are more diverse in nature. Ring cleavage can occur before or after chlorine removal and hence the resulting compounds may be even more problematic. For example, tetrachlorohydroquinone produced as a result of aerobic metabolism of PCP is more toxic than PCP (Irwin et al., 1997). It has been shown by many research groups that consortium, rather than individual bacterial species, and addition of a simple carbon source such as glucose, have been more successful in biodegradation of PCP (Mikesell and Boyd, 1986, Banerji and Bajpai, 1994, Yu and Ward, 1996). Number and position of chlorine atoms on phenol ring have been shown to substantially influence the extent and rate of biodegradation of chlorophenols (Annachhatre and Gheewala, 1996, Kim and Hao, 1999, Patel

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and Suresh, 2009). High Log Kow (>5) and hence, less water solubility (14 mg/L) of PCP indicate its tendency towards adsorption on solid surfaces. It also increases bio-accumulation potential of PCP. Piringer and Bhattacharya (1999) studied biodegradation of PCP under acidogenic conditions with glucose as a source of carbon and energy. The authors reported that the major mechanism of PCP removal was adsorption on biomass rather than biodegradation. Based on the discussion above, the objectives of the present study were to study the: 1) co-metabolic biodegradation of PCP under aerobic condition using a simple carbon source, 2) contribution of adsorption on solid surfaces in total removal of PCP, and 3) presence of any chlorinated metabolite in treated effluent that may be produced as a result of aerobic biodegradation.

MATERIALS AND METHODS Source of chemicals 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, potassium carbonate, and dichlorodiphenyl ethylene (DDE) were purchased from Sigma-Aldrich Chemical Company. Cyclohexane and components of mineral salts medium (MSM) were purchased from Merck India Ltd. Acetic anhydride was purchased from S.D. FineChem Ltd. Pentachlorophenol sodium salt (90%) was obtained from Fluka. Sucrose was purchased from a local grocery shop. All chemicals were of high purity and analytical grade. Potassium carbonate was baked in furnace at 400 0C, overnight, prior to use. No pretreatment was carried out with other chemicals. Deionized water obtained from Barnstead deionization system (18W) was used for preparing reagents.

Source of Microbial Culture Aeration tank mixed liquor was collected from M/s Metrochem Industries Ltd, Vadodara as a source of microbial culture. The industrial unit is engaged in manufacturing dyes and dye intermediates.

Activated Sludge Reactor and its operation A diagrammatic representation of continuous flow activated sludge unit is shown in Figure 1. Initially, one feed reservoir containing mineral salts medium (MSM), PCP, and sucrose was employed. However, excessive microbial growth, incapable of degrading PCP, was seen in the feed reservoir itself. Hence feeds from two separate reservoirs containing MSM and carbon source (sucrose + PCP), were pumped (250 mL/d from each reservoir) into the aeration tank using Gilson make dual channel peristaltic pump. The hydraulic retention time (HRT) and volume of aeration tank were 3 days and 1.5 L, respectively. The composition of MSM is shown in Table 1. Initial concentration of sucrose (commercial) was 1000 mg/L that was gradually decreased to 600 mg/L. PCP (sodium salt) concentration was varied between 5 and 20 mg/L. Influent was collected from the ends of PVC tubes discharging into the aeration tank while samples of treated effluent were collected from aeration tank (in form of mixed liquor) and/or settling tank for analysis. The samples (with or without sonication) were analyzed for residual PCP concentrations following derivatization and extraction (NCASI, 1986). Acclimatized culture of activated sludge reactor was also checked for its capacity to biodegrade PCP in batch system. Five milliliters of aeration tank mixed liquor was inoculated into 100 mL medium containing 5 mg/L of PCP, 1000 mg/L of KH2PO4 and K2HPO4 each, 500 mg/L of ammonium sulfate, 100 mg/L of magnesium sulfate and 600 mg/L of sucrose taken in 250 mL Erlenmeyer flasks. The flasks were incubated on an orbital shaker maintained at 300C and 150 RPM for 5 days. Following the stipulated incubation period, samples were withdrawn and analyzed for residual concentration of PCP.


577

AERATOR MSM

PCP + SUCROSE AERATION TANK (1.5 L)

CLARIFIER

RECYCLE

PERISTALTIC PUMP

Figure 1: Schematic diagram of continuous flow complete-mix reactor for aerobic biodegradation of PCP. Table 1: Composition of mineral salts medium (MSM) used for aerobic biodegradation of pentachlorophenol Sr No. 1 2 3 4 5

Compound KH2PO4 K2HPO4 CaCl2 (NH4)2SO4 MgSO4

Concentration, mg L-1 1450 1450 200 500 100

pH 7-7.5

Abiotic removal of chlorophenols in the aeration tank was determined by introducing the synthetic solution containing PCP and MSM (excluding sugar) in the aeration tank and aerating the same for time equivalent to hydraulic retention time of activated sludge system (3 days).

GC Analysis Procedure published by NCASI, CP-86.02 was adopted for the detection of chlorophenols. Following the incubation period, 3 mL culture samples were withdrawn and sonicated for 2 min prior to derivatization. Samples were derivatized by adding 78 L of 4.35M potassium carbonate solution and 90 L of acetic anhydride. Subsequently, derivatized samples were extracted twice by mixing with 1.5 mL cyclohexane on high-speed vortex mixer for 45 sec. Separation of cyclohexane was obtained by centrifuging the emulsion at 10,000 RPM for 2 min. 0.2 L of pooled extracts was injected for GC-ECD analysis. GC analysis was carried out using Agilent 6890N model equipped with ECD and FID. DB-5 column (30m x 0.32 mm ID x 0.25 M film thickness) was used. Temperature programme used was 1 min at 45oC, temperature ramp 1: 45-100oC @ 20oC/min, hold time 0.3 min, temperature ramp 2: 100-215oC @ 4oC/min, final hold time 1 min. Injector and detector temperatures were set at 210oC and 300oC, respectively. Injections were performed in splitless mode using nitrogen as the carrier gas (gas velocity 36 cm/s). Purge time and flow were set at 0.5 min @100 mL min-1. Calibration plots for all chlorophenols were prepared in concentration range of interest and were found to be linear with R2 values > 0.98.

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RESULTS AND DISCUSSION Sorption of PCP

22.743

Acclimatization of biomass required a time period of ~ 4 months. In the beginning of this period, substantial sorption of PCP was observed onto wall of PVC tubes feeding the reactor. The GC-ECD chromatogram shown in Figure 2 reveals that more than 80% PCP was sorbed onto walls. The removal of PCP reaching the aeration tank was also partly attributed to adsorption on biomass. This result is important in the sense that organo-chlorine compounds such as PCP have high Log Kow, and hence adsorb rapidly to reactor components. Thus proper material for the construction of reactor should be selected to minimize adsorption.

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Figure 2: GC-ECD chromatograms indicating sorption of PCP on the wall of PVC tubes feeding activated sludge unit 1 = feed from reservoirs, 2= feed at the inlet of aeration tank (at the ends of feed tubes), 3= aeration tank mixed liquor, peaks at 22.7 min and 31.79 min are PCP and internal standard (Dichlorodiphenyl dichloroethylene), respectively. Reactor Conditions: Initial concentration of PCP: 20 mg/L, HRT of aeration tank: 3 days, Time of analysis: 30 days after start-up of reactor

Once the sorption of PCP was recognized, PVC tubes were replaced with new tubes and flushing of the tubes was done using the feed water every week. This substantially reduced the loss of PCP between the feed reservoir and the ends of tubes. Initially, PCP degradation was monitored by the analyses of samples taken from feed reservoir and the settling tank. However, after noting the sorption of PCP in feed tubes, sample were collected from the ends of PVC tubes discharging into the aeration tank while samples of treated water was collected from aeration tank (in form of mixed liquor) and/or settling tank.

Co-metabolic Biodegradation of PCP using Sucrose as the Primary Carbon Source Results related to operation of activated sludge reactor for aerobic biodegradation of PCP are depicted in Table 2. The table does not include details of initial period of operation of the reactor during which, start-up of reactor and acclimatization of microbial consortium was carried out.


S. No.

1 2 3 4 5 6 7 8 9 10 11

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Table 2: Results of PCP biodegradation in activated sludge reactor Sampling points for PCP analysis Day of analysis % PCP after start-up of removal reactor PVC feed tubes outlets and aeration tank (mixed Day 122 93 liquor) Day 143 88 - Do PVC feed tubes outlets and aeration tank (mixed Day 143 95 liquor Æ sonicated for 2 min.) PVC feed tubes outlets and aeration tank (mixed Day 145 90 liquor) PVC feed tubes outlets and aeration tank (mixed Day 145 95 liquor Æ sonicated for 2 min.) (figure 3) PVC feed tubes outlets and aeration tank (mixed Day 153 87 liquor) Day 156 98 - Do Day 158 87 - Do Day 164 95 - Do Day 180 97 - Do Day 187 99 - Do – (figure 4)

Hz 100000

31.501

22.469

Details of reactor and Feed: Time period from day 1 to day 120 was reactor start-up and microbial consortium acclimatization period. Initial PCP and sucrose concentrations up to day 150 were 20 mg/L and 1000 mg/L, which were gradually reduced to 5 mg/L and 600 mg/L, respectively, during later part of the study.

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Figure 3: GC-ECD chromatograms showing PCP removal in activated sludge unit 1 = feed at inlet of aeration tank, 2= aeration tank mixed liquor, peaks at 22.5 min and 31.6 min are PCP and internal standard, respectively. Peaks at 15.8 min and 17.5 min represent 2,4,5-TCP and 2,3,5,6- and 2,3,4,6TeCPs, respectively. Reactor Conditions: Initial concentration of PCP: 5 mg/L, HRT of aeration tank: 3 days, Time of analysis: 187 days after start-up of reactor

From results presented in Table 2 and Figures 3 and 4 it may be noted that PCP degradation of ≥ 90% was achieved in activated sludge reactor. In addition, 90-95% removal of TCPs and TeCPs, which appeared as trace impurities in PCP sodium salt, were also observed (Figure 3). Once the culture was acclimatized to degrade PCP, sorption on biomass was found to be negligible as revealed by sonication of the mixed liquor samples prior to analysis (Figure 4). The results obtained in the present study agree with reports of Banerjee and Bajpai (1994) and Kao et al (2004), who demonstrated complete removal of PCP by oxidative biodegradation wherein the compound served either as a sole

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Hz 80000

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carbon source or as secondary substrate (co-metabolic). The microbial culture acclimatized to biodegrade PCP was able to achieve >90% removal of PCP in batch system after incubation of 5 days. This suggested versatility of microbial consortium.

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Figure 4: GC-ECD chromatograms showing residual PCP concentration in the treated mixed liquor of activated sludge unit before and after sonication. 1 = feed at inlet of aeration tank, 2 = mixed liquor analyzed before sonication, 3= mixed liquor analyzed following 2 min of sonication, peaks at 22.5 min and 31.6 min are PCP and internal standard, respectively. Reactor Conditions: Initial concentration of PCP: 10 mg/L, HRT: 3 days, Time of analysis: 145 days after startup of reactor

Abiotic removal of chlorophenols in the aeration tank following 3 days of aeration was negligible. Low volatility of PCP may be the reason for negligible abiotic removal. Aerobic biodegradation of chlorophenols has been reported to proceed through formation of chlorocatechols and chlorobenzoquinones followed by ring cleavage and subsequent mineralization in TCA cycle (Steiert and Crawford, 1985). GC-MS analysis of supernatant of settling tank connected to activated sludge reactor did not show the presence of chlorinated intermediates

CONCLUSION Following conclusions could be drawn from the present study: 1. Sorption of PCP on biomass and other solid surfaces was major cause of its removal during the reactor start-up and biomass acclimatization period. 2. Acclimatized biomass could achieve ≥ 90% removal of PCP. Sonication of biomass prior to extraction with cyclohexane revealed that this removal was mainly due to biodegradation. The acclimatized biomass could achieve similar removal of PCP in batch system too. 3. Chlorinated metabolites of PCP could not be detected in the treated mixed liquor.

ACKNOWLEDGEMENT The authors are grateful to IIT-Bombay for providing the necessary infrastructure to carry out this investigation.

REFERENCES


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1. Agency for Toxic Substances and Disease Registry (ATSDR) (2001) Toxicological profile for pentachlorophenol. 2. Annachhatre, A., P., Gheewala, S., H. (1996) Biodegradation of chlorinated phenolic compounds. Biotechnol. Adv., 14, 35-56. 3. Banerji, S.K. and, Bajpai, R.K. (1994) Cometabolism of pentachlorophenol by microbial species. J. Hazard. Mater., 39, 19-31. 4. Irwin, R.J., VanMouwerik, M., Stevens, L., Seese, M.D., and Basham, W. (1997) Environmental Contaminants Encyclopedia. National Park Service, Water Resources Division, Fort Collins, Colorado. 5. Kao, C. M., Chai, C. T., Liu, J. K., Yeh, T. Y., Chen K. F., Chen S.C. (2004) Evaluation of natural and enhanced PCP biodegradation at a former pesticide manufacturing plant. Water Res., 38, 663-672. 6. Kim, M. H., Hao, O. J. (1999) Cometabolic degradation of chlorophenols by Acinatobacter species. Water Res., 33, 562-574. 7. Mikesell, M. D. and, Boyd, S.A. (1986) Complete reductive dechlorination and mineralization of pentachlorophenol by anaerobic microorganisms. Appl. Environ. Microb., 52, 861-865. 8. National Council of the Paper Industry for Air and Stream Improvement, Inc. (NCASI) (1997) Methods manual: Chlorinated Phenolics in Water by In-Situ Acetylation/GC/MS Determination (CP-86.02). 9. Patel, U.D. and, Suresh, S. (2009) Biodegradation of chlorophenols under aerobic and anaerobic conditions: Influence of chlorine position, EnviroEnergy 2009, Chandigarh, India. 10. Piringer, G., and Bhattacharya, S.K. (1999) Toxicity and fate of pentachlorophenol in anaerobic acidogenic systems, Water Res., 33, 2674–2682. 11. Proposition 65, Office of Environmental Health Hazard, EPA, State of California, USA (2005). 12. Steiert, J., G. and Crawford, R., L (1985) Microbial degradation of chlorinated

phenols. Trends Biotechnol., 3, 300-305. 13. Yu, J., Ward, O. (1996) Investigation of the biodegradation of pentachlorophenol by the predominant bacterial strains in a mixed culture. Int. Biodeter. Biodegr., 37, 181-187.

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Assessment of Behaviour Polycyclic Aromatic Hydrocarbons in soil – at major traffic intercepts within Jalandhar City and their correlation with distance from the roadside. N. C. Kothiyal* and Vaneet Kumar**, Department of chemistry Dr. B.R. Ambedkar National Institute of Technology, Jalandhar, Punjab-14011 (India)

Abstract Polycyclic Aromatic Hydrocarbons (PAHs) are chemicals usually generated under inefficient combustion conditions. Such as insufficient oxygen by primary natural sources which are forest fire and volcanic activity, but most of the PAHs released in to the environments arise from anthropogenic sources, as a result of burning of fossil fuels, and motor vehicle exhaust. Higher molecular weight polycyclic aromatic hydrocarbons (more than three or four rings) are adsorbed on Particulate matter whereas lower molecular weight polycyclic aromatic hydrocarbon (less than three rings) remains suspended in the air for a longer time. The lighter PAHs (2-3 rings) are generally less toxic then the heavier ones (more than three or four rings). Incomplete combustion of organic materials from different urban sources are responsible for surface road soil contamination. In the only environment PAHs generated from automobile exhaust, drift in air and settle in nearby road soil depending upon metrological conditions (such as air, rain, humidity, temperature etc). In India, few studies have reported ambient PAHs concentration in Ahmadabad, Mumbai and Delhi. To our knowledge there has been a shortage of soil PAHs studies. Since PAHs are one of the most serious pollutants because of their carcinogenicity and mutagenicity. It is important to determine the amount of PAHs in soil as their concentration in soil correlates significantly with the corresponding levels in air. The aim of this study was to find out the (16 PAHs identified by EPA as potentional carcinogenic in the environment) concentration and type of PAHs in soil, with the different distance from the road side. Keywords: PAHs, Roadside, Soil, Pollutants etc. ______________________________________________________________ *To whom all correspondences should be addressed *E-mail: [email protected]

**E-mail: [email protected]

Introduction Polycyclic Aromatic Hydrocarbons are a group of over 500 compounds containing two or more fused aromatic rings system [1]. Incomplete combustion of petroleum oil in different automobile (urban sub urban sources) are responsible for surface, road side soils contamination with polycyclic aromatic hydrocarbons (PAHs) [2]. PAHs have been widely studied, and are known environmental pollutants, and an increasing particular concern has been paid to their adverse harmful effects on human body due to the carcinogenic and mutagenic properties of many PAHs species [3-6]. PAHs are abundant in the environment as pollutants. They are widely distributed in the atmosphere, existing in the particulate and gaseous phases. There is no commercial application for many PAHs however they are present in many products including crude oil, shale oil and coal tar [7]. Principle atmospheric sources are the combustion of fossil fuels, burnt refuse, coal and wood fires, coke oven emission and vehicle emission [8-9]. Natural sources include volcanoes and forest fires [10].


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Tobacco smoke human exposure to PAHs occurs through air, food, dust (soil) drinking water [11]. The lighter PAHs (2-3 rings), which are generally not carcinogenic, are mostly found in the gas phase while the heavier ones are mainly adsorbed with airborne particles. Heavier PAH (with more than three rings) are rapidly attached to existing particles, usually soot particles, by adsorption or condensation upon cooling of flue gas [12]. PAHs concentration in road soil was found to vary according to the distance from the source of pollution [13]. Butler et al. [14] have demonstrated much higher Benzo(a)pyrene(BaP) in surface of road dust concentration near complex road interchanges than in area of far distance it was reported that concentration of BaP ranged between 0.04 and 1.3 mg/kg in the soil or road dust from relatively rural areas of the eastern United State [15]. In this concern, Wild et al. [16] reported that concentrations of PAHs in UK soils are in the range of 0.1-54mg/kg with a mean of 2.32mg/kg. Moreover, Al-Haddad et.al. [16] estimated the PAH s components in Bahrain soil and concentration of various PAHs were found to fall within the range 0.01-42.58 mg/kg. Accumulation of PAHs in road dust should affect other media (e.g., air, drinking water, soil, dust, and plants) and significant exposure risk for human populations is strongly expected [17-19]. In India, few studies have reported ambient PAHs concentration in Ahmedabad [20], Delhi [21]. To our knowledge there has been a shortage of soil PAHs studies. Since PAHs are one of the most serious pollutants because of their carcinogenicity and mutagenicity [22-24] which have drawn attention of the scientific community, it is important to determine the amounts of PAHs in soil as their concentration in soil correlates significantly with the corresponding levels in air [25-26]. The principal objective of the present study was to determine the concentration, type, behavior, and distribution levels of PAHs (16 PAHs identified by EPA as potentional carcinogenic in the environment) in the roadside surface soil, with the different distance (1 Meter, 2 Meter, 3 Meter) in the road side soil.

MATERIAL AND METHOD Sampling sites Punjab is the most prosperous and developing state of the India. The traffic density of vehicle in Jalandhar city is very much higher between 9 am to 5 pm within major Chowk of the Jalandhar City. The sampling sites selected for the study inside the city were containing both residential and commercial places. These locations of sampling were chosen on the basis of high traffic density, urban populations and geographical dispersion. The ten major road intercepts within city environment of the Jalandhar are 1.Jyoti Chowk

2. Maqsuda Chowk

3. Mission Chowk

4. Patel Chowk

5. Nakodar Chowk

6. BMC Chowk

7. Footwall Chowk

8. Workshop Chowk

9. Bus Stand

10. DAV Chowk

Sampling period The soil samples were taken at the mid of January 2009. A total of around 30 samples were collected from ten major different chowks of the Jalandhar City. The soil samples were collected to characterized the PAH concentration at different distance from roadside soil and their types from selected city locations of high traffic density within the city.

Sampling Technique From each sampling location three soil samples were collected from1Meter, 2 Meter 3 Meter from roadside with different directions (Left and right side of road). The soil samples were collected from 6 cm soil depth. The bulk samples collected from sites were kept in labeled polyethylene bags and brought to laboratory. Large stones, leaves debris and other

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extraneous materials were sieved out before analysis. All the samples collected from various locations were dried in a hot air oven maintained at 40 to 60 0C for 24 hrs for removal of free moisture present in them. The samples were kept preserved in a desiccators kept in dark before extraction.

Glasses wares All glass wares of Borosil make (A grade) glass were used in this study. All glasswares were washed with nitric acid and washed with double distilled water before use every time.

Equipment PAHs in the samples were analyzed on Nucon microprocessor based Gas Chromatograph, Model No 5765 using BTX – 5 capillary column of 60 meter length.

Extraction of PAHs 20 gm of pre dried soil samples were heated again at 40 to 60 0C to remove any trace of moisture present. After drying samples were transferred in soxhlet apparatus and extracted using acetone and dichloromethane as solvents (1:1 ratio) at the rate of 3 cycles per hrs for 8 hrs. The extract was allowed to cool and filtered through a Whatman filter paper no. 41. Extract was concentrated to 1 ml using rotary evaporation at 60 0C under gentle vacuum .The samples were kept preserved in a amber colored sample tubes in refrigerator below 4 0

C before analysis. Samples were analyzed for type and concentration of PAHs by GC.

Result and Discussion A Total number of 30 samples were taken in this study to characterize the concentration and types PAHs from selected city location (Major Chowk of the Jalandhar City) of high traffic density within the city. From the table given below it was cleared that five major PAHs found in soil sample at DAV site were (1Meter, 2Meter, and 3 Meter) , Benzo(a) anthracene 10.6 µg/g (1M), Benzo(k) fluoranthene 25.66 µg/g (1M), Benzo(a) Pyrene (15.4) (1M), I (123 cd) pyrelene (14.9 µg/g (1M), Di B (ah) anthracene 26.81 µg/g (3M). The five major PAHs found in soil samples at Bus Stand (1M, 2M, and 3M) site were Chrysene 18.22 µg/g (1M), B(b) fluoranthene 22.07 µg/g(1M), B(k) fluoranthene 22.44 µg/g (1M), B(a) pyrene 19.61 µg/g (1M), Dib (ah) anthracene 17.42 µg/g (1M). The five major PAHs found in soil samples at Football Chowk (1M, 2M, and 3M) site were Chrysene 3.43 µg/g (1M), B(k) fluoranthene 3.46 µg/g (1M), I(123cd) pyrene 4.68 µg/g (1M), Dib (ah) anthracene 25.4 µg/g (1M), Benzo (ghi) pyrelene 23.24 µg/g (2 M). The five major PAHs found in soil samples at Nakodar Chowk (1M, 2M, and 3M) site were Benzo (a) anthracene 10.93 µg/g (1 M), Chrysene 9.51 µg/g (3 M), Benzo (a) fluoranthene 5.25 µg/g (3M), B(a) pyrene 8.41 µg/g (3 M), Di b(ah) anthracene 21.7 µg/g (1M). The five major PAHs found in soil samples at Workshop Chowk (1M, 2M, and 3M) site were Chrysene 10.91 µg/g (1M), Benzo (a) fluoranthene 5.96 µg/g (1M), B(k) fluoranthene 13.49 µg/g (2 M), Dib(ah) anthracene 25.42 µg/g (2M), B(ghi) pyrelene 5.58 µg/g (2M). The five major PAHs found in soil samples at Patel Chowk (1M, 2M, and 3M) site were B (ghi) pyrelene 15.85 µg/g (1M), Chrysene 9.56 µg/g (2M), Benzo(a) fluoranthene 11.3 µg/g (2M), B(a)pyrene 17.3 µg/g (3M), Di b(ah) anthracene 17.14 µg/g (3M).


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The five major PAHs found in soil samples at DAV Chowk (1M, 2M, and 3M) site were anthracene 13.15 µg/g (1M), Pyrene 28.4 µg/g (1M), Chrysene 26.6 µg/g (1M), Benzo (k) fluoranthene 13.99 µg/g (3M), Dib (ah) anthracene 26.1 µg/g (1M). The five major PAHs found in soil samples at Maqsuda Chowk (1M, 2M, and 3M) site were Phenthrene 2.53 µg/g (3M), Benzo (a) pyrene 7.91 µg/g (2M), I(123cd) pyrene16.55 µg/g (3M), Di Benzo (ah) anthracene 28 µg/g (3M), Benzo(ghi) pyrelene 5.98 µg/g (1M). The five major PAHs found in soil samples at Mission Chowk (1M, 2M, and 3M) site were Pyrene 6.45 µg/g (1M), B(a) anthracene 7.62 µg/g(2M), B (a) pyrene 7.76 µg/g (1M), I(123 cd) pyrene 7.5 µg/g (3m), Dib(ah)anthracene 25.8 µg/g (1M). The five major PAHs found in soil samples at BMC Chowk (1M, 2M, and 3M) site were Pyrene 10.2 µg/g (1M), B(a) anthracene 9.25 µg/g(1M), B (a) pyrene 8.12 µg/g (1M), I(123 cd) pyrene 11.3 µg/g (1M), Dib(ah)anthracene 14.2 µg/g (1M). The average concentration of 16 PAHs in soil samples at DAV Chowk (1M, 2M,3 M) were 12.26 µg/g, 3.28 µg/g, 4.11 µg/g. The average concentration of 16 PAHs in soil samples at Bus Stand (1M, 2M, and 3M) site were 10.8 µg/g, 4.14 µg/g, 4.11 µg/g. The average concentration of 16 PAHs in soil samples at Football Chowk (1M, 2M, and 3M) site were 1.6 µg/g, 5.5 µg/g ,2.2 µg/g. The average concentration of 16 PAHs in soil samples at Nakodar Chowk (1M, 2M, and 3M) site were 4.66 µg/g, 1.7 µg/g, 4.77 µg/g. The average concentration of 16 PAHs in soil samples at Workshop Chowk (1M, 2M, and 3M) site were 4.83 µg/g, 6.15 µg/g, 2.12 µg/g. The average concentration of 16 PAHs in soil samples at Patel Chowk (1M, 2M, and 3M) site were 6.76 µg/g, 3.6 µg/g, 2.6 µg/g. The average concentration of 16 PAHs in soil samples at DAV (1M, 2M, and 3M) site were 12.26 µg/g, 3.18 µg/g, 4.28 µg/g. The average concentration of 16 PAHs in soil samples at Maqsuda Chowk (1M, 2M, and 3M) site were 1.97µg/g, 3.34µg/g, 5.1 µg/g. The average concentration of 16 PAHs in soil samples at Mission Chowk (1M, 2M, and 3M) site were 4.41 µg/g, 3.44 µg/g ,1.09 µg/g. The average concentration of 16 PAHs in soil samples at BMC Chowk (1M, 2M, and 3M) site were 5.6 µg/g, 4.18 µg/g, 1.39 µg/g. From the result it was cleared five major PAHs found at different chowks was not same, and average concentration of PAHs was different at different distances from road side. In maximum cases PAHs concentration was found to be decrease with distance from the road side and in the few cases it was increase when distance from the roadside was to be increase.

Table 1 Type and concentration of PAHs found in roadside (1M, 2M,3M) soil.

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Pyrene

B(a)anthracene

Chrysene

4.87

2.62

5.67

10.6

8.51

2M

0.1

0.63

0.54

0.15

1.08

0.23

0.24

8.23

0.53

3M

0.06

0.39

1.11

0.64

5.27

0.22

0

0

0

2.05

1M

0.390

4.244

3.358

6.184

5.29

10.44

3.066

17.75

7.682

18.22

2M

0.49

1.87

2.53

1.31

3.28

3.55

1.36

1.28

13.7

3M

0.31

1.36

2.71

0.93

1.49

3.91

8.97

3.95

25.66

15.4

0.39

10.1

14.9 3.16

1.009

2.54

5.96

13.95

26.81

2.63

22.074

22.44

19.61

7.518

17.42

7.219

5.47

3.71

6.02

9.53

3.81

3.77

4.84

4.41

9.76

Chowk 2

Jyoti

0.78

0.11

B (ghi) pyrelene

Fluorene

3.34

Di b (ah) anth.

Anthracene

1.71

I(123cd) Pyrene

Phenanthrene

3.06

B(a) Pyrene

Fluorene

1.87

B(k) fluoranthene

Acenapthylene

0.12

fluoranthene

Acenapthene

1M

Benzo(b)

Naphthalene

Jyoti

Roadside

Distance from

1

Sample location

Sr. No.

Total Concentration of PAHs in µg/gm

8.32

1.89

20.9

4.89

Chowk 3

Jyoti Chowk

4

Bus Stand

5

Bus

6.11

2.22

Stand 6

Bus

2.15

5.01

6.4

13.4

2.12

Stand 7

Football

1M

0.25

0.41

0.18

0.47

0.31

0.63

0.24

0.39

1.76

3.43

1.81

3.46

1.09

4.68

5.27

1.22

2M

0

0

0

0.34

0

0

0

0

1.17

0.46

1.54

0.23

1.59

1.85

25.4

23.24

3M

0

0

0

0

0

0

0

0.21

0

0

1.82

0.96

0.3

0.89

1.41

12.3

1M

0.17

5.93

2.61

1.03

2.07

3.72

4.08

1.42

10.93

5.34

4.27

3.77

2.76

1.47

21.7

3.32

2M

0.034

0.17

0.23

0.21

1.03

4.17

0.58

4.98

0.89

0.51

0.66

0.33

3.48

4.55

1.26

4.57

3M

0.17

1.14

1.71

0.91

0.84

2.75

1.15

5.04

6.1

9.51

5.28

7.86

8.41

10.7

9.76

4.58

1M

0.48

1.6

3.18

1.53

2.65

2.63

1.19

5.12

2.87

10.91

5.96

5.57

2.29

0.18

26.4

2.18

2M

5.22

3.88

2.69

1.26

4.16

3.19

1.29

2.43

5.98

4.18

7.06

13.49

9.3

3.31

25.42

5.58

Chowk 8

Football Chowk

9

Football Chowk

10

Nakodar Chowk

11

Nakodar Chowk

12

Nakodar Chowk

13

Worksho p Chowk

14

Worksho p Chowk

International Conference on Emerging Technologies in Environmental Science and Engineering

15

October 26–28, Aligarh 0.21 Muslim University, India Worksho 3M 2009 0.12 1.23 Aligarh,0.21

2.13

1.02

0.23

0.32

3.21

2.12

1.20

4.1

1.0

2.1

6.1

587

1.1

p Chowk 16

Patel

1M

0.069

0.215

0.29

0.18

0.41

0.41

0.95

0.78

4.91

1.36

1.91

0.73

1.03

0.3

7.45

15.85

2M

0.71

3.17

2.51

1.58

4.43

7.18

11.8

3.33

6.34

9.56

11.3

9.02

13.4

7.93

8.16

7.87

3M

0.057

0.88

0.55

0.31

0.51

1.16

0.09

3.82

0.89

2.38

1.74

0.58

17.3

5.1

17.14

5.61

Chowk 17

Patel Chowk

18

Patel Chowk

19

DAV

1M

1.55

13.9

5.51

4.9

2.33

13.18

5.39

28.4

14.4

26.6

13.8

13.31

12.3

12.35

26.1

2.46

20

DAV

2M

0.27

0.84

1.66

0.89

0.28

2.017

3.46

4.1

1.8

0.86

1.64

1.25

5.41

2.72

22.52

2.79

21

DAV

3M

0.22

1.59

1.29

0.18

1.29

0.58

0

0

9.17

2.98

5.02

13.99

12.3

4.59

3.48

1.93

22

Maqsud

1M

0.041

0.008

0

0

0

0

0

0

0

0

0.71

0.35

3.11

1.23

4.41

5.98

2M

0

0

0

0

0

0

0

0

2.6

0.11

0.95

0

7.91

6.57

3.79

1.51

3M

0.032

0.17

0

0

2.53

0

0

0

0.63

1.44

0.75

2.13

6.16

16.55

28

1.74

1M

0.137

0.68

0.91

0.23

0.84

1.08

0.58

6.45

5.12

4.39

6.27

2.96

7.76

3.21

25.8

4.2

2M

0.088

0.71

0.64

0.83

0.95

2.86

0.077

4.89

7.62

4.56

3.28

3.33

3.12

1

19.6

1.62

3M

0.097

0

0.14

0.22

0.76

1.3

3.44

0

0

0

1.45

0

0

7.15

1.63

1.31

1M

0.17

2.42

2.99

1.29

3.56

2.84

1.98

10.2

9.25

5.7

8.09

5.55

8.12

11.3

14.2

2.33

2M

0.38

5.41

1.17

1.13

3.48

2.42

1.19

9.77

5.57

3.41

2.79

4.72

2.84

10.3

5.41

6.91

3M

0.033

3.17

0.44

0.25

0

0.77

0.15

0

3.15

1.71

0.92

0

1.76

1.08

5.96

0.19

a Chowk 23

Maqsud a Chowk

24

Maqsud a Chowk

25

Mission Chowk

26

Mission Chowk

27

Mission Chowk

28

BMC Chowk

29

BMC Chowk

30

BMC Chowk

588


Table 2 Average concentration of 16 PAHs found in roadside (1M, 2M, 3M) soil. Sr No

Sample location

Distance

from

Average

concentration

roadside

PAHs in µg/g.

1

Jyoti Chowk (JC1)

1 Meter

7.3

2

Jyoti Chowk (JC2)

2 Meter

3.2

3

Jyoti Chowk (JC3)

3 Meter

4.47

4

Bus Stand (BS1)

1 Meter

10.8

5

Bus Stand (BS2)

2 Meter

4.14

6

Bus Stand (BS3)

3 Meter

4.11

7

Football Chowk (FC1)

1 Meter

1.6

8


2 Meter

5.5

9


3 Meter

2.2

10

Nakodar Chowk (NC1)

1 Meter

4.66

11

Nakodar Chowk (NC2)

2 Meter

1.7

12

Nakodar Chowk (NC3)

3 Meter

4.74

13

Workshop Chowk (WC1)

1 Meter

4.83

14


2 Meter

6.15

15


3 Meter

2.12

16

Patel Chowk (PC1)

1 Meter

6.76

17

Patel Chowk (PC2)

2 Meter

3.6

18

Patel Chowk (PC3)

3 Meter

2.6

19

DAV

1 Meter

12.26

20

DAV

2 Meter

3.28

21

DAV

3 Meter

4.11

22

Maqsuda Chowk (MC1)

1 Meter

1.97

23

Maqsuda Chowk (MC2)

2 Meter

3.34

24

Maqsuda Chowk (MC3)

3 Meter

5.1

25

Mission Chowk (Mi C1)

1 Meter

4.41

26

Mission Chowk (Mi C2)

2 Meter

3.44

27

Mission Chowk (MiC3)

3 Meter

1.09

28

BMC Chowk (BMC1)

1 Meter

5.6

29

BMC Chowk (BMC2)

2 Meter

4.18

30

BMC Chowk (BMC 3)

3 Meter

1.39

of

12

C oncentrationof P A H s(inµg/g)

10

8

6

4

2

0 JC1

JC2

JC3

BS1

BS2

BS3

FC1

FC2

FC3

NC1

NC2

NC3

WC1

WC2

WC3

PC1

PC2

PC3

DAV1 DAV2 DAV3 MC1

MC2

MC3

Location of soil samples from roadside(1M,2M,3M)

MiC1 MiC2 MiC3 BMC1 BMC2 BMC3


589

Figure 1. Average concentration of PAHs at different chowks with1M, 2M, 3M distance from roadside soil.

Conclusion It was concluded from the study that 16 EPA PAHs found in soil in different concentration at different chowk and their concentration also varies with different distance from the roadside. Maximum concentration of Pyrene was found to be 28.4 µg/g at DAV Chowk soil sample and minimum concentration of Acenapthene was found to be 0.008 µg/g at Maqsuda chowk soil samples. When average concentrations of 16 EPA PAHs were taken than average concentration was found to be maximum at DAV Chowk 12.26 µg/g and were minimum at Mission Chowk 1.06 µg/g soil sample. Such a soil studies could be of great significance for the planers while considering environmental remedial measures.

Acknowledgements Authors are grateful to the authorities National Institute of Technology, Jalandhar for providing institute laboratory facilities to carry out this work at NIT, Jalandhar. One of the author Mr. Vaneet Kumar is grateful to MHRD for providing fellowship.

References 1. IPCS, 1998 Selected Non-Heterocyclic Polycyclic Aromatic Hydrocarbons. Environmental Health Criteria 202, United Nations Environment Programme, International Labour organization, World Health organization. 2. J.L. Hancock, H.G. Applegate, J.D. Dodd, Polycyclic Aromatic Hydrocarbons on Leaves, Atmos. Environ. 4 (1970) 363-370. 3. C.E. Bostrom, P. Gerde, A. Hanberg, B.Jenstrom, C.Johansson, T. Kyrklund, A. Rannug, M. Tornqvist, K. Victorin, R. Westerhom, Cancer risk assessment, indicator, and guideline for polycyclic aromatic hydrocarbons in the ambient air, Environ. Health Perspect. 110 (suppl. 3) (2002) 451-489. 4. IARC(International Agency of Research on Cancer), IARC Monograph on evolution of the carcinogenic Risk of Chemicals to Human, Polynuclear Aromatic Hydrocarbons, Art1, Chemical, Environmental and Experimental Data, vol. 32, Lyon, France, 1983. 5. IARC (International Agency of Research on Cancer), Overall evaluation of carcinogencity: An updating of IARC monograph. vols 1-42, suppl.7, Lyon, France, 1987. 6.

M.L. Lee, M. Novotny, K.D. Bartle, Analytical Chemistry of Polycyclic Aromatic

Compounds, Academic Press, New York, 1981. 7. ATSDR, 1995 Agency for Toxic Substances and Disease Registry. Toxicological Profile for Polycyclic Aromatic Hydrocarbons (PAHs). August 1995. Atlanta, Georgia. 8. COT 2001. Committee on Toxicity of Chemicals in Food, Consumer Products and the Environment. Annual Report 2001. Statement on Polycyclic Aromatic Hydrocarbons-Interim

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pragmatic guideline for use in emergencies. 9. DEFRA/EA, 2002b. DEFTA/EA R&D Publication CLR7 Assesment of Risks to Human Health from Land Contamination: An overview of the Development of Soil Guideline Values and Related Research .March 2002. 10. ATSDR, 1995 Agency for Toxic Substances and Disease Registry. Toxicological Profile for Polycyclic Aromatic Hydrocarbons (PAHs). August 1995. Atlanta, Georgia. 11. COT 2001. Committee on Toxicity of Chemicals in Food, Consumer Products and the Environment. Annual Report 2001. Statement on Polycyclic Aromatic Hydrocarbons-Interim pragmatic guideline for use in emergencies. 12. Kamens, R., Odum, J., Fan, Z.-H., 1995. Some Observation on Time to Equilibrium for semi volatile Polycyclic Aromatic Hydrocarbons (PAHs) Environ. Sci. Technol. 29, 43-50. 13. J.G. Li, X.D. Zhang, S.H Li, G.Q. Qi, X.Z. Liu, Source Seasonality of Polycyclic Aromatic Hydrocarbons(PAHs) in a Subtropical city, Guangzhou, South China, Sci. Total Environ. 355 (2006) 145-155. 14. J.D. Butler, V.W. Butter, C. Kellow, H.G. Robinson, Some Observations on the Polycyclic Aromatic Hydrocarbons (PAHs) Content of Surface Soils in Urban Areas, Sci. Total Environ. 38 (1984) 75-85. 15. ATSDR, (Agency for Toxic Substances and Diseases Registry), Toxicological profile for Benzo(a)Pyrene, Atlanta, G.A, 1990. 16. S.R. Wild, M.L Berrow, K.C Jones, The Persistence of Polycyclic Aromatic Hydrocarbons (PAHs) in Sewage Sludge Amended Agricultural Soils, Environ. Pollut. 7(1991) 141-157. 17. R.M. Barnes, Childhood Soil Ingestion: how much Dirst to Kids Eat? Anal. Chem. 62 (1990) 1033A. 18. A. Perico, M. Gottardi, V. Boddi, P. Bavazzana, E. Lanciotti, Assessment of exposure to Polycyclic Aromatic Hydrocarbons(PAHs) in police in Florene, Italy, through personal air sampling and biological Monitoring of the Urinary, through Personal Air Sampling and Biological Monitoring of the Urinary Metabolite 1- hydroxypyrene, Arch. Environ. Health 56 (2001) 501-512. 19. G. Falco, J.i. Domingo, J.M. Llobet, A. Texido, C. Casas, L. Muller, Polycyclic Aromatic Hydrocarbons(PAHs) in Foods: Human Exposure through the Diet in Catalonia, Spain, J. Food Prot. 66 (2003) 2325-2331. 20. Raiyani, C.V., Shah, J.A., 1993. Levels of Polycyclic Aromatic Hydrocarbons (PAHs) in ambient environment of Ahmedabad City. Indian J. Environ. Protect. 13 (3), 206-215. 21. Kannan, G.K., Kapoor, S.C., 2004. Analysis of Particle Size Fraction (PM10 and PM2.5) and PAHs of Urban Ambient Air. DRDO, Ministry of Defence, Delhi 110054, India. 22. IARC Monograph Evaluation, 1983. Carcinogens. Risks Humans, 32 pp. IARC (International Agency of Research on Cancer), 1987. IARC Monographs on the evalution of the carcinogenic risk of Chemicals to Humans, Suppl. 7. IARC, Lyons.


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E-WASTE A EMERGING POLLUTANTS OF PRESENT WORLD SWATI NANDI M.Sc (BIOTECH), B.Sc (BIOTECH),PGDBBM,PGDBI,M.PHIL

With the ever expending growth in modern technology and consumer durable product the useful life of electronic goods is shrinking and new electronic product are flooding the market. E-waste is generated from computer and related products and other electronic gadgets (television, refrigerator and washing machine and so on . In India reusability and recycling factor of computers and peripherals are higher then that in developed countries. In America & other European countries computer systems are replaced on an average every three years. In the case of developing countries like India in the last couple of years affordability of computers was limited to only a socio-economically advantaged section of the population. No reliable figures are available till today to quantify the computers generating as waste Even the developed countries mainly from Western Europe and North America are dumping their e-waste in developing countries from Asia. India and china are the first strategic option to dump e-waste as worker protections and environmental safety standards are weak. It can be assumed that these pollutants will find their way to the soil, water, and air during waste treatment and landfilling. Consequently, even a small amount of WEEE entering the residual waste will introduce relatively high amount Of heavy metals and halogenated substances. These pollutants will seriously affect the health of employees who manually sort and treat the waste by entering their body through respiratory tract, through the skin, or through the mucous membrane of the mouth and the digestive tract. The research about WEEE started up in the late eighties. Disposal and recycling methods, hazardous substances in electronic waste and material and financial flows were analyzed. These days, it is known that electronic waste contains a long list of toxic substances (EEA, 2003), (Hanke, 2001). Sakai et al. (2001) and Christmann et al. (1989) found that the incineration of e-waste leads to hazardous emissions. Further the exposure of workers in the recycling industry in Europe was evaluated by Hanke (2001). However, not much has been done in the field of recycling methods of developing countries. In the year 2003 ToxicsLink (2003) made a first study about the recycling of electronic waste in India. nine toxic or hazardous materials that are, or were used in IT and telecom equipment: mercury (or it compounds), lead (or its compounds), cadmium (or its compounds), beryllium (or its compounds), hexavalent chromium, brominated flame-retardants, polyvinyl chlorides (PVC) and polychlorinated biphenyls (PCBs). India already has a few small-scale regional recycling programme that are employed today. Two such units based in Chennai are in Eparisara and Trishyiraya. Opting


recycle business as an opportunity is useless in the absence of sufficient resources and quality standards to handle them. Small scale recycling plants in the absence of quality standards will create a future problem of health hazards and environmental issues. It will be purely an addition to more toxic elements like cadmium, lead-for example in the soil, water, air and above all in humans. Symptoms of heavy metal toxicity include mental confusion, pain in muscles and joints, headaches, short- term memory loss, gastrointestinal upsets, food intolerances, vision problem, chronic fatigue, and others.

Fig: Dump of E-waste As a result of increased production and decreased life spans, electronic waste is one of the fastest growing components of the waste stream.The toxic components in e-waste makes the landfill and incinerator disposal of these products particularly problematic. E-waste contains metals such as cadmium, lead, mercury, and brominated flame retardants that can pollute groundwater if disposed in a leaking landfill. The incineration of e-waste releases some of these heavy metals into the atmosphere while the remainder of these metals is sent to landfills as a component of incinerator ash. In landfills, these metals can produce contaminated leachate. Leachate is a liquid that forms in landfills from waste that can percolate through the soil carrying substances from the waste and has the potential to contaminate soil and waterbodies. To reduce the environmental impact of electronics use and disposal through reuse, donation, recycling, and buying greener electronic products are mainly used. Donating electronics for reuse extends the lives of valuable products and keeps them out of the waste management system for a longer time. Reuse, in addition to being an environmentally preferable alternative, also benefits society. By donating your used electronics, you allow schools, non-profit organizations, and lower-income families to use equipment that they otherwise could not afford

RECYCLING ELECTRONICS-Recycling electronics avoids pollution and the need to extract valuable and limited virgin resources. It also reduces the energy used in new product manufacturing. A growing number of municipalities are offering computer and electronics

593

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collections as part of household hazardous waste collections or special events. In addition, public and private organizations have emerged that accept computers and other electronics for recycling which may collect used products and send them to a recycler. Some electronics manufacturers are accepting household electronics for recycling. In some cases, these services are provided free-of-charge.

Buying Green Environmentally responsible electronics use involves not only proper end-of-life disposition of obsolete equipment, but also purchasing new equipment that has been designed with environmental attributes. Households, companies, and governmental organizations can encourage electronics manufacturers to design greener electronics by purchasing computers and other electronics with environmentally preferable attributes and by requesting takeback options at the time of purchase. When we will go for purchasing any electronic product Look for the electronics that: • Are made with fewer toxic constituents,Use recycled content, Are energy efficient (e.g., showing the“Energy Star” label),Are designed for easy upgrading or disassembly,Utilize minimal packaging,Offer leasing or takeback options It is estimated that total waste generated from electronic and electrical equipment (WEEE [waste electrical and electronic equipment]) in India is approximately 146 000 tonnes per year. The Indian states in the order of their contribution to WEEE are as follows. Maharashtra>Andhra Pradesh>Tamil Nadu>Uttar Pradesh>West Bengal>Delhi>Karnataka>Gujarat>Madhya Pradesh>Punjab. Cities in the order of their generation of WEEE are as follows. Mumbai>Delhi>Bangalore>Chennai>Kolkata>Ahmedabad> Hyderabad>Pune>Surat>Nagpur. BIOREMEDIATION APPROACH TO E-WASTE Plant are able to live in the various environments, in which soil is contaminated with hazardous amounts of toxic heavy metals, either occurring naturally or a anthropogenic sources such as Ewaste.Therefore it appears that selecting a more appropriate plant species for the phytoextraction i.e, removals of metals from contaminated soil. Indian mustard (Brassica juncea L.), Italian serpentine plant ( Alyssun beztolonii) and Thlaspi caerulescens are some of the most terrestrial plant species which were recently been used to extract toxic metal from soil, sediments and translocate these metals to the roots, harvestable stalks and leaves etc of the plants ( Baker and Brooks, 1989;Reeves, 1992; Baker et al.,1994;) Refferences:


1. Agarwal R, Ranjan R, Sarkar P. Scrapping the hi-tech myth: computer waste in India. New Delhi7 Toxics Link; 2003. 2. Baud I, Grafakos S, Hordjik M, Post J. Quality of life and alliances in solid waste management. Cities 2001;18(1):3–12. 3. CII, March 2006; India Together, June 2006; The Hindu, 15th June 2006; Hindu, 7th June 2005; CII, 2006 4.

Coalition (SVTC), San Jose, CA and Basel Action Network, Seattle, WA

5

D. Sinha-Khetriwal et al. / Environmental Impact Assessment Review 25 (2005) 492–504 504

6. Desrochers P. Industrial symbiosis: the case for market coordination. Journal of Cleaner Production 2004;12:1099– 110. 7. Empa. E-waste pilot study Delhi: knowledge partnerships with developing and transition countries. St. Gallen7 Empa; 2004 8. EPA (2002) Municipal Solid Waste in the United States: 2000 Facts and Figures. United States Environmental Protection Agency (EPA) EPA530-R-02-001, pp 150-160 9. Esty, Daniel C, Levy Marc, Srebotnjak Tanja, de Sherbinin Alexander. 2005 Environmental sustainability index: 10. EU. Waste electrical and electronic equipment; 2004. 11. Euromonitor. Electronics and appliances forecast 2003; 12. Euromonitor. World market for domestic electrical appliances: February 2004; Haque A, Mujtaba I, Bell J. A simple model for complex waste recycling scenarios in developing countries. Waste Manag 2000;20:625– 31. 13. Freeman M. H. 1989. Standard Handbook of Hazardous Waste Treatment and Disposal, McGraw-Hill Company, USA. 14. Gattuso D (2005) Mandated Recycling of Electronics. Competitive Enterprise Institute. 15. GII (2004) World Electronics Industry 2002-2007. Global Information Inc., Hartford, CT 16. ICER (2004) WEEE – Green List Waste Study. Industry Council for Electronic Equipment 17. Korhonen J, von Malmborg F, Strachan P, Ehrenfeld J. Management and policy aspects of industrial ecology: an emerging research agenda. Bus Strat Environ 2004;13:289– 305. 18. Lindhqvist T. Extended producer responsibility in cleaner production. Lund, Sweden7 The International Institute for Industrial Environmental Economics, Lund University; 2000.

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19. Means, J. & Hinchee, R.E. (1994) Emerging Technology For bioremediation of Metals. Lewis Publishers, Boca Raton, FL. 20. Mortality in IBM Workers,1969-2001Richard W. Clapp, D.Sc., MPH APHA Annual MeetingBoston, MANovember 7, 2006 21. MoEF (Ministry of Environment and Forest, Govt. of India). Hazardous wastes (management and handling)


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Dr. Izharul Haq Farooqui Organising Secretary Department of Civil Engineering A.M.U., Aligarh Sir, Please find herewith a full text of the paper entitled, “Mycoflora – an existing and emerging group of pollutants”, for the International Conference on Environmental Sciences to be held in October 2009 and oblige. Thanking you,

Yours sincerely,

(Neha Pathak) Research Scholar Enrol. No. GD-5980 Section of Plant Pathology Department of Botany A.M.U., Aligarh

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Mycoflora – an existing and emerging group of pollutants Neha Pathak and Razia K. Zaidi Section of Plant Pathology, Department of Botany A.M.U., Aligarh Abstract Agriculture developments are taking place in India and other countries in a view to accelerate the food production for feeding the ever increasing population. Agriculture refers to the ability of a farm to produce food indefinitely, without causing severe or irreversible damage to ecosystem. Agricultural production is generally achieved through a considerable increase it the use of biocontrol agents and different pesticides. Plants, insects, bacteria, fungi and other organism are a natural part of the environment. Some can benefit people in many ways whereas some can be pests that need to be controlled. Unlimited exploitation of nature by man disturbed the delicate ecological balance between living and non-living components of the biosphere. These disturbed conditions are playing an important role in the increase of biological pollutants and new varieties of viruses, bacteria and fungi are emerging. These pollutants not only contaminate their immediate environment but spread the infection to human beings, contaminate our air, soil and water, so it is the need of the hour to identify and check the spread of these living pollutants. An experiment was conducted in the lab to identify and isolate the pathogenic fungi. Different varieties of wheat like WH 896, HD264 were tested in lab and some important fungi like Rhizopus, Aspergillus, Fusarium and many more were identified, isolated and pure cultures were made during the experiment. Plant pathologists and mycologists are concerned with plant health and facing the tremendous challenge of finding new and innovative ways of controlling and minimizing pathogenic fungi without using chemicals, pesticides and fertilizers. We should use other effective ways of biocontrol and attempts are being made to use ecofriendly compounds like organic amendments and plant products which are believed to possess the antimicrobial and antinemic properties. These research efforts are of course very timely because of environmental concerns and variety of different fungi have become popular experimental organisms for studies of fundamental biological processes.


599

Mycoflora – an existing and emerging group of pollutants Neha Pathak and Razia K. Zaidi Section of Plant Pathology, Department of Botany A.M.U., Aligarh

Introduction Interaction between fungal infection and environmental variables have traditionally been studied from the perspective of the disciplines of mycology and environment. There are more than 81 plant diseases known worldwide. In fact all plants are vulnerable to attack by diseases, crop plant are frequent victims, and crop diseases can result in enormous agricultural and economic losses. Fungi are the agents responsible for much of the disintegration of organic matter and such they affect us directly by destroying food, fabrics, leather and other consumers good manufactured from raw materials subject to fungal attack. Air borne exposure of some fungi (mycoflora) are degenerative. They contribute to plants, trees and even people, slowly and subtly degenerating and dying, degenerating the cells, tissues and biological operating systems of our body. Fungi are of course tremendously, important to humans because of the plant diseases they cause. Most species of plant are subject to attack by a number of different types of fungal pathogen. Fungus associates with another organism may not seem directly related to human affairs (Milton and Hancock, 1981) and Singh and Faull (1982) have excellently reviewed the topic of biological control and feel that the challenging of one organism by another organism in a sterile environment may provide some information about the competitive ability of mycotoxigenic fungi. In nature, these seeds are harboured by a variety of microorganism both mycotoxigenic and saprophytic fungi interacting with each other. Fungi can utilize so many different substrates as food. They are capable of attacking many products we utilize, including fabrics, leather goods and other

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various types of cereals like maize, rice, wheat. Besides simply spoiling food, certain species of fungi also produce some very toxic substances known as mycotoxins. Heavy losses have been observed to be caused by seed-borne pathogen in various crops. Thomas (1937) initiated the work on mycoflora of wheat. Hewit (1965) initiated the work on seed-borne fungi. Triticum aestivum, commonly known as ‘Genhu’ is the important cereal crop of Indian agriculture and food security system. Wheat is the main and staple food or feed crop in several countries of Asia, Africa. It achieved the highest yield of 76.37 m tonnes each year. It is an important food crop next to cereals in India and covers an area of 12 million or more hectares. In India considerable amount of work has been carried out on various aspects of seed health and seed pathology of agriculture crop and its harmful effect on our environment. Materials and Methods Experiments were conducted to work out relationship between environment variables and effect of fungal diseases using grain samples of wheat (Triticum aestivum). So many fungal genera found to be associated with the deteriorated samples of wheat during storage by direct observation, standard blotter method, and agar plate method, wheat samples collected from different places. Wheat variety WH896 is used for experiments in laboratories. The germination tests were conducted on 400 seeds in accordance with ISTA rules (Anon, 1976) and following methods are used for seed testing and identification of fungal diseases.


601

1. By Blotter Method Study of external and internal seed mycoflora of Triticum aestivum: In the blotter method, for external seed mycoflora we have use 10 seeds in 5 petriplates. 3 well moistened sterilized blotting paper were placed in 5 sterilized petriplates at 9 cm diameter. In each petriplates 10 seeds were placed. Petriplates were incubated at 20±2oC for 8 days with cycles of 12 hours light and 12 hours darkness. After 8 days of incubation fungi which developed on the seeds were identified for internal seed mycoflora, we have sterilized seed surface by the dipping of seeds in 0.1% aqueous mercuric chloride for 2 or 3 minutes followed by repeated washing with sterilized distilled water. After then 3 well moistened sterilized blotting paper were placed in 5 sterilized periplates at 9 cm diameter. In each petriplates 10 surface sterilized seeds were placed. Petriplates were incubated at 20±2oC for 8 days with cycle of 12 hours light and 12 hours darkness. After 8 days of incubation, fungi which developed on the seeds were identified. By Potato Dextrose Agar Method Study of external and internal seed mycoflora of T. aestivum In this method petriplates of 9 cm diameter containing the agar media were used for both internal and external seed mycoflora. For external seed mycoflora, we have used 10 seed in PDA containing petriplates and incubated at 20±2oC for 8 days. And for internal mycoflora first we used 10 seed and sterilized them in 0.1% aqueous mercuric chloride for 2 or 3 minutes followed by repeated washings with sterilized distilled water. After that seeds were placed in PDA containing petriplates and incubated at 20±2oC for 8 days (Table II).

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Results and Discussion Over the years we have, however made great progress in protecting many of our important plant, crops and our environment from attack by pathogenic fungi. Some important pathogenic fungi have been identified, isolated and pure cultures we made in the lab during the experiment. So many fungal genera found to be associated with the deteriorated samples of wheat variety during storage by standard blotter method and agar plant method (De Tempe, 1953, Musket, 1948). Total samples collected from different places. Highest number of fungi were isolated by agar plate method or followed by standard blotter method. It is evident from table 1 that 9 fungi viz. Aspergillus flavus, A. niger, Aspergillus spp., Alternaria alternara, Rhizopus oryzae, Rhizopus sp., Penicillium spp., Mucor spp., Fusarium spp. were isolated from the external seed mycoflora by blotter method and Aspergillus niger, Alternaria alternate, Rhizopus spp. and Fusarium spp. were isolated from the internal seed myclora by blotter method. The evidence from table 2 is that fungi viz. Aspergillus flavus, A. niger, Alternaria alternate, Rhizopus spp., Mucor spp., Fusarium spp. were isolated from the external seed mycoflora by agar plate method and A. flavus, A. niger, A. alternate, Rhizopus spp. were isolated from the internal seed mycoflora by agar plate method. If we compare the results obtained from two standard methods (Blotter and Agar plate) for isolation of fungal species, it is found that both the methods of isolation are quite effective. By comparing external and internal seed mycoflora it is evident that more fungal species are found associated to the surface of the seeds and if we disinfect the seed surface by any of the methods, the number of pathogens can be reduced, we can minimize the pathogenic mycoflora from our corps by the careful handling of the crop material by pre-


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treatment of the seeds or other sowing material and this will be beneficial, as it will reduce the number of pathogens which are polluting our environment and can reduce the amount of pesticides which we use to kill these pests and pathogens and naturally by careful study of mycoflora development and their control, we will help the mankind and our environment form being more polluted. As a result plant pathologists and other concerned with plant health are facing the tremendous challenge of finding new and innovative ways of controlling fungal diseases without using chemicals for saving out environment. References Anonymous (1976). International rules for seed testing. Seed Sci. & Technol., 4: 1-180. Milton, N.S., Hancock, J.G. (1981). Selected topics in biological control. Ann. Rev. Microbiol. 35: 453-476. Singh, J., Faull J.L. (1982). Antagonism and biological control in; Biocontrol of plant disease vol. II (eds. K.G. Mukerji and Garg) CRC Press, I No. (Bocaraton), 40: 167-176. Singh, V. and Singh, R.N. (2007). Environmental variables in relation to spot blotch intensity and grain yield in wheat (Triticum aestivum) Proc. Nat. Acad. Sci. 77(B): 11. Muskett, A.E. (1948). Techniques for the examination of seed borne fungi. Trans. Brit. Mycol. Soc. 39: 74-83. Tempe, J.De (1953). The blotter method for seed health testing. Proc. Int. Seed Tst Assoc., 21: 133-151.

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Table 1 Seed Mycoflora of Triticum aestivum (wheat) var. WH-896 by Blotter Method External Seed Mycoflora S.No. Fungi isolated

Presence of fungus

Frequency (%)

Relative abundance

1.

Aspergillus flavus

+

50

20

2.

Aspergillus niger

+

40

15

3.

Aspergillus spp.

+

20

10

4.

Alternaria alternate

+

40

10

5.

Rhizopus oryzae

+

40

15

6.

Rhizopus spp.

+

50

05

7.

Mucor spp.

+

30

10

8.

Fusarium spp.

+

40

12

9.

Penicillium spp.

+

20

10

Frequency (%)

Relative abundance

20

12.5

30

21.2

20

12.5

10

8.4

Internal Seed Mycoflora S.No. Fungi isolated

Presence of fungus

1.

Aspergillus flavus

-

2.

Aspergillus niger

+

3.

Aspergillus spp.

-

4.


+

5.

Rhizopus oryzae

-

6.

Rhizopus spp.

+

7.

Mucor spp.

-

8.

Fusarium spp.

+

9.

Penicillium spp.

-


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Table 2 Seed Mycoflora of Triticum aestivum (wheat) var. WH-896 by PDA method External Seed Mycoflora S.No. Fungi isolated

Presence of fungus

Frequency (%)

Relative abundance

1.

Aspergillus flavus

+

40

14.2

2.

Aspergillus niger

+

60

5.25

3.

Aspergillus spp.

+

30

14.2

4.


+

50

18.2

5.

Rhizopus oryzae

+

30

14.2

6.

Rhizopus spp.

+

20

16.2

7.

Mucor spp.

-

8.

Fusarium spp.

+

40

6.2

9.

Penicillium spp.

-

Presence of fungus

Frequency (%)

Relative abundance

Internal Seed Mycoflora S.No. Fungi isolated 1.

Aspergillus flavus

+

20

10.1

2.

Aspergillus niger

+

30

20.2

3.

Aspergillus spp.

-

4.


+

30

18.6

5.

Rhizopus oryzae

+

10

10.1

6.

Rhizopus spp.

-

7.

Mucor spp.

-

8.

Fusarium spp.

+

10

10.1

9.

Penicillium spp.

-

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TSUNAMI OF EMERGING POLLUTENT-“E WASTE” AND TECHNOLOGIES TO OVERCOME THEM N.S. Varandani2 B.H.Shah3 D. J.Desai1 2 3 Prof. Plastics Technology, Prof. Environmental Engineering, Prof. Chemical Engineering, L. D. College of Engineering, Ahmedabad-380015. E-mail:- [email protected] 1

ABSTRACT: According to the Environmental Protection Agency (EPA), Americans alone, discard about 2 million tons of used electronics each year. This figure doesn't include the 128 million cell phones they toss every 12 months.

Ten years ago, the average life span of a computer was six years. Now it's two. Hence, by 2010, more than 70 million computers per year are projected to be sold annually in the United States with nearly half a million obsolete computers containing toxic materials projected to require management each year. Similar data studied for Canada, Europe, China and India revels that the electronics waste, through out the world is increasing at much faster rate.

Emerging Contaminants are suspected of causing adverse effects in humans and wildlife. Thus certain chemicals that have been recently detected in the environment are not new pollutants but are newly identified due to improved analytical techniques, causing acute or chronic toxicity and other adverse effects. Thus the relevance of emerging and new compounds and their impact on soil, water, and ecosystems are presented in this paper. If handled correctly, electronic waste presents a valuable source of secondary raw materials. Hence examples of few of the key new technologies included in this paper are Aerobic and Anaerobic Biological Treatment, Mechanical and Biological Treatment and Other Advanced Thermal Treatment such as Autoclaving. Keywords: e waste, emerging pollutants, Integrated Approch.

1. INTRODUCTION The benefits of the information revolution are clear for all to see. Devices such as PCs, faxes, mobile phones, music players and a host of others open up exciting possibilities for individuals and businesses alike. Yet there is a downside to this digital era - the growing mountain of electronic waste (e-waste). The waste from electronic devices contains hazardous ingredients classified by the Environmental Protection Agency (EPA) as "Permanent Biological Toxins," including Lead, Cadmium, Barium, Beryllium, Mercury and Brominated Flame Retardants. When burned, many release dioxins. In landfills, they seep into the groundwater and never break down. According to the EPA, Americans discard about 2 million tons of used electronics each year. That figure doesn't include the 128 million cell phones we toss every 12 months. By 2010, more than 70 million computers per year are projected to be sold annually in the United States, with nearly half a million obsolete computers containing toxic materials projected to require management each year in Washington state alone. By next year, obsolete computers amassed in the U.S. will number 500 million, according to the U.S. National Safety Council. Between now and 2009, more than 550 million computers and analog TVs — in addition to all of our portable electronic toys — will be thrown away in the continental United States.


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Many everyday consumer items now contain electronic parts. Every year an estimated 1 million tonnes of Waste Electronic and Electrical Equipments (WEEE) are discarded by householders and commercial groups in the UK alone. Dealing with this waste is an important issue as electronic goods are becoming increasingly short lived, and so ever increasing quantities of obsolete and broken equipment are thrown away. Electronic and electrical equipment makes up on average 4% of European municipal waste, and is growing three times faster than any other municipal waste stream. Electrical waste includes digital watches, fridges, TVs, computers and toys. Not only is this waste stream disparate in function but in addition the materials of which they are comprised vary considerably. For example an average TV contains 6% metal and 50% glass whereas a cooker is 89% metal and only 6% glass. Other materials used include plastics, ceramics and precious metals. The complex array of product types and materials make waste electrical and electronic equipment difficult to manage. The main component of waste electronic equipment is large household appliances known as white goods, which make up 43% of the total. The next largest component is IT equipment which accounts for 39%. Much of this is made up of computers, which rapidly become obsolete. Televisions also represent a large proportion, with an estimated 2 million TV sets being discarded each year. Current tonnages of WEEE collected and recycled in the UK is given in Table:1 Table:1 Current Tonnages of WEEE Collected and Recycled in the UK Type Raisings Collected % Recycled Telecom 8,000 4,000 50 Video / Sound 72,000 3,200 4 IT 357,000 94,600 26 Large Household Appliances 392,000 345,300 88

2. CREATION OF ENVIRONMENTAL PROBLEMS The disposal of electronic and electrical appliances in landfill sites or through incineration creates a number of environmental problems.

Loss of Resources When obsolete materials are not recycled, raw materials have to be processed to make new products. This represents a significant loss of resources as the energy, transport and environmental damage caused by these processes is large. The discarded computers and a hip of wires is shown in the Fig:1 In 1998 it was estimated that of the 6 million tonnes of electrical equipment waste arising in Europe the potential loss of resources was 2.4 million Tonnes of ferrous metal 1.2 million Tonnes of plastic 652,000 Tonnes of copper 336,000 Tonnes of aluminum 336,000 Tonnes of glass

608


Figure: 1 The Discarded Computers and a Hip of Wires. This was in addition to the loss of heavy metals, lead, mercury, flame retardants and more. The production of these raw materials and the goods made from them entails environmental damage through mining, transport, water and energy use. For example, according to a recent UN study, the manufacture of a new computer and monitor uses 240 kg of fossil fuels, 22 kg of chemicals and 1500 litres of water. Similar quantities of materials are used in the manufacture of an average car. The nature of many of these materials is such that they can be recycled with relative ease preventing the waste associated with producing new raw materials.

Damage to the Environment and Health Caused by Hazardous Materials Another major problem is the toxic nature of many of the substances, including arsenic, bromine, cadmium, halogenated flame retardant, hydro chlorofluorocarbons (HCFCs), lead, mercury and PCBs. The estimated number of fridges and freezers being disposed in the UK is 3 million units annually. These units contain gases such as chlorofluorocarbons (CFCs) and hydro chloro fluoro carbons (HCFCs) used for the coolant and insulation. Both CFCs and HCFCs are greenhouse gases which when emitted into the atmosphere, contribute to climate change. Fluorescent lighting contains potentially harmful substances such as highly toxic heavy metals, in particular mercury, cadmium and lead. If they enter the body, these substances can cause damage to the liver, kidneys and the brain. Mercury is also a neurotoxin and has the potential to build up in the food chain. The mercury content is the main concern with fluorescent lighting. A four-foot long fluorescent tube may contain over 30 milligrams of mercury. The EC permissible limit for mercury in drinking water is 1 part per billion, equivalent to 0.001mg a litre. According to a survey by consultancy ERA Technology, electrical equipment manufacturers are reacting "very slowly" to a legal requirement to remove lead from their products by July 2006, almost 2/3 of companies have no planned date for completing the switch to lead-free technologies. Finding suitable landfill sites is also becoming an increasing problem, particularly in the South East, where large quantities of electronic waste arise. New rules in force from July 2004 call for the cessation of co-disposal of hazardous and non-hazardous wastes. In the South and South East of England there are currently no landfill sites able to accept hazardous waste.

3. METHODS SUGGESTED TO OVERCOME THESE ISSUES When buying new electronic or electrical items, choose ones which are durable, and which can be upgraded in the future if possible. Consider first if a current item of equipment can be upgraded, rather than being completely replaced.


609

If an appliance has stopped working, before discarding it, see if it can be repaired. In some areas there are projects which take household furniture and basic electrical equipment such as cookers and fridges to pass on to low-income households. Rather than put unusable small appliances in the bin, take them to your local civic amenity site where they can be added to other scrap for recycling. If your workplace has computers, mobile phones or toner cartridges which are no longer needed, these can be donated. Re-Use However good your intentions, you should NEVER leave your old computer equipment in an alley, exposing it to the neighbor hood kids and the elements. Give it to a friend or a reputable reuse organisation like Computers for Schools. Repair or replace parts rather than entire systems whenever possible. Consider buying refurbished systems from reputable organisations instead of new.

Reduce Resist the pressures of planned obsolescence and the temptation to prematurely upgrade. Think about what your computer needs really are. Consider sustainable software like Ubuntu Linux that extends the lifespan of your computer. Even if you are running a proprietary operating system like Windows or Mac, you can start the change now by choosing free programs, like the Firefox web browser, Open Office productivity suite or others. For more alternatives, see webi.org or the Free Software Foundation Try to use a multi-use product, instead of many items that have one function.

Recycle Before you give up your hardware to an organisation, do your research. Statistically speaking, it will probably be shipped overseas and dumped or burned, unless you do your homework. But good solutions are out there. Beware that your computer can pass through many hands, and organisations may be unaware, or mislead you intentionally. Don't be fooled by pretty websites. Both recyclers and nonprofit re-use organisations can promise anything they like. Ask lots of questions, and don't be afraid to ask for verification. What is a company's environmental/business record like? Where do they send their materials? How can they prove it? Are there any environmental organisations that will vouch for them? Can you visit inside their recycling facility? If you are not satisfied with their answers, walk away. Don't let your computer be another poor statistic.

4. AN INTEGRATED APPROACH TO ELECTRONIC WASTE RECYCLING: WEEE has been identified as one of the fastest growing sources of waste in the EU, and is estimated to be increasing by 16-28 per cent every five years. Within each sector a complex set of heterogeneous secondary wastes is created. Although treatment requirements are complicated, the sources from any one sector possess many common characteristics. However, there exist huge variations in the nature of electronic wastes between sectors, and treatment regimes appropriate for one cannot be readily transferred to another. A very large number of treatment technologies are available, both established and emerging, that singly and in combination could address the specific needs of each sector. However, no single set of treatment methods can be applied universally. A range of techniques is currently applied for retrieving components and materials from WEEE. The essential features of these systems generally conform to a scheme of: sorting/disassembly; size

610


reduction; separation. The ability of the UK to competitively address these issues will hinge on the further development of technologies relevant to recycling. These will fall into three areas: 1 2 3

Technologies that can enhance existing methods; Technologies that are entirely new to the field and introduce new capabilities for recovery of materials and components; and Technologies that are at the research stage and have not yet been implemented in any field, but demonstrate relevant possibilities.

A Network Recycling study concluded that it was not practical to have a skip for each of the ten different categories of WEEE, and recommended simplification of the ten WEEE categories into five covering: Data compiled in previous studies on arising of WEEE, expressed as weight and units for the ten categories, used sales data from 2003 as the starting point. Information was obtained from manufacturers, retailers, trade associations and market research organisations. The studies estimated that 939,000 tonnes of domestic equipment were discarded in the UK in 2003. This comprised 93 million items of equipment. Table: 2 show the arising of domestic WEEE in the UK in 2003. Table: 2 Arising of domestic WEEE in the UK in 2003 Categories of domestic WEEE Tonnage % discarded (K Tonnes) Large house hold appliances 644 69 Small house hold appliances 80 08 IT/Telecoms Equipments 68 07 Consumer Equipments 120 13 Tools 23 02 Toys, leisure and sports Equipments 02 Zn>Cr except for Red Soil and Red Soil + 1% Cement. (Tanit, Surapon, Nanthanit, 2009). The adsorption capacity of Sodium and Potassium was better with 3% cement content. Highly charged cations tend to be held more tightly than cations with less charge and secondly cations with a small hydrated radius are bound more tightly and are less likely to be removed from the exchange complex. The combined influence of these can be summarized by the lysotropic series Al3+ > Ca2+ > Mg2+ > K+ > Na+ > H+. The adsorption rankings for Sodium and Potassium were K>Na, which confirms with earlier work. (Mohammed .S.A.S, Maya Naik, et al, 2009) Freundlich Isotherm The Freundlich parameters shown in table 2 represent the batch test results with the metal retention as a function of the initial metal concentration. This is used to model adsorption on heterogeneous surfaces and multilayer sorption. The Freundlich isotherm is linear if 1/n = 1 and as 1/n decreases the isotherm becomes non linear. The variation was linear for both Langmuir and Freundlich. The goodness of fit varied between 0.9884 to 0.9058 for Langmuir and for Freundlich it varied between 1 to 0.9096. The goodness of fit varied between 0.9884 to 0.9058 for Langmuir and for Freundlich it varied between 1 to 0.9096, which suggests both isotherm models fit very well. Freundlich adsorption constant varied between 28.765 mg/g to 21.03 mg/g. the adsorption intensity 1/n varied between 0.115 to 0.98.Higher values of Kf and 1/n indicate that greater metal uptake is occurring as confirmed by (Cynthia.A.Coles. Raymond.N.Yong., 2006).

672


pH dependent adsorption of Copper Red Soil RD + 3 % Lime RD + 6 % Lime Rd + 1 % Cement

3.5

RD + Fly Ash

35 30 25 20 15 10 5 0

RD RD + 3% Lime RD + 6% Lime RD + 1 % Cement RD + 3 % Cement 4

1.4

4.7

7.0

4E +0 0 2E +0 7.0 0 8E -0 1

RD + 3 % Cement

14 8E +0 0 2E +0 0

Sorption Coefficient in Milli Moles / gram of Soil

1200 1000 800 600 400 200 0

Amount Adsorbed in Milli moles of copper/gram of Soil

Sorption behaviour of Copper

6

8

Concentrati on in Mi lli Mole s/ litre

10

RD + Fly Ash

12

pH

Figure. 1 – Sorption Behaviour of Copper for Different Mixtures.

Figure. 6 – pH Dependent Adsorption of Copper. RD

pH depended adsorption of Zinc

Sorption Coefficient in Milli Moles /gram of Soil

250 200

RD + 3 % Cement RD + Fly ash

150 100 50 0 13.7

6.88E+00 4.59E+00 3.44E+00 1.38E+00 6.88E-01

RD + 3% Lime Amount Adsorbed in millimoles/gram of soil

RD RD + 3 % Lime RD + 6 % Lime RD + 1 % Cement

Sorption Behaviour of Zinc

35 30

RD + 6 % Lime

25 20 15

RD + 1% Cement

10 5 0

4

6

8

Figure. 2 – Sorption Behaviour of Zinc for Different Mixtures.

pH dependent adsorption of Chromium

2. 88 E+ 00 2. 16 E+ 00 8. 65 E01 4. 33 E01

0

Red Soil + 3 % Cement Red + Fly Ash

Amount Adsorbed in Milli Moles / gram of soil

Red Soil + 1 % cement

0

RD + Fly Ash

Red Soil + Cr

Red Soil + 6 % Lime

4. 33 E+ 0

RD + 3% Cement

12

Figure. 7 – pH Dependent Adsorption of Zinc.

Red Soil + 3% Lime

140 120 100 80 60 40 20 0 8. 65 E+ 0

Sorption coefficient in Milli Moles / gram of Soil

S orption Behaviour of Chromium

10

pH

Concentration in Milli Moles / litre

20 RD

15

RD + 3 % Lime

10

RD + 6 % Lime

5

Rd + 1% Cement

0 4

6

8

C once ntration in Milli Mole s / Litre of Contaminant

10

RD + 3% Cement

12

RD + Flyash

pH

Figure. 3 – Sorption Behaviour of Chromium VI for Different Mixtures.

Figure. 8 – pH Dependent Adsorption of Chromium (VI).

Sorption Be haviour of Sodium

RD

60

150

RD + Fly Ash + Sodium

100

RD + 3% Cement + Sodium

50

RD + 1% Cement + Sodium

0 0.039 1.96E- 1.30E- 9.78E- 3.91E- 1.96E02 02 03 03 03 C once ntration in Milli Mole s /Litre of C ontaminant

RD + 6%Lime + Sodium

Amount Adsorbed in Millimoles/gram of Soil

Sorption Coefficient in Milli moles / gram of soil

pH Dependent Behaviour of Sodium 200

RD + 3% Lime + Sodium

50

RD + 3% Lime

40 RD + 6% Lime

30 20

RD + 1% Cement

10 RD + 3% Cement

0 4

6

10

12 50% RD + 50 % Flyash

pH

RD + Sodium

Figure. 4 – Sorption Behaviour of Sodium for Different Mixtures.

8

Figure. 9 – pH Dependent Adsorption of Sodium.

Sorption Be haviour of Potassium RD + Fly Ash + Potassium 12 0

80 60 40 20 0 0 .0 2 3 1.15E- 7.6 7E- 5.75E2. 02 03 03 3 0 E03

1.15E03

RD + Potassium

C o nc e nt ra t io n in M illi M o le s / lit re o f c o nt a mina nt

Figure. 5 – Sorption Behaviour of Potassium for Different Mixtures

pH dependent behaviour of Potassium RD

30 Amount Adsorbed in Millimoles/gram of Soil

RD + 3% Cement + Potassium RD + 1% Cement + Potassium RD + 6% lime + Potassium RD +3% lime + Potassium

10 0

25

RD + 3 % Lime

20 RD + 6 % Lime

15 10

RD + 1% Cement

5 0

RD + 3% Cement 4

6

8

pH

10

12 50 % RD + 50% Flyash

Figure. 10 – pH Dependent Adsorption of Potassium.

pH dependent Sorption In order to investigate the effect of pH on adsorption to different mixtures, metal solutions of 100ppm and an S/L ratio of 1:20 was used at pH ranging from 4 to 12. Batch adsorption tests were done according to ASTMD 4646 – 87(Reapproved 2001). The highest removal efficiency was obtained at pH range of 6 to 8. At lower pH the adsorption efficiency decreases. The effect of pH changes due to the type of adsorbent used and its behaviour in solution and the type of ions adsorbed. From the figure 6, 7, 8, 9 and 10 it can be observed that as the pH increases, adsorption efficiency also increases particularly at the near neutral pH for copper the probable reason might be for alkaline mixtures specific adsorption of copper onto CaCO3 is likely to take place in waste-soil


673

systems and precipitation may be an important mechanism of retention. (McBride, M. B.; D. R. Bouldin. 1984) For Zinc from the figure 7 it can be observed that the adsorption efficiency is decreasing at pH of 12, also at pH of 4 it shows an increase, probably this trend is shown due to some experimental errors. But for red soil and fly ash the maximum adsorption takes place at a pH of 7 the probable reasons are in soil lime system the pH of the system increases immediately due to this there is a possibility of formation of ZnOH + species and also to some extent precipitation of Zinc onto the surface of the soil. The ZnOH + species get adsorbed onto the soil surface along with Zinc ions, in addition to zinc retention through ion exchange and adsorption mechanism. This leads to an increase in the total capacity of soil to retain more amount of Zinc. (Kurdi. F.; H. E. Doner. , 1983). In a Soil Fly Ash system the adsorption was good, reason may be Cr 6+ gets chemically included in cementious compounds of Fly Ash. (Dimitris Dermatas et al, 2003) Also there is lot of activity taking place continuously in the form of redox reactions under certain conditions Cr 6+ gets converted into a stable Cr3+ but again it gets reversed to Cr 6+ . Hence it becomes difficult to stabilize Cr 6+. (Grove, J. H; B. G. Ellis. 1980).The adsorption increases with decreasing pH due to protonation of the hydroxyl groups, this reaction can be described as a surface complexation reaction between the Cr 6+ species and the surface hydroxyl sites.(Bradl, 2004)At low pH H+ ions compete for the available adsorption sites; this might be the probable reason for low retention of K+ and Na + ions at low pH conditions. (Mohammed .S.A.S, Maya Naik, et al, 2009). Table 1 - Comparative Metal Adsorption Capacities. Sl No 1. 2. 3. 4. 4. 5. 6. 7. 8. 9

Adsorption Cu Adsorption Capacity Zn Adsorption Capacity Cr Adsorption Capacity Na Adsorption Capacity K Adsorption Capacity Adsorption onto Red Soil Adsorption onto Red Soil + 3% Lime Adsorption onto Red Soil + 6% Lime Adsorption onto Red Soil + 1% Cement Adsorption onto Red Soil + 3% Cement Adsorption onto Red Soil +50 % Fly Ash

Ranking RD3C>RD3L>5RD5FA>RD6L>RD>RD1C. RD3L>RD3C>RD>RD1C>5RD5FA>RD6L. 5RD5FA>RD>RD1C>RD3L>RD6L>RD3C. RD3C>RD1C>RD>5RD5FA>RD3L>RD6L. RD3C>RD1C>RD>5RD5FA>RD3L>RD6L. Zn>Cu>Cr, K>Na Cu>Zn>Cr, K>Na Cu=Zn>Cr, K>Na Zn>Cu>Cr, K>Na Cu>Zn>Cr, K>Na Cu>Zn>Cr, K>Na

Abbrevations :- RD-Red soil, RD3L-Red Soil+3%Lime, RD6L-Redsoil+6% Lime, RD1C-Redsoil + 1% Cement, RD3C- RedSoil+3% Cement, 5RD5FA-50%Red Soil+50%Flyash.

Table 2 - Isotherm parameters of Metals in different Adsorbates. Metals

Freundlich Isotherm

Adsorbate

Sl No

Kf mg/g

n (Adsorption intensity)

Langmuir Isotherm R2

Vm mg/g

K

R2

(Monolayer Adsorption Capacity)

1.

Copper

Red Soil Red Soil + 3 Lime Red Soil + 6 Lime Red Soil + 1 Cement Red Soil + 3 Cement 50% Red Soil 50% Fly Ash

21.03

1.05

0.9248

57.21

0.07

0.9535

%

20.91

5.67

0.9144

98.62

0.12

0.9058

%

21.21

4.8

0.9103

74.99

0.15

0.9243

%

21.39

8.66

0.9124

49.61

0.11

0.9076

%

20.63

7.70

0.9480

104.02

0.06

0.9047

+

20.76

1.02

0.9096

96.06

0.08

0.9138

674

2.

3.

4.

5.

International Conference on Emerging Technologies in Environmental Science and Engineering October 26–28, 2009 Aligarh Muslim University, Aligarh, India Zinc

Red Soil

21.35

4.25

0.9179

73.72

1.23

0.9568

%

20.97

4.74

0.9104

75.00

0.14

0.9632

%

20.85

6.06

0.9382

48.20

0.09

0.9130

%

21.55

6.18

0.9130

55.45

0.10

0.9458

%

20.87

7.40

0.9797

73.80

0.11

0.9606

+

21.92

5.10

0.9436

54.80

0.14

0.9286

Chromium

Red Soil + 3 Lime Red Soil + 6 Lime Red Soil + 1 Cement Red Soil + 3 Cement 50% Red Soil 50% Fly Ash Red Soil

25.84

1.24

0.9370

27.96

1.81

0.9844

%

22.01

1.02

0.9858

23.59

0.43

0.9487

%

20.25

1.60

0.9442

15.24

0.16

0.9884

%

28.76

6.26

1.0000

19.49

0.14

0.9337

%

26.95

1.27

0.9006

14.38

0.16

0.9302

+

27.16

6.20

1.0000

71.68

0.16

0.9884

Sodium


23.06

2.63

0.9914

43.34

0.12

0.9829

%

17.21

1.32

0.9732

35.05

0.32

0.9305

%

23.29

9.07

0.9380

30.76

0.33

0.9831

%

22.75

2.44

0.9245

50.32

0.20

0.9800

%

21.55

3.16

0.9259

66.37

0.50

0.9270

+

23.26

6.02

0.9870

35.99

0.13

0.9661

Potassium


23.40

2.70

0.9820

50.54

0.43

0.9709

Red Soil + 3 Lime Red Soil + 6 Lime Red Soil + 1 Cement Red Soil + 3 Cement 50% Red Soil 50% Fly Ash

%

23.38

3.69

0.9791

40.45

0.29

0.8233

%

22.98

3.83

0.9941

33.53

0.44

0.9031

%

21.95

2.06

0.9113

67.37

0.67

0.9021

%

20.93

2.05

0.9361

77.39

0.43

0.9126

+

22.98

2.75

0.9430

45.61

0.54

0.9478

Morphological observations by SEM and EDS SEM observations shown in figure 11 reveals that the large fractions of Fly ash consists of either empty hollow spheres known as cenospheres or hollow spheres packed with large number of smaller spheres known as plerospheres. At the higher size range, irregular porous sponge like particles were detected. Microcrystals were also observed on surface of large cenospheres as well as on the smaller entrapped spheres. The irregular porous sponge like particle crystals seems to be of aluminosilicate. This is widely used as an adsorbent for removal of metals. The main crystalline material of zeolite is aluminosilicate indicating possibility of using Red soil and Fly Ash as an adsorbent for removing metal ions. Energy dispersive spectroscope (EDS) analysis indicates the presence of Mullite, quartz and the typical plerospheres containing Si, Al, Ca, Na and Fe. (Young Sook, Shim etal 2003).

Figure. 11 - SEM images of 50% Red Soil + 50% Fly Ash mixture, spiked with hexavalent Chromium.


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4. CONCLUSIONS 1. 2. 3. 4. 5. 6. 7. 8.

The Red Soil along with admixtures has been found to retain heavy metals and alkali metals effectively. For different dilution ratios, it was found that adsorption efficiency decreases with increasing dilution ratio. Sorption coefficient (Amount Adsorbed) increased with decreasing concentration. Emperical Adsorption Models like Langmuir and Freundlich were applied for the experimental data and both were found to be varying linearly. Monolayer sorption capacity was obtained using Langmuir isotherm, which was used to arrive at adsorption rankings for different mixtures. The goodness of fit varied between 0.9884 to 0.9058 for Langmuir and for Freundlich it varied between 1 to 0.9096, which suggests both isotherm models fit very well. Constant pH batch adsorption studies were carried out at pH of 4, 6, 8, 10, and 12. It was found that adsorption is pH dependent, maximum adsorption takes place at a pH range of 6 to 8 for all elements, except for Hexavalent Chromium. Confirmatory tests were done by taking scanning electron microscopy (SEM) images and Electron Dispersive spectroscopy (EDS). The irregular porous sponge like particle crystals seems to be of aluminosilicate. This is widely used as an adsorbent for removal of metals. The main crystalline material of zeolite is aluminosilicate indicating possibility of using Red soil and Fly Ash as an adsorbent for removing metal ions. Energy dispersive spectroscope (EDS) analysis indicates the presence of Mullite, quartz and the typical plerospheres containing Si, Al, Ca, Na and Fe.

5. ACKNOWLEDGEMENTS Sincere thanks for their encouragement to Administrator Mr. Abdul Hameed SA, Principal Dr. Chaitanya Kumar M.V., HOD of Engineering Chemistry, Prof. Sanaulla PF of HKBK College of Engineering, Bangalore5600 45. We are highly indebted for the Scholastic help rendered by Prof. Dr. PV Sivapullaiah, Prof of Civil Engineering, and Mr. Mughal Arif Ali Baig, Research Scholar, Indian Institute of Science (IISc) Bangalore 560012. 6. REFERENCES ASTM(2004)., International American Standard Testing Method D3987 – 85 (reapproved 2004), Standard test Method for shake extraction of solid waste with water, USA, p1 – 5. ASTM. (2001), International American Standard Testing Method D4646 – 87 (reapproved 2001), Standard test Method for 24-h Batch – Type Measurement of Contaminant Sorption by Soils and Sediments, USA, p1 – 5 . Cynthia.A.Coles. Raymond.N.Yong., (2006), Use of equilibrium and initial metal concentrations in determining Freundlich isotherms for soils and sediments. Engineering Geology.,85, p19-25. Dimitris dermatas. Xiaoguang Meng. (2003). Utilization of fly ash for stabilization/ solidification of Heavy metal contaminated soils, Engineering Geology., 70, p377-394. Grove, J. H ; B. G. Ellis. (1980), Extractable chromium as related to soil pH and applied chromium. Soil Sci. Soc. Am. J. 44, p238-242. Heike.B.Bradl. (2004). Adsorption of Heavy metal ions on soils and soils constituents., Journal of Colloid and Interface Science., 277, p1 18. Jeffery GH, Bassett S, Mendham J, (1997). Vogel’s Text Book of Quantitative Chemical Analysis, 5th Edition, EBS Publishers. Joan E McLean., Bert E, (1992).Behaviour of Metals in Soils, Report no 540 S- 92-018, Environmental Protection Agency, USA. Kurdi, F.; H. E. Doner. (1983). Zinc and copper sorption an interaction in soils. Soil Sci. Soc. Am. J. 47, p873-876. Mohammed.S.A.S, MayaNaik. Syed Tanveeruddin., (2009). Influence of additives on the retention of metal ions in a soil of Bangalore, India. Ambiente & Agua – An Interdisciplinary Journal of Applied Science., 4(1), p20 – 36. Morrerra.M.T. Echeverria.J.C., Mazkiaran.C. Garrido.J.J., (2001). Isotherms and sequential extraction procedures for evaluating sorption and distribution of heavy metals in soils. Environmental Pollution., 13, p135 – 144. Sevil veli. Bilge Alyuz.,(2007). Adsorption of copper and zinc from aqueous solutions by using natural clay. Journal of Hazardous Materials., 149, p226 – 233. Tanit, Surapon, Nanthanit, (2009)., Potential use of Lateritic and marine clay soils as Landfill liners to retain heavy metals, Journal of Waste Management, 29, p117 – 127. Young Sook Shim, Young Keum Kim, (2003)., The adsorption characteristics of Heavy Metals by various particle sizes of MSWI bottom ash, Journal of Waste Management, 23, p851 – 857.

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USE OF WASTE HUMAN HAIR AS FIBRE REINFORCEMENT IN CONCRETE Shakeel Ahmad1*, Farrukh Ghani1, J. N. Akhtar2 and M. Hasan3 1 2 3

Dept. of Civil Engineering, Aligarh Muslim University, Aligarh 202002, India

CES, University Polytechnic Aligarh Muslim University, Aligarh 202002, India

P.G. Student, Dept. of Civil Engineering, Aligarh Muslim University, Aligarh 202002, India

Abstract Reinforcement by fibres can offer a convenient, practical and economical method of overcoming many deficiencies. Hair fibre an alternative non degradable fibre is available in abundance which creates environmental problem similar to Fly Ash (FA). To see the effect of human hair fibre on compressive, crushing strength and cracking control to economise concrete, and reduction of environmental problems, the present study has been undertaken. Experiments were conducted on concrete prisms with varying percentage of Human Hair Fibre (HHF) i.e. 0%, 1%, 1.5%, 2% and 2.5% by weight of cement. Next, in the plain concrete, cement has been replaced with10% fly ash by weight and same HHF percentage variations were used to make Hair Fibre Reinforced Fly Ash Concrete (HFRFAC). After wards, in HFRFAC 6% brick powder was added further to make Hair Fibre Reinforced Fly Ash Brick Powder Concrete (HFRFABC). Further, the HFRFAC was mixed 1.5% lime powder to make Hair Fibre Reinforced Fly Ash Lime Powder Concrete (HFRFALC). For each combination, three cubes were tested for their properties. The result shows that there is encouragable enhancement in its mechanical properties investigated with the addition of human hair fibres. Maximum strength has been obtained in the lime combination case with 2% HHF addition. Keywords: CC, HFRFAC, HFRFABC, HFRFALC, human hair fibre, Fly ash, Lime *

Corresponding author Email: [email protected]. Mobile No: +91-9412877550

INTRODUCTION The most important issue concerning a cement-based matrix is its inherent brittleness. Fibre reinforced composites provide a solution to improve the compressive, tensile, crushing and impact strength, control the cracking and the mode of failure by means of post cracking ductility


677

and change the flow characteristics of material in the fresh state. Reinforcement by fibres can offer a convenient, practical and economical method of overcoming many deficiencies, particularly in application where convention reinforcement by steel bars carefully positioned to obtain maximum benefit from the reinforcement is unsuitable. Furthermore, the provision of small size reinforcement as an integral part of the fresh concrete mass can be advantageous in terms of fabrication of products and components.

Sekar [1] state that the behavioral efficiency of the composite material is far superior to that of plain concrete and many other construction materials of equal cost. Due to this benefit, the use of Fibre Reinforced Concrete (FRC) has steadily increased during the last two decades. It is also rapidly gaining acceptance as suitable materials for repairing, rehabilitation and renovation of concrete structures. The amount of Portland cement in a concrete mix and replacing it with fly ash, the same strength could be achieved while the internal temperature of the concrete could be greatly reduced. If this material, along with other techniques had not been employed it is estimated that it would have taken approximately 150 years for the Hoover Dam face to cool to ambient temperature [2]. It is best to have as much volume as possible filled with strong, durable aggregate particles with enough paste (comprised of as much C-S-H and as little lime as possible) to coat every particle. Also, voids should not be present in the paste unless they are specifically provided as microscopic entrained air bubbles to provide durability in freeze-thaw environments [3]. According to Chan [4] the transformation from a brittle to a ductile type of material would increase substantially the energy absorption characteristics of the fibre composite and its ability to withstand repeatedly applied shock or impact loading. Fly ash affects the plastic properties of concrete by improving workability, reducing water demand, reducing segregation and bleeding, and reducing corrosion of reinforced steel, Akhtar [5]. Siddique [6] states that the addition of san fibres reduces the workability, having insignificant effect to compressive strength, increases the splitting tensile strength, flexural strength and tremendously enhanced the impact strength of fly ash concrete as the percentage of fibres increased. McCarthy et al. [7] studied to examine the use of high levels of low-lime fly ash (high volume FA) as a cement component in concrete. The results indicate that FA levels up to 45% by mass can be combined with Portland cement to produce the range of practical concrete design strengths. Gesoglu et.al [8] concluded that the surface treatment with water glass provided a marked increase in the aggregate strength and a reduction in the water absorption. The light weight concrete (LWCs)

678


made with such light weight aggregates (LWAs) had a compressive strength of as high as 60 MPa. Yazıcı [9] test results indicate that self-compacting concrete (SCC) could be obtained with a high-volume Fly Ash (FA). Ten percent Silica Fume (SF) additions to the system positively affected both the fresh and hardened properties of high-performance high-volume FA SCC. Although there is a little cement content, these mixtures have good mechanical properties, freeze–thaw and chloride penetration resistance. EXPERIMENTAL PROGRAMME Materials Used The Fly ash collected through electrostatic precipitators of N.T.P.C, Dadri (U.P.) India conforming to I.S: 3812 [10]. Crushed stone aggregates of 20 mm and 10 mm maximum sizes were used as coarse aggregates as per I.S: 383 [11] and locally available coarse sand was used as fine aggregate. The cement used was Ordinary Portland Cement (OPC) of 43 grade conforming to I.S 8112 [12]. The physical properties of materials are given in Table 5 and the results of elemental analysis of fly ash along with their range for different materials are given in Table 3. The different properties of Sand and aggregate are shown in Table1. Table1 Water absorption, specific gravity and fineness modulus of Aggregates Aggregate

30 min Water Absorption

Specific Gravity

Fineness modulus

Sand

0.420 %

2.60

2.875

10 mm

0.385 %

2.63

3.588

20 mm

0.390 %

2.64

3.765

PREPARATION OF SPECIMENS To determine the compressive strength, cubes of 150 mm size were prepared. The concrete mix was designed to get the compressive strength of 20 MPa. The water cement ratio of 0.5 was adopted corresponding to the target mean strength according to I.S 456 [13]. The mix proportion for each test series is given in Table 4. Three cubes of each series were prepared for determining compressive strength. The material was weighed, dried and placed on a level platform, hair fibres were sprinkled gently on it and was mixed using mixer. The measured amount of water was added to the dry mix. Care was taken to prevent agglomeration of fibres and to ensure their uniform


679

distribution as far as possible. The concrete was poured in three equal layers in the moulds of the cube, also properly placed and compacted. The specimens were immersed for curing in potable water tank. Figures 4 to 6 show human hair fibres, empty moulds, and specimen under curing. Table 2 Properties of Cement S.NO Properties 01

02

03

04

05

06

Requirement as per Observed Values IS: 8112-1989

Setting Time (min) (a) Initial (b) Final Compressive Strength of 1:3 Cement sand mortar(N/mm2) (a) 3 days (b) 7 days Tensile Strength of 1:3 Cement Sand mortar (N/mm2) (a) 3 days (b) 7 days Compressive Strength of 1:3 Cement sand mortar with 2% Hair fibre (N/mm2) (a) 3 days (b) 7 days Tensile Strength of 1:3 Cement Sand mortar with 2% Hair fibre (N/mm2) (a) 3 days (b) 7 days Percentage of water requirement for normal Consistency (%)

Table 3 Properties of Fly ash used Components Present Fly ash Class C

30 600

27 345

22.5 32.4

20.50 28.00

-2.5

1.85 2.25

-

19.50 29.50

_ _

1.80 2.35

_

28

Components

Present Fly ash Class C

SiO2

46-60

MgO

0.2-4

Al2O3

21-28

SO3

0-0.4

Fe2O3

05-09

Na2O

0-0.3

CaO

0.5-6

K 2O

0-0.2

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Table 4 Mix Proportion of Different Cubes Mix Proportion Cube

CA Cement

F-A

FA 10 mm

Designation ( kg

m3 )

( kg

m3 ) ( kg

m

3

powder

20 mm )

Hair Fibre

Brick

( kg

m

3

( kg

m3 )

content

%

(%)

m3 )

( kg

)

Lime

0.00 CC 0.00 HFRFAC 1.00 HFRFAC 1.50 HFRFAC 2.00 HFRFAC

403.20 362.88 362.88 362.88 362.88

672.0 672.0 672.0 672.0 672.0

470.0 470.0 470.0 470.0 470.0

873.6 873.6 873.6 873.6 873.6

30.16 30.16 30.16 30.16

-

-

0.00 0.00 1.00 1.50 2.00

2.50 HFRFAC

362.88

672.0

470.0

873.6

30.16

-

-

2.50

0.00HFRFABC

338.69

672.0

470.0

873.6

30.16

-

0.00

1.00HFRFABC

338.69

672.0

470.0

873.6

30.16

21.91 21.91

-

1.00

1.50HFRFABC

338.69

672.0

470.0

873.6

30.16

21.91

-

1.50

2.00HFRFABC

338.69

672.0

470.0

873.6

30.16

21.91

-

2.00

2.50HFRFABC

338.69

672.0

470.0

873.6

30.16

21.91

-

2.50

0.00HFRFALC

333.61

672.0

470.0

873.6

30.16

1.5

0.00

1.00HFRFALC

333.61

672.0

470.0

873.6

30.16

21.91 21.91

1.5

1.00

1.50HFRFALC

333.61

672.0

470.0

873.6

30.16

21.91

1.5

1.50

2.00HFRFALC

333.61

672.0

470.0

873.6

30.16

21.91

1.5

2.00

2.50HFRFALC

333.61

672.0

470.0

873.6

30.16

21.91

1.5

2.50

* FA = Fine Aggregate, CA = Coarse Aggregate, F-A = Fly Ash, CC = Cement Concrete; HFRFAC = Human Fibre Reinforced Fly Ash Concrete; HFRFABC = Human Fibre Reinforced Fly Ash Brick powder Concrete; HFRFALC = Human Fibre Reinforced Fly Ash Lime Concrete.

COMPRESSION TESTING OF CUBES The cubes were tested in compression after proper curing for 28 days as per IS code specifications. One of the specimens under test is shown in Fig.1. The stress-strain curves of different test series of CC, HFRFAC, HFRFABC and HFRFALC have been plotted and shown in Figs. 25-28 respectively. Each plotted stress-strain curve is the average of the three cube test results. The initial tangent modulus from the stress strain curves has been taken as the modulus of elasticity. The variations of Poisson’s ratio compressive strength and crushing strain with the variation in the percentage of fibres have been shown in Figs. 24, 29 and 30 respectively. It is observed from Figs. 25-28 that all of the stress-strain curves are parabolic with almost linear upto 0.3 f c' , where, f c' is


681

the uniaxial compressive strength. The initial tangent modulus of all the specimens is almost independent of the quantity of fibres. The compressive strength of CC, HFRFAC, HFRFABC and HFRFALC increases almost linearly with increase in the percentage of fibres (Fig 29). The compressive strength of HFRFABC and HFRFALC increases 22.69% and 26.34% respectively at 2% hair fibre with respect to the compressive strength of Plain concrete. The increase in compressive strength due to the addition of fly ash is because of the formation of additional calcium silicate hydrates in the hydrated cement matrix. The crushing strain of different test series of concrete is plotted in Fig. 30. It is observed from this figure that the crushing strain increases linearly with the increase in the quantity of fibres in CC, HFRFAC, HFRFABC as well as HFRFALC. The increase in crushing strain of HFRFABC and HFRFALC with the increase in the quantity of fibres from 0.0 to 2.0% is 16% and 30 % respectively which indicates that the addition of fibres introduces ductility in concrete. The Poisson’s ratio of concrete has been calculated from the measurement of lateral strain. The variation of Poisson’s ratio of different specimens with the percentage of fibres is plotted in Fig. 24. It is observed from the figure that the Poisson’s ratio increases almost linearly with increase in the percentage of fibres. As the percentage of fibre increases from 0.0% to 2.0%, the value of Poisson’s ratio increases by 5% for HFRFABC and 6.5% for HFRFALC. The low increment indicates that there is no much effect of hair fibre on the Poisson’s ratio. The observed crack patterns in the failure of cubes have been shown in Figs.7-22. Most of the cracks are almost along the line of action of the load, which indicates that the failure is mainly by lateral tension and shear. The observed cracks are not straight but have branches, which may be due to the presence of fibres. The first visual crack observed by naked eye is at 0.30 f c' in CC,

HFRFAC,

Fig. 1 Test under progress

HFRFABC

Fig. 2 Test under progress

and

HFRFALC.

Fig. 3 Mixing of Hair Fibre

682


Fig. 4 Human Hair Fibre

Fig. 5 Cube specimens

Table 5 Physical properties of materials S. No. Materials Physical Properties Specific Gravity 2.

Fly Ash

Optimum Moisture Content (Standard Proctor Test) Maximum Dry Density Specific Gravity

3.

Fine Aggregate (Coarse sand)

Water Absorption (30 min) Fineness Modulus Silt Content

4.

5.

6.

Coarse Aggregate (MSA = 10 mm)

Coarse Aggregate (MSA = 20 mm)

Human hair Fibre

Specific Gravity

Fig. 6 Cube under curing

Value 1.85 at 25 0C 18% 1.28 g/cc 2.61 0.44% 2.87 2.46% 2.64

Water Absorption (30 min)

0.40%

Fineness Modulus

3.578

Specific Gravity

2.63

Water Absorption (30 min)

0.39%

Fineness Modulus

3.750

Diameter Aspect Ratio (Length / Diameter)

* MSA = Maximum Size of Aggregate

17- 100 micron Nil


Fig 7 Tested CC Cube

Fig 10 Tested 1.5 FRFAC Cube

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Fig 8 Tested 0.0FRFAC Cube Fig 9 Tested 1.0 FRFAC Cube

Fig 11 Tested 2.0 FRFABC Cube

Fig 12 Tested 2.5 FRFABC Cube

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Fig13 Tested 0.0 FRFABC Cube


Fig19 Tested 1.0 FRFALC Cube

Fig14 Tested 1.0 FRFABC cube


Fig15Tested 1.5 FRFABC Cube

Fig18 Tested 0.0FRFALC Cube

Fig20 Tested 1.5 FRFALC Cube Fig21 Tested 2.0FRFALC Cube


Fig22 Tested 2.5FRFALC Cube

Figure 23 Variation of ‘E’

685

Figure 24(a) Variation of ‘Poisson’s Ratio’

Figure 24 (b) Variation of ‘Poisson’s Ratio’

686


Figure 25 Stress vs Strain variation



Figure 28 Stress vs Strain variation of different cocnrete


Figure 29 Compressive strength variation

687

Figure 30 Crushing strain variation

CONCLUSIONS The conclusions derived from the present study are: The compressive strength, crushing strain and Poisson’s ratio of HFRFABC and HFRFALC increase almost linearly with increase in the percentage of hair fibres from 0% to 2%. The stress-strain curves of HFRFABC and HFRFALC are parabolic with almost linear upto 30% of the uniaxial compressive strength. The initial tangent modulus of HFRFABC and HFRFALC is 28 GPa for both HFRFABC and HFRFALC which is independent of the quantity of fibres. The compressive strength of HFRFABC and HFRFALC increases 22.69% and 26.34% respectively at 2% hair fibre with respect to the compressive strength of Plain concrete.

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The increase in crushing strain of HFRFABC and HFRFALC with the increase in the quantity of fibres from 0.0 to 2.0% is 16 and 30 % respectively which indicates that the addition of fibres introduces strength in concrete. There is nominal increase in the value of Poisson’s ratio with the increase in the fibres content. Most of the cracks are almost along the line of action of the load, which indicates that the failure is mainly due to lateral tension and shear. The cracks are not straight but have branches, which may be due to the presence of the fibres. REFERENCES [1] [2] [3] [4] [5] [6] [7] [8] [9]

[10] [11] [12] [13]

Sekar T, Fibre reinforced concrete from industrial waste fibres – a feasibility study,' Journal Institution of Engineers (India) CV Vol. 84, 2004. http://www.lmcc.com/news/summer2006/summer2006-08.asp. http://www.flyash.com/data/upimages/press/HWR_brochure_flyash.pdf. http://www.jsce.or.jp/committee/concrete/e/newsletter/newsletter8-VietnamJoint (CHANH) _2.pdf. Akhtar J N, A study of permeability of fibre reinforced fly ash concrete, M. Tech dissertation, Department of Civil Engineering 2006. Siddique R, Properties of concrete incorporating high volumes of class F fly ash and san fibres, Cement and Concrete Research, 2004; 34: Issue 1, 37-42. McCarthy M J, Dhir R K, Development of high volume fly ash cements for use in concrete construction, Fuel 2005;84: 1423–1432. Gesog˘ lu M. et al., Effects of fly ash properties on characteristics of cold-bonded fly ash lightweight aggregates Construction and Building Materials 2007; 21: 1869–1878. Yazıcı H, The effect of silica fume and high-volume Class C fly ash on mechanical, chloride penetration and freeze–thaw resistance of self-compacting concrete, Construction and Building Materials 2008;22: 456–462. I.S. 3812, Specification for fly ash for use as pozzolana and admixture (First Revision) 1981. I.S. 383, Indian Standard specification for coarse and fine aggregates from natural sources for concrete (Second Revision) 1971. I.S. 8112- 43, Grade ordinary Portland cement-specification (first revision) 1989. I.S. 456, Plain and reinforced concrete-code of practice (fourth revision) 2000.


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SEISMIC STABILITY OF MUNICIPAL SOLID WASTE LANDFILLS: A C0NCERN Asif uz zaman Department of Civil Engineering Hindustan College of Science & Technology, N.H#2, Farah, Mathura,-281122, India. [email protected]

ABSTRACT: Over the last decade, the seismic response of landfills made of municipal solid waste has drawn Considerable attention mainly due to the environmental and public-health issues that could be raised in the event of a failure. Municipal solid waste landfills located in seismic impact zones be designed to resist earthquake hazards. However, due to lack of well documented case histories, analytical procedures for evaluating the seismic performance of waste fills are not well established. Typically, procedures that were developed to analyze the seismic stability of earth embankments are applied to landfills, but waste fills are significantly different from earth embankments. In this regard, the application of pseudo static stability and seismically induced deformation analyses to waste fills was assessed. The results of onedimensional wave propagation analyses indicate that the seismic stability of waste fills depends primarily on the dynamic properties and height of the waste fills, and the characteristics of the design bedrock motions (intensity, frequency content, and duration).Nevertheless, there are several associated technical issues that have not been adequately investigated. One of these is the impact of local site conditions on the earthquake-induced accelerations and, thereby, on the seismic design of a landfill. Local site conditions may play a significant role in the seismic response of a landfill. However, this role cannot be judged a priori as beneficial or detrimental, as it depends not only on soil conditions and seismic excitation, but also on the material and geometric characteristics of the landfill. Keywords: Municipal solid waste landfills; Seismic design; Site conditions; Slope stability; Dynamic soil-structure-interaction.

INTRODUCTION Considerable attention has been focused over the last few decades on developing procedures to analyze the seismic performance of earth embankments [e.g., Newmark (1965), Seed and Martin (1966), Makdisi and Seed (1978), Marcuson et al. (1992)]. Typically, the seismic stability of embankments is assessed by means of pseudo static slope stability analyses or seismically induced permanent deformation analyses, which may include seismic loadings, estimated from wave propagation analyses. In addition, fully coupled non linear dynamic finite-element analyses can be performed. Some of these approaches have been calibrated through the use of case histories, and it is generally accepted that their use can provide insight on the seismic performance of earth embankments. This does not imply that the theoretical basis of these methods is strictly correct; it implies that the results obtained from these methods have been compared with the performance of embankments in a number of cases and, with the use of good engineering judgment, these methods can be applied to design earth embankments. Municipal solid waste (MSW) landfills constitute large and important geo-structures, the safety and serviceability of which are directly related to environmental and public health issues. Even though no

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remarkable failure has been recorded worldwide as a consequence of an earthquake, serious damage has been repeatedly observed, raising the issue of seismic vulnerability of MSW landfills. These geostructures became the subject of systematic research following the Northridge earthquake (1994). Based on available observational data, Matasovic et al. (1995) introduced five levels of seismic damage on landfills ranging from little damage to general instability with significant deformations. An emerging area of concern is the seismic performance of waste fills. New municipal solid-waste landfills (MSWLF) or lateral expansions located in seismic impact zones be designed to resist earthquake hazards. The seismic response of waste repositories causes concern because dynamic loads may produce relative movements within the waste, bottom liner system, cover system, foundations, and their interfaces. These movements could damage the liner, with a consequent loss of sealing, and/or disrupt the function of the cover or leachate and gas collection systems. Unfortunately, at this time, it is not possible to rely on case histories to demonstrate regulatory compliance because the existing regulations precede the possibility of assessing the seismic performance of waste fills by examining well-documented case histories. Given the profession’s experience with the procedures developed to analyze the seismic stability of earth embankments, these procedures have been applied to waste fills. However, waste containment liner and cover systems employed in landfills are often constructed with layers of vastly dissimilar materials such as high-density polyethylene (HDPE) and compacted clay liners or geo-synthetic clay liners (GCLs): waste materials are often heterogeneous, their physical properties are difficult to assess, and they typically, change with time; and irregular landfill configurations may not be as amenable to simplified dynamic response analyses. Accordingly, studies are needed to address these concerns adequately. As most of the aforementioned damages are related to slope instabilities either of the waste mass of the landfill or of the supporting soil, seismic slope stability analysis is a critical component of the design procedure. Recent practice is based on three main families of methods that differ primarily in the accuracy the earthquake motion and the dynamic response of the slope is represented. These three categories consist of: stress-deformation methods, methods based on limit-equilibrium analysis and displacement-based approaches. The most accurate methods are considered to be the stress-deformation methods, which are typically performed using dynamic finite element analyses. In general, these methods are used to describe the nonlinear behavior of the material with the highest possible accuracy, but they require sophisticated constitutive models involving a large number of parameters that cannot be easily quantified in the laboratory or in situ. Because of their complexity, these methods are practically excluded from the seismic design of MSW landfills. On the other hand simplified seismic stability procedures are widely used in geotechnical practice. A crude index of seismic slope stability (or instability) is the factor of safety evaluated in a pseudo-static fashion in the realm of conventional limit equilibrium analysis. An alternative family of methods utilizes displacement-based approaches to predict permanent slope displacements induced by earthquake shaking. The key step in the pseudo-static methods is the selection of a seismic coefficient, as the later controls the pseudo static forces in the soil and waste masses, whereas for the displacement-based methods permanent displacements are calculated using either acceleration- time histories (Newmark (1965) approach) or seismic coefficients (Makdisi and Seed (1978) approach). Thus, it becomes evident that slope stability methods require an accurate estimation of the acceleration levels induced on the examined landfill. Therefore, pertinent response analyses incorporating the ‘‘local site conditions’’ should precede any kind of seismic slope stability analysis. Note that the term ‘‘local site conditions’’ is used here to describe not only the soil conditions of the site (stratigraphy, geomorphology, topography), but the geometric and mechanical properties of the landfill as well.


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CURRENT REGULATIONS AND PRACTICE New waste units and the lateral expansion of existing units shall not be located in seismic impact zones, unless all containment structures, including liners, leachate collection systems, and surface water control systems, are designed to resist the maximum horizontal acceleration (MHA) in lithified earth material for the site. Seismic impact zones are defined as areas with a 10% or greater probability that the maximum horizontal acceleration in lithified material will exceed 0.1g in 250 years. As per the current practice, the seismic stability of landfills is usually based on pseudo static limit equilibrium slope stability analyses, or on the analyses of seismically induced permanent deformations. Pseudo static slope stability analysis is often performed using a seismic coefficient estimated from procedures developed for earth embankments. This approach to selecting a seismic coefficient may be unreliable for landfills, as the dynamic characteristics of landfills differ from those of earth embankments. Seed and Bonaparte (1992) conducted a survey of five leading engineering firms to determine the methods they used to perform seismic analysis of landfills. A majority of these firms “virtually never perform response analyses for the actual (or proposed) waste fill materials” because of the difficulties associated with estimating their properties. The firms generally perform 1D dynamic response analysis to evaluate local site effects and, in most cases, the MHA (maximum horizontal acceleration), calculated at the ground surface for the soil profile, without the waste fill in place, is used to estimate the seismic loading. This MHA value is then used in pseudo static slope stability analyses, or the calculated ground acceleration-time history is used in a seismically induced permanent deformation analysis. The design is judged to be acceptable in terms of seismic performance if the calculated pseudo static factor of safety is atleast 1.5, or if the seismically induced permanent deformations are tolerable. No standards for acceptable limiting permanent deformations have been established, but it is generally assumed that maximum seismic displacements of 15 cm to 30 cm are tolerable for well-designed lined waste fills (Seed and Bonaparte 1992), although the basis for this assumption is obscure. The dynamic response analyses of waste landfills require the selection of acceleration- time histories representative of the design-level seismic motion in hypothetical outcropping rock and the estimation of the dynamic properties of the waste fill and foundation materials. The design earthquake events are chosen based on local and regional fault characteristics. Although, there are no established standards for selecting representative acceleration-time histories, three or four recorded and/or synthetic bedrock acceleration-time histories scaled to the design-level MHA may be used, as is commonly done in earth dam design. Earthquake records should be chosen from sources relevant to the site, including both nearfield lower magnitude events and far-field higher magnitude events, where appropriate. With regard to dynamic material properties, there is relatively little data regarding the seismic shear wave velocity Vs of waste materials, and established shear modulus degradation and damping curves for waste materials do not exist. Sharma et al. (1990) measured an average shear wave velocity of 200 m/s using down-hole tests at a landfill in Richmond, California. Anderson et al. (1992) reported an average shear wave velocity of 244 m/s based on a seismic refraction survey performed at a land fill. Singh and Murphy (1990) reported shear wave velocities, measured at landfills in California by the cross-hole and down-hole techniques, ranging from 30 to 275 m/s. Shear wave velocity measurements performed by Kavazanjian (1994) at ten landfills in southern California indicated that Vs increased with age and depth. Values near the landfill surfaces were as low as 80 m/s for newly placed, un-compacted waste and about twice that value for older, compacted waste. Vs values increased linearly with depth and, at a depth of 20 m, the Vs ranged from 150 m/s for young waste to as high as 300 m/s for older, compacted waste. At a depth of 30 m, the median waste Vs was 340 m/s. These data, as well as other published results, indicate that shear wave velocities for municipal waste fill can range from 50 to 350 m/s. values near the top of this range correspond with greater depths in older waste fills.

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Until recently the shear modulus degradation and damping characteristics of waste materials were assumed to be similar to peat because of the relatively low unit weights and high compressibilities of both peat and waste materials. Based on the results of in situ tests to estimate the small strain shear modulus of waste fill, Singh and Murphy (1990) proposed a modulus degradation curve intermediate to those of clay and peat. Since borings through some waste fills indicate that 10% to 30% of the recovered materials can be soils used as daily cover, the modulus and damping curves might be a combination of those developed for sand, clay, and peat. Additional work is required to develop procedures to measure the dynamic properties of waste fills.

EARTH EMBANKMENT SEISMIC ANALYSES APPLIED TO WASTE LANDFILLS Pseudo-static Analysis In pseudo static slope stability analyses, a factor of safety is computed using a limit equilibrium method in which a static, horizontal force, intended to represent the destabilizing effects of the earthquake, is applied to the potential sliding mass. The horizontal force is expressed as the product of a seismic coefficient k, and the weight W, of the potential sliding mass. This pseudo static slope stability method has been applied to embankments composed of materials that do not undergo significant strength loss as a result of earthquake shaking; if the factor of safety approaches unity, the embankment is considered unsafe. The pseudo static analysis requires the use of appropriate material strengths in determining the critical sliding surface. An acceptable factor of safety and seismic coefficient must then be selected for each potential sliding mass. Since the seismic coefficient designates the horizontal force to be used in the stability analysis, its selection is crucial. However, the selection of the seismic coefficient must be coordinated with the selection of material strengths and safety factor to achieve a satisfactory design [e.g., Seed (1979)]. Several methods are used to determine an appropriate value for the seismic coefficient (Seed and Martin 1966). For earth embankments, case histories, which have guided the selection of appropriate seismic coefficients, are available. However, since case histories describing landfill performance under strong shaking are not available, the selection procedure should take into account the deformable nature of the material above the potential slip surface. This then can be accomplished from a dynamic response analysis by determining a horizontal equivalent acceleration (HEA) calculated as the average of each acceleration value within the potential sliding mass weighted by the differential mass, which it acts upon any particular instant in time. Seed and Martin (1966) showed that if the potential slide mass can be represented as a triangular wedge the average HEA is equivalent to the shear force caused by the ground motions acting at the base of the sliding wedge divided by its mass. However, the procedure proposed by Seed and Martin (1966) assumes the shear stresses are constant along the base of the potential sliding mass. Dynamic finite element analyses have shown that the shear stress can vary significantly across some two-and three- dimensional embankment sections (Mejia and Seed 1981). A major limitation of the pseudo static approach is that the horizontal force, representing the effects of an earthquake, is constant and acts only in one direction. In a limit equilibrium analysis, the safety factor equals to one when the activating forces (or moments) equal the resisting forces (or moments); hence, a condition of incipient motion is all that can be considered. With statically applied loads, the destabilizing loads remain constant until very large displacements occur. With dynamically applied loads, the forces may act in one direction for only a few tenths of a second before its direction is reversed. The result of these transient forces will be a series of displacement pulses rather than the monotonic failure of slope. In engineering practice, failure is determined by whether or not the accumulated displacement is tolerable.


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Normally, a certain amount of limiting displacement during an earthquake event is considered tolerable. For this reason, safety factors as low as 1.0 have been considered acceptable for embankments when used with seismic coefficients, which represent peak accelerations. For waste fills, current federal guidance is that a safety factor of at least 1.2 is necessary, irrespective of the seismic coefficient used in the pseudo static stability analysis. This can be expensive to achieve if the maximum horizontal equivalent acceleration (MHEA) is adopted as a seismic coefficient. In such cases, the seismic stability of landfills can be assessed in terms of seismically induced permanent deformations, although guidance on the acceptable levels of permanent deformations is not available.

Seismically induced permanent deformations Newmark (1965) proposed that the seismic performance of earth embankments be evaluated in terms of permanent deformations developed during strong shaking. The analysis assumes that relative slope movements would be initiated when the inertial forces on a potential sliding mass were large enough to overcome the yield resistance along the slip surface, and that these movements would stop when the inertial force decreased below the yield resistance and the velocities of the ground and the sliding mass coincided. The yield acceleration can be represented as the average acceleration producing a horizontal inertial force on a potential sliding mass, which gives a factor of safety of unity in a pseudo static analysis. By integrating the average acceleration acting on the sliding mass in excess of this yield acceleration as a function of time, the relative velocity and displacement of the sliding mass can be estimated. The yield acceleration is a function of embankment geometry, material strength, and the location and shape of the potential sliding mass [e.g., Sarma (1975)]. The magnitude of the seismically induced permanent displacements calculated by a Newmark analysis depends primarily on the yield acceleration of the waste fill and the intensity, duration and frequency content of the equivalent acceleration-time history (Makdisi and Seed 1978).

ONE DIMENSIONAL WAVE PROPAGATION ANALYSIS OF LANDFILLS One- dimensional wave propagation analyses can be performed to investigate the relative importance of the factors that influence the seismic response of landfills. These factors include the subsurface soils, landfill height, waste unit weight, shear modulus and damping characteristics of the waste, and the characteristics of the ground motions. Although, two-dimensional (2D) dynamic response analyses may be appropriate for irregular waste fill geometries, the profession typically uses 1D analyses because of the uncertainties associated with the input data. Regarding the evaluation of the dynamic response of MSW landfills Bray et al. (1995) performed one-dimensional (1-D) equivalent linear analyses to a series of typical MSW landfills and soil profiles to compute acceleration levels at various elevations and the associated factors of safety in pseudo-static slope stability analyses. Their results indicate that the seismic stability of landfills depends not only on the dynamic properties and thickness of the waste, but also on the characteristics of the ground motion applied. On the other hand, records and analyses of hills and valleys have shown that local site conditions of a site (either in two or in three dimensions) may alter substantially the surface ground motion by: (a) amplifying the ground motion, (b) elongating its duration, and (c) generating differential motions, phenomena which will be referred hereafter to as ‘‘aggravation’’ Bard (1997). Recent analyses have shown that geomorphic and topographic conditions may profoundly aggravate the surface ground motion in the presence of small material damping, while material nonlinearity may substantially suppress aggravation by diminishing scattered body waves, especially horizontally propagating surface waves [Gazetas et al. (2002) and Psarropoulos et al. (2006)]. Therefore, in most cases aggravation depends not only on the geometrical and mechanical properties of a surface formation, but also on the amplitude of the excitation.

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To examine the reliability of 1-D analysis methods for the evaluation of the seismic response of landfills, Rathje and Bray (2001) compared the results obtained from 1-D and 2-D equivalent linear analyses. They found that 1-D analyses tend to underestimate the maximum horizontal acceleration along the slope by about 10% on average, and along the crest by 20% on average, mainly due to base rock topography amplification. Based on these results they proposed a scaling factor of 1.3 on the maximum horizontal acceleration derived from 1-D analyses, to account for 2-D topographic aggravation.

EFFECTS OF AN UNDERLYING SOIL LAYER The existence of a soil layer under the landfill may affect the overall dynamic response of the geostructure. In this case the designer should consider the extreme (but not improbable) phenomenon of double resonance in which the eigen period of the geo-structure coincides not only with the eigen period of the soil layer but with the predominant period of the excitation as well. Furthermore, in cases of moderate or strong seismic excitation, the materials (both soil and waste) are expected to behave nonlinearly. This nonlinearity is expressed primarily by an increase in material damping and degradation in stiffness. Although increased damping leads, in general, to a reduction of the amplification, the change in stiffness may increase or decrease the geo-structure’s response, depending on the circumstances. The presence of a relatively soft soil layer under a landfill is expected to affect substantially the response in terms of both peak and spectral acceleration. Another important aspect is the observed sensitivity of the landfill’s seismic response to changes in the material properties of the underneath soil layer. A minor change in soil material properties may affect significantly the overall response of the landfill in terms of spectral accelerations. This depends again on the characteristics of the seismic excitation and the degree of nonlinearity.

EFFECTS OF WASTE PROPERTIES The potential inhomogeneity in waste properties may also have a great effect on the response of the landfill. An increase in VS of the lower half of the landfill increases the overall stiffness of the structure, and thereby reduces its eigen period. Therefore, in the linear case it is expected that the landfill will be more vulnerable to low-period excitation. On the other hand, as nonlinearity increases the structure becomes gradually more flexible, its eigen period increases, and, therefore, long-period excitations influence the acceleration levels in the landfill to a greater extend. Mechanical properties of the waste consist also a very important issue for the numerical analysis of landfills. Under this perspective, researchers have performed in situ measurements using various techniques in order to determine the shear-wave velocity of waste. For instance, Kavazanjian (1994) conducted measurements utilizing spectral analysis of surface waves (SASW) method in the Coastal Landfill, California. Houston et al. (1995) performed measurements using the Downhole method at the Northwest Regional Landfill Facility, California. Idriss et al. (1995) derived a best estimate of the shearwave velocity profile for Operating Industries Inc. (OII) landfill in California, performing measurements using a combination of suspension logger, SASW testing and a down-hole logging procedure. All measurements revealed a significant increase in shear-wave velocity, VS, with depth. Kavazanjian et al. (1995), after comparing the results from a series of measurements, presented an estimate of the variation of VS with depth. The nonlinear behavior of waste materials has been also investigated in a number of studies using strong motion records from the OII landfill, which were obtained at the toe and the crest of the landfill. Singh


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and Murphy (1990) and Kavazanjian and Matasovic (1995) analyzed the available recordings and proposed curves, both for modulus degradation and damping increase of the waste materials. Idriss et al. (1995) performed back calculations for the OII site, and showed that for large shear-strain range, modulus reduction was significantly less than expected by previous estimations. The authors suggested that this discrepancy could be attributed to the improvement of waste material properties with time.

CONCLUSION Seismic response of MSW landfills is certainly a complex dynamic soil-structure-interaction problem, controlled mainly by the local site conditions and the characteristics of the excitation. On the other hand, current design practice is based on simplified methods and simplistic seismic codes, while certain technical issues have not been investigated with the proper realism. When the materials (soil and waste) behave linearly (which is the case for minor earthquakes) the response of the landfill is affected exclusively by the geometrical and mechanical properties of the landfill and the soil. In contrast, when a moderate or severe earthquake occurs the materials behave nonlinearly, and in that case the degree of nonlinearity dominates any amplification or aggravation phenomena. The effects of local site conditions on the response of a geo-structure, such as a MSW landfill, cannot be regarded a priori as beneficial or detrimental. Moreover, there are no established procedures to determine appropriate combinations of seismic coefficient, safety factor and material strengths that will result in acceptable permanent deformations of waste fills, as has been proposed for earth embankments; hence the seismic performance of waste fills in areas of high seismicity should be assessed in terms of the seismically induced permanent deformations. Seismically induced permanent deformations are generally estimated using a Newmarktype analysis and a double integration procedure. The duration of strong shaking is a major parameter in determining seismically induced permanent deformations. Limit equilibrium methods can be used to estimate the yield acceleration along the critical bottom liner interface. The results of 1D dynamic analysis indicate that the equivalent acceleration-time history used to calculate permanent displacements is influenced by the dynamic characteristics of the waste fill and foundation soils, as well as by the input rock motion. Characterizing the properties of the waste fills adequately is an important step in evaluating the seismic performance of a waste landfill. Thus, site-specific response studies are an essential component of calculations to estimate permanent displacements of waste fills. Consequently, a general conclusion that can be drawn is that proper seismic design of landfills should be performed on a case-by-case basis in order to be capable of taking into consideration, apart from the seismological conditions, the specific local site conditions and the individual characteristics of each landfill. It is obvious that the overall response depends not only on the geometrical properties of the landfill and the frequency content of the base motion, but also on the amplitude of excitation affecting the mechanical properties of the landfill as well.

REFERENCES Anderson, D.G., Hushmand, B., and Martin, G.R. (1992).“Seismic response of landfill slopes”. Proc., ASCE Specialty Conf. on stability and Perf. of slopes and Embankments-II, ASCE, Newyork, N.Y., 973989. Bard, P.Y. (1997).“ Local effects on strong ground motion: basic physical phenomena and estimation methods for microzoning studies”. Notes of the Advanced Study Course SERINA (Seismic Risk: An Integrated Seismological, Geotechnical and Structural Approach), Thessaloniki, Greece.

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Bray, J.D., Augello, A.J., Leonards, G.A., Repetto, P.C., and Byrne, R.J. (1995).“Seismic Stability procedures for solid waste landfills”. ASCE J. Geotechn. Eng., 121(2):139–51. Gazetas, G., Kallou,P.V., and Psarropoulos, P.N. (2002).“ Topography and soil effects in the ms 5.9 Parnitha (Athens) earthquake: the case of adames”. Natural Hazards, 27:133–69. Houston, W.N., Houston, S.L., Liu, J.W., El Sayed, A., and Sanders, C.O. (1995).“In-situ testing methods for dynamic properties of MSW landfills”. In: Earthquake design and performance of solid waste landfills. ASCE Geotechnical Special Publication, vol. 54, 73–82. Idriss, I.M., Fiegel, G.L., Hudson, M.B., Mundy, P.K., and Herzig, R. (1995). “Seismic response of the operating industries landfill”. In: Earthquake design and performance of solid waste landfills. ASCE Geotechnical Special Publication, vol. 54, 83–118. Kavazanjian, E. Jr. (1994).“SASW testing at solid waste landfill facilities”. Proc., Workshop on Res. Priorities for seismic Des. of solid waste landfills, Dept. of Civ. Engrg., Univ. of southern Calif., Los Angeles, Calif.,26-27. Kavazanjian, E.J., and Matasovic, N. (1995).“ Seismic analysis of solid waste landfills”. In: Y.B., Acar and D.E., Daniel, editors. Geoenvironment 2000. ASCE Geotechnical Special Publication No 46, 1066– 80. Kavazanjian, E.J., Matasovic, N., Bonaparte, R., and Schmertmann, G.R. (1995). “ Evaluation of MSW properties for seismic analysis”. In: Acar YB, Daniel DE, editors. Geoenvironment 2000, ASCE Geotechnical Special Publication, vol. 46, 1126–41. Makdisi, F.I., and Seed, H.B. (1978).“Simplified procedure for estimating dam and embankment earthquake-induced deformations”. J. Geotech Engrg., ASCE, 104(7), 849-867. Marcusion, W.F. III, Hynes, M.E., and Franklin, A.G. (1992).“Seismic stability and permanent deformation analyses: The last twenty five years”. Proc., ASCE Specialty Conf. on stability and Perf. of slopes and embankments- II, ASCE, Newyork, N.Y., 552-592. Matasovic, N., Kavazanjian, E.J., Augello, A.J., Bray, J.D., and Seed, R.B. (1995). “Solid waste landfill damage caused by 17 January 1994 Northridge earthquake”. In: M.C., Woods, R.W., Seiple, editors. The Northridge California earthquake in 17 January 1994, Sacramento, California, USA: California Department of Conservation, Division of Mines and Geology Special Publication; vol. 116. Mejia, L.H., and Seed, H.B. (1981).“Three dimensional dynamic response analyses of earth dams” .Rep. No. UCB/EERC-81-15, Earthquake Engrg. Res. Ctr., Univ. of Calif., Berkley. Calif. Newmark,N.M. (1965).“Effects of earthquakes on dams and embankments”. Geotechnique, London, England, 15(2), 139-160. Psarropoulos, P.N., Tazoh, T., Gazetas, G., and Apostolou, M. (2006).“ Linear and non-linear valley amplification effects on seismic ground motion”. Soils Foundations, accepted for publication article in press. Rathje, E.M., and Bray, J.D. (2001).“ One and two dimensional seismic analysis of solid waste landfills”. Can., Geotechn., 38:850–62. Sarma,S.K. (1975). “Seismic stability of earth dams and embankments”. Geotechnique, London, England, 25(4), 743-71. Seed, H.B. (1979). “Considerations in the earthquake-reistant design of earth and rockfill dams”. Geotechnique, London, England, 29(3), 215-263.


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Seed, H.B., and Martin, G.R. (1966).“The seismic coefficient in earth dam design.” J. Soil Mech. and Found. Div., ASCE, 92(3), 25-58. Seed, R.B., and Bonaparte R. (1992).“Seismic analysis and design of lined waste fills: Current practice”. Proc., ASCE Specialty Conf. on stability and Perf. of slopes and Embankments- II, ASCE Newyork, NY., 1152-1187. Sharma, H.D., Dukes, M.T., and Olsen, D.M.(1990).“Field measurements of dynamic moduli and poisson’s ratios of refuse and underlying soils at a landfill site”. ASTM STP 1070, geotechnics of waste landfills-theory and practice, A. Landva, and G.D. Knowles, eds., ASTM, Philadelphia, 259-284. Singh, S., and Murphy, B. (1990).“Evaluation of the stability of sanitary landfills”. ASTM STP 1070, geotechnics of waste landfills-theory and practice, A. Landva, and G.D. Knowles, eds., ASTM, Philadelphia, 240-258

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MUNICIPAL SOLID WASTE MANAGEMENT IN BESAT CITY (IRAN) N. Mokhtarani Faculty of Engineering, Tarbiat Modares University, P.O.Box: 14155-143, Tehran, Iran B. Mokhtarani Chemistry & Chemical Engineering Research Center of Iran, P.O.Box 14335-186, Tehran, Iran M. R. Alavi Moghaddam Dep. of Civil & Env. Eng., Amirkabir University of Technol., Tehran 15875-4413, Iran H. Khaledi Mehr Jahesh Kimia Company, P.O.Box 13445-1381, Tehran, Iran

ABSTRACT Besat city is located in the south of Iran in the coastline of Persian Gulf. At this time, the population of this city is about 14000. The physical waste analysis showed that food wastes are the main component of municipal solid waste. The amount of solid waste, which generates in this city, is 13 ton per day. This amount of solid waste will be increased up to 28 metric ton per day in 2017. At present, there is no recycling and reuse of municipal solid waste in this city. Municipal solid wastes are collected every day and transferred to the disposal sites. The method of disposal is land treatment, which causes severe environmental pollution in the region. According to the results of the present study, the recycling of municipal solid waste components at source and converting the food wastes to compost are the best methods for municipal solid waste management in this city. Keywords: Compost, Disposal, Municipal Waste, recycling, Waste Management.

1. INTRODUCTION Solid waste is a serious environmental problem in both developed and developing countries. In recent years, most developing countries have started to improve their municipal solid waste management practices. The increasing amount of wastes generated by rapid urbanization in these countries is usually not properly managed. Solid waste management systems in developing countries must deal with many difficulties, including low technical experience and low financial resources which often cover only collection and transfer costs, leaving no resources for safe final disposal (Collivignarelli, et al. 2004). Improper management of solid waste has been reported by several researchers in different cities of developing countries (Berkun, et al. 2005; Chung and Carlos, 2008; Imam, et al. 2008; Sharholy, et al. 2008). Inadequate management of solid waste in most cities of developing countries leads to problems that impair human and animal health and ultimately result in economic, environmental and biological losses (Alavimoghadam, et al. 2009). Generations of a huge amount of MSW have produced a lot of environmental problem in all over the world. In order to overcome of these environmental problems, a proper waste management is essential. Waste management is defined as the collection, transport, processing, recycling or disposal of waste materials. The term usually relates to materials produced by human activity, and is generally undertaken to reduce their effect on health, the environment or aesthetics. Waste management is also carried out to recover resources from it. Waste management can involve solid, liquid, gaseous or radioactive substances, with different methods and fields of expertise for each.

Corresponding author, Tel: +982182884921, Fax: +982182883332, E-mail: [email protected]


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Waste management practices differ for developed and developing nations, for urban and rural areas, and for residential and industrial producers. Management for non-hazardous residential and institutional waste in urban areas is usually the responsibility of local government authorities, while management for non-hazardous commercial and industrial waste is usually the responsibility of the generator. Waste management methods vary widely between areas for many reasons, including type of waste material, nearby land uses, and the area available. Usually Waste management is classified to several steps including: waste generation, waste handling and separation, storage and processing, collection, transfer and transport, and final disposal. The reason for this classification is identification and separation of the duty of each step (LaGrega, et al. 2001; Tchobanoglous, et al. 1993). This paper presents an overview of current municipal solid waste management in Besat city, and provides several recommendations for system improvement. Besat city is located in the south of Iran in the coastline of Persian Gulf. There are so many petrochemical plants near to this city and in order to reside the employers of these petrochemical plants, the National Petrochemical Company of Iran (NPC) has established this city since 1990. The population of this city was about 14000 in 2008 and expected to increase to 31000 during the next 10 years. The weather of this area is very hot and humid and the temperature sometimes goes up to more than 45oC in August.

2. MATERIALS AND METHODS This research was conducted for 1 year in Besat city. To investigate the present situation of Besat solid waste management, several questionnaires were prepared and distributed among various branches of the municipality and other related organizations. The collected data for different MSW functional elements were based on the data from the above-mentioned questionnaires, visual observations by the authors and several interviews and meetings with responsible persons, including engineers working in the municipality.

3. RESULTS AND DISCUSSION The current state of Besat MSW management, its challenges and our recommendations for improvement of the system are discussed in this section.

3.1. Quantity and Quality of MSW The quantity and quality of solid waste is a first step for designing of a proper MSW management system. The information about the characteristics of solid waste has a great importance on selection of the equipment and optimal design of the other steps of solid waste management such as collection, transport, processing, final disposal, etc. In order to measure the quantity and quality of solid waste in Besat city, several measurements were conducted in the disposal site. These measurements have done on two different times of year, summer and autumn for two weeks. Table 1 shows the amount and type of solid waste generation in Besat city. The results of the average weight percent of home solid wastes analysis (Green Waste, Construction Waste and Hospital Waste not included) are reported in table 2. As shown, the food wastes have the highest average composition in these analyses. Table 1. The solid waste generation in Besat city, 2008 Type of Waste

Quantity (Ton/day)

Composition

Home Wastes

6

Organic material, plastic, paper, glass

Green Wastes

2-3

Bark, wood, cardboard, grass

4

Brake, stone, cement

Construction Wastes

700


Hospital Wastes

Hazardous waste

0.36

Table 2. Composition of home wastes in Besat, Iran Weight Percent summer autumn

Component

Average

PET

0.99

0.56

0.78

Textiles

0.75

0.74

0.74

Rubbers & plastics

1.63

1.59

1.61

Paper & cardboard

2.43

3.93

3.18

Glass

2.02

1.77

1.90

Metals (all types)

1.20

1.10

1.15

Leachate

1.12

1.63

1.37

Food wastes

89.87

88.69

89.28

Variations of MSW generation and the average generation rate (G.R) of solid waste in Besat in the period of 2008-2017 are presented in Figure 1. The annual home G.R rates growth are considered to be 1% (Jahesh Kimia Co., 2008). As shown in Figure 1, the average waste generation rate in this city (in 2008) is about 950 g/capita per day. In spite of 1% increasing of home waste generation rates and growing of MSW up to 28 Ton per day in 2017, the average MSW generation rate will decrease to near 900 g/capita per day in the same year. The reason for this reduction of generation rate is due to decrease of construction wastes in Besat city during next years.

Figure 1. MSW Generation Rates, 2008 to 2017

3.2. Current State of MSW Management in Besat City As it was mentioned before, the solid waste management has several functional elements, including waste generation, waste handling and separation, storage and processing, collection, transfer and transport, and final disposal. In this section, the current state of different functional elements of Besat MSW management is discussed.

Waste generation, handling, storage and processing: According to the data collected, about 13 Ton per day of MSW generated in this city in 2008. The MSW are collected from the storage containers which install in front of the houses and near to the commercial units. These containers have different volume and most of them are built from metal.


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The method of handling, storage and processing of solid wastes at the source plays an important role in public health, aesthetics and the efficiency of the MSW system (Abdoli, 1995). Unfortunately in Besat city, the separation of MSW is not considered and no processing was carrying out by inhabitant. Collection & Transport: Collection of solid waste is a difficult and complex task. The organic parts of MSW can be easily degraded, which causes offensive odors and leachate in storage containers (Alavimoghadam, et al. 2009). In Besat city the MSW are collected by private company which has contracted with the municipality of city. The collection of residential waste are conducted in the night but other waste such as green waste, commercial and construction wastes are collected in the day. There is not any transfer station in the city and all of the collected MSW transfer to the disposal site directly.

Final disposal: Safe and reliable long-term disposal of waste is an important component of integrated solid waste management. Landfilling, incineration and composting are three main methods of MSW disposal in the world. In Besat city, the MSW are disposed in the dumping area which is located about 15 km far from the center of the city.

3.3. The Plan of MSW Management in Besat City In this section the plan for different steps of MSW management in Besat city are presented. This plan is proposed according to the amount of MSW and the population of Besat in 2017.

Source separation of MSW: Source separation of wastes (especially organic wastes) will not only bring economic benefit, but will also makes the recycling of other components more efficient (Aydin and Kocasoy, 2004). Separation of MSW in source is the most effective method for recycling and reuse. A systematic source separation of MSW program in the Besat city is proposed as follows: In this plan, two white, two yellow, two blue and seven black plastic bags are distributed in each family every week. The white bags are specific for papers, magazine, books and newspapers. The plastics, metals, cans, PET and tetra packing materials are inserted in the yellow bags. The blue bags are specific for special wastes such as the wastes which generated in bathroom and dirty tissues. These wastes are collected two times in a week. The personnel of this plan with the special uniform are called each house and give the necessary information to the resident. The food wastes are stored in the black bags and collected daily. In order to separate the glass wastes, some special container are inserted in the city and the residents should bring their glass wastes to these containers. In crowded area and commercial places four types of storage container are inserted. The white containers are belongs to the papers and cardboards; yellows containers are specifics for plastics, metals, cans and PET; red containers are for glass material and blue containers are specific for food wastes.

The storage plan: Due to the hot and humid weather of this city, the MSW storage time should be minimized. The storage of MSW in long time, generate a huge amount of leachate and bad odors. In order to prevent this problem, MSW should be stored in proper containers with suitable caps. The storage container should be washed periodically. The container should be easily transport by the persons who collect the MSW. Due to the climate of this area, it is recommended the container built from plastics with light color.

The plan for collection & transfer: the proposed systems for collection of MSW in Besat are as follow: Mechanical: in this system the loading, compaction and offloading are performed mechanically. Semi mechanical: in this system the loading is performed manually but compaction and offloading are achieved mechanically. Manually: in this system loading is performed manually and other steps are not executed. Table 3 shows the proposed collection system for different wastes in Besat. In this system, For Hazardous, construction and Green wastes, manually collection was selected. The waste from

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residential area (home Waste) are collected in both semi mechanical and mechanical and in other region such as commercial area are collected in mechanical form. Table 3. The proposed system for collection of MSW in Besat city Solid waste

Type of system

Food wastes

Mechanical & semi mechanical

Paper & cardboard

Mechanical

Rubbers & plastics

Mechanical

Construction waste

Manually

Green waste

Manually

Glass Hazardous waste Special waste

Mechanical Manually Semi mechanical

The plan for waste disposal: Disposal of MSW is the last functional element of integrated solid waste management. In Iran, Landfilling, open dumping and composting are the main methods of waste disposal. As shown in Figure 2, about 5% of MSW in Besat are recyclable and will be increased to more than 7% in 2017. According to this figure more than 62% of MSW of Besat is compostable, less than 5% can be burned and maximum 30% must be disposed in landfill.

Figure 2, proposed municipal solid waste disposal in Besat, Iran

Hence the proposed plan for the reuse and disposal complex of Besat is consisted of the following units: Recycling and reuse unit: this unit recycles the valuable materials from the MSW and sells them to the companies which use from these materials. Recycling and reuse will assist to reduce the amount of MSW in disposal site. Composting unit: as the weight percent of organic materials in this waste is considerable, establishment of a composting plant can be beneficial. It is possible to produce more than 20000 tons of fine compost during the next 10 years. This enormous organic fertilizer can be used as a conditioner in agricultural soil and also landscape extension of Besat. Incineration unit: this unit burns some hazardous and the special wastes and its capacity would be 5 ton/day. Landfill: this unit disposes the inorganic materials, ash and the other wastes which cannot be burns in incinerator. The main part of landfill disposed materials will be due to construction wastes. But


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as the construction in Besat will decrease in the future, the amount of waste that must be disposing into landfill will be reduced to 18% of total produced MSW in 2017.

4. CONCLUSION In this research, the present situation of MSW management in Besat city is investigated. The results of this study showed that about 13 Ton of MSW are generated daily in this city and this amount will be increased to 28 Ton in 2017. The results of MSW analysis showed that about 90 percent of home wastes (62% of total waste) are organic materials which are very suitable for converting to compost. The average waste generation rate in this city is expected to be 950 g/cap. day, but because of decrease of construction waste during the next years, it is predicted to decrease to near 900 g/cap. day in 2017. As the amount of MSW will be increased in the next years, the need to a proper MSW management is essential for this city. Source separation of MSW is the first activities for reducing of MSW in disposal site. Planning for storage, collection and transportation and establishment of reuse & disposal complex are the next necessary actions for proper waste management in Besat. There are many challenges for the solid waste management system of this city. Lack of resources, infrastructure, suitable planning, leadership, and public awareness are the main challenges. Any substantial change in the MSW management is not possible without close cooperation between the responsible persons and citizens. Efforts should be made by the municipality to increase public awareness and participation regarding solid waste management issues through the media, including local newspapers and television.

5. REFERENCES Abdoli, M.A., 1995, Solid waste management in Tehran, Waste Management and Research, 13, 519– 531. Alavimoghadam, M. R., Mokhtarani, N., Mokhtarani, B., 2009, Municipal solid waste management in Rasht City, Iran, Waste Management, 29, 485–489. Aydin, G.A., Kocasoy, G., 2004. Significance of Source Separation and Composting of Wastes of Istanbul: From Theory To Practice, CD-ROM of ISWA World Congress, October 17–21, Rome, Italy. Berkun, M., Aras, E., Nemlioglu, S., 2005, Disposal of solid waste in Istanbul and along the Black Sea coast of Turkey. Waste Management, 25, 847–855. Chung, S.S., Carlos, W.H.Lo., 2008. Local waste management constraints and waste administrators in China. Waste Management, 28 (2), 272–281. Collivignarelli, C., Sorlini, S., Vaccari, M., 2004. Solid Wastes Management in Developing Countries, CD-ROM of ISWA 2004 World Congress, October 17–21, Rome, Italy. Imam, A., Mohammed, B., Wilson, D.C., Cheeseman, C.R., 2008. Solid waste management in Abuja, Nigeria. Waste Management, 28 (2), 468–472. Jahesh Kimia Company Reports, Municipal solid waste management in Besat city (in Persian), 2008. LaGrega, M.D., Buckingham, P.L., Evans, J.C., 2001, Hazardous waste management, 2nd edition, Mc-Graw Hill publication, New York. Sharholy, M., Ahmad, K., Mahmood, G., Trivedi, R.C., 2008, Municipal solid waste management in Indian cities – A review, Waste Management, 28 (2), 459– 467. Tchobanoglous, G., Theison H., Vigil, A.S., 1993, Integrated solid waste management, Mc-Graw-Hill international edition.

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INTEGRATED SOLID WASTE MANAGEMENT APPROACH FOR JALANDHAR CITY, PUNJAB M.K.Kaushik, Lecturer, DAV Institute of Engineering & Technology, Jalandhar, Punjab Dr.Arvind Agnihotri Prof. & Dean( Academic Programmes), Deptt. of Civil Engg., NIT, Jalandhar Dr. Ajay Bansal Asstt. Prof., Deptt. of Chemical Engg., NIT, Jalandhar

Abstract Solid waste refers to all discarded household, commercial waste, non-hazardous institutional and industrial waste. It also includes street sweeping, construction debris, agricultural waste and other non hazardous and non toxic solid waste. Environmentally acceptable management of municipal solid waste (MSW) has become a global challenge due to limited resources, an exponentially increasing population, rapid urbanization and worldwide industrialization. In Punjab, various cities are facing problems due to ever increasing amount of waste and improper waste management practices. Jalandhar is one of the cities which are facing similar problems of poor waste management. This problem can be managed by various alternatives such as composting, incineration, recycling and land filling, but in present situation only by use of these alternatives Municipal Co-operation is unable to handle the huge amount of solid waste. Further, the use of various alternatives requires advance studies on composition and generation of solid waste. Only after proper sorting and analysis of solid waste these alternatives could be properly implemented. The present study aims to study various solid waste generating sources and their transport as well as management options in the Jalandhar city area of Punjab. This also requires in depth studies of solid waste composition and its generation .For this purpose Jalandhar city’s solid waste was collected from Variana Village dump site and sorted at source, for analysis of different components. By this study, it has been found that more than 50% of waste is biodegradable which is mixture of fruit and vegetable waste mainly. This huge amount is followed by ash and earth mix waste compromising around 25% of the total waste generated; yard waste is nearly 7% followed by paper, plastics, rags and very small amount of glass and rubber materials. Using this composition study it is can suggested to the Municipal Co-operation ,Jalandhar to use composting and recycling for the waste management as major alternatives for solid waste management in the area because these options permits resource recovery and utilization of various useful components of the waste ,land filling could also be used as last alternative. Bio-reactor landfilling technology could also be used for the proper management of huge amount of bid-gradable waste. Keywords: Non-hazardous, Biodegradable, Recycling, Land-filling, Bioreactor landfill.

INTRODUCTION Solid waste refers to all discarded household, commercial, non-hazardous, industrial waste. It also includes street sweeping, construction debris, agricultural waste and all other non hazardous, non toxic waste materials. It can also be defined as the material that has no longer any value to the person who is responsible for its generation. It does not normally include human excreta. Solid waste is generated by domestic, commercial, industrial, healthcare, agriculture and mineral extraction activities and accumulates in streets and other public places. Environmentally acceptable management of municipal solid waste (MSW) has become a global challenge mainly due to limited resources, an exponentially increasing population, rapid urbanization and worldwide industrialization. In Punjab, various cities are facing problems due to ever increasing amount of waste and improper waste management practices. Jalandhar is one of the cities which are facing similar problems of poor waste management. This problem can be managed by use of various waste management alternatives but presently, these are also unable to handle the huge amount of solid waste generated. Realizing the need for proper and scientific management of solid waste, the


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Municipal Solid Waste (Management and Handling) Rules, 2000 were notified by the Ministry of Environment and Forests, Govt. of India. The objective of these Rules was to make every municipal authority responsible for the implementation of the various provisions of the Rules within its territorial area and also to develop an effective infrastructure for collection, storage, segregation, transportation, processing and disposal of Municipal Solid Wastes (MSW). The indiscriminate dumping of municipal solid wastes in water bodies and low lying areas is a common practice followed by most of the municipalities with no consideration of its effect on the environment. Moreover, the lack of the basic information regarding generation, collection, transportation and disposal of solid waste is also noticed in the study area. Waste management is the collection, transport, processing, recycling or disposal, and monitoring of waste materials. The term usually relates to materials produced by human activity, and is generally undertaken to reduce their effects on health, environment and aesthetics. Waste management is also carried out to recover resources from it. Waste management can involve solid, liquid, gaseous or radioactive substances, with different methods and fields of expertise for each. Waste management practices differ for developed and developing nations, for urban and rural areas, and for residential and industrial producers. Management for non-hazardous residential and institutional waste in metropolitan areas is usually the responsibility of local government authorities, while management for non-hazardous commercial and industrial waste is usually the responsibility of the generator. Across the country, many communities, organizations and individuals have found innovative ways to reduce and better manage MSW through a coordinated mix of practices. However, the most environmentally sound management of MSW is achieved when these approaches meets the norms laid down by the MSW Rules. Not much headway has been achieved by our municipalities in the implementation of the Municipal Solid Waste (Management and Handling) Rules. Thus there is a need to understand the implementation issues related to solid waste management with a view to provide eco-friendly, sustainable and community-based solutions to waste management problems.

STUDY AREA A large volume of domestic solid waste is generated in both urban, as well as rural areas. It includes organic and inorganic waste. Local bodies are responsible for its management within a city. In Punjab, 3017.05 tones of municipal solid waste is generated daily. Out of this, the 4 municipal corporations (Ludhiana, Jalandhar, Amritsar, and Patiala) account for 1830 Tones per day (TPD) generation of MSW in Punjab. All the other districts of the state generate the remaining 1137.5 TPD municipal solid waste. Ludhiana generates 29% followed by Jalandhar 13% of total MSW generated in the state. The various dumping sites of Jalandhar are as follows:- 1.Varriana village 2.Suchi village 3. Pucca Bagh. Out of these three sites only first sites (Varriana village) is in working conditions. Earlier Suchi village site was also used for dumping of all the waste of city, but the site was soon restricted for solid waste dumping, as the site was very close to Indian Oil Cooperation Storage stations. But still the site is used ill-legally for dumping medical wastes. As the views taken from the people living in the nearby locality, it was evidenced that illegal use of site has created hazardous condition in surrounding areas, as dumpers set fire to the medical wastes. The site of Varriana village is located far from city on Kaputhala road (approx 4.2km) and has no such restrictions and problems.

MATERIALS AND METHODS Population growth, rapid urbanization and other development activities during the past few decades have been responsible for environment pollution and resources degradation. The rapid urbanization has seriously aggravated the problem of municipal or domestic garbage disposal and its management. Municipal solid waste consists of kitchen waste, fruit and food waste, house sweeping, glass, paper, plastic, metal, rags, packing material, etc. The constituents of solid waste continuously changes with time. Therefore, samples have been taken from the dumping site, and then from these collected samples composite samples have been prepared by using equal weightage of the solid waste.

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The sample collected is kept in cool places, so that the bacteriological activities may not change the characteristics of solid waste before its examination. Sampling of solid waste is done by making a composite sample with collection of different samples of different areas and mixing it for a total weight of 18.5 kg. This collected sample is carried to the laboratory at DAVIET for further analysis. Test samples have been preserved in a plastic bags and analysis of all parameters were conducted within 2 to 4 days of sampling. Samples of raw solid waste are taken from the dumping site situated at Warriana pind, Jalandhar. These samples were weighed and manually separated by hand to get various components of the sample by weight. The sampling point was leading accessible and free from any hazards. A classification system was used to describe characteristics both in their initial state (as delivered to a landfill) and also in altered states. Placing of waste in landfills, changes different properties such as size and shape due to physical forces such as compaction and overburden of waste itself. Degradation occurs with time also changes different characteristics of leachate and waste itself over time. Components are sorted into material groups (paper/ cardboard, flexible plastics/ rigid plastics, metals/ minerals, wood, leather, textiles, organics and miscellaneous materials. Components in each material group are divided into the following subdivisions: 1. Reinforcing components (one and two dimensional; e.g., plastic bags, sheets of paper etc.) 2. Compressible components (three dimensional components): High compressibility (e.g., putrescible materials, plastic packaging etc.) Low compressibility (e.g., metallic cans etc.) 3. Incompressible components (three dimensional; e.g., bricks, pieces of metal etc.) Size of waste components is graded within each shape related subdivision and degradation potential of material groups within each size range is assessed. Various analysis of solid waste and leachate were conducted according to the procedures used and has been given in manual for solid waste analysis published by NEERI, Nagpur, India.

Table No. 1 Various analysis for solid waste samples collected from Varriana dump site. Parameters Examined Permeability (hydraulic conductivity) Moisture content Volatile solids Energy content (calorific value) Fixed carbon N, P, K (%)

Methods used for the Examination Constant head permeability test Wet-weight relationship (By percent weight) Proximate analysis (% by weight) By bomb calorimeter (lab. scale) By combustible residue after volatile matter removed By Ultimate analysis

Table No. 02 Various analyses for Leachate samples collected from Varriana dump site. Parameters Examined Chemical oxygen demand (COD) Bio-chemical oxygen demand (BOD) Chlorides Sulphates pH Conductivity (µS)

Methods used for Examination Dichromate reflux technique standard method 3 days 270 C BOD test method Argentometric method Gravimetric method By pH meter By conductivity meter

RESULTS AND DISCUSSIONS Before the designing of reactor for accelerated decomposition of organic solid waste and also for the production of solid waste manure it was necessary to have the information regarding the


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various constituents of solid waste. This examination was also necessary due to the following purposes:1. To know the strength, characteristics, constituents and condition of the solid waste and leachate produced. 2. To control and regulate the performance of solid waste treatment works on day to day basis, according to the solid waste and leachate characteristics. Physico-chemical analysis of municipal solid waste and leachate was done. The average density of solid waste was around 300 kg/m3. Composition of the solid waste was studied on the site and it was found that municipal solid waste samples contain 51.23% fruit and vegetable waste and 4.9% paper waste. It also includes 5% plastic and 7.08% yard waste. Ash and other materials were nearly 6.5%. This waste also includes very small percentages (>1%) of rags, glass, rubber and other miscellaneous objects. Chemical properties of the waste indicate that the C/N ratio is around 24.0. The average moisture content in city waste was around 33.3%, while the average calorific value was found to be 932 kcal/kg. The physical composition of solid waste in the MCJ area is shown in figure 01. for March, 2009. Components of solid waste

Percentage by weight

Fruit and vegetable waste

51.23 %

Garbage

18.81 %

Yard waste

7.08 %

Ash and Earth

6.54 %

Paper

4.9 %

Plastics

4.9 %

Rags

4.09 %

Glass

1.36 %

Rubber

0.82 %

Miscellaneous

0.27 %

Ash and Earth 7%

GlassRubberMisc.>1% Plastics Rags1% 1% 4% Paper 5% 5% Fruit and vegetable waste 51%

Yard waste 7% Garbage 19%

Composition of Solid Waste in MCJ Area, 2009 Fig. 1:- Compostion of solid waste at dumping site of Warriana Pind, Jalandhar,Punjab

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Leachate samples were analyzed for its BOD, COD, Chlorides and sulfates values. COD values were determined by using Dichromate Reflux Technique method. In COD test, a strong chemical oxidizing agent was used in an acidic medium to measure the oxygen equivalent of organic matter that can be oxidized. The value for COD was 3500 mg/l. which indicate presence of high organic matter content in the leachate samples. The BOD values for the leachate samples was 930 mg/l. these values clearly shows that there will be high oxygen requirements for the complete biological stabilization of organic matter present in leachate. So, instead of organic treatment, we can adopt anaerobic treatment methods. This anaerobic treatment will produce biogas, which is a very good renewable energy resource and will be important for the generation of electricity. Low values of chlorides. 91.97 mg/l and also, for sulfates in the leachate samples favors for the biological treatment of leachate samples. The permeability test performed for the solid waste samples shows that the values of coefficient of permeability K was nearly 6.33x 10-3 cm/sec. these vales shows that the leachate can easily pass through the solid waste samples, if provided as a packing material. Leachate flowing through will degrade the organic matter present through the microbial action. The vales of void ratio obtained (e = 0.31) as well as degree of saturation also support the same. The vales of nutrient analysis for the solid waste samples such as nitrogen (0.71%), phosphorus (0.82%) and potassium (0.71%) also support the biological treatment option as these nutrients levels can provide sufficient support for the growth of microorganisms.

Fig: 02:- Waste dumping site at Warriana Pind, Kapurthala road, Jalandhar, Punjab.

Fig.03 :- Transportation of solid waste at dumping site of Warriana Pind, Jalandhar.


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The problem related to SW management and the prevailing SW management practices in the MCJ have been evaluated vis-à-vis the standard SWM methods, and suggestions have been put forward keeping in mind the ground realities and system limitations. In Jalandhar city most of the residential areas have limited storage spaces for solid waste. In these areas, waste is mostly of a biodegradable nature. In some places of the city open dumping of the garbage has been noticed which could results into health hazards as well as fly nuisance.

Fig. 04:- Waste characterization at dumping site of Warriana Pind, Jalandhar. Punjab. HANDLING: There are various other problems that could be related to improper handling and storage of solid waste has been noticed in the area. Stray animals like pigs, dogs and cows further increases the problem of spreading and littering of solid waste as they are generally seen at the site of handling and storage of solid waste. COLLECTION AND TRANSPORTATION Solid waste is collected from the bins generally from every point. This collection from residential areas is carried out daily as the organic matter decomposes rapidly due to hot climatic condition generally prevailing in the area. Hand driven cart pullers collect the solid waste from door to door. These cart pullers segregate the plastic bags, polythene and metal, which is then sold to kabariwalas. From this waste, non degradable solids could be separated from organic waste materials, which can be recycled. Further, this collection method is also economically feasible. For transportation of solid waste, vehicles are used. The use of vehicles depends on physical layout of the roads and cost of manpower available and maintenance provisions. Truck tippers, tractor trailer etc. are mainly used for the transportation of solid waste to the site. PRESENT SCENARIO FOR SOLID WASTE MANAGEMENT IN JALANDHAR CITY First problem is of littering done by the residents. Street sweeping in the core areas city is done regularly and fairly well whereas in some areas it is done neither daily nor regularly. Householders particularly from slums, low income and middle income groups and shopkeepers frequently throw waste on streets and roads and also into open spaces. Open drains after collection hours causes excessive littering as well as clogging of drainage system. To solve this problem waste storage containers should be given to shopkeepers and slum dwellers.

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Second problem is of poor conditions of containers and the unhygnic areas around them. More than half of collection and storage is done by using open storage enclosures and these results in a unhygienic conditions, foul smell and odor and proliferation of flies and vectors in those areas. Open enclosures should be removed and closed containers should be kept on their places. Volume of storage bins should also be designed by overestimating the generation of waste, not underestimating as it is done currently. The next problem is of distribution of labor and resources. Handcarts and sanitation workers are distributed to each area on population basis as per the norms applicable in the country. This mean, that the amount of carts and workers is very less, to handle this problem. The number of sanitation carts and workers should be also increased. Other problems like poor working conditions, inadequate maintenance of the collection vehicles. It should be solved and last but not the least the collection cost should also be decreased.

WASTE DISPOSAL OPTIONS A number of disposal options are available in form of repetitive technology like sanitary land filling, incineration and composting. The Municipal Cooperation Jalandhar has signed a MoU with Punjab Grow more Fertilizers Ltd. for converting waste into manure using the waste sanitation treatment technology. The main advantage of this waste sanitation treatment is that in this treatment technology area requirement is less. Relatively clean refuse is generated by the process, which can be used for land filling and other related applications. Polythene and plastic materials that have been segregated can be recycled. The landfill operation could be used for the solid waste management. It is a biological method of waste treatment. Solid waste can be stabilized by dividing into five distinct phases within the overall process. In the first phase aerobic bacteria deplete the available oxygen. As a result temperature increases. In second phase, anaerobic conditions established and hydrogen, carbon dioxide gases are is evolved. In the third phase, methane is liberated and in the fourth phase methnogenic activities become stabilized .In the last phase, the system returns to aerobic conditions within the landfill. The duration pf each phase varies with environmental conditions prevailing in the area.

FUTURE TECHNOLOGIES These results strongly support the use of Bioreactor landfill technology for the municipal solid waste of Jalandhar city. Bioreactor landfill is a municipal solid waste landfill that uses enhanced biochemical processes to transform and stabilize the decomposable organic waste within short time of 5 to 10 years as compared to long time of 30 to 100 years required for conventional landfills. Bioreactor landfills are gaining popularity worldwide and they have also being demonstrated at various landfill sites. A bioreactor landfill can be classified as anaerobic, aerobic, or hybrid. In an anaerobic bioreactor landfill, moisture is added to the waste using re-circulated leachate and non-indigenous liquids to obtain optimal moisture levels. Biodegradation occurs in the absence of oxygen which results into enhanced rate of methane production established. An aerobic bioreactor landfill involves addition of moisture through recirculation of leachate that has been collected from the leachate collection and removal systems. Sometime, air is also injected into the landfill through vertical or horizontal wells to promote aerobic activity and waste stabilization in the landfill. The hybrid technique utilizes both aerobic and anaerobic methods to accelerate waste degradation. Compared to conventional “dry tomb” landfills, a bioreactor landfill rapidly stabilizes Municipal Solid Waste into a stabilized form where potential for contaminant leaching is minimized and therefore, adverse environmental effects are also reduced. The material that remains in the landfill after stabilization consists of non-biodegradable waste with residual biodegradable materials. Metal, plastic and glass can be recycled in advance by using appropriate


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recycling techniques .The residual bio-degradable material can be used for the composting. During the process of landfill stabilization, waste mass is lost mainly through the production of landfill gas. The resulting landfill mass will settle, with decreasing volume of the placed material in landfill.

REFERENCES 1. Dixon, N., and Jones, R. V. (2005). “Engineering properties of municipal solid waste.” Geotext. Geomem. 23(3), 205-233. 2. Fungaroli, A., and Steiner, R. (1979). “Investigation of sanitary landfill behavior.” Final Rep. U.S. EPA 600/2-79-053a, Vol, 1. 3. Gotteland, P., Gachet, C., and Vuillemin, M. (2001). “Mechanical study of municipal solid waste landfill.” Proc., 8th Int. Waste Management and landfill Symp, CISA, S. Margherita di Pula, Cagliari, Italy, 425-433. 4. Doedens, H., Cord-landwehr. K., (1989), “Leachate recirculation in sanitary land filling: process, technology and environmental impacts.” T.H. Christensen, R. Cossu., and R. Stegmann, Eds., Academic press, London. 5. Gurijala K. R., Suflita J. M., (1993), “Environmental factors influencing methnogensis of refuse in landfill samples.” Env. Sci. & Tech., 27(6): 1176-81. 6. Tchobanoglous, G., Theisen H., and Vigil S.A.,(1993), “Integrated Solid Waste Management: Engineering Principles and Management Issues” Mcgraw-Hill, New York, 7. U.S. Environment Protection Agency (1993), “Standards for the Use or Disposal of Sewage Sludge.” Fed. Reg., 58(32), p. 9248. 8. Zekkos D., et al. (2006). “Unit weight of municipal solid waste.” J. Geotech. Geoenviron. Eng., 132(10) ,1250-1261. 9. NEERI (1995), “ Strategy papers on SWM in India” Aug-1995. 10. Ladhar S. S.,(1998)., “Municipal Solid waste management, Environmental issues in technical education”. Chandigarh. Punjab state council for science and technology. 11. Shukla S. R., (1992)., “Solid-waste management- Indian scenario.” In: Picford J., editor, Water, Environment and management of 18th WEDC Conference. Kathmandu, Nepal 30 august- 3 September 1992. 12. Ministry of Environment and Forest notifications ,New-Delhi, 2000 13. Singhal S. P.,(2001), “Solid waste management India : Status and Future Directions. 14. Kreith, F. (1994), Editor “Hand book of solid waste management” New York McGraw-Hill. 15. United States Environment Protection Agency (1989). “Decision makers Guide to solid waste management,” Washington, U.S. Environment Protection Agency. 16. United States government (1989)., Office of technology assessment. Facing America’s Trash; “What next for municipal solid waste?” Washington OTA.

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INDUSTRIAL SOLID WASTE MANAGEMENT IN A PETROCHEMICAL COMPLEX (IRAN)

N. Mokhtarani Faculty of Engineering, Tarbiat Modares University, P.O.Box: 14155-143, Tehran, Iran B. Mokhtarani Chemistry & Chemical Engineering Research Center of Iran, P.O.Box 14335-186, Tehran, Iran

ABSTRACT The aim of this study was to optimize different functional elements of the industrial wastes producing in a petrochemical complex. According to the data collected, more than 63000 metric ton per year of industrial wastes are generated in this complex. Because of different types of the products and diversity of the industrial residues, the industrial solid wastes were classified to hazardous, lowhazardous and non-hazardous with the weight percentage of 71%, 28% and 1% respectively. In most cases, Recycling and reuse is an important tool for minimization of these wastes. If suitable techniques are performed, the amount of hazardous wastes generates in this complex will be reduced about 80%. According to the obtained results, more than 56 percent of the total wastes in this complex can be sold; 41% must be disposed in the landfill and only 3% should be burned in the incinerator. Keywords: Disposal, Hazardous Waste, Industrial waste, Petrochemical complex, Waste Generation. 1. INTRODUCTION Nowadays industrial solid waste is a serious environmental problem in developing countries. Due to the rapid industrial growth in these countries, the amounts of industrial waste are increasing. Highly toxic and hazardous materials are injurious to both human health and environmental quality. A vast array of flammable, explosive, caustic, acidic and highly toxic chemical substances are used and produced by industries, agricultural and domestic sectors (Cunningham, 2003). Management of industrial solid wastes is distinctly different from the approach used for municipal solid waste (Freeman, 1989). There is a lot of similarity in the characteristics of wastes from one municipality or one region to another, but for industrial wastes, only a few industrial sectors or plants have a high degree similarity between products and wastes generated (Woodard, 2001). Improper management of industrial waste generates a number of problems for environment. For proper management of industrial wastes, it is necessary to get exact information and data about the waste characteristics, climatic conditions and the effect of these wastes on human health and environment. Major groups of industrial materials and solid wastes are harmful or hazardous and must be controlled properly. An advanced system of industrial solid waste management is composed of several functional elements including: Generation and storage; Pollution prevention and waste minimization; Recycling and reusing; Collection and transfer and Treatment and Disposal (LaGrega et al. 2001). In such a system, all steps of management from the generation of waste to the final disposal step are considered carefully. Industrial wastes, varies greatly, depending on factors such as type and number of industrial plants, economic situation, and environmental regulations. In this study, the industrial solid waste management in a Petrochemical Complex has been investigated. This complex established in 1973 and at present consisted of 16 petrochemical plants in Corresponding author, Tel: +982182884921, Fax: +982182883332, E-mail: [email protected]


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operation. In order to find appropriate techniques for the waste minimization, Quantitative and qualitative analyses of the industrial solid wastes were accomplished. Furthermore, the industrial solid wastes were classified according to their hazards characteristics. Finally, the appropriate methods for waste minimization of these residues were proposed. 2. MATERIALS & METHODES Solid waste management of this complex was studied in a period of one year. To investigate the present situation of industrial waste management, it is necessary to get information about the wastes, which generated in this complex. For this reason, several questionnaires were prepared and distributed among various units and other related organizations. The collected data were based on the data from the above-mentioned questionnaires, visual observations by the authors, available reports and several interviews and meetings with responsible persons including the engineers who are working in these complex HSE section. In order to have qualitative analysis, some samples were taken and send to the accredited laboratory.

3. RESULTS & DISCUSSION

3.1. Industrial Solid Waste Generation and Characteristics Industrial waste production and composition depend on many factors, such as stage of development; socio-economic, climatic and geographical conditions; and collection frequency (Collivignarelli et al., 2004; Tchobanoglous et al., 1993). Data on quantity variation and generation are useful in planning for collection and disposal system (Sharholy et al., 2008). As mentioned this complex has 16 main units and the characteristics and amount of each industrial waste was identified in each unit. According to the data collected for industrial solid waste generation, more than 63000 metric ton of industrial wastes are generated in this petrochemical complex annually. The quantity and type of these wastes are summarized in table 1. Table 1. The industrial solid wastes generated. Waste type

Quantity (ton/year)

Fuel oil residues

15700

Low quality polymer

14000

Spent catalyst

450

sludge

26000

Coke & hydrocarbon

2500

Packaging materials

1100

Spent adsorbent

2200

Overhaul wastes

1000

Clay

100

Total

63050

The type of industrial waste, are very varied in each unit and for this reasons the waste management in this region is a complex task. In order to overcome this problem, the industrial solid wastes were classified to hazardous, low-hazardous and non-hazardous waste materials. This classification was accomplished based on the information, which is reported by international organization such as Basel (Basel convention, 2006) or US Environmental Protection Agency (US Environmental Protection Agency, 2006, US EPA's Chemical Compatibility Chart, 2006) or information extracted from MSDS (Material Safety Data Sheet) for each component.

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According to the obtained data, the weight percentage of hazardous, low hazardous and non hazardous wastes are shown in figure 1. As the figure shows, more than 70% of industrial wastes are classified as hazardous waste. The main hazardous wastes in this petrochemical complex are fuel oil residues, waste oils, low quality polymers, spent adsorbents and molecular sieves, spent catalysts, contaminated clays and different types of sludge.

Figure 1. Classification of industrial waste (wt %)

3.2 Industrial Solid Waste Minimization (Recycling & Reuse) Recycling and reuse of valuable materials is an important tool for minimization of industrial wastes. This method is very important from the economic point of view. If a suitable technique can be applied, the cost of final disposal can be diminished. By using recyclable material as a feed in the production process, the cost of feed material will be decreased and ultimately the cost of production will be reduced. Minimization of industrial waste reduced the volume and toxicity of waste (LaGrega et al. 2001). In this study the results indicated that there is a significant potential for recycling and reuse. Possible application and utilization of hazardous wastes in this complex are reported in table 2. As shown among the 63000 Ton/year industrial waste which generated, 34850 ton will be recycled or reused. By applying recycling / reuse techniques in this petrochemical complex the amount of hazardous waste will be reduced about 80%. Table 2. Possible application and utilization of hazardous wastes Waste Type

Quantity (ton)

Possible Application and Utilization

Fuel oil residues

15700

Carbon black production

Low quality polymers

14000

Plastic industries

Spent catalysts

450

Regeneration

Coke & hydrocarbons

2500

Refining and reuse

Spent adsorbents

2200

Regeneration

Total

34850

The most important ways for minimization of industrial waste in this complex are: - Source separation of industrial waste according to recyclable and non- recyclable material - Waste oil mixing prevention and recycling of waste oil. - Applying the optimum condition in process in order to reduce the industrial waste.


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- Selling the recyclable material to the accredited recycling factories. - Foundation a proper environmental management in the complex.

3.3. Industrial Solid Waste Storage The proper storage of industrial waste must be performed after source separation. At present, the storage system of industrial waste in this complex is not suitable and the industrial wastes are stored in non-proper container. In order to perform a suitable storage of industrial waste the following comments are proposed: - The industrial waste must be storage in a proper container and in a safe environment. - The industrial waste must be storage according to their chemical compatibility. - The international labels should be placed on containers. To prevent any unusual problem the storage place of industrial waste should be checked regularly.

3.4 Industrial solid waste collection & transfer The Industrial solid waste collection and transfer is one of the important steps of industrial solid waste management and must be accomplished by the special teams. This step is a complex task because the industrial wastes are not generated regularly and each type of industrial waste have different period of generation. In order to perform a proper collection and transfer the public health and safety problem must be considered. The recyclable waste should be collected in each unit and transfer to the recycling and reuse plant, at least once a week. The collection and transfer of non hazardous wastes must be conducted like the municipal wastes. The collection and transfer of hazardous wastes should be performed under special cares and Basic rules of public health and safety should be considered. For this reason the following comment are proposed: - Leakage preventions should be considered during collection and transportation - The persons who are collecting these wastes should have suitable dress and prevent from any contact to these materials. - The Incompatible reactive waste materials must be separated during collection and transfer. - The international labels should be placed on containers and transportation vehicles. - The transfer of hazardous waste must be tracked by detail shipping manifests. - The trucks, which transfer the hazardous waste, must be well equipped. - The trucks should be transferred the hazardous waste to the disposal site in low traffic times of the day. - The industrial waste containers should be selected from compatible materials. In order to reduce the environmental pollution and health risk to the people who are living in this region the use of transfer station is not recommended. So, it is suggested to transfer all of the industrial waste to the disposal site directly.

3.5. Treatment and Disposal of Industrial Waste Treatment and disposal is the final steps for the industrial wastes management. In this step, the industrial wastes are disposed according to their danger potential, physical, and chemical properties. The important methods for disposal of industrial wastes are treatment, recycling, incineration, stabilization and landfilling. Figure 2 shows the proposed method for disposal of industrial wastes in this complex. As shown, 56% (near 35000 ton) of industrial waste can be treated and recycled annually. These wastes can be sold to the other factories and are very useful from economical point of view. The results of this study also show that more than 25800 tons of industrial waste should be sent to the landfill and less than2000 ton to the incinerators annually.

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Figure 2. Proposed disposal method for industrial solid waste

At this complex, the non-recyclable industrial wastes that enter the disposal area are classified into three categories including: 1. Waste which can be landfilled directly (non-hazardous wastes), 2. Waste that needs stabilization prior to landfilling (hazardous waste) 3. Low hazardous wastes, the low hazardous wastes are solid wastes, which are doubtfully to be hazard. The methods for disposal of these wastes are shown in figure 3.

Figure 3. The proposed disposal diagram for industrial solid wastes The landfill of industrial wastes should be equipped with two separate layers and the liquid collection system must be installed in order to prevent leakage of industrial leachate. Monitoring of landfill is an important task in waste management and the landfill must be controlled regularly. Improper control of landfill may results of the pollution of water resource and contamination of soil as well as generation of landfill gases and exposure of human to chemical gases (Basel convention tech. guideline, 2002).


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4. CONCLUSION The aim of this study was to develop a management concept for industrial waste products in a petrochemical complex. The obtained results showed that about 63000 ton of industrial wastes are generated in this region annually. Fuel oil residues, spent adsorbents, sludge and spent catalysts are the major parts of produced wastes in this study. The analysis reveals that 71 percent of these wastes are hazardous and must be disposed under special cares. By applying recycling / reuse techniques in this petrochemical complex the amount of hazardous waste will be reduced about 80%. This study also indicated that more than 56 percent (35000 ton/year) of the total wastes are recyclable and can be sold to the accredited recycling factories; 41% must be disposed in landfill and only 3% should be burned in the incinerator. Special care is necessary during the collection and transfer of industrial wastes. The waste products that enter the disposal area can be classified into three categories (i.e. nonhazardous waste, hazardous waste and low hazardous waste) and must be dumped in separate landfill compartments. By implementation of the integrated solid waste management in this complex, the environmental impacts of the wastes will be minimized.

5. REFERENCES Basel convention on the control of trans-boundary movements of hazardous wastes and Their Disposal, ,( access date: 2006), adopted from http://www.basel.int/text/con-e.htm Basel convention technical guidelines on specially engineered landfill, Report No. 2. Basel convention series, 2002, Switzerland. Collivignarelli, C., Sorlini, S., Vaccari, M., 2004. Solid Wastes Management in Developing Countries, CD-ROM of ISWA 2004 World Congress, October 17–21, Rome, Italy. Cunningham, W. P., Cunningham, M. A., Saigo, B. W., (2003) Environmental science, a global concern. McGraw-Hill Publications, New York, USA. Freeman, H.M. (1989) Standard Handbook of Hazardous Waste Treatment and Disposal. Mc-Graw Hill Publications, New York, USA. LaGrega, M.D., Buckingham, P.L., & Evans, J.C. (2001) Hazardous Waste Management, 2nd edn. Mc-Graw Hill Publications, New York, USA. Sharholy, M., Ahmad, K., Mahmood, G., Trivedi, R.C., 2008. Municipal solid waste management in Indian cities – A review. Waste Management 28 (2), 459–467. Tchobanoglous, G., Theison, H., Vigil, A.S., 1993. Integrated Solid Waste Management. McGrawHill International Edition. US Environmental Protection Agency, (access date: 2006), Identification and listing of hazardous waste, 40 CFR, Chapter I , PART 261, adopted from http://ecfr1.access.gpo.gov. US EPA's Chemical Compatibility Chart, (access date: 2006), A method for determining the compatibility of chemical mixtures, EPA-600/2-80-076, adopted from www.epa.gov. Woodard, F. (2001) Industrial Waste Treatment Handbook. Butterworth- Heinemann Publications, USA.

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A BRIEF NOTE ON NATURE, HANDLING AND MANAGEMENT OF HAZARDOUS WASTE Danish Shahab, Zoofishan*, M.Y.K. Ansari, Zeba Khan, Sana Choudhary, Honey Gupta & Alka Cytogenetics and Mutation Breeding Lab, Department of Botany, Aligarh Muslim University, Aligarh-202002, U.P. (INDIA) *Dolphin P.G. Institute of Paramedical and Natural Sciences Manduwala, Ckrata Road, Dehradun- U.K. (INDIA) E-mails: [email protected] & [email protected]

Abstract: Today, it is a matter of great concern that our lives are being affected by waste particularly hazardous waste and waste disposal is becoming a major problem in developing countries. The term “hazardous waste” includes all the toxic chemicals, radioactive materials and biological or infectious waste which affect the human as well as the animal health, causing some serious diseases. In developing countries especially in India and China, the expansion of market is going on vary rapidly and developed countries have a keen sense that India and China are big markets for the consumption of their manufactured products so most of the developed countries are ready to invest money in India and China to establish their production units for selling their daily needed products in these markets and getting profit. In order to compete them, some local businessmen are also manufacturing the same products at low prices but they do not have the adequate recycling and disposing facilities for industrial waste, which is formed as byproducts during the manufacturing of these products and sometimes the technologies required for the recycling and disposing these hazardous byproducts are expensive to use and local businessmen can not afford such technologies at present product’s maximum retail price (MRP). On the other hand, developing countries also have no adequate recycling and disposing facilities for waste particularly, for hazardous waste and to import these technologies from other developed countries is an expensive deal. It is a natural phenomenon that excessive and unplanned utilization of resources will create more waste. Ultimately, it becomes necessary to aware about the nature, handling and management of hazardous waste because we daily utilize these products like fluorescent lights, batteries, cell phones, televisions, pesticides etc. for a convenience in our lives. This article is a small effort to make familiar the masses about the types of hazardous waste, their harmful effects on human as well as on animal health and their disposing measures because there is an interconnection in between human and animal health.


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Introduction: “MAN CREATED PLASTIC BAG, TIN, ALUMINIUM, THE CELLOPHONE WRAPPER & PAPER PLATE. THIS WAS GOOD BECAUSE MAN COULD TAKE HIS AUTOMOBILE & BUY ALL HIS FOOD IN ONE PLACE. HE COULD SAVE WHICH WAS GOOD TO EAT IN FRIDGE & THROW AWAY WHICH HAS NO FURTHER USE. SOON THE EARTH HAS COVERED WITH PLASTIC BAGS, CANS & DISPOSABLE BOTTLES. THERE WAS NO SPACE TO SIT DOWN OR WALK. THEN MAN SHOOK HIS HEAD & CRIED “LOOK AT THIS GODAWFUL MESS…………………………” ART BUCHWALD

Any kind of material that is not needed by the owner, producer, or processor due to the exponential growth of human activities is known as waste. Waste has become a problem that needs to be managed it is an important environmental and public issue through out the world. The term Hazardous donates the potential of any substance to pose a threat to life or material. The waste, which is produced during healthcare activities as well as industrial activities, carries a higher potential to infect or to make injury to the living system. Basically, inadequate and inappropriate handling of hazardous waste may have serious impact on public health and environment. Mainly waste are of two types: 1.Hospital Waste: Waste, which is generated during the diagnosis, treatment or immunization of human beings or animals or in research activities, 2. Industrial Waste: Waste, which is generated as byproducts by any industry and posses a potential hazard to human health and environment.

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TAKE A LOOK ON TYPES OF HOSPITAL AND INDUSTRIAL WASTE Types of Hospital Waste Types of Industrial Waste 1. Infectious Waste: Waste containing 1. Domestic Waste: Like sewage, house hold pathogens e.g. laboratory culture, waste from garbage , bulky waste including packaging isolation wards, swabs, blood cultures and materials, furniture and used cars etc. equipments which come in contact with infected patient excreta etc. 2. Pathological Waste: Human tissues or 2. Factory Waste: Like slaughter house waste, fluids e.g. body parts, blood, body fluids etc. braveries paper mill waste steel mill waste and power plants waste etc.

3. Pharmaceutical Waste: Expired vaccines 3. Oil Industry Waste: Like oil spills, oil and tablets along with their containers etc. leaks etc. 4. Sharps: waste like needles, syringes, 4. e-Waste: Waste, which is created from infusion sets, scalpels, knifes blades and discarded computers etc. broken glasses etc. 5. Pharmaceutical cum Genotoxic Waste: 5. Construction Waste: Waste from buildings Waste containing drugs which are used in that are demolished or renovated and materials discarded after completing a building etc. cancer therapy and genotoxic drugs etc.

6. Chemical Waste: Waste containing 6. Extra-active Industry Waste: Mining, chemicals like lab reagents, film developer, quarrying and slurries etc. expired disinfectant and solvents etc. 7. Metallic Waste: Batteries, broken 7. Agriculture Industry Waste: Organic thermometers and blood pressure gauges etc. waste from plants and animals and irrigation water containing pesticides etc.

8. Pressurized Containers: Gas cylinders and 8. Food Processing Waste: Organic solid and aerosol cans etc. liquid waste come from discarded food materials etc.

9. Radioactive Waste: Unused liquid 9. Nuclear Waste: Waste from nuclear from radio therapy, and absorbent power plants and nuclear weapons etc. paper etc.


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SOURCES OF HOSPITAL & INDUSTRIAL WASTE: Types of Waste

Hospital Waste

Industrial Waste

Sources of Waste The areas involve in generation of hospital waste are as governmental hospitals, private hospitals, nursing homes, physicians’ office/clinics, dispensaries, medical research and training centers, mortuaries, dentist office/clinics, blood banks and collection centers, laboratories, vaccination centers, biotechnology institutions, paramedical colleges, slaughter houses, animal houses, medical stores etc.

Point sources

Those which have a permanent place from where it can be cured for e.g. big and small industries (pharmacy, textile, plastic, rubber) factories, pesticide stores, etc.

Non point sources

Those which do not have a fix place from where it can be cured for e.g. farming lands, orchids, local nurseries, gardens etc.

Diseases caused by the hazardous waste in human beings: Broadly these diseases can be classified into two categories viz. Infectious and genetic diseases. Infectious Diseases: Hazardous waste can cause physical as well as chemical injury and infectious diseases like rashes, burns, illness and poisoning. Heavy metals like lead, mercury, copper, zinc etc. and gamma radiations have long term effects on human health and are responsible for several chronic health problems viz. poisoning, lung diseases, cardiovascular diseases, renal disorders, miscellaneous diseases and several gamma radiation induced diseases etc. Genetic Diseases: Haemophillia, Down’s syndromes etc.

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Renal disorders caused by heavy metals -Renal nephritis -Urinary track ulcers -Cancer of bladder etc. Cardiovascular diseases caused by heavy metals Lung diseases caused by heavy metals -Acute respiratory infections -Bronchitis -Chronic bronchitis -Emphysema -Alveolitis etc.

-Hypertension -Shock etc.

Infectious diseases caused by heavy metals and gamma rays in human beings Poisoning caused by heavy metals

Miscellaneous disease caused by heavy metals -Risk of congenital malformation etc.

-Chronic mercury poisoning disease etc. Diseases caused by gamma rays -Leukemia -Lymphoma cancer -Stomach tumor -Urinary track tumor -Lung cancer etc.

Chart-1: Showing different types of infectious diseases caused by the long term effects of heavy metals and gamma rays in human beings


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Chart-2: Showing different diseases caused by different types of hazardous agents in human beings Diseases caused by biological hazardous agents -Cancer of lungs , skin & urinary bladder -Dermatitis -Eczema -Tetanus -Encephalitis -Psittacosis -Brucellosis -Hydatidosis -Actinomycosis -Fungal infections etc.

Diseases caused by physical hazardous agents – Heat: Heat hyperpyrexia , Heat exhaustion, Heat syncope, heat cramps etc. -Cold: Trench foot, Frost bite etc. -Light: Occupational cataract etc. -Pressure-Caisson disease etc. -Noise: Occupational deafness etc. -Radiation: Cancer, Aplastic anemia etc. -Electricity- Burns etc.

Diseases caused by different hazardous agents in human beings

Diseases caused by chemical hazardous agents -Gases: CO2, CO, NH3, N2, H2S, HCL causes gas poisoning -Dust (Pneumoconiosis) ¾ Inorganic dust: Coal dust causes ANTHRACOSIS Silica causes SILICOSIS Asbestos causes ASBESTOSIS Iron causes SIDEROSIS ¾ Organic (vegetable dust): Cane fibre causes BAGASSOSIS Cotton dust causes BYSSINOSIS Tobacco causes TOBACOSSIS Hay or Grain dust causes FARMER’S LUNG

724


Diseases caused by the hazardous waste in animals: Recently, parkimon’s disease came into knowledge in animals. Study carried out in the University of Washington reveals that rodenticide could cause parkimon’s disease among monkeys affecting their brains. Study on monkey therefore supports the claim that chronic pesticides exposure may cause the same disease among human beings because brain of monkey is similar to that of human being. For conducting this study, two monkeys were taken and were exposed to the rodenticide over a period of 18 to 19 months respectively, after this period both of them show the symptoms of the Parkimon’s disease. Another experiment was done on a mice and it took four years to show the similar symptoms of this disease.

Remedies used to combat the hazardous waste: Hazardous waste may be processed by an appropriate combination of methods, such as 1. Recycling 2. Solidification 3. Incineration 4. Neutralization 5. Chemical disinfection 6. Wet & dry thermal treatment 7. Microwave irradiation 8. Aerobic oxidation 9. Anaerobic fermentation 10. Secure land filling

1. Recycling: It is the processing of a used item or any waste in to useable form. A good way of dealing with solid waste problem is to recycle it. There is a large global recycling industry and recycling has multiple benefits like ¾ Reduces environmental degradation ¾ Makes money out of waste material ¾ Saves energy that would have gone into waste handling & product manufacturing e.g. when aluminum is remolded, there is considerable saving in cost so this process is


however energy intensive, making paper from waste pulp rather than virgin pulp saves 50% energy, every ton of recycled glass saves energy equal to 100 liter of oil. Examples might include lead-acid batteries or electronic circuit boards where the heavy metals can be recovered and used in new products.

2. Solidification: The process of solidification or inertization involves in mixing waste with other cement & other substance before disposal. 65% of pharmaceutical waste, 15 % of lime, 5% of water is mixed to make cemented cubes & then these are transported to a suitable storage site. This method is relatively inexpensive but is not applicable to infectious waste.

3. Incineration: It is high temperature dry oxidation process that reduces organic & combustible waste to inorganic, incombustible matter. This process is done with that material which can not be recycled or reused. There are three types of incinerator (a) Double chamber pyrolytic incinerator (b) Single chamber with static grate furnace (c) Rotary kilns operating incinerator Incineration has good disinfection efficiency and drastically reduces weight & volume of waste. This technique is inexpensive and there is no need of highly trained operators. Some drawbacks effects of this technique are significant emission of atmospheric pollution, need for periodic removal of slag & soot, massive emission of black smoke fly ash & odors

4. Neutralization: Neutralization means to render inactive. Some hazardous waste can be processed so that the hazardous component of the waste is inactivated, making it a non-hazardous waste. An example of this might include a corrosive acid that is neutralized with a basic substance so that it is nolonger corrosive.

5. Chemical disinfection: Chemical are added to waste to kill or inactivate the pathogens. Chemical disinfection is most suitable for treating liquid waste such as blood, urine, stools or hospital sewage. Solid wastes including microbiological cultures, sharps etc. may also be disinfected chemically with certain

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limitations. This technique is for high efficient disinfection under operating condition but it requires highly qualified technicians for operation of the process.

6. Wet & dry thermal treatment: Wet thermal treatment or steam disinfection is an environmentally sound technique and based on exposure of shredded infectious waste to high temperature, high pressure steam. Disadvantage Shredders are subject to frequent breakdowns and poor functioning.

7. Microwave irradiation: Most microorganism are destroyed by the action of microwave of a frequency of about 2450 MHz. The water content within the waste is rapidly heated by the microwaves and the infectious components are destroyed by heat conduction. It has a good disinfection efficiency under appropriate operating conditions but needs relatively high investment and operating costs

8. Aerobic oxidation: It has two methods (a) Compostion (b) Vermiculture

(a) Compostion: Composting is the biological decomposition of organic compounds present in wastes, under controlled aerobic condition. The temperature of waste heaps is increased by self heating mesophilic and thermophilic microorganisms. The end product of composting is a biologically stable product, used as a soil conditioner, fertilizer, bio-filter material or fuel. The objective of composting can be stabilization, volume and mass reduction, drying, elimination of phototoxic substances and undesired seeds and plant parts, and sanitation.

(b) Vermiculture: It is the process of degradation of organic wastes by earthworms with following objectives¾ To upgrade the value of the original waste material, so that it can be reused in agricultural fields to increase productivity.


¾ To produce upgraded materials in situ at a comparatively faster rate, by accelerating the rate of degradation of material that usually take a long time for degradation under normal composting process. ¾ To obtain a final product, free of chemical or biological pollutants. The efficiency of different earthworms, capability of inhabiting a high percentage of organic material, adaptability with respect to environmental factors, high fecundity rate with low incubation period, smallest period of interval from hatching to maturity and high growth rate, consumption, digestion and assimilation rates, have made them the most preferred organisms among animals to be used in the waste degradation process.

9. Anaerobic fermentation: Anaerobic fermentation has been used successfully for many years as a treatment for wastewater, sewage, and manure. However, anaerobic digestion of municipal solid waste is a relatively new technique, which has been developed in the past 10-15 years. Only biodegradable household wastes. That organic or vegetable origin can be processed in anaerobic digestion plants. Garden waste can also be included

10. Secure land filling: In this process the infectious waste is firstly treated to minimize the hazard of waste and then this waste is buried deeply in the surface of earth away from the city. It is a cost effective. There is no need of skilled workers for secure land filling but it is dangerous for the workers involved in this practice and can not help in managing radiation waste.

Important information regarding hazardous waste: ¾ D.B. Boralkar and Cloude Alvares (members of Supreme Court Monitoring Committee on Hazardous Waste) observed in 2004 that state pollution control boards (SPCBs) do not have the capability to deal with hazardous waste. ¾ Ravi Agarwal (An official in Delhi based NGO) says instead of new rules better implementation of existing rules regarding regulation, evaluation and monitoring of waste is required. ¾ Rules regarding waste management states that if a material contains less than 60% contamination by a hazardous constituent then it is eco-friendly. ¾ In May, 1997 the apex court ordered that no permission would be given by any authority for the import of hazardous of waste items which have been banned under the basal convention.

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¾ Now, the hazardous materials (management, handling and Tran’s boundary movement) rule 2007 has been displayed on the ministry’s website which replaces the hazardous Waste (Management and handling) rule 1989. ¾ The rules given by Ministry of Environment and Forest (MOEF), India have been criticized for violating conventions’ norms for minimizing hazardous waste and its control measures.

Table-1: Bio-Medical waste should be segregated into containers/bags at the point of generation of the waste. The color coding and the type of containers used are shown below Category of waste

Kinds of waste

Category No. 1

Human anatomical waste (Human tissue, organ, body parts) Animal waste (Organ, fluids, body parts)

Category No. 2

Color of plastic bags used for storage Yellow

Mode of disposal of waste

Yellow

INCENERATION

Yellow/Red

MICRO WAVING /INCINERATION

White/Blue

DISINFECTION/ MICROWAVING SECURE LAND FILL

INCINERATION

Category No.7

Waste from lab cultures, stocks of Micro organisms, human & animal Culture used in labs) Waste sharps(Needles, syringes, blades, glass) Discard medicines & drugs(Expired & old dated medicines) Solid waste (Blood, fluid, bedding material) Liquid waste (Lab washings)

Category No.8

Incineration ash (Ash from bio-medical waste)

Black

SECURE LAND FILL

Category No.9

Chemical waste (Insecticides, pesticides)

Black

SECURE LAND FILL

Category No.3

Category No.4 Category No.5 Category No.6

Black

Yellow /Red

INCINERATION/ AUTOCLAWVING

White/Blue

DISINFECTION


Measures taken by Indian citizens to overcome this problem: Enabavi: An example of collective effort against the use of synthetic pesticides in agricultural practices Enabavi is a village of 52 families and the villagers are using non pesticidal management rule (NPM). The farmer does away the use of any synthetic pesticide in agriculture. They are using traditional methods pf pest control and beside of it they are also using various home made concoctions made from neem , garlic , Chilies , plants , herb extract, cow dung and cow urine along with pheromone traps that cure pests. First of all, it helps in controlling the hazardous waste. Secondly, it also saves the money. They are doing this job to make their village “A Chemical free village”.

Conclusion: With an increase in urban population in our country, waste generation in cities has increased many times and the management of these wastes has become first priority for ruling political party. Not enough progress has been made for the treatments of bio-medical and nuclear waste. Specialized disposal methods are remain to develop to dispose these waste safely. Several researches are being carried out to develop innovative techniques by which we can convert hazardous waste to non toxic metabolites in our country. But for achieving these goals public and private organizations should join their hands together and citizens should also be aware about the nature, handling and management of hazardous waste to make our country “CLEAN & GREEN”

Acknowledgements: 1. Mohapatra, P. K. 2006. Textbook of Environmental Biotechnology. I.K. International Publishing house Pvt. Ltd. ISBN: 81 882 3754 x 2. Park, K. 2007. Preventive and Social Medicine. 19th Edition. Published by M/S Banarsidas Bhanot. 19th Edition. ISBN: 81 901 2828 0. 3. Rai, A.N. 2005. Textbook of E.V.S. Goyal Brothers Prakashan, New Delhi. Ist Edition. 4. Verma, R. 2008. Environmental Studies. Kamal Publishing House. 5th Edition.

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5. Ananthanarayan, R. and Panikar, C.K.J. 2005. Textbook of Microbiology. Orient Longman Private Ltd. Hyderabad, India. 7th Edition.ISBN: 81 250 2808 0. 6. Down to Earth magazine, 15 March, 2004. 7. Down to Earth magazine, 31 December, 2004 8. www.wikipedia.org


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SUSTAINABLE DEVELOPMENT THROUGH INTEGRATED SOLID WASTE MANAGEMENT APPROACH Ankur Kumar Student, VII Sem, B.Tech , Env. Engg, ISMU Gurdeep Singh HOD, Dept. of ESE, ISMU Tauseef Zia Siddiqui Environment Cell, HZL, Chittorgarh

ABSTRACT: As waste management issues gain public awareness, concern has risen about the appropriateness of various disposal methods. Within our modern scheme of waste management, disposal is the last phase. Most people acknowledge that disposal will always be needed (the exception being those advocating zero-waste policies). Several options are available like composting, land filling and Incineration and pyrolysis etc. Composting is considered to be the best option to deal with the waste generated, as discussed in length in the paper. Composting helps reduce the waste transported to and disposed of in landfills. During the preparation, we come across and learned that several developing countries established large-scale composting plants that eventually failed for various reasons. Landfills have also been widely unsuccessful in our country because the landfill sites have a very limited time frame of usage and the cost of operating and maintaining the landfill site is very costly affair taken into account the liability factor in the long run. Incineration, which can greatly reduce the amount of incoming municipal solid waste and bio-medical waste, is the second most common method for disposal in developed countries. However, incinerator ash may contain hazardous materials including heavy metals and organic compounds such as dioxins, etc. None of the three methods mentioned here are free from long term impacts. The aim of this paper is to focus on pollution prevention (P2) and not at the end of the pipe. This research work concludes that Integrated Solid waste management option can only bring Sustainability in true sense. An integrated waste management system entails a careful analysis of what is in the waste stream and offers ideas on practices to recover the various materials at the point of highest value. The best strategy is to match its unique position with the mix of activities that will best serve it now and far into the future.

Keywords: Integrated Solid Waste Management (ISWM), Sustainable Development.

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1.0 INTRODUCTION As the amount of solid waste generation has gone increasing day by day due to technological advancement, higher standard of living, urbanization, etc. no single method suffice as a universal solution. Rather a plethora of options has jeopardized the situation of solid waste management in absence of proper understanding and suitability to the specific conditions. A whole bench of options ranging from composting, land filling and incineration and pyrolysis etc. are available while no single method is acceptable at all locations and in all situations. This call for a whole new concept of Integrated Solid waste management (ISWM) option which considers the full range of waste streams to be managed and views the available waste management practices as a menu of options from which waste managers can select the preferred option based on site specific environmental, economic and social considerations. The goal of sustainable solid waste management is the recovery of more valuable products from that waste with the use of less energy and a more positive environmental impact. The practice of the three R’s (reduction, reuse, recycle) fits very well within the sustainable development concept. Rather than relying on a waste reduction hierarchy (Fig.1.1), integrated solid waste management (ISWM) suggests optimization of the system.

.


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2.0 ISWM PRINCIPLES The ISWM concept takes as a point of departure four basic principles: 1. Equity: all citizens are entitled to an appropriate waste management system for environmental health reasons. 2. Effectiveness: the waste management model applied will lead to the safe removal of all waste. 3. Efficiency: the management of all waste is done by maximizing the benefits, minimizing the costs and optimizing the use of resources, taking into account equity, effectiveness and sustainability. 4. Sustainability: The waste management system is appropriate to the local conditions and feasible from a technical, environmental, social, economic, financial, institutional and political perspective. It can maintain itself over time without exhausting the resources upon which it depends. Thus ISWM provides a comprehensive solution to the waste management problem taking into account the ideals of sustainable development.

Figure 2.1 Conceptual Framework of ISWM

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3.0 A CASE STUDY OF ISMU 3.1 Findings and Discussions A major portion of Solid waste generated inside ISMU typically in hostels was found to have high quantity of organic content to the tune of 50% or more.

Figure 3.1.1 Average Physical Characteristic of Waste in ISMU from Hostels Collection, transportation and segregation of waste were not done properly resulting in improper management and littering of wastes. No proper waste management option was exercised and as a result all waste was being dumped into numerous sites in and around ISMU campus. Awareness and public participation in waste management was very low and often dustbins were not available for proper storage of waste. All this called for an integrated solid waste management approach to study the best possible option of treatment which eventually comes out to be composting owing to high quantity of organic and biodegradable component in solid waste. Based on this an ISWM model has been devised which can take care of any Indian situational framework of production of solid waste be it an academic institution or a city. The following model shows the basic methodology in which ISWM can be followed. The data in brackets demonstrates the present situation which can be altered to suit the local conditions.


Waste reduction/ reuse

WASTE GENERATION (0.25-0.5 kg/capita)

On site processing / Disposal

On Site Storage

735

Resource conservation

Source Separation

RECYCLING

COLLECTION (70-90)% generation)

(Recovery 5-7%)

Revenue

(

TRANSPORT (70-80)% of generation)

Composting (Less than 3%) Transfer Station

Waste Processing

Revenue

RECOVERY

Energy Recovery (less than 1%) Revenue Revenue (User Fee)

DUMP/LANDFILL (Typically 90% of amount transported)

Figure 3.1.2 ISWM Model of SWM for a typical Indian Organization

In order to put this model into action an institutional framework is also proposed to carry out the functions in a lucid manner which is valid for any type of Indian Institution.

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ACTIVITY

Waste Segregation

MONITORING INSTITUTION

IMPLEMENTING CAPACITY BUILDING INSTITUTION INSTITUTION Generators Gov., NGOs & Media

Institution to monitor Staff & Inhabitants

Primary Collection

Institution to monitor

Secondary Collection Transportation

Integrated SWM facility

Land filling

Private Operator

Staff & Inhabitants


Private Operator


Private Operator

Gov., NGOs & Media

Composting

Figure 3.1.3 Proposed Framework for any Institution for ISWM implementation

4.0 CONCLUSION In view of complexities and wide variations in the characteristics of solid waste as well as sitespecific conditions a more holistic approach is needed to take into account the various stakeholders and management options in the form of ISWM .In the present Indian condition Composting comes out to be best option after application of principles of ISWM . Composting not only insures best management option it also promotes sustainable development in the form of organic ameliorate thus preventing the use of harmful fertilizers. It has become possible to come up to this conclusion only after we apply ISWM principles at all stages of solid waste management.


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5.0 REFERENCES Wilson, David C. and Angela C. Tormin. (2000). Planning Guide for Strategic Municipal Solid Waste Management in Major Cities in Low-income Countries. The World Bank/SDC. London, UK: Environmental Resources Management. Dulac, Nadine. (2001).The Organic Waste Flow in Integrated Sustainable Waste Management: Tools for Decision-makers. Gouda, the Netherlands: WASTE. Muller M. and L. Hoffman. (2001). Community Partnerships in Integrated Sustainable Waste Management: Tools for Decision- makers. Gouda, the Netherlands: WASTE. Developing and Implementing Integrated Solid Waste Management Systems for Tribal Nations: A Training Course Prepared by the Tribal Association for Solid Waste and Emergency Response (TASWER) and the Solid Waste Association of North America (SWANA), Spring 2003.

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EFFECT OF COAL-ASH AMENDED SOIL ON GROWTH, YIELD AND PHOTOSYNTHETIC PIGMENTS OF CALENDULA OFFICINALIS L. Iram, Athar Ali Khan and Minu Singh Air Pollution Unit, Department of Botany, Aligarh Muslim University Aligarh-202002

ABSTRACT Coal-ash is a major particulate air pollutant produced by Thermal Power Plants during coal combustion. It has a vast potential for use in agriculture as an amendment, especially due to its physical conditions. The present study was carried out at the Department of Botany, A.M.U. Aligarh to evaluate the effect of varying levels of coal-ash amended soil viz., 0,25,50,75 and 100% on growth, yield and photosynthetic pigments of Calendula officinalis L. Observations were recorded on various growth parameters (Plant height, fresh weight, dry weight per plant, number of leaves per plant and leaf area), yield attributes (number of capitula per plant, diameter of inflorescence and number of ray florets per capitula) and photosynthetic pigments (total chlorophyll content and carotenoid content). The results of the experiment revealed that 25 % coal-ash amended soil significantly enhanced growth, yield and photosynthetic pigments of Calendula officinalis over their respective controls. However, higher levels of coal-ash amended soil showed deleterious effect on various parameters studied. Key words: Calendula officinalis, coal-ash, growth, photosynthetic pigments and yield.

1. INRODUCTION Coal-ash is a major particulate air pollutant, generated during combustion of coal in coal fired power plants. Application of coal-ash in agriculture is a fast emerging and promising field of research. Coal-ash affects plant growth because of two important attributes. Firstly, it is rich in micronutrients and secondly its fine particle size improves soil texture (Khan and Bhardwaj 2002). The responses determined so far range from beneficial effect of small concentrations of nutrients at low coal-ash levels to the toxic effect at high concentrations (Druzina et al.1983, Singh 1993, Chang et al. 1977). Utilization of coal-ash in agriculture as a fertilizer would not only be a solution to the problem of coal-ash disposal but would also decrease the use of chemical non- nitrogen fertilizer. Medicinal plants produce diverse assortment of organic constituents from the earliest times, herbs have been prized for their pain relieving and healing abilities, and today still rely on the curative properties of plants in about 75 % of our medicine. Among the medicinal plants Calendula officinalis occupies a prominent position in ancient and modern systems of medicine. It has vulnerary, antiinflammatory, chloretic and antispasmdic properties. It is not often used internally now a days, but extract, tinctures and ointment are sometimes and externally to heal wound, bed sores, persistent ulcers, varicose, veins, gum inflammations and skin rashes. In the pharmaceutical industry the bright orange pigment in the flowers are used to make medicinal preparations more attractive. Present study was conducted to assess, in an objective manner, the impact of coal-ash application on growth, yield and photosynthetic pigments of Calendula officinailis L. (Family Asteraceae).

2. MATERIALS AND METHODS For this study coal-ash was collected from Kasimpur Thermal Power Plant situated 16 km away from Aligarh and brought to the Department of Botany, AMU, Aligarh. After that, pots of 30 cm size were filled with a mixture of garden soil and coal-ash in different ratios (100 % Soil, 75 % Soil: 25 % Coal-ash, 50 % Soil : 50 % Coal-ash, 25 % Soil : 75 % Coal-ash 100 % Coal-ash). The experiment was conducted in the month of November. Seedlings of Calendula officinalis were brought from University nursery and were transplanted to the prepared pots of 30 cm. Each treatment was replicated


739

3 times. Sampling was done at 70 days after planting (DAP) and various growth parameters (Plant height, fresh weight, dry weight per plant, number of leaves per plant and leaf area), yield attributes (number of capitula per plant, diameter of inflorescence and number of ray florets per capitula) and photosynthetic pigments (total chlorophyll content and carotenoid content) were observed. Total chlorophyll content was estimated by the method of Mackinney (1941). Whereas, carotenoid content was analysed as per method suggested by MacLachlan and Zalik (1963). The uniform cultural operations including plant protection measures were provided to each pot. The experimental data were analysed using the analysis of variance according to Gomez and Gomez (1984).

3. RESULTS Data presented in table-1 clearly show that the application of 25 % coal-ash amended soil was found beneficial for plant growth, yield attributes and photosynthetic pigments of Calendula officinals L. However, higher doses of coal-ash (50,75 and 100%) proved deleterious for these parameters. 25 % coal-ash significantly improved plant height, fresh wt per plant, dry wt per plant, number of leaves per plant and leaf area by 37.5 %, 41.3 %, 42.9 %, 36.9 % and 35.2 % respectively, over control. Correspondingly, number of capitula per plant, diameter of inflorescence and number of ray florets per capitula was found to be elevated by 50.1 %, 13.0 % and 35.0 % relative to the control. Similarly, total chlorophyll content and carotenoid content was enhanced by 16.4 % and 19.8 % at 70 days after planting.

4. DISCUSSION Coal-ash has a vast potential for use in agriculture as an amendment, especially due to its physical conditions, which are conducive for plant growth, as well as due to the presence of macro and micronutrients in it. In the present investigation, 25 % coal-ash application was found beneficial for plant growth yield and photosynthetic pigments of Calendula officinalis L. The beneficial effect of coal-ash at lower levels (10-30%) have already been observed on many crops – cabbage, chickpea, cucumber, lentil, maize, potato, tomato, wheat etc. (Mishra and Shukla 1986, Singh 1989, Raghav and Khan 2002, Faizan 2002). However, higher levels (50 to 100%) were found harmful for all these parameters. This shows that the available nutrients present in coal-ash were beneficial at certain levels for utilization of a particular plant species. Similar results have also been observed in cucumber, maize, tomato, wheat, soyabean and potato plants (Khan and Khan1996, Pasha et al. 1990, Raghav 2006). It might be due to presence of excess or toxic substances in coal-ash at higher level which became toxic to plants. The significant effect of coal-ash amendment on photosynthetic pigments may be due to the fact that coal-ash improves the nutrient status of soil by altering its physiochemical characteristics. These results are also supported by the finding of Singh et al. (1994) and Khan and Khan (1996).

5. CONCLUSION It is therefore, concluded that the lower doses of coal-ash showed beneficial effect on plant growth, yield and photosynthetic pigments of Calendula officinalis L. However, higher doses proved deleterious for this plant.

740


Table 1. Impact of coal-ash application on growth, yield and photosynthetic pigments of Calendula officinalis L.at 70 days after plantings (DAP). Concentration Plant of coal ash height (cm) (%)

Fresh weight per plant(g)

Dry weight per plant (g)

Number of leaves per plant

Leaf area (cm2)

Number of capitula per plant

Diameter of Inflorescence per plant (cm)

Number of ray florets per plant

Total chlorophyll content -1

(mg g FW)

Carotenoid content (mg g-1 FW)

0 (T0)

38.66

15.28

3.52

39.67

36.03

9.33

5.76

53.33

1.430

0.394

25 (T1)

53.17

21.59

5.03

54.33

48.70

14.00

6.53

72.00

1.664

0.472

50 (T2)

29.09

11.40

2.73

30.67

30.43

7.00

5.33

43.67

1.339

0.360

75 (T3)

24.41

9.46

2.27

26.33

25.32

5.33

4.67

37.33

1.298

0.336

100 (T4)

18.80

7.11

1.71

21.00

19.58

4.33

4.33

30.67

1.239

0.325

LSD at 5%

4.39

1.75

0.43

4.32

5.17

1.68

0.39

6.32

0.047

0.021


741

6. REFERENCES Chang, A, C, Lund, L, J, Page, A, L, and Warneke, J, E, 1977, Physical properties of coal-ash amended soils, Journal of Environmental Quality, 6, p267-270. Druzina, V, D, Miroshracheuko, E, D, and Chertov, D, D, 1983, Effect of industrial pollution on nitrogen and ash in meadow phytocoenotic plants, Batanichnyi Zhurnal, 68, p1583. Faizan, S, 2002, The Impact of Fly ash Application in Soil on Crop Productivity and Microbial Ecosystem, Ph. D. Thesis, Aligarh Muslim University, Aligarh. Gomez, K, A, and Gomez, A, A, 1984, Statistical Procedure for Agricultural Research, 2nd Edition, John Wiley and Sons, New York. Khan, M, R, and Khan, M, W, 1996, Effect of fly ash on growth and yield of tomato, Environmental Pollution, 91, p105-111. Khan, S, Bhardwaj, R,K, 2002, Effect of fly ash on the growth, development and metal ion uptake by broad bean (Capsicum frutescens) plants, Ecology, Environment and Conservation, 8, p47-50. Mackinney, G, 1941, Absorption of light of chlorophyll solutions, Journal of Biological Chemistry, 140, p315-322. MacLachlan, S. and Zalik, S, 1963, Plastid structure, chlorophyll concentration, free amino acid composition of chlorophyll mutant of barley, Canadian Journal of Botany, 41, p1053-1062. Mishra, L, C, and Shukla, K,N,1986, Effects of fly ash deposition on growth, metabolism dry matter production in maize and soyabean, Environmental Pollution, 42, p1-13. Pasha, M,J, Khan, M,W, and Siddiqui, Z,A, 1990, Effect of soil amendments with fly ash of thermal power plant origin on root-knot nematode on cucumber, Nematologica, 36, p381. Raghav, D, 2006, Studies on the Effect of Particulate Air Pollutants Application on Potato (Solanum tuberosum L.) Ph.D. Thesis, Aligarh Muslim University, Aligarh. Raghav, D, and Khan, A, A, 2002, Impact of industrial particulate pollutants applied to soil on growth and yield of tomato, Thailand Journal of Agricultural Sciences, 35, p187-194. Singh, K, 1993, Impact Assessment of Root-Knot Nematode on Air Pollution Stressed Plants,Ph.D. Thesis, Aligarh Muslim University, Aligarh. Singh, N, Singh, S, N, Yunus, M and Ahmad, K, J, 1994, Growth response and element accumulation in Beta vulgaris L. raised in fly ash amended soils, Ecotoxicology, 3, p287-298. Singh, S, K, 1989, Studies on Interaction of Air Pollutants and Root-Knot Nematodes on Some Pulse Crops, Ph. D. Thesis, AMU, Aligarh.

Advanced Oxidation Process


745

CATALYTIC WET AIR OXIDATION OF OXALIC ACID Shyamal Roy* and Anil Kumar Saroha Department of Chemical Engineering, Indian Institute of Technology, Delhi, India Abstract: Catalytic wet air oxidation (CWAO) is an attractive and useful technique for treatment of effluents where the concentrations of organic pollutants are too low for the incineration and when biological treatments are ineffective, e.g. in the case of toxic effluents and other pollution control techniques are not economically feasible. In the CWAO process, the organic contaminants dissolved in water are either partially degraded by means of an oxidizing agent into biodegradable intermediates or mineralized into innocuous inorganic compounds such as CO2, H2O and inorganic salts, which remain in the aqueous phase. In contrast to other thermal processes, CWAO produces no NOx, SO2, HCl, dioxins, furans, fly ash, etc. The CWAO of oxalic acid in waste water was studied over Pt/Al2O3 catalyst at atmospheric pressure. The effects of air flow rate, initial concentrations of oxalic acid, agitation (rpm), temperature, catalyst loading ,catalyst dosage, size of the catalyst and kinetics were studied. Keywords: Catalytic wet air oxidation; Atmospheric pressure; Oxalic acid, Pt/Al2O3.

1. INTRODUCTION: An immense array of organic compounds is currently widely used, and many of these are potent contaminants when they are released into freshwater ecosystems. In a great majority of industrial processes, water is used as a solvent, reaction or transport medium; therefore, it is not surprising that efforts have been made for the abatement of pollutants from industrial aqueous waste streams in the last two decades. Oxalic acid is present in the effluent discharged from various industries such as textiles industries, metal treatment industries, plastics industries, photography industries, refinery industries, petrochemicals industries, pharmaceuticals industries, agrochemicals industries, pulp and paper industries. Oxidation of phenol leads to formation of carboxylic acid such as formic acid, oxalic acid and acetic acid. It causes severe irritation and burns to skin, eyes, and respiratory tract. It is harmful if inhaled or absorbed through skin. Wet air oxidation (WAO) process is a very attractive and useful technique for treatment of effluents where the concentrations of organic pollutants are too low for the incineration process and when biological treatments are ineffective, e.g., in the case of toxic effluents [1,2].WAO was applied to removing total organic carbon (TOC) such as insoluble polymers[3],wastewater [4,5,6,7], and certain organic compounds [ 8,9]. The efficient removal of pollutants via WAO process requires very high temperature and pressure, typically in the range 473–573K and 7–15MPa, respectively [10].However, the severe reaction conditions can lead to high installation costs, and practical applications of this process are limited.The use of catalysts makes the process more attractive by achieving high conversion at considerably lower temperature and pressure [1, 11, 12].Gonul Gunduz and Meral Dukkance[13] studied the catalytic wet air oxidation of oxalic acid in aqueous solution in a stirred reactor over a Pt (0.7% in wt)/Al2O3 catalyst at atmospheric pressure, in a concentration range of oxalic acid of 500-3000 ppm, and at a temperature range of 313-353 K. The conversions obtained after 5hr were 28.96 %, 45.98 %and 30.74 % for initial concentrations of 500, 1500, 3000 ppm, respectively. Dong-Keun Lee and Dul-Sun Kim [14] studied the catalytic wet air oxidation of oxalic acid and they found that, oxalic acid could be oxidized at 353K and atmospheric pressure on a Pt (1% in wt)/Al2O3 catalyst. They carried out the reaction in batch reactor. But, no detailed information on effects of catalyst loading, temperature and kinetics has been reported in CWAO of oxalic acid over Pt/Al2O3 catalyst studied. Gallezot et al. [15] studied the total oxidation of aqueous solutions of carboxylic acids by air in a slurry reactor over the temperature range 180°C – 200°C and oxygen partial pressure of 0.3–1.8 MPa in the presence of a 2.8% Ru/TiO2 catalyst. Shende and Mahajani [16] studied the kinetics of WAO of glyoxalic acid and oxalic acid in absence and presence of cupric sulfate catalyst at 393-518K and 0.345-1.38 MPa oxygen partial pressure. They found that the wet air oxidation of oxalic acid required more severe conditions as compared to glyoxalic acid.

746


The reaction mechanisms and kinetics model have been discussed. Imamura et al. [17] studied oxidation of oxalic acid at 385K–433K by using Co/Bi [5/1] complex catalyst. They have observed about 30% TOC removal at 413K. All these studies, however, have still the problems of the operation at high temperature and high pressure. Till now study of CWAO of carboxylic acids at atmospheric pressure was almost unexplored. The aim of this study is to investigate CWAO of oxalic acid (OA) at atmospheric pressure over a Pt/Al2O3 catalyst and to study the effects of air flow rate, initial concentrations, temperature, catalyst loading, catalyst dosage, size of the catalyst and kinetics of oxalic acid degradation.

2. EXPERIMENTAL 2.1. Materials High purity oxalic acid supplied from Qualigens Chemicals, was used without further purification. Platinic chloride (Hexachloroplatinic acid, CDH) was used as the precursor of Pt/Al2O3 catalyst. γ- Al2O3 (Qualigens Chemicals) was used as the support of Pt/Al2O3 catalyst. All other chemicals used were of analytical reagent grade.

2.2. Catalyst preparation The catalyst for the present study was prepared by excess solution impregnation (ESI) method. Platinum with Pt loading catalysts supported on Alumina (Pt/Al2O3) (0.2wt.%,0.3wt.%,0.4wt.%,0.5wt.%,0.6wt%,0.7wt.%)ware prepared by excess solution impregnation using preconditioned γ-Al2O3 support and Hexachloroplatinic acid (CDH) as metal precursor. Water used in all these experiments was double distilled water prepared in the laboratory. The quantity of Hexachloroplatinic acid required for the specific catalyst with pre-determined% Pt contents was calculated from the stoichiometry.


747

Fig.1. Preparation of Pt/Al2O3 by Excess Solution Impregnation (ESI) method.

The amount of Pt solution of desired concentration was used for 100g of alumina spheres and stirred continuously for 4 hr. The excess water from the slurry was removed in a rotary vacuum evaporator at 80°C.The residue was then dried at 110°C for 24 hr in an oven followed by calcinations at 550°C in air for 4 hr for complete decomposition of Pt oxide salts and deposition of the metal on the support structure. The catalysts with 0.2 wt.%,0.3 wt.%,0.4 wt.%,0.5 wt.%,0.6 wt.%,0.7wt.% of Pt content were used for the oxidation process.

2.3. Reaction procedures: The experiments were performed in a four necks round bottom flask of capacity two liters. During the experiment there was a possibility of water vapors escaping out of the flask at high temperature. This could lead to a change in the volume of the solution can cause an error in calculating the concentration of oxalic acid. To avoid the escaping of water vapor from the flask, a condenser was placed at the top of the flask to reflux the water vapor.

Cool ing water out 4

C oo lin g wa te r in

3

6

5

1.Compressor2.Air flow 3.Roatameter4.Condenser 5.Cotact thermometer6.Automatic pipette7.Fourneck glass reactor 8.Magnetic bar 9.Temperature controller 10.Agitation(rpm) controller 11.Heating mantle

7

2

8

9

10

1 11

Fig.2 Schematic diagram of the experimental set-up

A known quantity of oxalic acid solution and catalyst was taken in the flask and air, drawn from a compressor, was bubbled through the solution. The progress of the reaction was monitored by withdrawing samples from the flask at regular time intervals and titrating against NaOH solution using phenolphthalein as a indicator to get the concentration of oxalic acid in the sample. The percentage degradation of oxalic acid, namely oxalic acid conversion, was calculated from Equation (1)

× 100

(1)

where COA,0 is the initial concentration and COA is the concentration of oxalic acid at that time. 3. RESULTS AND DISCUSSION 3.1. Characterization of the catalysts: The SEM micrographs of the catalysts are shown in Fig.3 and Fig.4. The images taken for the catalyst showed that most of the surface is covered with active sites. Platinum particles were finely dispersed on the surface of Al2O3 support. The image after 5 hr of operation showed no traces of carbon deposition on the surface [Fig.4]. There was no trace of carbon deposition on the catalysts used in the present study. The BET surface area of the catalyst was 125m2/g.

748


Magnification: 10,000 K X Fig. 3.SEM micrographs of catalyst 0.5wt% Pt/Al2O3 before use

Magnification: 10,000K X Fig. 4.SEM micrographs of catalyst 0.5wt% Pt/Al2O3 Pt/Al2O3 after use

EDX result in Fig.5 showed that there were only alumina, platinum and oxygen in the catalyst, and chlorine element was not found. Hydrogen reduction reaction was not performed during the preparation of the Pt/Al2O3 catalyst; therefore, it is speculated that alumina took part in the H2PtCl6 and chlorine was removed in the course of calcinations. cps/e V 60 0

10

50 0

40 0

6

O

Al Pt

Lin (Counts)

8

Pt

30 0

d=1.95433

10 0

2

d=1.39252

20 0

4

0 2

10

20

30

40

50

60

70

8

2 -T h e ta - S ca le Fil e: P t-Al2 O3 0 .5 %.raw - Typ e: 2 Th /Th l oc k ed - Sta rt: 2.00 0 ° - E nd: 80 .0 00 ° - Step: 0.05 0 ° - S te p ti m e: 1. s - T em p.: 25 °C (R oom ) - T im e S ta rted: 0 s - 2-T he ta : 2.0 00 ° - T h eta: 1 .000 ° - D is play pl Ope ration s: Im po rt

0 2

4

6

8

10 ke V

12

14

16

18

20

Fig.5.Elemental analysis of (0.5wt. %)

Fig 6.XRD of (0.5 wt. %)

Pt/Al2O3 catalyst by EDX.

Pt/Al2O3 catalyst

XRD result in Fig.6 showed that Pt crystal grains existed in the catalyst and the characteristic peaks were observed at 2θ=40.2°, 44° and 64.36°. It indicated that the particles dispersing on the surface of alumina were metallic Pt grains.

3.2 Effect of air flow rate and agitation speed on oxalic acid degradation: Effect of agitation speed and air flow rate on the oxalic acid degradation against time can be observed in Fig.7 and Fig.8. It is seen that the degradation of oxalic acid with time does not vary for air flow rates higher than 2 l/min [Fig.7] and for agitation speeds of 400 rpm or higher [Fig.8]. Since the catalyst is in powder form, it can be assumed that there is no internal mass transfer limitations, so that, it can be accepted that for agitation speed ≥400 rpm and gas flow rates ≥2 l/min the catalytic process was chemically controlled.

Initial concentration: 1500 ppm, Catalyst dosage: 2 g/l, Temperature: 373K, Catalyst loading:

Initial concentration: 1500 ppm, Air flow rate:2l/min, Catalyst dosage: 2 g/l,


0.5 wt. % Pt/Al2O3,Agitation: 400rpm, Catalyst size: 45-75µm Fig.7.Effect of air flow rate on oxalic acid degradation

749

Temperature: 373K, Catalyst loading: 0.5 wt. % Pt/Al2O3, Catalyst size: 45-75µm Fig.8.Effect of agitation on oxalic acid degradation

3.3 Effect of temperature on degradation: As observed from Fig.9 the increase of temperature from 323K to 373K leads to an increase of oxalic acid conversion from 25% to 67%.This is due to the increase in reaction rate constant, k but only a slight difference was observed when temperature was further increased up to 383K from 373K.This may be due to the effect of oxygen solubility which decreases with the increasing temperature.

3.4 Effect of initial concentration of OA on degradation: It was observed from Fig.10 that about 67% destruction of OA could be achieved in 300 min for an initial concentration of 1500 ppm at 373K. However, about the same conversion (45.37%, 53.75%, 62.18%, 57.98% and 41.17 %) was obtained for initial OA concentrations of 500ppm, 1000ppm, 2000ppm, 2500ppm and 3000 ppm within 300 min.

Initial concentration: 1500ppm, Air flow rate: 2 l/min,

Air flow rate:2l/min, Catalyst dosage 2 g/l,

Catalyst dosage: 2 g/l, Catalyst loading: 0.5 wt.% Pt /Al2O,

Temperature: 373K, Catalyst loading:

Agitation: 400 rpm, Catalyst Size: 45-150µm

0.5wt.%Pt/Al2O3, Agitation:

Fig.9.Effect of temperature on degradation

400 rpm, Catalyst size: 45-75µm Fig. 10.Effect of initial concentration of OA on degradation

As seen, initial rate rises to a maximum and then falls with increasing concentration of oxalic acid. This indicates that surface reaction on two adjacent Pt active sites, based on Langmuir-Hinshelwood kinetics, can be assumed to be the rate determining step in the concentration range of 500-3000 ppm oxalic acid used in this study [18]. On the other hand, the competition between reactant molecules for active sites in catalyst particles and the presence of less oxygen than required for OA concentration of 3000ppm decreases the degradation degree with the increase in concentration from1500ppm to 3000ppm.

3.5 Effect of loading of Pt (weight %) on oxalic acid degradation: Platinum content within the catalyst support was varied by increasing the concentration of the Hexachlproplatinic acid. Experiments were performed using the standard catalyst dosage2g/l.

750


Initial concentration: 1500 ppm, Air flow Rate: 2 Initial concentration: 1500 ppm, Air flow Rate l/min, Catalyst dosage: 2 g/lit, Temperature: 373K, 2 l/min, Catalyst dosage: 2 g/l, Agitation: 400 rpm, Catalyst size: 45-75µm Temperature: 373K, Agitation: 400 rpm Fig.11.Effect of Pt loading on oxalic acid degradation Fig. 12.Effect of catalyst sizes on OA degradation

At increasing platinum loading, the degradation rate hardly increased. It is observed from Fig.11 that maximum conversion [about67%] achieved at 0.5wt % loading of platinum metal, beyond 0.5 wt% Pt/Al2O3 conversion decreases. This confirms that high platinum loading is not required to optimize the process. This result may be explained by a reaction limited to the surface of the catalyst.

3.6 Effect of catalyst sizes on oxalic acid degradation: The size of catalyst particles was varied to test the influence of diffusion mechanisms on the control of degradation rates. Decreasing particle size has a significant effect on the resistance to intraparticle mass transfer, especially in the case of lowporosity materials.In Fig.12, it is observed that maximum degradation kinetic achieved at size 45-75 µm. Beyond the size 45-75µm, degradation kinetics decrease. It also possible to suggest that the reaction was limited to the external surface of the catalyst or to thin external layers of the particles and that the internal platinum crystals did not significantly contribute to the reaction.

3.7 Effect of catalyst dosage on oxalic acid degradation: As observed from Fig.13 the increase of catalyst dosage from 0.5 g/l to 2 g/l leads to an increase of oxalic acid conversion from 36.13% to 67.22%.The results show that when the catalyst dosage is increased beyond 2g/l degradation of oxalic acid is decreased [Fig.13]. This effect of the catalyst dosage can be explained by Gomes et al.[19,20]with a heterogeneously catalyzed free-radical mechanism. Higher concentration of catalyst per unit volume of solution increases the rate of the initiation step, which is the oxygen assisted radical formation from the hydrocarbon adsorbed at the surface of the catalyst. Desorption of the radicals is a fast step and leads to a high concentration of free-radicals in solution causing an increase in the rate of the free-radical termination step and consequently initial rate of the reaction decreases.


751

Initial concentration: 1500 ppm, Air flow Rate: 2 l/min,Temperature: 373K, Agitation: 400 rpm, Catalyst Size: 45-75µm Fig. 13.Effect of catalyst dosage on oxalic acid degradation

3.8 DETERMINATION RATE & ORDER 3.8.1 Determination of Rate of the reaction from the graph of effect of initial concentration on oxalic acid degradation: Initial rates (rOA, 0) calculated from Fig.10 and using equation (2) are

given in Table 1. As seen, initial rate rises to a maximum and then falls with increasing concentration of oxalic acid. This indicates that surface reaction on two adjacent Pt active sites, based on LangmuirHinshelwood kinetics.

- rOA, 0 =

× COA, 0

(2)

Table1.Rates calculated from Fig.10 and equation (2) COA,0 (ppm) COA.0(Mol / L) rOA.0(Mol/ L.min) 500 0.0055 0.0166 1000 0.0113 0.0322 1500 0.017 0.0552 2000 0.0226 0.0512 2500 0.0283 0.0490 3000 0.033 0.0450 3.8.2 Determination of Order of the reaction using Table 1: It was found from Fig.14 that the

oxalic acid oxidation followed 0.755th order kinetics with respect to oxalic acid concentration at atmospheric pressure.

Fig.14 Initial rate versus initial concentration plot.

3.8.3. Determination of Rate of the reaction from the graph of effect of catalyst dosage on oxalic acid degradation: Initial rates (rOA, 0) calculated from Fig.13 and using equation (3). As seen,

initial rate rises to a maximum and then falls with increasing catalyst dosage.

752

-rOA,0=


×

(3)

Table 2.Rates calculated from Fig. 12 and equation (3) Catalyst Dosage(g/L)

COA.0(Mol / L)

rOA.0( Mol /hr. gPt)

ln(ms)

0.5

0.017

2.352

-0.693

1.678

1.0

0.017

2.55

0

1.352

1.5

0.017

3.42

0.405

1.229

2.0

0.017

4.1112

0.693

1.185

2.5

0.017

3.153

0.916

1.083

3.0

0.017

2.85

1.098

1.113

Fig.15 Initial rate vs catalyst dosage plot.

ln(-rOA,0)

Fig.16 ln(rOA,0) vs 1/T graph

3.8.3. Determination of Order of the reaction from the Figure 15: It was found by plotting ln(rOA,0) versus ln(ms) plot that the oxalic followed a 0.323th order kinetics with respect to catalyst dosage at atmospheric pressure. 3.9 Determination of Activation Energy of the reaction: Rate calculated from Fig.9 and then from the Arrhenius plot of ln(rOA,0)as a function of 1/T [Fig.16], it was found that activation energy of the reaction was 25.6kJ/mol. 4. CONCLUSION: Oxalic acid is a very stable carboxylic acid and shows high resistance to complete oxidation over Pt/Al2O3 catalyst. Degradation of oxalic acid remains below 68% under the conditions used in this study. A proportional decrease in the initial rate was observed with increasing catalyst dosage. This effect catalyst dosage was explained by a heterogeneously catalyzed free-radical mechanism. Kinetic study performed on Pt/Al2O3 catalyst led to the following empirical initial rate equation of oxidation of oxalic acid Rate Equation, -rOA,0 = 257.237 e –2567/T COA,0 -0.755 C Pt -0 .3 23 ,Where COA is the oxalic acid concentration (mol/l) and CPt is the Pt concentration (gmPt/l). The results obtained are potentially of application and could be competitive with other advanced oxidation systems since oxalic acid is an end product of the chemical oxidation of many priority pollutants of water such as phenols. The better knowledge of catalytic oxidation could be of value to carry out the complete oxidation of different water pollutants. REFERENCE [1]Levec J., Pintar A., Catalytic oxidation of aqueous solutions of organics. An effective method for removal of toxic pollutants from waste waters, Catal. Today 24 (1995) 51–58.


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[2]Randall T.L, Knopp P.V.,Detoxification of specific organic substances by wet oxidation, J Water Pollut. Control Fed. 52(1980) 2117–2130. [3]Mantzavinos D., Hellenbrand R., Livingston A.G., Metcalfe I.S., Catalytic wet air oxidation of polyethylene glycol,Appl.Catal.B11(1996) 99–119. [4]Chang C.J.,Lin J.C.,Effects of temperature and Cu2+ catalyst on liquid-phase oxidation of industrial waste waters,J.Chem.Tech.Biotechnol.57 (1993)355–361. [5]Pintar A.,Levec J.,Catalytic liquid-phase oxidation of refractory organics in waste water, Chem. Engg. Sci. 47(1992) 2395–2400. [6]Dietrich M.J., Randall T.L., Channey D.J., Wet air oxhdation of hazardous organic in wastewater, Environ. Progr. 4 (1985) 171–177. [7]Lin S.H., Ho S.J.,Catalytic wet-air oxidation of high strength industrial waste water, Appl. Catal. B 9 (1996)133– 147. [8]Atwater J.E., Akse J.R.,Mckinnis J.A.,Thompson J.O., Aqueous phase heterogeneous catalytic oxidation of trichloroethylene, Appl. Catal. B11(1996) L11–L18. [9]Hogan T., Simpson R., Kin M., Sen A.,A broad spectrum catalytic system for removal of toxic organics from water by deep oxidation using dioxygen as the oxidant, Catal. Lett. 40 (1996) 95–99. [10]Zimmerman E.J., New Waste Disposal Process, Chem. Eng. 56 (1958) 117–120. [11] Mishra V.S., Mahajani V.V,Joshi J.B., Wet air oxidation, Ind. Eng. Chem. Res. 34 (1995)2–48. [12]Luck F.,A review of industrial catalytic wet air oxidation processes, Catal. Today 27 (1996)195–202. [13]Gonul Gunduz, Meral Dukkanci,Catalytic Wet Air Oxidation of Oxalic Acid at Atmospheric Pressure, International Journal of Chemical Reactor Engg.5(2007)Article-A-36. [14]Lee,Dong-Keun, Kim,Dul-Sun, Catalytic Wet Air Oxidation of Carboxylic Acids at Atmospheric Pressure, Catalysis Today 63(2000)249-255. [15] Gallezot,P.,Chaumet S.,Perrad A.,Insardb P., Catalytic Wet Air Oxidation of Acetic Acid on Carbon -Supported Ruthenium Catalysts, Journal of catalysis 168(1997)104-109. [16] Shende R.V. and Mahajani V.V., Kinetics of Wet Air Oxidation of Glyoxalic Acid and Oxalic Acid, Ind. Engg.Chem. Res.33 (1994)3125-3130. [17] Imamura S., Kinunaka H., Kawabata N.,The wet oxidation organic of compounds catalyzed by Co-Bi complex oxide, Bull. Chem. Soc. Jpn.55 (1982) 3679–3680. [18] Froment G.F., Bischoff K.B.,Chemical Reactor Analysis and Design, John Wiley and Sons, Secod Edition,1990. [19]Gomes, H. T., Figueiredo, J. L., Faria, J. L., Serp, Ph., Kalck, Ph., Carbon-supported Iridium Catalysts in the Catalytic Wet Air Oxidation of Carboxylic Acids: Kinetics and Mechanistic Interpretation, Journal of Molecular Catalysis A : Chemical, 182-183, (2002a) 47-60. [20]Gomes, H.T., Figueiredo, J.L., Faria, J.L.,Catalytic Wet Air Oxidation of Butyric Acid Solutions Using Carbon supported Iridium Catalysts, Catalysis Today, 75(2002b)23-28.

754


A NOVEL ROUTE FOR WASTE WATER TREATMENT: PHOTOCATALYTIC DEGRADATION OF METHYLENE BLUE Savitri Lodhaa*, and Pinki B. Punjabib a

Laboratory of Applied Chemistry, Department of Applied Sciences, Marwar Engineering College & Research Centre, Jodhpur ,Rajasthan (INDIA) b

Photochemistry and Solar Energy Laboratory,

Department of Chemistry, University College of Science, M. L. Sukhadia University, Udaipur – 313002, Rajasthan (INDIA) *

Email: [email protected]

SUMMARY Advanced methods are in demand for removal of persistent organic pollutants from waste water and ground water. Photocatalysis can be useful tool in the treatment of some recalcitrant and toxic pollutants. In fact, it is being applied today in several industrial processes. Photocatalytic degradation of methylene blue (MB) has been reported by thiocyanate complexes of iron, copper and cobalt and hydrogen peroxide. The effect of different parameters, such as the pH, concentration of the complexes and dye, amount of H2O2 and light intensity on the rate of photocatalytic degradation of MB was investigated. The disappearance of organic molecule was observed spectrophotometrically and it follows first-order kinetics. A tentative mechanism for the degradation of dye has also been proposed.

KEYWORDS: Photocatalytic degradation; methylene blue; metal complexes; hydrogen peroxide. 1. INTRODUCTION Water is a basic requirement of all living beings. Increasing population and industrialization led to water pollution. One of the important pollutants of water is the dye effluents of various textile industries. In an expanding industrialized world the problem of degradation of pollutants has become very serious from ecological point of view. Textiles, tannery, paper, pulp and printing industries are the biggest sources of polluting the environment. The effluents of these industries are highly colored, complex and toxic. Several methods of treatment of effluents have been undertaken from time to time, the most common of which are chemical precipitation and biological methods. However, these methods suffer from many disadvantages like chemical handling, sludge disposal and long term biodegradation. Colored solution containing dyes from industrial effluents may cause skin cancer due to photosensitization and photodynamic damage. On the contrary, bleached dye solution is non-toxic and harmless. Secondly, dye containing colored water is of almost no use, but if this colored solution is bleached to give colorless water, then it may be used for washing, cooling, irrigation and cleaning purposes. Therefore, removal of these toxic substances from water seems necessary. A number of attempts have been made to remove these dyes from polluted water like adsorption, thermal dehydration, chemical transformation etc., but photocatalytic degradation seems to be the most promising technique, since it is of low cost and less time consuming. Photochemical degradation of dyes employing Fenton reagent provides a newer method for the treatment of waste water containing dyes effluents. Fenton reaction involves the formation of hydroxyl and perhydroxyl radicals. Fenton reagent is an established reagent for degradation of dyes but main demerit of the reagent is that the reaction stops after complete consumption of Fe2+ ions, whereas, in photo-Fenton reaction, Fe2+ ions are regenerated from Fe3+ ions with an additional requirement of light. This makes the process cyclic in nature and photochemical degradation proceeds smoothly. Recently, several reports by many scientists on the photocatalytic degradation of dyes and organic pollutants have been published. Legrini et al. [1] reported the photochemical process for water treatment. Lopez et al. [2] investigated the hydroxyl radical initiated photodegradation of 4-chloro-3,


755

2 5-dinitrobenzoic acid in aqueous solution. Evidence for an additional oxidant in the photoassisted Fenton reaction was given by Pignatello et al. [3]. Ruppert et al. [4] studied the photo-Fenton reaction as an effective photochemical wastewater treatment process. Pignatello et al. [5] reported the degradation of PCBs by ferric ion, hydrogen peroxide and UV light. Chen et al. [6] investigated the photo-Fenton degradation of malachite green catalyzed by aromatic compounds under visible light irradiation. Xie et al. [7] studied the photoassisted degradation of dyes in the presence of Fe3+ and H2O2 under visible irradiation. Photocatalytic degradation of direct Yellow 12 dye using UV/TiO2 in a shallow pond slorry reactor was studied by Toor et al. [8]. Nerud et al. [9] reported the decolorization of synthetic dyes by the Fenton-reagent and the Cu/Pyridine/H2O2 system. Comparative photocatalytic studies of degradation of a cationic and an anionic dye was done by Hasnat et al. [10]. Chen et al. [11] observed the electrochemical degradation of bromo-pyrogallol red in presence of cobalt ions. Garcia et al. [12] investigated the comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems. Photodegradation of acid red 114 dissolved using a Photo-Fenton process with TiO2was carried out by Lee et al. [13]. Methylene blue was selected as a model compound for the present study because large intravenous doses of methylene blue produces nausea, abdominal and precardial pain, dizziness, headache, profuse swelling, sweating, mental confusion and formation of methemoglobin. Many scientist bleached this dye by various processes, but no attention has been paid to the photocatalytic degradation of methylene blue in presence of metal complexes such as [Fe(SCN]2+, [Cu(SCN)]+, [Co(SCN)]+ and H2O2. A comparative study of these complexes on photocatalytic degradation of methylene blue has also been reported. The method is very effective and economic too, and the most important advantage of this process is that the rate of the degradation is very fast.

2. EXPERIMENTAL DETAILS The photochemical degradation of methelene blue (REIDEL) was studied in the presence of a transition metal complex, i.e., [Fe(SCN)]2+, [Cu(SCN)]+ or [Co(SCN)]+, H2O2 and light.A stock solution of methelene blue (1.0×10-3 M) was prepared in doubly distilled water. The Complex [Fe(SCN)]2+ was prepared by mixing FeCl3 (1.0×10-3 M, Himedia) and KSCN(1.0×10-3 M, Himedia) in a 1:1 ratio. The [Cu(SCN)]+ and [Co(SCN)]+ complexes were prepared in a similar manner. H2O2 (30%, Merck) was a commercial product and was used as received. The reaction mixture containing dye (10-5 M), complex (10-5 M) and hydrogen peroxide was exposed to light for a certain period depending on the employed complex. A 200 W tungsten lamp (Philips) was used for the irradiation. The intensity of light at various distances was measured by a “Suryamapi” (CEL Model 201). The pH of the solution was measured using a digital pH meter (Systronics Model 335). The desired pH of the solution was adjusted by the addition of previously standardised 0.050 M sulphuric acid and 1.0 M sodium hydroxide solutions. A visible spectrophotometer (Systronics Model 106) was used for measuring the absorbance of the reaction mixture at regular time intervals.

3. RESULTS AND DISCUSSION An aliquot of 3.0 mL was taken out from the reaction mixture at regular time intervals and the absorbance was measured spectrometrically at max = 665 nm. It was observed that the absorbance of the solution decreases with increasing time intervals, which indicates that the concentration of methylene blue decreases with increasing time of exposure. A plot of 2 + log A versus time was linear and follows pseudo-first order kinetics. The rate constant was measured using following expression: k = 2.303 × Slope The data for this typical run are represented graphically given in Figure 1. For iron complex/H2O2 system, the reaction proceeded in two phases. The first phase was an induction period [14], in which radicals were generated, whereas the major degradation of the dye occurred in second step, as shown by the sharp decrease in the absorbance.

756


3

Iron complex Copper complex

2.50

Cobalt complex

2.00

2 + log A

1.50

1.00

0.50

0.00 0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

Time (min )

Fig. 1 : A Typical Run

3.1

Effect of pH

The effect of pH on photocatalytic degradation was investigated in the pH range 2.0 – 5.0, 7.0 – 9.0, and 7.5 – 10.0 for iron, copper and cobalt complexes, respectively. The results are reported in table 1. The Photochemical degradation of methylene blue was maximum at pH 3.0, 8.0 and 9.0 for iron, copper and cobalt complexes, respectively. The photochemical degradation depends strongly on the pH of the reaction medium. In case of iron complex, it was observed that rate of degradation of dye increased on decreasing pH from 5.0 to 3.0. It may be due to dominance of eq. (1) over eq. (2), where OH– ions are generated. These OH– ions are removed by increasing H+ ion concentration on decreasing pH. This will facilitate the eq. (1) forming more OH radicals, which will be utilized for oxidative degradation of methylene blue as well as thiocyanate radical. On decreasing the pH further i.e. below 3.0, the reaction rate decreases again. It may be attributed to the fact that eq. (2) starts dominating over eq. (1) as Fe(OH)3 is less soluble than Fe(OH)2 and generation of OH radicals by eq. (2) is retarted at lower pH than 3.0 [15]. In case of copper and cobalt complexes, reaction proceeds faster in basic medium. It may be explained that rate of degradation of dye increases on increasing pH from 7.0 to 8.0 and 7.5 to 9.0 for copper and cobalt complexes respectively. It may be due to dominance of eq. (2) over eq. (1), for copper complex and eq. (3) over eq. (4) for cobalt complex system, respectively, where H+ ions are generated. These H+ ions are removed by increasing OH– concentration on increasing pH. This will facilitate the eq. (2), for copper complex and eq. (3) for cobalt complex system, respectively forming more OH radicals, which will be utilized for oxidative degradation of methylene blue as well as thiocyanate radical. Further increase in pH beyond 8.0 and 9.0 for copper and cobalt complexes respectively is decrease in rate of degradation, which can be attributed as the dominance of eq. (1) over eq. (2) where OH- ions are generated. + ⎯→ M(n+1) + –OH +•OH Mn+ + H2O2 ⎯

(n+1)+

M

⎯→ Mn+ + •OH + H+ + H2O ⎯ hν

... (1) ... (2)


757

4

⎯→ Mn+ + •OH + H+ M(n+1)+ + H2O ⎯

... (3)

+ ⎯→ M(n+1) + –OH +•OH Mn+ + H2O2 ⎯

... (4)

hν

TABLE – 1 Effect of pH

pH

[Fe(SCN)]2+ / H2O2 System [Methylene Blue] = 5.00×10–5 M H2O2 = 0.2 mL Complex = 1.75×10–5 M Light Intensity = 60 mW cm–2

[Cu(SCN)]+ / H2O2 System [Methylene Blue] = 2.50×10–5 M = 0.3 mL H2O2 Complex = 1.75×10–5 M Light Intensity = 70 mW cm–2

[Co(SCN)]+ / H2O2 System [Methylene Blue] = 2.5×10–5 M H2O2 = 0.2 mL Complex = 1.75×10–6 M Light Intensity = 40 mW cm–2

k1×104(s-1)

k2×104(s-1)

k × 104 (s–1)

k × 104 (s–1)

2.0

0.26

0.81

–

–

2.5

0.75

2.11

–

–

3.0

1.53

11.05

–

–

3.5

0.10

0.16

–

–

4.0

0.04

0.13

–

–

4.5

0.03

0.10

–

–

5.0

0.02

0.06

–

-

7.0

_

_

2.82

-

7.5

_

_

4.80

3.65

8.0

_

_

5.37

3.94

8.5

_

_

3.96

4.27

9.0

_

_

3.66

4.61

9.5

_

_

-

3.61

10.0

_

_

-

1.97

3.2

Effect of hydrogen peroxide

The effect of amount of H2O2 on the rate of photocatalytic degradation of methylene blue was also investigated. The results are reported in table 2. The photochemical degradation of methylene blue was maximum at 0.2 mL for iron complex, but the rate increases continuously up to 0.7 mL H2O2 in case of copper and cobalt complex systems respectively. It may be explained on the basis that the increasing amount of H2O2 will provide more OH radicals responsible for oxidative degradation of methylene blue. But after a fixed amount of H2O2 (0.2 mL) further increment in amount of H2O2 will produce more –OH ion along with OH radicals and as a result, the pH of the medium increases, resulting into a decrease in the rate of degradation in case of iron complex. A different kind of behaviour in copper and cobalt complex systems respectively was observed. In this case a continuous increase in the rate of degradation of methylene blue was observed on increasing the amount of H2O2 from 0.0 to 0.7 mL. It may attribute to the fact that eq. (6) does not dominate over eq. (5) in this case and as such; no decrease in the rate was observed even on increasing the amount of H2O2.

⎯→ Mn+ + •OH + H+ M(n+1)+ + H2O ⎯

... (5)

+ ⎯→ M(n+1) + –OH +•OH Mn+ + H2O2 ⎯

... (6)

hν

758


5 TABLE-2 Effect of H2O2

H2O2 [mL]

[Fe(SCN)]2+ / H2O2 System [Methylene Blue] = 5.0×10–5 M Complex = 1.75×10–5 M Light Intensity = 60 mW cm–2 pH = 3.0

[Cu(SCN)]+ / H2O2 System [Methylene Blue] = 2.50×10–5 M Complex = 1.75×10–5 M Light Intensity = 70 mW cm–2 pH = 8.0

[Co(SCN)]+ / H2O2 System [Methylene Blue] = 1.0×10–5 M Complex = 1.75×10–5 M Light Intensity = 40 mW cm–2 pH = 9.0

k1×104(s-1)

k2×104(s-1)

k × 104 (s–1)

k × 104 (s–1)

0.0

0.06

0.16

0.66

0.38

0.1

0.45

0.81

1.35

2.30

0.2

1.53

11.05

3.08

2.88

0.3

1.37

10.23

3.36

3.07

0.4

1.36

10.03

3.69

3.26

0.5

1.33

9.82

3.83

3.45

0.6

1.22

9.40

4.02

4.22

0.7

1.06

7.37

5.37

4.61

3.3

Effect of concentration of complexes TABLE-3 Effect of complex concentration

Complex con.×106 M

[Fe(SCN)]2+ / H2O2 System [Methylene Blue] = 5.00×10–5 M H2O2 = 0.2 mL Light Intensity = 60 mW cm–2 pH = 3.0

[Cu(SCN)]+ / H2O2 System [Methylene Blue] = 2.50×10–5 M H2O2 = 0.2 mL Light Intensity = 70 mW cm–2 pH = 8.0

[Co(SCN)]+ / H2O2 System [Methylene Blue] = 2.5×10–5 M H2O2 = 0.2 mL Light Intensity = 40 mW cm–2 pH = 9.0

k1×104 (s-1)

k2×104 (s-1)

k × 104 (s–1)

k × 104 (s–1)

0.00

0.22

0.25

0.83

0.85

0.25

0.38

0.80

-

2.30

0.50

0.46

0.90

-

2.88

0.62

-

-

2.89

-

0.75

0.75

3.01

-

3.45

1.00

1.13

6.03

-

4.04

1.25

1.51

7.03

3.30

4.32

1.50

1.51

9.05

-

4.43

1.75

1.53

11.05

-

4.61

1.87

-

-

4.13

-

2.50

-

-

4.34

-

3.12

-

-

4.54

-

3.75

-

-

4.74

-

4.37

-

-

5.37

-

The effect of concentration of complexes on the rate of photocatalytic degradation of methylene blue was observed by keeping all other factors identical. The results are reported in table 3.It is clear from the data that the rate of photocatalytic degradation increases on increasing concentration of complexes. The rates were determined upto the concentration 4.37 × 10 –5 M for all the three systems, because


759

6 beyond this limit the rates were extremely fast and it was not possible to record the observation correctly due to experimental limitations. This increasing trend may be explained on the basis that on increasing the concentration of complexes more molecules of complexes were available to take part in reaction. This results in an enhanced generation of the OH radicals and as a consequence the rate of photocatalytic degradation of dye also increases.

3.4

Effect of methylene blue concentration

The effect of methylene blue concentration on the rate of photochemical degradation was observed and the results are given in table 4. The rate of degradation was found to increase with increasing concentration of methylene blue upto 5.00×10–5 M, 2.50×10–5 M and 2.50×10–5 M for [Fe(SCN)]2+, [Cu(SCN)]+ and [Co(SCN)]+ complexes, respectively. Further increase in concentration beyond these limits decreases the rate of degradation. This may be explained on the basis that on increasing the concentration of methylene blue, the reaction rate increases as more molecules of dyes were available for degradation, but further increase in concentration after certain limit causes retardation of reaction. It is because at the higher concentration, the dye molecules themselves act as filter for incident light, thus proper intensity of the light does not reach the molecules present in the interior of the reaction mixture, which results in decrease in rate of degradation. Moreover, at the higher concentration the number of collisions between dye molecules increases whereas, collision between dye and OH radicals decreases. As a consequence, rate of reaction is retarded. TABLE-4 Effect of dye concentration [Methylene Blue] × 105M

[Fe(SCN)]2+ / H2O2 System = 0.2 mL H2O2 Complex = 1.75×10–5 M Light Intensity = 60 mW cm–2 pH = 3.0

[Cu(SCN)]+ / H2O2 System = 0.2 mL H2O2 Complex = 1.75×10–6 M Light Intensity = 70 mW cm–2 pH = 8.0

[Co(SCN)]+ / H2O2 System = 0.2 mL H2O2 Complex = 1.75×10–6 M Light Intensity = 40 mW cm–2 pH = 9.0

k1×104 (s-1)

k2×104(s-1)

k × 104 (s–1)

k × 104 (s–1)

1.50

_

_

4.02

1.03

2.00

1.42

7.66

4.70

3.07

2.50

-

-

5.37

4.61

3.00

1.48

9.68

5.04

4.10

3.50

-

-

4.76

3.94

4.00

1.53

10.08

4.56

3.85

4.50

-

-

4.35

3.58

5.00

1.53

11.05

4.23

3.07

6.00

1.02

10.25

-

-

7.00

0.76

10.89

-

-

8.00

0.50

10.08

-

-

Unsuitable steric orientation is also one of the major factors for decrement in the rate of reaction [16, 17].

3.5

Effect of light intensity

The effect of light intensity on the photocatalytic degradation of methylene blue was investigated. The results are reported in table 5. The data indicate that an increase in the light intensity, increases the rate of reaction and maximum rates for iron, copper and cobalt complexes systems have been found at 60.0 mw cm-2 , 70.0 mw cm-2 and 40.0 mw cm-2 respectively. It may be explained on the basis that as the light intensity was increased, the number of photons striking per unit area also increased, resulting into a higher rate of degradation. Further increase in the light intensity beyond this limit results in decrease in the rate of reaction. It may be probably due to thermal side reactions.

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7 TABLE-5 Effect of light intensity Light intensity mW cm–2

[Fe(SCN)]2+/ H2O2 System [Methylene Blue] = 5.0×10–5M H2O2 = 0.2 mL Complex = 1.75×10–5 M pH = 3.0

[Cu(SCN)]+ / H2O2 System [Methylene Blue] = 2.50×10–5 M H2O2 = 0.2 mL Complex = 1.75×10–6 M pH = 8.0

[Co(SCN)]+ / H2O2 System [Methylene Blue] = 2.5×10–5 M H2O2 = 0.2 mL Complex = 1.75×10–6 M pH = 9.0

k1×104 (s-1)

k2×104 (s-1)

K × 104 (s–1)

k × 104 (s–1)

10.0

0.43

0.57

3.87

3.86

20.0

0.65

8.06

4.19

4.04

30.0

0.87

8.25

4.48

4.32

40.0

1.10

8.44

4.65

4.61

50.0

1.31

9.59

4.78

4.43

60.0

1.53

11.05

5.07

4.32

70.0

1.29

10.90

5.37

4.20

80.0

1.31

8.83

4.78

4.04

4. MECHANISM On the basis of the experimental observations and corroborating the existing literature a tentative mechanism has been proposed for the degradation of methylene blue in presence of iron and copper complexes, H2O2 and light [18]. [M (SCN)]n

h

Mn

SCN

... (1)

Mn+ + H2O2 → M (n+1) + + ¯OH + ●OH M

(n + 1) +

SCN

hν

+ H 2 O ⎯⎯ ⎯→ M

8

OH

n+

+

SO 2– 4

•

...…(2)

OH + H

NH 4

+

CO 2

... (3) 2 H2O

... (4)

Dye + •OH ⎯⎯→ Pr oducts

... (5)

• OH + •OH ⎯⎯→ H O 2 2

...(6)

2 H2O2 ⎯⎯→ 2 H2O + O2

...(7)

(Here M stands for iron and copper) The above proposed mechanism is applicable for both iron and copper complexes. In case of Cobalt complex, following mechanism has been proposed.

[M (SCN)] n +

hν + ⎯⎯ ⎯→ M(n + 1) + + SCN –

...(8)

hν M(n + 1) + + H 2 O ⎯⎯ ⎯→ Mn + + • OH + H +

...(9)

Mn + + H 2 O 2 ⎯⎯→ M(n + 1) + + – OH + • OH

...(10)

SCN –

8 OH

SO24 –

Dye + •OH ⎯⎯→ Pr oducts

NH 4

CO2

2 H2O

...(11) ...(12)


761

8 • OH + • OH ⎯⎯→ H O 2 2

...(13)

2 H2O2 ⎯⎯→ 2 H2O + O2

...(14)

Photo-Fenton reaction is one of the examples of classical photocatalytic process in homogeneous system that involves H2O2 - iron (III) - visible radiations. The thiocyanate complex of Fe3+ gives Fe2+ and thiocyanate radical on exposure to light. Fe2+ ion decomposes hydrogen peroxide into OH radical, –OH ion and itself oxidized to Fe3+ions. Fe3+ion decompose water photochemically to give OH radical and Fe2+ions. Thiocyanate radical and dye are decomposed by hydroxyl radicals to simpler ions/molecules like sulphates ion and ammonium ions, carbon dioxide, water etc. Similar explanation applies for degradation of methylene blue by copper complex /H2O2. The mechanism for Photocatalytic degradation of dye by cobalt complex differs from the mechanism for iron and copper complexes. In case of cobalt complex, thiocyanate ion is involved, whereas in case of iron and copper complexes thiocyanate radical is formed. The release of thiocyanate ion from its cobalt complex was ascertained by its spot- test [19], however, the negative spot test of thiocyanate ion in case of iron and copper complexes indicated that SCN• radicals are released in these reactions and not SCN- ions.

5. CONCLUSION The rate of photocatalytic degradation of methylene blue is enhanced by metal complexes. The increasing order of the rate with different metal complexes and Photo-Fenton reagent is as follows– [Fe(SCN)]+2 > [Cu(SCN)]+ > [Co(SCN)]+ >Photo-Fenton reagent. The hydroxyl radicals degrade the methylene blue. The participation of OH radicals as an active oxidizing species was confirmed by using hydroxyl radical scavengers, like 2-propanol, where the rate of photodegradation was drastically reduced. Further, this method is more advantageous over other methods, since it does not add to pollution, any further. The active oxidizing species, the hydroxyl radicals, will dimerise to give hydrogen peroxide, which may degrade ultimately to water and oxygen.

6. ACKNOWLEDGEMENT We acknowledge to the Director of Marwar Engineering College & Research Centre, Jodhpur (Rajasthan) for providing me laboratory facilities during this research work. We are also thankful to Prof. S.C. Ameta for valuable critical discussions. One of us SL is thankful to the UGC for the award of JRF.

7

REFERENCES

1). Legrini, O., Oiveros, E., and Braun, A.M. (1993) Chem. rev., 93, 671 -698 2). Lopez, J.L., Einschlag, F.S.G., Gonzalez, M.C., Capparelli,A.L.,Oliveros, E.,Hashem, T. M., and Braun, A.M.(2000) J. Photochem. Photobiol. 137, 177-184 3). Pignatello, J. J.,Liu, D., Huston, P. (1999) Environ. Sci. Technol. 33, 1832-1839 4). Ruppert, G., Baur, R., Heisler, G. (1993) J. Photochem. Photobiol. A., 73, 75-78 5). Pignatello, J. J., Chapa, G. (1994) Environ. Toxicol. Chem, 13, 423-427 6). Chen, F., He, J., Zhao, J., Yu, J. C. (2002) New J. Chem. 26, 336-341 7). Xie, Y., Chen, F., He, J., Zhao, J., Wang, H. (2000) J. Photochem. Photobiol. A. 136, 235-240

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9 8). Toor, A.P.,Verma, A., Jotshi, C.K., Bajpai, P.K., Singh, V. (2006) Dyes and Pigments, , 68(1), 5360 9). Nerud, F., Baldrian, P., Gabriel, J., Ogbeifon, D., (2001) Chemosphere, 44(5), 957-961 10). Hasnat, M. A., Siddiquey, I. A., Niruddin, A. (2005) Dyes and Pigments, 66(3), 185-188 11). Chen, J., Liu, M., Zang, J., Xian, Y., Jin, L. (2003) Chemosphere, 53 (9), 1131-1136 12). Garcia, J. C., Oliveira, J. L., Silva, A. E. C., Oliveira, C. C., Nozaki, J., Souza, N. E. (2007) Journal of Hazardous Materials, 147(1-2), 105-110 13). Lee, J. M., Kim, M. S., Hwang, B., Bae Wookeun Kim, B. W. (2003) Dyes and Pigments, 56(1), 59-67 14). Chen, F., Ma, W., He, J., Zhao, J. (2002) J. Phys. Chem. 106 A, 9485-9488 15). J.A. Dean, “Lange’s Handbook of Chemistry” McGraw-Hill, New York (1978) ch.5 16). K.J. Laidler, “Chemical Kinetics” McGraw-Hill, New York (1994) p 65 17). Jain, A., Punjabi, P. B., Sharma, V. K., Ameta, S. C. (2007) J. Indian Chem. Soc. 84, 996-1003 18). Lang, K., Lunak, S. (2002) Photochem. Photobiol. Sci. 1, 588-591 19). F. Feigl, V. Anger, “Spot Tests in Inorganic Analysis” Elsevier, Netherlands (2005) p 432.


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PHOTODEGRADATION OF ORANGE G UNDER SOLAR IRRADIATIONS Ajay Bansal1, Neetu Divya, Nishkam Batta, Saurabh Kumar Department of Chemical Engineering Dr B R Ambedkar National Institute of Technology, Jalandhar, 144011, Punjab, INDIA

ABSTRACT The discharge of color effluent is a common phenomenon in industries such as textile, leather, plastics, paper, food and cosmetics. Since dyes are known to cause allergic dermatitis, skin irritation, cancer and mutation, their treatment is necessary, before they are discharged safely. Various physical, chemical and biological methods are used for the effluent treatment but each method has its own advantages and disadvantages. Orange G is a typical acid azo dye that is used in many food and textile applications and is found in the discharged wastewater. In the present article, degradation of Orange G dye has been investigated under solar irradiations with and without hydrogen peroxide. Solar radiation and H2O2 resulted in significant degradation of the dye although the effect of either of them individually was very small. The declourization was studied to elucidate the effect of various process parameters such as pH, concentration of dye and different doses of H2O2. Further COD analysis of the dye was done to study the mineralization of the dye under sunlight. Results showed the efficient degradation of Orange G for typical process conditions. Keywords: Decolorization efficiency; Kinetics; COD; Solar/H2O2

1. INTRODUCTION

A large amount of water is consumed by textile industries between 25-250m3 per tone of product depending on the operating processes. And also it is largest colorants consuming industry [Lucas and Peres 2007].According to an estimate annually 700000 tone dyes are produced [Cho and Zoh 2007].And approximately 60-70% dyes are used by textile industries. The extensive use of dyes in these industries produces large amount of colored wastewater, which has to be treated to minimize the adverse effect on environment. Many conventional treatment techniques applied by textile industries such as chemical coagulation/flocculation, membrane separation (ultrafiltration, reverse osmosis) or elimination by adsorption (activated carbon, Orange peels, Rice husk etc.). Biological treatment is not an effective solution to these effluents due to the complex structure of some dyes that provokes resistances to biodegradation. The advance oxidation process could be a good alternative to treat textile dyes from the wastewaters. Photocatalysis using H2O2 (homogeneous catalyst) has been an effective alternative for the complete degradation of dyes [Villafan-Vidales et al., 2007]. This process leads to production of OH· readicals in presence of solar irradiation by absorbing radiation, which are able to participate in a series of reactions leading to the degradation of organic pollutants.

H 2O2 + hv → 2 HO ⋅ These radicals are capable of oxidizing organic compounds (RH) and producing organic radicals (R˙), which are highly reactive and can undergo further oxidation [Modirshala and Behnajady 2006]. Solar/H2O2 process has advantage of no sludge formation during the treatment process can be carried out under ambient conditions. Orange G is a typical acid azo dye that is used in many food and textile applications and is found in the discharged wastewater. The –N=N– azo group, two functional group –SO3Na and –OH present in OG dye structure. These groups provoke adverse effect on dye degradation. Sun et al. (2006) studied the kinetics of orange G dye using nano-sized Sn(IV)/TiO2/AC photocatalyst under acidic medium and established that Langmiur-Hinshelwood kinetic model explains the degradation of the dye. Dong et al. (2008) studied the solar degradation of two azo dyes (Mordant Black 5 and Acid Black 234) using Fe(III)-oxalate complexes/H2O2. It was found that the high concentration of H2O2, oxalate and Fe(III) did not benefit for dye degradation. The dye degradation followed the pseudo-first-order reaction kinetics. And also mineralization depends upon the level of solar exposure. 1

Corresponding author: Email: [email protected] ; Ph 09417223839

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Divya et al. (2009) studied the degradation of Orange G azo dye using H2O2 homogeneous photocatalysis with acidic medium under UV irradiation and found that the optimum dose of H2O2 is 0.5% of sample for 50 ppm OG solution. It is summarized that various researcher focused their studies on degradation of azo dyes with Fe(III)oxalate complexes/H2O2, UV/H2O2, UV/TiO2 and UV/Fentons process etc. However, a limited amount of literature available on the degradation of the azo dye under solar/H2O2 processes. The objective of present work was to study the solar/H2O2 decolorization of Orange G solution and analyze the mineralization. The influence of pH, different concentrations of dye, H2O2 dose on degradation of Orange G was investigates.

2. MATERIAL & METHODS 2.1 Reagents The azo dye Orange G (OG) 90% (Fig.1., Table.1), H2O2 (30% w/v), HCl (34%), Sodium hydroxide pellets purified (NaOH) were all procured from S. D. Fine Chemicals Limited, Mumbai, India. For the adjustment of pH of working sample 0.1N HCl and NaOH was prepared. Ferrous ammonium sulphate (NH3(FeSO4)2.6H2O), potassium dichromate (K2Cr2O7), silver sulphate (AgSO4), mercury sulphate (HgSO4), ferroin indicator, Sulphuric acid (H2SO4) were used for COD analysis and procured from S. D. Fine Chemicals Limited, Mumbai, India.. They were used without any further treatment. 2.2 Experimental Stock solution of the dye (1000 ppm) was prepared with double distilled water from which working solution (50 ppm) was prepared. Then pH was adjusted using 0.1 N NaOH and 0.1N HCl (pH/lon 510, Eutech pH meter). For solar degradation, twenty milliliters of the working solution of the dye (50 ppm) was taken in a beaker then H2O2 was added. The zero time reading was taken and the solution was then subjected to solar irradiation. Aliquots were taken at regular intervals to analyze the percent decolorization and mineralization of the dye.

2.3 Analysis 2.3.1 Color Removal The UV–vis smart spectrophotometer (Lamotte, Italy) with single beam was used to record the absorbance of the test samples. The maximum absorbance wavelength, λmax for Orange G was 490 nm. The concentration of the dye at different reaction times was estimated by measuring the absorption intensity. The degradation studies are reported as ‘η’ called photodegradation efficiency and defined as follows [Divya et al., 2009]: Photodegradation efficiency

⎛

η (%) = ⎜ 1 − ⎝

C Co

⎞ ⎟ × 100 ⎠

Where the C0 is the initial concentration of dye, and C is the concentration of dye at any reaction time t (min).

2.3.2. Percent COD removal The total mineralization of OG has been measured by using the COD removal. Estimation of COD had been done by standard methods. The efficiency of dye mineralization was estimated using the following expression [Aleboyeh et al., 2008]:

⎛ CODt % COD removal = ⎜1 − ⎝ CODi

⎞ ⎟ × 100 ⎠

Where CODt corresponds to time t and CODi correspond to initial conditions.


765

3. RESULTS AND DISCUSSION 3.1 Effect of dye concentrations The experiments were conducted with three concentrations of OG (10, 30 and 50 ppm). The decolorization of dye was found to depend on the initial concentration of the dye (Fig.2.). From Fig.2 it was clear as the dye concentration increases from 10 to 50 ppm the time required for decolorization was also increases i.e. 70, 165 and 420 min respectively. Hence, as the initial concentration of dye increases the degradation rate was decreases. The increase in dye concentration decreases the probability of reaction between dye molecules and the hydroxyl radicals generated in the reaction medium reducing the decolorization efficiency [Monteagudo et al., 2008]. The irradiation of dye solution with solar light in the presence of H2O2 caused nearly complete decolorization OG. The results indicated that the photodegradation efficiency of OG was higher at low concentration. For higher concentration of OG (50 ppm) it took rather long time of approximately 7 hr for near total degradation in comparison to 70 min for 10 ppm solution. Probably it happened because at the high initial concentration of dye, the color might have hindered the penetration of light into the bulk of the reaction sample (Divya et al. 2009). Consequently, the degradation of the dye decreased as the dye concentration increased.

3.1.1 Kinetics study Orange G azo dye followed the pseudo-first-order reaction kinetics for decolorization during Solar/H2O2 homogeneous photocatalysis in acidic medium (Fig.3.).

r =−

dC = kC dt

Where ‘r’ is the reaction rate, ‘C’ is the concentration (mg/l) of Orange G and ‘k’ is the pseudo-firstorder decolorization kinetics rate constant (min-1) for photochemical reaction. This equation can be integrated between t = 0 and t = t, yielding:

ln

Co = kt C

Where, Co is the initial concentration of Orange G. The correlation coefficient (R2) and ‘k’ values are reported in Table.2.

3.2 Effect of pH pH is an important parameter for solar/H2O2 processes. The hydrogen ion concentration affects the production rate of hydroxyl radical. To study the effect of pH on degradation of OG, experiments were conducted at different pH values (up to 1.0 - 9.0 pH). Increase in pH of OG solution from 1.0 to 2.0 led to an enhanced OG degradation efficiency (Fig.4.). The dye degradation was high at 2 pH. In alkaline medium the oxidizing species hydroxyl anion (HO2-) is also formed (HO2- anion is the conjugated base of H2O2). This HO2- anion reacts with •OH radical and residual H2O2, consequently lowers the degradation efficiency of OG (Murugandham and Swaminathan 2004).

H 2O2 + HO2− → H 2O + O2 + ⋅OH ⋅OH + HO2− → H 2O + O2− It was also observed that maximum degradation occurred at pH 2 and with high pH value resulted in less degradation of the dye. The lowering of degradation efficiency at higher pH range is due to reduction of hydroxyl radical concentration. Under these conditions H2O2 undergoes photodecomposition to water and oxygen and dose not form hydroxyl radical ( Murugandham and Swaminathan 2004). hv 2 H 2O2 ⎯⎯ → 2 H 2O + O2

3.3 Effect of Hydrogen Peroxide dose The experiments were conducted at different hydrogen peroxide doses from 0.1 to 0.9 ml (Fig.5.). Doses of H2O2 are significantly affected the solar/H2O2 degradation process. The results indicate that

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the rate of degradation of OG increased with increase in H2O2 concentration up to 0.7 ml, but above it, there was a decrease in the degradation. This is because hydrogen peroxide inhibits the electron–hole recombination and could act as an alternative electron acceptor to oxygen at its low concentration. ⋅

O + H 2O2 → OH − + ⋅OH + O2

Whereas over the optimum concentration, surplus H2O2 molecules play the role as a hydroxyl radical quencher, lowering the hydroxyl radical concentration. It generates less reactive •OOH radical (Dong et al., 2008):

H 2O2 + ⋅OH → ⋅OOH + H 2O Similar results have also been reported in the literature (Divya et al., 2009, Cho and Zho 2007, Murugandham and Swaminathan 2004). From the present experiments we observed that 0.7 ml H2O2 was an optimum dose for decolorization during solar irradiation. In case of 0.7 ml H2O2 dose and 2pH the degradation efficiency was 45% higher than that corresponding to 0.1 ml H2O2 and 3pH (Fig.6.).

3.4 COD removal To determine the extent of mineralization of Orange G, COD values of the solution were measured during the solar irradiation in presences of H2O2. Percent COD removal gradually decreased with increase in time for solar irradiation (Fig.7.). 52% COD removal was achieved after 7 hr solar irradiation. The following stoichiometry of the mineralization of Orange G could be suggested, C16 H 10 N 2 Na 2 O 7 S2 + 42H 2 O 2 → 16 CO 2 + 45H 2 O + 2HNO 3 + 2NaHSO 4

3.5. Comparative study Sun et al. (2006) used Sn(IV)/TiO2/AC under 300 W high pressure mercury light for Orange G degradation and observed 99.1% degradation in 60 min (Fig.8). Divya et al. (2009) used two 15 W tubes under UV/H2O2 photocatalysis process and achieved 88% degradation of Orange G azo dye in 150 min. Divya et al. (2009) achieved the degradation 99.9 % in 90 min with additional source of 125 W bulb. Whereas in the present study 94.4% degradation has been observed with solar/H2O2 in 420 min under 0.1 ml H2O2 dose and 3pH for 50ppm OG solution. But 96% degradation has been observed with solar/H2O2 in 180 min under 0.7 ml H2O2 dose and 2 pH for 50 ppm OG solution. The obvious better degradation achieved by Sun et al. (2006) has the disadvantage of using metal complex catalyst Sn(IV)/TiO2/AC, which may increase the cost of the process. Further the adsorption process as incorporated by Sun et al. has its own inherited disadvantages. Also UV light source used by Divya et al. (2009) may increase the cost of the process. In present work 96% degradation achieved which is better than the 88% degradation achieved by Divya et al. (2009) under similar conditions but without solar irradiations. As such the present results appear to be more promising from the environmental concern.

4. CONCLUSIONS The photodegradation process using solar irradiation with H2O2 offers a valuable alternative for the degradation of Orange G dye dissolved in water. In the present work it was found that the degradation of the dye decreased as the dye concentration increased under acidic medium with small amount of H2O2. It was achieved nearly complete color removal (i.e. 96%) with 2 pH and 0.7 ml H2O2 dose. Dye decolorization followed the pseudo-first-order reaction kinetics. Further 52% dye mineralization in terms of COD removal was achieved in 7 hrs under solar irradiations.

REFERENCES Marco S. Lucas, Jose A. Peres, Degradation of Reactive Black 5 by Fenton/UV-C and ferrioxalate/H2O2/Solar light processes. Dyes and Pigments 74 (2007) 622-629. Il-Hyoung Cho, Kyung-Duk Zoh, Photocatalytic degradation of azo dye (Reactive Red 120) in TiO2/UV system: Optimization and modeling using a response surface methodology (RSM) based on the central composite design. Dyes and Pigments 75 (2007) 533-543. H.I. Villafan-Vidales, S.A. Cuevas, C.A. Arancibia-Bulnes, Modeling the solar photocatalytic degradation of dye. Journal of Solar Energy Engineering 129 (2007) 87-93.


767

N. Modirshahla, M.A. Behnajady, Photooxidative degradation of Malachite Green (MG) by UV/H2O2: Influence of operational parameters and kinetic modeling. Dyes and Pigments, 70 (2006) 54-59. N. Divya, A. Bansal, A.K. Jana, Degradation of acidic Orange G dye using UV-H2O2 in batch photoreactor. International Journal of Biological and Chemical Sciences 3 (2009) 54-62. M. Muruganandham, M. Swaminathan, Photochemical oxidation of reactive azo dye with UV–H2O2 process. Dyes and Pigments 62 (2004) 269-275. J.M. Monteagudo, A. Duran, C. Lopez-Almodovar, Homogeneous ferrioxalate-assisted solar photoFenton degradation of Orange II aqueous solutions. Applied catalysis B: Environmental 83 (2008) 46-55. Jianhui Sun, Xiaolei Wang, Jingyu Sun, Ruixia Sun, Shengpeng Sun, Liping Qiao, Photocatalytic degradation and kinetics of Orange G using nano-sized Sn(IV)/TiO2/AC photocatalyst.. Journal of Molecular Catalysis A: Chemical 260 (2006) 241–246. Y. Dong, L. He, M. Yang, Solar degradation of two azo dyes by photocatalysis using Fe (III)-oxalate complexes/H2O2 under different weather conditions. Dyes and Pigments 77 (2008) 343-350. A. Aleboyeh, M. E. Olya, H. Aleboyeh, Electrical energy determination for an azo dye decolorization and mineralization by UV/H2O2 advanced oxidation process. Chemical Engineering Journal. 137 (2008) 518–524. Table.1. Physical and chemical characteristics of dye (Divya et al., 2009) S.No. 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. c

Title Dye name Abbreviation Generic name Color Index (C.I.) Appearance Chemical formula Molecular Weight λmax, nm ε c, Abs ml/mg Toxic fumes

Properties Orange-G OG Acid orange 10 16230 Orange to red-orange powder C16H10N2Na2O7S2 452.37 490 46.9 (20,683) Carbon monoxide, carbon dioxide, nitrogen oxides, sulfur oxides.

Extinction coefficient (Owusu-Apenten, 2002)

Table.2. Kinetics parameters for OG decolorization S.No.

Dye Concetrations, ppm

R2

k

1. 2. 3.

10 30 50

0.992 0.902 0.994

0.0339 0.0098 0.0037

Fig.1. Structure of Orange G azo dye

768


1.0 0.9

C/Co 10 ppm C/Co 30 ppm C/Co 50 ppm

0.8 0.7

C/Co

0.6 0.5 0.4 0.3 0.2 0.1 0.0

0

30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 480

t,min Fig.2. Decolorization of OG for different concentrations during solar irradiation [0.1 ml H2O2, 3pH, 20ml OG sample] 3

ln(Co/C) 10ppm

1

ln(Co/C) 30ppm ln(Co/C) 50ppm

0.9

2.5

0.8 0.7

2

1-C/Co

ln(Co/C)

0.6 1.5

0.5 0.4 0.3

1

0.2 0.1

0.5

0 0

0 0

30

60

90

120

150

t,min

180

210

240

270

Fig.3. pseudo-first-order kinetics for decolorization of OG with different concentrations during solar irradiation [0.1 ml H2O2, 3pH, 20ml OG sample]

1

2

3

4

5

6

7

8

9

10

pH

Fig.4. Effect of pH on OG degradation after 3 hr solar irradiation [50ppm, 0.1ml H2O2, 20 ml sample]


769

1.2

C/Co (0.7, 2) C/Co (0.1, 3)

1.1 1.0

1

0.9 0.8

0.8

1-C/Co

0.7

C/Co

0.6

0.4

0.6 0.5 0.4 0.3

0.2

0.2 0.1

0 0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.0

0.9

0

30

H2O2 , ml

CO DRem oval

% COD Removal

40 30 20 10

0

1

2

120

150

180

210

Fig.6. Decolorization of OG during solar irradiation under different dose of H2O2 and pH

60

0

90

t,min

Fig.5. Effect of H2O2 dose on OG degradation after 3 hr solar irradiation [50ppm, 2pH, 20 ml sample]

50

60

3

4

5

6

t,hr Fig.7. % COD removal of OG [50 ppm, 0.7 ml H2O2, 2 pH]

7

8

770


Fig.8. Parity plot for present data and the data due to Sun et al., 2006 and Divya et al., 2009


COMPARATIVE STUDIES OF ZnO AND ZnS AS PHOTOCATALYST ON DEGRADATION OF HYDROQUINONE N.Shanmuga Sundaram1, S.Sindhu2, Dr.Lima Rose miranda3 1

PG Student, Department of Chemical Engineering, Anna University, Chennai-25, Tamil Nadu, India 2 Lecturer, Department of Chemical Engineering, Amrita School of Engineering, Coimbatore-641 105, Tamilnadu, India. 3 Assistant Professor, Department of Chemical Engineering, Anna University, Chennai-25, Tamil Nadu, India

ABSTRACT The particles of ZnO and ZnS were used as photocatalyst in the degradation of hydroquinone as organic pollutants in a batch photocatalytic reactor, with UV light. The effect of process parameters such as initial concentration of hydroquinone, catalyst loading, pH, irradiation time and UV lamp intensity on the extent of degradation was investigated. The process followed pseudo first order kinetics model and the apparent rate constant decreased with increase in the initial concentration of hydroquinone. The optimum catalyst loading was observed at 0.02 and 0.025% for ZnO and ZnS respectively. The degradation of hydroquinone was found to be effective in the basic media. The degradation rate of hydroquinone was increased with increasing irradiation time and more effective in high intensity.

INTRODUCTION Environmental problems associated with hazardous wastes and toxic water pollutants have been attracted much attention. Among them, phenolic compounds are one of the major groups of organic pollutants in wastewaters produced from textile and other industrial processes. PDihydroxybenzene (p-DHB), known as hydroquinone, is a phenolic compound with two –OH groups. It is a toxic and strong irritant pollutant found in effluent waste streams of many processes including those concerned with dyestuff, photography, paint and varnishes industry. Among various physical, chemical and biological techniques for treatment of wastewaters, heterogeneous photocatalysis has been considered as a cost-effective alternative for water remediation. The superiority of photocatalytic technique in wastewater treatment is due to its advantages over the traditional techniques, such as quick oxidation, no formation of polycyclic products, oxidation of pollutants in the ppb range. Photocatalysis is a process by which a semiconductor materials absorbs light of energy more than or equal to its band-gap, thereby generating electrons and holes, which can further generate free-radicals in the system to oxidize the substrate. The resulting free-radicals are very efficient oxidizers of organic mater [20]. In recent years, the photocatalytic degradation of various kinds of organic and inorganic pollutants using semiconductor powders as photocatalysts has been extensively studied [17]. The most commonly studied photocatalysts are TiO2, ZnO and ZnS. Among the various semiconductors the TiO2 is generally considered to be the best photocatalyst and has been widely used for the detoxification of water from a number of organic pollutants. However, wide spread use of TiO2 is uneconomical for large scale water treatment operations. It has become an imperative to find an alternative to TiO2. Many attempts have been made to study photocatalytic activity of different semiconductors such as TiO2, ZnO and ZnS and CdS [16]. ZnO appears to be a suitable alternative to TiO2 by comparative it with ZnS and its photodegradation mechanism has been proven to be similar to that of TiO2 [18-19]. This paper deals with comparison of ZnO and ZnS as photocatalyst on degradation of hydroquinone and found that the degradation was much more effective than other systems, if using ZnO. Degradation followed a first order kinetics and the

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ZnO enhanced the degradation process. In this experimental research, a photocatalytic reaction with UV irradiation was used to study the degradation of hydroquinone and the effect of various parameters was studied.

MATERIALS AND METHODS Materials All chemicals and solvents used were analytical grade. Hydroquinone was purchased from Fischer Scientific. The photocatalysts such as ZnO, ZnS (purchased from Central Drug House), Silver nitrate solution (purchased from RANBAXY), 4-Aminoantipyrine (purchased from MERCK), Potassium ferricyanide (purchased from FINAR REAGENTS),Distilled water purchased from Modern Distilled waters.

Apparatus Used The instruments used for the project were UV photo reactor, UV spectrophotometer, pH meter, magnetic stirrer and centrifuge.

Preparation of hydroquinone solution The stock solution of 1000 mg/L was prepared by dissolving 1.0 g Hydroquinone in 1000 ml of distilled water. The experimental solution was prepared by diluting the stock solution with distilled water when necessary.

Setup Take an annular vertical reactor with the capacity of 900ml and a conical shape in the lower parts of its body. The UV lamp was positioned inside a quartz tube and fully immersed to achieve the maximum light utilization. The solution was mixed well using magnetic stirrer to fluidize the catalyst particle with the solution. For regulating the temperature, the reactor was equipped with a water flow jacket, using an external circulating flow of a thermostat bath

Procedure and Analysis The analysis of hydroquinone was studied at different concentrations (100,200,300,400,500,ppm) for 2 hrs. Samples were taken for every 10min,first an hour and then 15min, for another 1 hour. To run the experiment 900ml of a solution of known ppm with the appropriate amount of catalyst was transferred to the reactor. The cooling water supply is essential before switch on the lamp while starting the reactor. After starting the reactor, the samples were taken at regular time intervals. The samples then centrifuged in order to the separation of catalyst particles. The samples then analyzed to find the unknown concentration of the solution after degradation using UV spectrophotometer by forming complex with the addition of Ammonia solution, Phosphate buffer solution to attained the required pH, 4-Aminoantipyrine and Potassium ferricyanide solutions. The wavelength for analyzing the sample in UV- Spectrophotometer was 500nm. Then, the degraded percentage was calculated by means of OD value.

Schematic diagram of photocatalytic reactor:


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RESULTS AND DISCUSSIONS Effect of UV light and without UV light

Degradation %

Data at different conditions were obtained and analyzed using the parameter R, as the degradation %(or efficiency in R, %) as: R = (Co-C)/Co *100 where R is degradation efficiency in percentage; Co is organic solution before irradiation; C is organic solution after irradiation for time t. To examine the influence of UV light on photocatalytic degradation, the experiments were carried out with UV light and without UV light to degrade the hydroquinone into inorganic substances CO2 and H2O [1].The degradation % of hydroquinone with UV light and without UV light can be obtained using UV source of 250W intensity under temperature 303K and after 120min irradiation as 48% and 19% respectively and this is due to one or more excited photons interacting with one target molecule where it is low in the absence of UV light is shown in the fig 1. Therefore direct photolysis of phenol solutions at the tested conditions is not a very effective method for mineralization [8].

100 90 80 70 60 50 40 30 20 10 0

UV light without UV light

0

20

40

60

80

100

120

Time (min) Figure 1(Effect of UV light and without UV light on degradation of hydroquinone under solution concentration=100ppm; pH=6.7; temp=303K)

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Effe ct of initia l conce ntra tion of hydroquinone 3.5 3

C/Co

2.5 100ppm

2

200ppm 300ppm

1.5

400ppm 1

500ppm

0.5 0 0

20

40

60

80

100

120

Tim e (m in)

Figure 2. (Effect of initial concentration of hydroquinone varies from 100 to 500ppm under pH=6.7; temp=303K)

Effect of initial concentration Fig.2 shows the residual concentration of hydroquinone as a function of time for different initial concentrations. These initial concentrations include 100, 200, 300, 400 and 500ppm. The initial concentration has a profound effect on the degradation rate for the same irradiation time. The percentage removal is smaller for higher initial concentration. The degradation % was maximum for low initial concentration and minimum for higher initial concentration [2].The observed exponential decay can be described in terms of a pseudo-firstorder kinetic model: (−rA) = −dC/dt = Kuv C (1) where kUV is the pseudo-first-order kinetic constant and C is the concentration of dye. Upon integration, the residual concentration as a function of time is ln Co/C = Kuvt (2). Plots of ln Co/C versus t represent straight lines, with a slope of which, upon linear regression, is the apparent rate constant (kuv). Values for kuv and linear regression coefficients for different initial concentrations are listed in Table 1. From the R2 values, which exceeded 92%, the linear relationship is obvious [12]. Therefore, the reaction can be approximated to be pseudo-first-order. Values for kuv are decreasing with initial concentration. This decrease in kuv values can be attributed to decreasing fractional site coverage of hydroquinone with increasing initial hydroquinone concentration. 3.5

100ppm

3

200ppm 300ppm

ln(Co/C)

2.5

400ppm

2

500ppm 1.5

Li

1 0.5 0 0

20

40

60 Tim e (m in)

80

1 00

120


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Figure3.(Kinetics studies on effect of initial concentration of hydroquinone varies from 100 to 500ppm under pH=6.7; temp=303K) Table 1 Apparent first order rate constant, kuv and linear regression coefficient, R2 for different initial concentrations of hydroquinone. Kuv (min-1) 0.0204 0.0158 0.0133 0.011 0.0094

Solution Concentration Co(ppm) 100 200 300 400 500

R2 0.9051 0.9694 0.9721 0.9736 0.9807

Effect of catalyst dosage

Photocatalytic activity of ZnO Heterogeneous photocatalytic process consists on utilizing the near UV radiation to photoexcite a semiconductor catalyst in the presence of oxygen. Under these circumstances oxidizing species, either bound hydroxyl radical or free holes, are generated. Many catalysts have been tested, although ZnO in the anatase form seems to possess the most interesting features, such as high stability, good performance and low cost [8]. A series of experiments was carried

Degradation %

Catalyst conc of ZnO on degradation of hydroquinone 100 90 80 70 60 50 40 30 20 10 0 0

0.005

0.01

0.015

0.02

0.025

0.03

Catalyst dosage %

Figure 4. (Effect of catalyst loading (ZnO) varies from 0.005 to 0.025% on degradation of hydroquinone under solution =100ppm; pH=8; temp=303K) out to find the influence of ZnO concentration varied from 0.005 to 0.025%. The rates of reaction have been found in some cases to improve, as catalyst concentration increases and then falling slowly or becoming nearly independent of concentration. The results are in agreement with our previous works and those reported in the literature [7,16] for different organic materials. Results illustrated in Fig. 4 shows the variation of degradation of hydroquinone with catalyst concentrations up to about 0.02%, the degradation increases; while it decreases mildly above this concentration during the same irradiation times. Similar behavior was observed for other times of irradiation. A possible explanation is that increased turbidity of the solution reduces the light transmission through the solution, while below this level of concentration; it is assumed that the catalyst surface and the absorption of light by ZnO particles are limiting [1]. Photocatalytic activity of ZnS The initial rate of photocatalytic degradation of many pollutants is a function of the photocatalyst dosage [17] Fig 5.illustrate the photodegradation of hydroquinone, in the different dosage of

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0.005 to 0.03% with irradiation time of 120min. Because increasing in active sites, the rate of degradation is increased to maximum degradation efficiency in the presence 0.025% of photocatalyst. However, as the loading was increased beyond the optimum amount, the degradation rate decreased due to increasing the opacity of the suspension samples and therefore increasing the light scattering. In these conditions, the penetration depth of the photons is decreased and less catalysts particles could be activated.

Degradation%

Effe ct of catalys t dos age (ZnS) 90 80 70 60 50 40 30 20 10 0 0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

Tim e (m in)

Figure 5 .(Effect of catalyst loading (ZnS) varies from 0.005 to 0.03% on degradation of hydroquinone under solution =100ppm; pH=10; temp=303K)

Effect of pH The photocatalytic degradation of hydroquinone acid was carried out at different pH values in the range of 2 to 12 . The maximum degradation of hydroquinone was observed at pH in the range of 6 to 8 at the end of 120min. The degradation rate was found to be high in basic media [16]. The higher degradation rate at pH in the range of 6 to 8 and decreased rate at lower pH was reported in the photocatalytic degradation of hydroquinone on ZnO (0.02%). An increase amount of OH− radicals at high pH values could enhance the production of hydroxyl radicals, that turns to increase the photocatalytic activity. Effect of pH of different catalyst on degradation of hydroquinone 100 90

Degradation %

80 70 60

ZnS (0.03%)

50

ZnO(0.025% )

40 30 20 10 0 0

2

4

6

8

10

12

14

pH

Figure 6. (Effect of pH of ZnO and ZnS on degradation of hydroquinone under solution=100ppm; temp=303K; irradiation time=120min) Similarly the photodegradation of hydroquinone (100ppm) was studied in amplitude pH of 2.0– 12.0 in the presence of photocatalysts as ZnS (0.025%). The results for irradiation time of 120min are shown in Fig 6, the maximum degradation efficiency was obtained in alkaline pH 10 for


hydroquinone. Therefore, the surfaces of photocatalysts are positively charged in acidic solutions and negatively charged in alkaline solutions. As a result, it is not surprise the increasing of the adsorption of hydroquinone molecules (with positive charge) on the surface of photocatalysts in alkaline solutions and thus the increasing of degradation efficiency of hydroquinone. A low pH is associated with a positively charged surface which cannot provide hydroxyl group which are needed for hydroxyl radical formation.

Effect of UV lamp intensity and irradiation time Fig.7a represents the percentage degradation of the hydroquinone at different UV lamp intensity of 250 and 400W at optimum catalyst loading of ZnO (0.02%) and organic solution concentration (100ppm).Under the experimental condition, the percentage degradation of hydroquinone of 250 and 400W was 81% and 92% respectively achieved within120min.

Figure7a. (Effect of UV lamp intensity of ZnO (0.02%) on degradation of hydroquinone under solution=100ppm; pH=8; temp=303K) Similarly Fig.7b represents the percentage degradation of the hydroquinone at different UV lamp intensity of 250 and 400W at optimum catalyst loading of ZnS (0.025%) and organic solution concentration (100ppm).Under the experimental condition, the percentage degradation of hydroquinone of 250 and 400W was 68% and 82% respectively achieved within 120min.

Figure7b. (Effect of UV lamp intensity of ZnS (0.025%) on degradation of hydroquinone under solution=100ppm; pH=10; temp=303K)

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The photo catalytic degradation of hydroquinone takes place on the surface of ZnS and ZnO where •OH and O2 • – radicals are trapped in the holes of reactive species. Oxygen and water are essential for photo catalytic degradation [11]. The •OH radicals are strong enough to break the bonds in the organic molecules adsorbed on the surface of ZnS and ZnO. The amount of ZnS and ZnO and concentration of hydroquinone are constant, the number of •OH and O2 • – radicals increases with the increase in the irradiation period and hence the hydroquinone molecules are degraded as stated above into smaller fragments.Both the catalyst ZnO and ZnS, the degradation rate increased as the light intensity increased. When the energy of the incident photon exceeds the energy gap, the electron at the valance band may be excited to the conduction band, leaving a positive hole in the valence band. Since the energy of the incident photon kept illuminating, the electron–positive hole pair would be generated continuously [15].Therefore, the larger the light intensity, the larger was the formation of the electron–positive hole pairs makes the degradation rate of hydroquinone was increased.

CONCLUSION The photocatalytic degradation of hydroquinone using ZnO and ZnS has been studied. The experimental results fit a pseudo-first-order kinetics model with a decreasing rate constant as the initial concentration of hydroquinone increases. This means that the more diluted initial solution, the higher is degradation rate of hydroquinone. This trend could be attributed to decreasing fractional site coverage by hydroquinone molecules. The effect of catalyst loading of ZnO was higher than ZnS on the degradation rate of hydroquinone. ZnO was found to be quite stable and undergoes photo corrosion only to a negligible extent. The effect of pH, irradiation time and UV lamp intensity has been also studied. Degradation rate in the basic media is much higher than that in the acidic media. The irradiation period could enhance the degradation percentage and also the degradation rate was more effective as the light intensity increases.

REFERENCES 1. H. Nejati et al., Enhanced photocatalytic degradation of pollutants in petroleum refinery wastewater under mild conditions, Journal of Hazardous Materials 148 (2007) 491–495 2. Khalil A. Halhouli et al., Effect of pH and temperature on degradation of dilute dihydroxybenzene, in aqueous titanium dioxide suspension irradiated by UV light Journal of Photochemistry and Photobiology A: Chemistry 200 (2008) 421–425 3. Ferda Candan et al., Disinfection of E. coli by the Ag-TiO2/UV system: lipidperoxidation Journal of Photochemistry and Photobiology A: Chemistry 143 (2001) 241–244 4. Ali Samilb, et al Applied Catalysis B: Environmental Photocatalytic degradation kinetics of diand tri-substituted phenolic compounds in aqueous solution by TiO2/UV 58 (2005) 211–216 5. Kang-Jin KimJournal et al, Photochemistry and Photobiology A: Chemistry 125 Enhanced photodecomposition of 4-chlorophenol in aqueous solution by deposition of CdS on TiO2 (1999) 19±125 6. Mantana Moonsiri et al., Effects of Pt and Ag on the photocatalytic degradation of 4-chlorophenol and its by-products , Chemical Engineering Journal 97 (2004) 241–248 7. B. Swarnalatha, Y. et al Journal of Molecular Catalysis A: Chemical 223 Studies on the heterogeneous photocatalytic oxidation of 2,6-dinitrophenol in aqueous TiO2 suspension (2004) 161–165 8. Miguel Rodríguez et al., Fenton and UV-vis based advanced oxidation processes in wastewater treatment: Degradation, mineralization and biodegradability enhancement, Departament d’enginyeria química i metal·lúrgia, April, 2003 9.Osman Malik Atanur et al, Applied Catalysis B: Environmental 58 Photocatalytic degradation kinetics of di- and tri-substituted phenolic compounds in aqueous solution by TiO2/UV (2005) 211–216


10.Guo-Min Zuo et al, Journal of Hazardous Materials B128 Study on photocatalytic degradation of several volatile organic compounds (2006) 158–163 11. Brijesh Pare et al., ZnO assisted photocatalytic degradation of acridine orange in aqueous solution using visible irradiation, Des alination 232 (2008) 80–90

12. Cláudia Gomes Silva et al, Journal of Photochemistry and Photobiology A: Chemistry 181 Photocatalytic and photochemical degradation of mono-, di- and tri-azo dyes in aqueous solution under UV irradiation (2006) 314–324 13. A. Valentine Rupa et al., Effect of deposition of Ag on TiO2 nanoparticles on the photodegradation of Reactive Yellow-17, Journal of Hazardous Materials 147 (2007) 906– 913 14. C. Sahoo et al., Photocatalytic degradation of Methyl Red dye in aqueous solutions under UV irradiation using Ag + doped TiO2, Desalination 181 (2005) 91-100 15. Kuo-Hua Wang et al., The photocatalytic degradation of trichloroethane by chemical vapor deposition method prepared titanium dioxide catalyst, Journal of Hazardous Materials B95 (2002) 161–174 16. B. Sivasankar et al., kinetic study on the photocatalytic degradation of salicylic acid using ZnO catalyst, Journal of Hazardous Materials,2008. 17. Chen Shifu et al., Preparation, characterization and activity evaluation of p–n junction photocatalyst p-ZnO/n-TiO2, Applied Surface Science 255 (2008) 2478–2484 18. K.Pirkanniemi and M.Sillanpaa, Heterogeneous water phase catalysis as an environmental application: a review, Chemosphere, 48 (2002) 1047. 19. B.Dindar and S.Icli, Unusual photoreactivity of zinc oxide irradiated by concentrated sunlight, J. Photochem. Photobiol. A:Chem. 140 (2001) 263. 20. Hamid Reza Pouretedal et al., Nanoparticles of zinc sulfide doped with manganese, nickel and copper as nanophotocatalyst in the degradation of organic dyes, Journal of Hazardous Materials 162 (2009) 674–681

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INTERNATIONAL CONFERENCE ON EMERGING TECHNOLOGIES IN ENVIRONMENTAL SCIENCE AND ENGINEERING, DEPARTMENT OF CIVIL ENGINEERING, A.M.U. ALIGARH, INDIA OCTOBER 26-28, 2009 SOLAR PHOTO CATALYTIC TREATMENT OF TEXTILE WASTEWATER Shashi kant Dubey Sr. Lecturer, Hindustan College of Science and Technology, Farah, Mathura Brajesh Chauhan Environmental Engineering Section, CED, Aligarh Muslim University, Aligarh P. K. Sharma Sr. Lecturer, Hindustan College of Science and Technology, Farah, Mathura

ABSTRACT: The last decade has marked good footprints in the area of wastewater treatment using Advanced Oxidation Processes (AOPs). The areas of application range across different industries: textile, pulp and paper etc., to municipal wastewater. Much research has been done on the synthetic compounds used in the above industries since the last ten years, using both UV and visible light. But there is a considerable gap in the study of the use of AOP for live industry effluents, using direct solar energy. In this work, industry effluent was taken and characterized. The results showed that wastewater is having very high pollution load in terms of COD and color. The effluent was treated using titanium dioxide as a photo catalyst in a shallow pond slurry type reactor. The results showed maximum efficiency for COD and color removal than conventional treatments. The work suggests the advanced treatment of textile wastewater in solar photo catalytic reactors.

Keywords: AOP; advanced oxidation process; textile wastewater; solar energy.

1. INTRODUCTION Developed countries are characterized by the production of waste products as an index of the standard of living. Developed countries, consisting 23% of the world's population, utilize 78% of the resources and produce 82% of the waste products. These countries are facing the problems of biological contamination, contamination by heavy metals and intensive nutrients, and organic contamination of water.


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Phenols, pesticides, fertilizers and detergents are usually non-biodegradable or persistent, which affects the environment severely. Moreover, these compounds can transform into potentially dangerous substances during drinking water treatment processes, such as chlorination giving chlorocarbons (Marhaba and Washington, 1998). Industries involved in the disposal of these types of compounds are mainly pharmaceutical industries paper and pulp industries, leather-tanning industries and textile industries. The wastewater from these industries has the problems of color, solids, BOD, COD, pH, high nitrogen content and is mostly non-biodegradable. Of all these industries, textile industries are of major concern. According to the US EPA, an average dyeing facility generates 1-2 million gallons of wastewater per day. Estimates suggest that about 10% of the dyes are lost in the wastewater (Young and Yu, 1997). Moreover, reactive dyes are highly water soluble and non-biodegradable under aerobic conditions (Neppolian et al., 2001; Rodriguez et al., 2002). Marmagne and Coste (1996) reported that reactive dyes have a higher non-biodegradability factor than other dyes. Residual colour is imparted by insoluble dyes having low biodegradability. Different unit operations involved in textile production like sizing, scouring, desizing, bleaching, washing, mercerization dying and finishing yield wastewater with high pH, temperature, organic matter, non-biodegradable matter, toxic substances, detergents and soaps, oil and grease, sulphide, sodas and alkalinity. BOD 5/COD ratio is a count of biodegradability as reported by the work of Marmagne and Coste (1996) Dyes generally have high COD values (Marmagne and Coste, 1996). Moreover, as they have a very low biodegradability factor (BOD/COD) they are difficult to treat with the help of biological treatment processes. Toxicity is the main problem encountered by bacteria engaged in the degradation of dyes, which makes it very difficult to treat it by biological processes. Anaerobic processes, however, have been reported to be sparingly effective, but they have limited applications (Stylidi et al., 2003). Physicochemical treatments are either pollutant specific or they have low degradation rates in general and prove uneconomical, being energy extensive. So there was a necessity to increase the biodegradability of the textile wastewater to treat it with the help of biological processes, which are highly economical. Glaze and Chapin (1987) defined Advanced Oxidation Processes (AOPs) as near ambient temperature and pressure water treatment processes involving the generation of highly reactive radicals (hydroxyl radicals) in sufficient quantity for water purification. They are very promising for remediation of contaminated ground, surface an wastewater containing non-biodegradable organic pollutants. Hydroxyl radicals are very reactive specie attacking most of the organic pollutants. The attack of a hydroxyl radical initiates a complex cascade of oxidative reactions leading to mineralization. Acids, aldehydes, aromatics, amines, alcohols and dyes (antraquninone, diazo, monoazo) can be degraded by hydroxyl radicals. Ozonisation and H2O2/UV as pretreatment to a textile wastewater was found to enhance the effectiveness of subsequent biological treatment (Alaton and Balciog, 2002). The photo catalytic organic content reduction of synthetic municipal wastewater has been studied at pilot plant scale (Kositzi et al., 2004). Sattler et al. (2004) have implemented solar photo catalytic water detoxification in industrial (paper mill) effluent, as the effluent contains polyphenolic polymer lignin-non-biodegradable substances; photo catalysis is a suitable method for degradation. The photocatalytic degradation of dimethoate, an organic phosphorous pesticide, has been investigated by Evgenidou et al. (2005) by using TiO2 and ZnO as catalysts, and TiO2 proved to be more efficient since the oxidation and decomposition of the insecticide was processed at higher reaction rates. Muruganandham and Swaminathan (2004) used TiO2 for decolourisation and degradation of an azo dye. Adams et al. (1997) reported that many synthetic and natural organic molecules are bio-recalcitrant. Cost is a prohibitive factor in the treatment of these

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compounds with the help of AOPs. Scott and Ollis (1996) and Marco et al. (1997) reported that investment cost for biological processes range from 5 to 20 times less than chemical ones while treatment cost range from 3 to 10 times less. So, chemical treatment may be used as a pretreatment to increase the biodegradability of wastewater (Parra et. al., 2000; 2002; Sarria et al., 2001). AOPs coupled with biological treatment are seen as viable solution for economic treatment of bio recalcitrant organic compounds in wastewater. 2. MATERIAL AND METHODS Raw effluent sample was collected from the equalization tank of S.R. Industries (Textile Unit), Dera Bassi (Punjab, India). The sample was checked for some initial parameters/characters (given in Table 1) and then it was subjected to solar photo catalytic treatment. Table-1. Characteristics of raw textile effluent from S.R.Industries

S. No.

Parameter

Range

1.

pH

10-11

2.

Temperature

400C

3.

COD

1300-1400 mg/L

4.

BOD

300-350 mg/L

5.

TDS

7000-8000 mg/L

6.

TS

8000-9000 mg/L

7.

TSS

700-800 mg/L

8.

BOD/COD

0.2-0.25(app.)

9.

TKN

109 mg/L

2.1 Reagents and chemicals used The photo catalyst was TiO2 , procured from Degussa's Indian Branch, Bombay. Hydrogen peroxide (Ranbaxy laboratories) was used as an oxidant. BOD, COD, TKN, Color, TDS and TSS were analyzed according to the procedures in standard methods (APHA Standards for examination of water and wastewater). All chemicals were used as received. In all the experiments distilled water was used.

2.2 Apparatus Used Radiometer: Solar UV Intensity was measured hourly on experimental days with an Eppley (model no.33013) radiometer.


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pH meter: The pH was measured with the help of a pH meter (ELICO). Filtration: Samples after the photo catalytic treatments were filtered through Whattman's filter paper (No. 42).

COD digester: COD digester was used for the digestion of samples in the process of COD determination. A semi automatic autoclave (EQUITRON) was also used for the same. Shallow pond slurry type reactor: Glass bowls were used for the photocatalytic reaction, having a capacity of 1000 ml. The catalyst was used in the form of aqueous slurry with the sample.

2.3 Preparation of the sample Wastewater collected from the textile industry was highly concentrated. So, to get the values within range, the sample (100 ml) was diluted in the ratio 1:1. Distilled water was used for all the dilutions. Initial pH was checked. The catalyst was added in a wide range from 0.1% to 1% to optimize the process for maximum pollutant degradation. H2O2 (30%) was added in the range of 0.5-2.5 ml/200 ml to check optimum volume for the process. Finally, the reaction vessel was kept over the magnetic stirrer under sunlight.

2.4 Procedure The sample was treated in natural sunlight for four hours. The intensity of UV radiation was measured continuously with the help of a radiometer. Samples were withdrawn after every one hour and filtered. COD of the samples was then measured as per the standard methods. The results were then optimized with regard to oxidant addition, pH adjustments. The tests were repeated for consistency.

3. RESULTS AND DISCUSSIONS 3.1 Wastewater characteristics The sample from the equalization tank of S.R. Industries Ltd. Chandigarh, India was found to have following values of pollution parameters as listed in Table 1. The absorption spectrum of the raw sample shows several peaks in the UV and visible regions (Figure 1), indicating the presence of several organic chromophoric compounds in the wastewater and the need for the degradation studies for complete mineralization.

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Figure-1. Absorption spectra of raw effluent

3.2 Effluent characteristics after solar photo catalytic treatment Effluent characteristics were determined after photo catalytic pretreatment process under optimized conditions i.e., at TiO2 concentration of 1.0 g/l (0.1%), 1 ml/200 ml of oxidant (H2O2), operating pH of 5.5. Table 2 shows the parameters analyzed after the photo catalytic treatment of the sample wastewater and their values, showing a major reduction in pollution load. Table-2. Characteristics of textile wastewater after solar photo catalytic treatment S.No.

Parameter

After Photocatalytic Treatment (mg. L-1) (Optimized Conditions)

1.

COD

100-150 (after4 hrs)

2.

BOD

60-80 (after4 hrs)

3.

BOD/COD

0.5-0.6 (app.)

4.

TDS

4300

5.

TKN

17.1

6.

pH

7.8


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As shown in Figure 2, the absorption spectra of the sample after photo catalytic treatment shows no peak in the visible region, indicating the mineralization several organic chromophoric compounds previously present in the wastewater. Figure-2. Absorption spectra of textile effluent after solar photo catalytic treatment.

4. CONCLUSIONS Solar photo catalysis can be used for treatment textile wastewater, which is supposed to be nonbiodegradable. First of all, due to the high cost of chemical treatments, biodegradability tests should be carried out, since for biodegradable compounds classical biological treatments are, at present, the cheapest and most environmentally compatible processes. Thus, solar photo catalysis treatment is an eco-friendly way to reduce the pollution load of wastewater.

ACKNOWLEDGEMENTS The authors of this paper are grateful to Dr. Anita Rajor (Lecturer, Thapar University, Patiala, India), Mr. Anoop Verma (Lecturer, Thapar University, Patiala, India), Dr. A. S. Reddy (Asst. Prof. Thapar University, Patiala, India) and Dr. R.C. Maheswari (Principal, HCST, Farah, India), for their valuable suggestions and help.

REFERENCES Adams, C., Randall, A. and Byung, J. (1997) 'Effects of ozonation on the biodegradability of substituted phenols', Wat. Res., Vol. 31, pp.2655-2663. Alaton, I. and Balcioglu, I. (2002) 'The effect of pre-ozonation on the H 2O 2/UV treatment of raw and biological pre-treated textile industry wastewater', Water Sci. Technol., Vol. 45, pp.297-304.

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Evgenidou, E., Fytianos, K. and Poulios, I. (2005) 'Photocatalytic oxidation of dimethoate in aqueous solutions', Journal of Photochem and Photobiol A: Chem., Vol. 175, pp.29-38. Glaze, W. and Chapin, D. (1987) 'The chemistry of water treatment processes involving ozone, hydrogen peroxide and ultraviolet radiation', Ozone Sci. and Eng., Vol. 9, pp.335-342. Kositzi, M., Poulios, I., Malato, C.J. and Campos, A. (2004) 'Solar photocatalytic treatment of synthetic municipal wastewater', Water Research, Vol. 38, pp.1147-1154. Marco, A., Esplugas, S. and Saum, G. (1997) 'How and why to combine chemical and biological processes for wastewater treatment', Water Sci. Technol., Vol. 35, pp.321-327. Marhaba, T. and Washington, M. (1998) 'Drinking water disinfection and by-products: history and current practice', Advanced Environ. Res., Vol. 2, pp.103-115. Marmagne, O. and Coste, C. (1996) Color Removal from Textile Plant Effluents, American Dyestuff Reporter, April. Muruganandham, M. and Swaminathan, M. (2004) 'Solar photocatalytic degradation of a reactive azo dye in TiO2 suspension', Solar Energy Materials and Solar Cells, Vol. 81, pp.439-457. Neppolian, B., Sakthivel, S., Arabindoo, B., Palanichamy, M. and Murugesan, V. (2001) 'Kinetics of photocatalytic degradation of reactive yellow 17 dye in aqueous solution using UV irradiation', J Environ. Sci. Health Part A. Tox Hazard Subst. Environ. Eng., Vol. 36, pp.203-213. Ollis, D.F., Pellizetti, E. and Serpone, N. (1991) 'Destruction of water contaminants', Environ. Sci. Technol., Vol. 25, p.1523. Parra, S., Malato, S. and Pulgarin, C. (2002) 'New integrated photocatalytic-biological flow system using supported TiO2 and fixed bacteria foe the mineralization of isoproturon', Appl. Catal. B: Environ., Vol. 36, pp.131-144. Parra, S., Sarria, V., Malato, S., Peringer, P. and Pulgarin, C. (2000) 'Photochemical versus coupled photochemical-biological flow system for the treatment of two biorecalcitrant herbicides: metobromuron and isoproturon', Appl. Catal. B: Environ., Vol. 27, pp.153-168. Rodriguez, C., Dominguez, A. and Sanroman, A. (2002) 'Photocatalytic degradation of dyes in aqueous solution operating in a fluidised bed reactor', Chemosphere, Vol. 46, pp.83-86. Sarria, V., Parra, S., Invernizzi, M., Péringer, P. and Pulgarin, C. (2001) 'Photochemicalbiological treatment of a real industrial biorecalcitrant wastewater containing 5-amino-6-methyl-2benzimidazolone', Water Sci. Technol., Vol. 44, pp.93-101. Scott, J.P. and Ollis, D.F. (1996) 'Engineering models of combined chemical and biological processes', J. Environ. Eng., Vol. 122, pp.1110-1114. Stylidi, M., Kondarides, D.I. and Verikios, X.E. (2003) 'Pathways of solar light induced photo catalytic degradation of azo dyes in aqueous TiO2 suspension', Appl Catal B: Environment, Vol. 40, pp.271-286.


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Young, L. and Yu, J. (1997) 'Ligninase-catalysed decolorization of synthetic dyes', Water Res., Vol. 31, pp.1187-1193.

Role of GIS in Environmental Engineering


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SPATIAL VARIATION IN WATER AND SEDIMENT QUALITY IN THE MARINE ENVIRONMENTS OF LAKSHADWEEP ISLANDS, INDIA: A CASE STUDY IN KAVARATHI AND CHETHLATH E.P. Nobi*, E. Dilipan, K. Sivakumar and T. Thangaradjou Centre of Advanced study in Marine Biology, Annamalai University, Parangipettai-608 502. Tamilnadu, India *[email protected] EXTENDED ABSTRACT The Lakshadweep islands are located in a geographical area bounded between 8 and 12ºN and 72 and 74ºE, about 200-400km off the south west coast of India. The pelagic and oceanic waters of Lakshadweep were very little explored for their water and sediment quality. Considering this fact a rapid survey was carried out during January and February 2009 to record the physico-chemical characteristics of the water and sediments in the lagoon areas Kavarathi and Chethlath Islands. Ten sampling stations were randomly selected at each islands and GPS guided point source field data were collected. The data were brought into GIS platforms using ArcView 3.3 and the data’s are interpreted. The spatial distribution maps of the different parameters were produced using ArcGIS software. The result showed clear variation in the spatial distribution of different parameters, within the islands. However the variations are within the optimal ranges given to the seagrass environs. From the results it is inferred that anthropogenic factors are not having more control over the water and sediment quality rather than the natural activities.

Water and sediment quality is vital for the survival and well being of the living resources, especially in the coastal and estuarine areas. The pattern of distribution of physico-chemical parameters including nutrients plays a major role in the spatial and temporal variations in the abundance and diversity of many marine organisms. In an area like Lakshadweep where the lives of the people depend on the primary links to the marine ecosystem, the variation in the ambient environment parameters can change the momentum of their lives (Anu et al., 2009). These islands are endowed with coral reefs and seagrasses while mangroves were seen in few locations (Jagtap, 1998). World wide decline of these important ecosystems were reported due to the variation in the ecological conditions. Coral reef and seagrasses are unique in embracing a surfeit of floral and faunal species with higher biological productivity. Seagrasses play a major role in maintaining the local ecology (Sridhar et al., 2008) where as variation in physico-chemical parameters can strongly affect the functioning of these ecosystems. Considering all these factors, a pilot study was conducted on the seagrass ecosystems of lagoon areas of Kavarathi and Chethlath islands. Lakshadweep group of islands comprise of 27 islands, 3 reefs and 6 submerged sand banks in the Arabian Sea between 80 00’ and 120 30’ N latitude and between 71000’ and 74000’ E longitude at a distance of 200 to 400km from the main land. For the present study Kavarathi and Chethlath was selected to understand the spatial variation in the physico chemical environment prevailing in the study area. Kavarathi island is located at a distance of 404km from Kochi and is located between Agathi on the west and Androth island on the east. The maximum length of this island is about 6km and has an area of 4.96sq.km. Where as Chethlath island is located nearly 432 km away from the Kerala coast and it is only 2.68km long and 0.59km wide. Both this islands are rich in marine flora and fauna. 10 random sites were selected in both the islands to collect the sediment and water sample.

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For understanding the ecology of seagrass beds of Lakshadweep islands, field survey was carried out to record the in situ environmental parameters, hydrographical and sediment characteristics of the selected locations. Atmospheric and surface water temperature was recorded using LCD portable Digital MultiStem thermometer. Salinity was recorded using a hand held refractometer (Atago, Japan). Water pH was determined using a pH meter (pH testr 2, Oakton). Soil salinity and pH of the sediment samples was recorded using Robust and Water proof hand held pH meter (pH 315i/SET, Germany). Concentrations of water nutrients viz. nitrite, nitrate and reactive silicate were determined by following the methods described by Strickland and Parsons (1972). Ten sampling stations were randomly fixed in each island and GPS locations were noted down using a hand held Global Positioning System (etrax, Garmin). The field data were brought into GIS platforms using ArcView GIS 3.3 and the data’s are interpreted. The spatial distribution map of the different parameters was produced using ArcGIS software. Air and surface water temperature recorded at the two islands comprising 20 sampling locations were ranged from 28.9 to 35.90C and 27.8 to 31.50C respectively. In case of sediment temperature it ranged from 26.3 to 29.80C. Lower air, surface water and sediment temperature was recorded from the Kavarathi island, where as higher atmospheric and sediment temperature was recorded in Chethlath island. In case of surface water temperature higher value was recorded again in the Kavarathi island in the 10th sampling location. Temperature is considered as one of the important parameter that controls the physiological activities of corals (Kannapiran et al., 2008), as the lagoons of Kavarathi and Chethlath are surrounded by coral reefs, the variation in the temperature can cause severe impact on the reef metabolism. The spatial distribution graph of the temperature showed only a minor variation in the values with respect to different sampling sites. Salinity of the two islands varied from 33 to 37ppt registering the lower concentration at Chethlath island and higher at Kavarathi island. Sediment salinity showed only lesser variation with Chethlath island registering the lower value of 32ppt and Kavarathi registering the higher value of 35ppt. Water pH ranged from 7.9 to 8.3 recording the lower value and higher value in two different sampling sites of Kavarathi island, where as in case of sediment pH, Chethlath island recorded the lower value of 7 and Kavarathi island recorded the higher value of 8.4. The present value observed for temperature, salinity and pH are comparable to that of reports from other coral reef (Sridhar et al., 2008; Kannapiran et al., 2008) and seagrass areas of mainland. Nutrients are considered to be the important parameter in the coastal environment, which influences the growth, reproduction and metabolic activities of biotic components (D’Alia, 1988). Nutrient concentrations in the 20 sampling locations varied significantly. In the present study nitrite concentration ranged from 0.128 M to 0.635 M, registering the lower concentration at Kavarathi and the higher concentration at Chethlath island. Nitrate is known as the nutrient which enhances the coastal productivity, during the present study, nitrate concentration varied between 0.32 to 3.88 M. Contradictory to the nitrite concentration, the lower concentration of nitrate was recorded at Chethlath and the higher was at Kavarathi. Silicate concentration varied between 11.95 to 19.05 M, with Kavarathi registering the lower concentration and Chethlath registering the higher value. More over the spatial distribution map of the parameters analysed showed clear variation in the spatial distribution of different parameters both in intra and inter islands. From the present investigation, it has been well observed that air and surface water temperature showing a gradual increase when compared to the the past years. This increase in temperature can cause severe impact on the healthy coral and seagrass ecosystems of these two islands. Further the spatial distribution map plotted clearly depicts the variation in different parameters with respect to different stations. From this study it is recommended that the analysis of


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the environmental parameters using GIS tools can clearly point out the variation in the concentration and is also found as a cost effective tool for environmental monitoring.

Reference Anu, G., Nair, S.M., Kumar, N.C., Jayalakshmi, K.V., Pamalal. D, 2009, A baseline study of trace metals in a coral reef sedimentary environment, Lakshadweep Archipelago, Environmental Earth Sciences, DOI: 10.1007/s12665-009-0113-6. Jagtap, T.G, 1998, Structure of major seagrass beds from the three coral reef atolls of Lakshadweep, Arabain Sea, India, Aquatic Botany, 60, p397–408. Strickland, J. D. H and T. R. Parsons, 1972, A practical handbook of seawater analysis, Bulletin of Fish Research Bd. Canada, 167: 310pp. Kannapiran, E., L. Kannan., A. Purushothaman and T. Thangaradjou, 2008, Physico-chemical characteristics of the coral reef environment of the Gulf of Mannar Marine Biosphere Reserve, India, Journal of Environmental Biology, 29(2), p215-222. D’Elia, C.F, 1988, The cycling of essential elements in coral reefs, In: Concepts of ecosystem ecology (Eds: L.R. Poomeroy and J. J. Albert). Springer, Newyork.pp.195-230. Sridhar, R., T. Thangaradjou and L. Kannan, 2008, Comparative investigation on physico-chemical properties of the coral reef and seagrass ecosystems of the Palk Bay, Indian Journal of Marine Sciences, 37(2), p207-213.

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GIS: AN EMERGING TOOL IN ENVIRONMENTAL SCIENCE AND ENGINEERING Ritesh Vijay1*, Puja J. Khobragade1, Asheesh Sharma1 and R. A. Sohony1 Author for correspondence Environmental Systems Design and Modeling Division National Environmental Engineering Research Institute Nehru Marg, Nagpur 440020, Maharashtra, India Email: [email protected] Phone: 0712 2249990, Fax: 0712 224990 Abstract: In order to respond to the complex environmental challenges in air, water and soil quality, energy and resource utilization, waste management and development impacts, we need to develop an improved scientific and technical understanding of environmental issues. Geographical Information System (GIS) plays a vital role in environmental science and engineering for analysis and in formulating the quick mitigation plan for high risk environments. GIS is one of the key emerging technology and tools in the environmental data framework for data validation, digital data transfer standard, data retrieval/ dissemination and analysis. GIS can serve as a means to integrate everincreasing volumes of diverse spatial and non-spatial environmental data, from numerous sources at local, regional and national scales into a manageable whole. Since, it is the technical basis for the multimedia approach in environmental decision making, users with GIS experience are able to utilize its functionality to query, display and produce maps and reports from environmental data sets. The poster represents the role of GIS activities in environmental monitoring, assessment, mitigation, planning and management. Environmental science and engineering issues like rainfall- runoff estimation, siting and sizing of reservior, suitable site and structure selection for artificial recharge of groundwater, assessment of soil erosion and sediment yield, water, noise and air quality, mapping of hazard prone areas due to sea level rise, biodiversity studies using high resolution satellite imagery, solid waste management etc. are highlighted in the poster. GIS based evaluations portrayed can be made available to a wider audience viz. environmental agencies, regulator authorities, research / academic personnel for better management and taking decisions. Key words: GIS, environment, science, engineering.

1. INTRODUCTION Throughout human history, technology has been a key factor in facilitating and driving change. The role of computer-based technologies in environmental management is not new, recent development and innovations have offered the potential to improve how analysis and policy makers solve problem and make decisions concerning the environment through the use of computers. Geographic Information Systems (GIS) is powerful tool in environmental science and engineering. People are


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attracted to GIS because it offers a more powerful way of thinking and presenting information in general and geographically referenced information in particular. This technology can create an environmental change on spatial and temporal scale never before possible. As computing and satellite sensors have advanced in the past few decades, GIS, Global Positioning Systems (GPS,) and Remote Sensing (RS) have vastly improved our ability to map our world and the universe. “GIS empowers us to solve environmental problems of a changing world faced by humankind in the new millennium” (Lo et a.l. 2003, Jha et al. 2007). A number of new tools and techniques such as models currently exist for abstracting, simulating, and understanding complex details of physical, biological, and social systems and subsystems can be effectively used in environmental science and engineering but GIS represents an emerging technologies that can facilitate resourse identification and evaluation. GIS tecnology is already being used in larger scale. It is frequently claimed that GIS is an integrated technology because of the way in which it links together diverse type of information drawn from variety of sources, such as information from field, remote sensing etc (Saraf 1998 ). With invention of technologies like remote sensing and GIS and developments in the computational technology the process of data collection analysis has become faster and cheaper. GIS is a collection of computer hardware, software, and geographic data for capturing, managing, analyzing, and displaying all forms of geographically referenced information. GIS applications are tools that allow users to create interactive queries, analyze spatial information, edit data, maps, and present the results. Modern GIS technologies use digital information, for which various digitized data creation methods are used.

2. OBJECTIVE OF POSTER To represent the role of GIS activities in environmental monitoring, assessment, mitigation, planning and management. Environmental science and engineering issues like rainfall- runoff estimation, siting and sizing of reservior, suitable site and structure selection for artificial recharge of groundwater, assessment of soil erosion and sediment yield, water quality, noise and air quality, mapping of land use land cover study using high resolution satellite imagery, etc. are highlighted in the poster.

3. APPLICATION AREA 3.1 Rainfall- runoff Water is an important natural resource and proper management of water resource both on surface and underground is essential for economic and social development of a country. In the recent times, the irregular monsoons and frequent reccurence of droughts asssociated with the change in environment has resulted in very severe scarcity of water resources. GIS has become a powerful tool in delineating watersheds, analyzing runoff and other application in hydrology. Case study: A GIS based algorithm has been developed and applied to estimate the rainfall- runoff relationship of Sathanur reservior catchment based on Soil Conservation Service (SCS) model (Vijay et al, 2006). The algorithm was executed successfully by rainfall data for computation of runoff depth in all the sub watersheds. Figure 1 describe the land use land cover practices in the study area. Soil group based on hydrological classification is defined in Figure2. Rainfall data in each sub watersheds is shown in Figure 3. Curve number (CN) as per SCS model was estimated and presented in Figure 4. Finally runoff under different antecedent moisture conditions is estimated and presented in Table 1.

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Figure1: Landuse/ landcover map of the study area Figure2: Hydrological soil group in the study area

Figure3: Rainfall data of the sub watersheds

Figure4: CN based on landuse and soil groups

Table 1: Weighted CN and rainfall-runoff distribution of the sub-watersheds SubWatershed

`

weighted CN

AMC I AMC II AMC III 42.97 64.21 80.49 1 2 40.41 61.75 78.78 3 43.09 64.32 80.57 4 52.81 72.71 85.97 5 58.99 77.40 88.74 6 48.11 68.82 83.55 58.97 77.38 88.73 7 8 57.30 76.16 88.02 56.57 75.62 87.71 9 10 60.33 78.36 89.28 58.94 77.37 88.71 11 54.03 73.67 86.55 12 13 62.03 79.55 89.95 14 53.95 73.61 86.52 AMC – Antecedent Moisture Condition

rainfall in cm 84.47 84.79 90.35 83.03 90.55 74.52 65.17 77.83 70.71 75.41 71.31 67.34 103.68 94.21

runoff in cm AMC I 51.16 48.73 56.63 58.73 70.63 46.92 46.22 57.16 49.87 56.90 52.05 44.91 85.58 70.32

AMC II AMC III 68.19 76.89 66.92 76.42 74.02 82.78 71.65 77.84 81.48 86.47 61.17 68.34 56.30 61.13 68.25 73.49 60.94 66.25 66.90 71.57 62.37 67.25 56.66 62.43 95.58 100.07 83.20 89.23

3.2 Computation of reservoir storage and submergence The main function of a reservoir is to store water and thus to stabilize its flow. In designing dams, the volumes that need to be determined are storage and submergence that submerge the land use against storage. Cross- section, spot levels, and contours can be used to estimate volumes. The first two methods are generally used to calculate earthwork, while the third is used to determine reservoir staroge capacity (Agor 1992). Case study: A GIS based algorithm has been developed and applied to compute storage capacities and submergence scenarios of resevoirs with varying dam heights (Vijay et al. 2006). The computation is based on a digital elevation model (DEM) (figure 5) of the topography and triangulated irregular networks (TIN).

Figure5: Digital Elevation model

Figure6: Submergence for a 100 m reservoir height


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Figure7: Elevation- storage and elevation- submergence for water reservoirs Figure 6 shows the submergence at proposed reservoir sites due to 100m height of dam. Algorithms computes storage and submergence at different heights as presented in figure 7 at different reservoir sites.

3.3 Site and Structure selection for artificial recharge The groundwater scenario in India, which receives a substantial amount of annual rainfall, is not very encouraging primarily due to the imbalance between recharge and groundwater exploitation (Ravi shankar & Mohan 2005). A GIS based hydrogeomorphic approach can provide the appropriate platform for spatial analysis of diverse data sets for decision making in groundwater management and planning. Case Study: The study presents the methodology implemented through GIS techniques to provide more accuracy in identification and suitability analysis for finding recharge zones (Figure 8) based on weighted index overlay analysis and locating suitable sites by apply Boolean logic with suggested structures for artificial recharge (Figure 9) as per Central Ground Water Board manual. The GIS based algorithm is implemented in a user-friendly way using arc macro language on Arc/Info platform.

Figure 8: Zone selection for recharge

Figure 9: Sites and suggested structures for recharge

3.4 Soil Erosion Soil erosion in the watershed is of major concern, because it leads to degradation of land (Jasrotia & Sing, 2006). Erosion promotes critical losses of water, nutrients, soil organic matter and soil biota, harming forests, rangeland and natural ecosystems. Water and wind is the major agent of soil erosion. Case study: The Grid representation of soil erosion give the variation of soil erosion rate in tons per hectare at each cell of watershed and it vary according to all spatial and seasonal parameters of the area. Figure 10 show the analysis of the soil erosion rate occurring in the study area within the various watershed boundaries based on landuse, soil type, organic matter, rainfall intensity, crop management and control erosion practies.

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Figure 10: Soil Erosion Rate in the different Watersheds

3.5 Land Use Land Cover The land use land cover pattern is an outcome of natural and socio-economic factors and their utilization by man in time and space. To understand how LULC affects and interacts with environmental systems, information is needed regarding what changes occur, where and when they occur, the rates at which they occur, and the social and physical forces that drive those changes (Lambin et al. 2003). The remotely sensed data coupled with GIS help in the quantitative appraisal of changes in land use land cover and biomass/ vegetation vigour of an area (Chakraborty et al. 2001). Remote Sensing is a powerful technique for surveying, mapping and monitoring earth resources. Case Study: Remotely sensed satellite data in conjunction with available other data sources have been used to find such land uses. In this study, LANDSAT TM, IRS-1C LISS III, and IRS-P6 LISS III data were used to identify the land use status of the study area. The LULC under different images and time are given in Figure 11. Graphical presentation and change in land use land cover with respect to time is given in Figure 12.

Landsat TM (1990)

IRS-1C LISS III (1998) IRS-P6 LISS III (2005) Figure 11: Landuse Map of the study area


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Figure12: Graphical representation of the change in land use land cover

3.6 Water Quality Analysis Water is essential to the human life and health of environment. Water quality involves careful management of both groundwater and surface water. The increasing demand for water as a result of an increasing population has placed pressure on the water quality (Kannel et al. 2008). Water quality models are used to determine the kind and amount of effluent the point source may discharge without violating water quality standards (Doppelt 1996, Freeman 1990, Patrick 1992, Korfmacher 1998). Case Study: Monitoring and assessment of water quality using GIS technologies for spatial distribution of coastal water quality. Natural neighbourhood interpolation technique has been used to create spacio-temporal distribution map. The spatial distribution of FC and BOD in Mumbai coastal and creeks are given in Figure 13 and Figure 14 respectively.

Figure 13: Distribution of FC

Figure 14: Distribution of BOD

3.7 Noise Environment Currently, noise pollution in urban environment is one of the serious issues of concern in major cities of world. Noise in a particular region is influenced by the volume of traffic on the highway, in addition to other causative factors like existing infrastructure and industrial setup etc. Analyzing and modeling of traffic noise help the planning of environmental friendly roads (Yilmaz et al. 2006). GIS provides an excellent platform for managing and editing the data necessary to run a noise mapping simulation (Kucas et al. 2007). Case study: GIS based noise simualtion model has been developed to generate noise levels in Versova region of Mumbai, India considering mobile and point sources (Sharma et al). Various meterological parameters and effect of land use land cover on noise attenuation are also considered in the model. Noise were predicted for point as well as mobile sources. FHWA and point models are considered

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together to estimate the noise cummulatively. Figure 15 represents the average noise level during day time in the Versova region of Mumbai.

Figure 15: Day time noise level in versova

3.8 Air Environment With rapid urbanization and industrialization, the pollution is increasing at an alarming rate in most of metropolitan cities of India. Various dispersion models are use to estimate and predict the downwind concentration of air pollutants emitted from sources such as industrial plants and vehicular traffic. GIS has been significantly used in urban air quality analysis in recent years because of its capability for visualization and database storage (Jin et al. 2005). Case Study: The Industrial Source Complex Short Term (ISCST3) algorithm calculates concentration of pollutant from a wide variety of sources. In the present study GIS and a Gaussian plume model, ISCST3, was used to estimate ground level concentration of pollutant emitted from mobile as well as stationary sources. Figure 16 represent the RSPM level in Bandra region of Mumbai.

Figure 16: RSPM Level at Bandra region

4. CONCLUSIONS


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GIS techniques are effectively used in various environmental science and engineering fields namely rainfall- runoff, computation of reservoir storage and submergence, site and structure selection for artificial reacharge, soil erosion, land use land cover, water, noise and air environment. GIS functionality provides a powerful set of tools for modeling spatial problems more precisely. GIS is a playing a vital role in the field of science and engineering because of it visualization capabilties and also as data storage, retreiaval and analysis. The GIS based application will be immensly useful for decision making bodies like environmental managers, regulatory authorities, research groups etc for environmental planning and management.

5. AKNOWLEDGEMENT Authors are thankful to Director NEERI, for providng encouragement, necessary infrastructure, support and permission to publish this GIS based applications.

6. REFERENCES Agor R, 1992, A textbook of surveying and leveling, New Delhi, India, Khanna publishers, p397-444. Bonham, Carter G F, 1994, Geographical Information Systems for Geoscientists, Modelling with GIS, Pergamon Press, Oxford. Lein James K, 1997, Environmental decision making: An information technology approach. Saraf A K, Choudhury P R, 1997 Integrated Application of Remote Sensing and GIS Ground water exploration in Hard Rock Terrain, Depart. of Hydrology Roorkee vol 1, 435-442. Korfmacher K S, 1998, Water quality modeling for environmental management: Lessons from the policy sciences, Kluwer Academic Publishers. Policy Sciences 31, p35-54, 199 Tripathi, Nitin kumar & Bajpai, Vishwa nath, 1998, Remote sensing in geoscience, Amol publications pvt.Ltd. New Delhi. Chakraborty Debashish, Dutta Dibyendu and Chandrasekharan H, 2001, Land use indicators of a watershed rajsthan using remote sensing and GIS , Journal of the Indian Society of Remote Sensing, Vol. 29, No. 3. Lambin E F, Geist, H J and Lepers, E, 2003, Dynamics of land-use and land-cover change in tropical regions, Annual Review of Environment and Resources, 28, p205-241. Lo C P, Yeung AKW , 2003, Concepts and techniques of geographic information systems, PrenticeHall, New Delhi Jin Taosheng & Fu Lixin, 2005, Application of GIS modified models of vehicle emission dispersion, Atmospheric Environment 39, p6326-6333 Ravi Shankar, M N and Mohan G, 2005, A GIS based hydrogeomorphic approach for identification of sitespecific artificial- recharge techniques in the Deccan Volcanic Province, J. Earth Syst. Sci. 114, No, 5, p505–514. Jasrotia, A S and Singh, R 2006, Modelling runoff and soil erosion in a catchment area, using the GIS, in the Himalayan region, India, Environ Geol, vol.51, p29–37. Yilmaz G, Hocanli Y 2006, Mapponig of noise by using GIS in Sanliurfa, Environmental Monitoring and Assessment, 121, p103–108.

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Vijay R, Pareek, A & Gupta, A, 2006, Estimation of Rainfall- Runoff Using Curve Number: A GIS based Development of Sathanur Reservoir Catchment, Journal of environ. Science & Engg, Vol.48, No.4, p267-270. Vijay R, Gupta A & Devotta, S, 2006, Computation of reservoir storage capacity and submergence using GIS, Surveying and land information science, Vol.65, No.4, p255-258. Kucas A, Hoej J, and Frederiksen R, 2007, Efficient Noise Mapping using ArcGIS and detailed Noise Propagation Simulation, ESRI European User Conference. Jha, Madan K & Chowdary V M, 2007, Challenges of using remote sensing and GIS in developing nations, Hydrogeology Journal, 15, p197–200. Kannel P R, Lee S & Lee Y S, 2008, Assessment of spatial – temporal pattern of surface and ground water qualities and factors influencing management strategy of groundwater system in an urban river corridor of Nepal, Journal of Environmental Management 86, p595–604. Sharma A, Vijay R, Sardar V, Sohony R & Gupta A, 2009, Development of noise simulation model for stationary and mobile sources: a GIS based approach, Environ. Model Assess, DOI 10.1007/s10666-009-9197-3. Joshi P K, Kumar M, Paliwal Ambica, Midha Neha & Dash P P, 2009, Assessing impact of industrialization in terms of LULC in a dry tropical region (chhattisgarh), India using remote sensing data and GIS over a period of 30 years, Environ Monit Assess, 149, p371–376.


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DEVELOPMENT OF GIS BASED NOISE SIMULATION MODEL:A CASE STUDY OF MUMBAI, INDIA Asheesh Sharma*, B.Tech, Ritesh Vijay, M.Tech, Rajiv Sohony, Phd *Author for correspondance Environment System Design & Modelling Divsion National Environmental Engineering Research Institute Nehru Marg, Nagpur-440020 Telefax - +91 712 2249990 [email protected]

ABSTRACT In the rapidly urbanizing country like India, the transportation sector is growing rapidly, which has led to overcrowded roads and traffic noise pollution. Noise of a particular region is influenced by the volume of traffic on the highway passing nearby it, in addition to other causative factors like infrastructure development and industrial setup etc. In the present study, a GIS based Noise Simulation Model has been developed to generate noise levels senario of Versova region of Mumbai, India. The study area comprises: effect of infrastructure, road network layout traffic volume and various mechanical component like Sewage Pumping Station (SPS) and Waste Water Treatment Facilities (WWTF). In this way, commutative noise simulation for point and mobile sources of noise are considered.The GIS based model has been calibrated with observed and simulated noise levels and correlation was found to be 0.77.

Keywords: Noise, simulation, GIS, point and mobile source.

INTRODUCTION Noise contamination owing to transportation in cities along with infrastructure development, industrial noise, airport noise and community noise are among important environmental health consequences. Therefore it is important to monitor the effects of existing infrastructure and to study the possible effects on the environment when new infrastructure is planned. Based on studies provided by the various model De Kluijver et al. (2000), the design with the least environmental impact can be selected and measures can be devised by which further environmental impact is reduced. In this way, these studies affect the decision-making process. Many researches have been done on noise prediction modeling including the CRTN model, To et al. (2002), Abbott and Nelson (2002) and Hepworth et al. (2006), FHWA model, Rochat and Reherman (2005), Pamanikabud and Tansatcha (2003) and Hankard et al. (2006), RLS90 model, Coensel et al. (2006), EMPA model, Desarnaulds et al. (2004) and OAL model, van Leeuwen (2002) and the ASJ model Chung et al. (1998) etc. In most of the studies earlier done on noise prediction, a point source of noise or traffic volume on the road has been measured and based on these measurements noise model of a region has been predicted Nirjar et al. (2003) and Mehdi (2002), while in other studies measured noise level has been provided to software for noise prediction Chung et al. (1998). A common criticism of the existing models is that, they are not user friendly and the results are not always presented in a format that can be easily visualized. Visualization is of particular importance in analyzing and predicting the noise levels Brown (1994). Most of the data required for traffic noise simulation and prediction, such as road schemes, earth profiles, noise barriers and buildings, have spatial 3-dimensional characteristics. To resolve problems relating to a spatial data manipulation, a geographic information system (GIS) was selected and integrated with traffic noise model. GIS is an important tool in spatial analysis and modeling. It has been widely used in environmental modeling to study various meteorological parameters Goodchild et al. (1993).

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Based on the literature, far-reaching integration of GIS and noise prediction models are widely used Moragues (1996) and Li (2000) while present GIS based algorithm serves as a pre and post-processor for noise simulation. The objective of the paper is to develop an integrated GIS based noise simulation model for both point and mobile sources. The GIS based algorithm uses FHWA model and combined with other geographical information such as land use, road traffic, and atmospheric effect like temperature, humidity and areas sensitive to noise. An external program in FORTRAN 77 is developed to estimate the combine effect of various noise sources based on the input provided from the GIS environment. Results obtained from the FORTRAN program again imported to GIS for noise level visualization.

METHODOLOGY The methodology involved in the noise simulation includes three phases which are defined as follows

Phase 1 Phase 1 involves preparation of thematic layers which includes digitization of road network and possible sources of noise i.e. point and mobile on ArcGIS 9.3 platform. Creation of database involves vehicular inventory, meteorological parameter, noise barriers etc through external database and linkage with thematic layers. The distance calculation between mid point of road segment and simulated noise point has been calculated. The simulation points placed where maximum noise levels are expected in the study area (highways, major roads and point sources).Similarly the distance between point sources of noise which includes aerators of WWTF and mechanical equipments of SPS and simulation points are computed. In this way cumulative noise due to mobile as well as point source at each simulation point is considered.

Phase 2 In this phase, algorithm has been developed to compute noise level collectively for both the point and mobile sources. A FORTRAN program has been written to execute GIS based distance calculation to predict cumulative noise level due to point and mobile sources at different simulation noise points. The Ldn noise descriptor divides every 24-hour period into daytime period (0600 to 2100 hours) and nighttime period (2100 to 0600 hours). Noise level during the nighttime is more sensitive therefore Leq for night time is increased by 10 db. Ldn is the 24-hour energy average (Rau, 1980). L dn = 10 log

1 ⎡ Leqi / 10 (L +10 )/ 10 ⎤ + ∑ 10 eqi / 10 ⎢ ∑ 10 ⎥ 24 ⎣ daytime nighttime ⎦

(1)

Phase 3 Cumulative noise levels estimated in phase 2 at different simulation points has been used to visualize the effect of the noise spatially due to point as well as mobile source in the region.

RESULT AND DISCUSSION The GIS based noise simulation model predicts the noise at various simulation noise points. The noise levels at these simulation points are the result of


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cumulative effect of point as well as mobile sources. Noise level are measured on ten location namely S1, S2…..S10 at Versova region of Mumbia shown in (Figure.1).

Figure.1:Study Area: Versova region in Mumbai, Figure.2: Noise level of Versova region around India existing SPS and WWTF

The noise levels at the simulation points are used to represent the spatial distribution of noise 24 hourly average in the region as shown in (Figure.2). The spatial distribution of noise at the WWTF region in the range of 64 – 70 dB is comparatively higher than the other regions due to continuous operation of aerators. Similarly the noise near SPS region is in the range of 60 – 64 dB comparably higher than other minor roads due to heavy traffic flow. The measured noise levels at the observation points are compared with the simulation points as shown in (Table. 1) The correlation coefficient between the observed and simulated noise levels is 0.77 at 95% confidence level. The correlation illustrates that the model can simulate the noise level in the other region with incorporation of local climatic and geographical conditions. The noise levels in the WWTF and SPS region are exceeding the limit of 55 dB in the daytime as per Indian Noise Standard as shown in the (Table. 2).

Table 1: Comparison between observed and simulated noise levels S.No

Sites

1 2 3 4 5

s1 s2 s3 s4 s5

6 7 8 9 10

s6 s7 s8 s9 s10

Location Versova SPS Near PS E-Engg Office Near Workshop Left back corner Main gate1 Versova WWTF Center of aerated lagoon Starting pt of aerated At Left corner In Front office yard Main gate2 Correlation coefficient

Observed (dB)

Simulated (dB)

66.2 59.3 55.6 57.3 64.5

60.2 58.0 57.9 58.6 61.0

71.3 64.5 57.1 63.5 58.7

67.3 59.8 59.4 60.7 53.2

Table 2:Ambient noise standards

0.77

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Area Industrial Area Commercial Area Residential Area Silence Zone a

Day Time Leq (dBa)

Night Time Leq (dBa)

75 65 55 50

70 55 45 40

Central Pollution Control Board, Ministry of Environment and Forest Government of India

Although the effect of noise in WWTF region is high and localized by aerators. Since there is no developmental activities in the region and effect of dense plantation and mangroves which minimize it’s propagation towards residential area as visualized in noise distribution plot in (Figure. 2). The noise effect around Versova SPS propagates in the residential area which is matter of concern and requires proper control measures in terms of noise barrier to reduce the noise propagation.

CONCLUSION Noise sources and barriers, landuse patterns, environmental and meteorological parameters offer unique challenges in applying noise simulation. The purpose of this integrated GIS based development is to simulate the noise for point as well as mobile sources and visualization of the cumulative noise levels with respect to space and time. The spatial distribution of the noise provides the noise levels around any point, line and area in the study region for better planning and management. Based on the simulation results, noise barriers and green belt can be designed to check the propagation of the noise due to traffic, industries, development and construction activities.

ACKNOWLEDGMENT The authors are grateful to the Director of NEERI for providing encouragement, the necessary infrastructure support and kind permission to publish this GIS Based simulation Model.

REFERENCE Abbott, P. G., Nelson, P. M., 2002. Converting the UK Traffic Noise Index la10,18h to EU Noise Indices for Noise Mapping. Project Record: EPG 1/2/37 – Adapt UK Road Traffic Noise Calculation Method for Noise Mapping (UK) Bert, D. C., Vanhove, F., Logghe, S., Wilmink, I., Botteldooren, D., 2006. Noise Emission Corrections at Intersections Based on Microscopic Traffic Simulation Acoustics Research Group, Department of Information Technology, Netherlands. Brown, A. L., Lam, K.C., 1994. Can I play on the road, Mum? Traffic and roads in Australia. Road and Transport Research (3), 11–23 Chung, E., Kuwahara, M., Oshino, Y., 1998. Integration of road traffic noise model (ASJ) and traffic simulation (AVENUE) for built-up area. Institute of Industrial Science,& Center for Collaborative Research , University of Tokyo , Energy and Environment Research Division, Japan Automobile Research Institute, Japan. Central Pollution Control Board, Ministry of Environment and Forest Government of India. Available on website: http://envfor.nic.in/cpcb


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National Physical Laboratory, 2005. Chapter 2: General physics Section 2: Acoustic Subsection 2.4.1: The speed and attenuation of sound, Kaye & Laye Table of Physical and Chemical content. Available on website: http://www.kayelaby.npl.co.uk De Kluijver, H., Stoter, J., Utrecht, R.C., 2000. Noise Mapping and GIS: Optimizing Quality, Accuracy and Efficiency of Noise Studies (Paper presented at the 29th International Congress and Exhibition on Noise Control Engineering, Netherlands). Desarnauldsa,V., Monay, G., Carvalho, A., Noise Reduction by Urban Traffic Management Bureau ing. G. Monay, 25, av. Vinet, CH-1004 Lausanne, Switzerland, Univ. Porto, Fac. Engineering, Acoustics Lab., P-4200-465 Porto, Portugal. ESRI ArcGIS 9.1 software, Redlands, California, 380 New York Street, Available on website: http://www.esri.com Goodchild, M. F., Parks, B.O., Steyaert, L.T., 1993. Environmental modeling with GIS. New York: Oxford University. Goodchild, M. F., Steyaert, L.T., Parks, B.O., 1996. GIS and environmental modeling: progress and research issues. GIS World: Fort Collins. Hepworth, P., Trow, J., Vincent, Hii. 2006. Reference Settings in Noise Mapping Software –a Comparison of the Speed of Calculation for Different Software (Euro noise 2006 , England) Hankard, M., Cerjan, J., Leasure, J., 2006. Evaluation of the FHWA Traffic Noise Model (TNM) for highway traffic noise prediction in the state of Colorado Report. No. Cdot-2005-21 Final report. Highway Traffic Noise Analysis and Abatement Policy and Guidance by U.S. Department of Transportation Federal Highway Administration Office of Environment and Planning Noise and Air Quality Branch Washington D.C. 1995 Mehdi, M.R., 2002. Appraisal Noise Pollution Traffic and Land use patterns in Metropolitan Karachi through and remote sensing technology, PhD thesis University of Karachi, Karachi/Institute of Environmental Studies. Moragues, A., Alcaide, T., 1996. The use of geographical information system to assess the effect of traffic pollution. Science of the Total Environment,189/190, 267–273. Li, B.G., Tao, S., Lam K.C., 2000. A noise-GIS system for traffic noise prediction and planning. Journal of Environmental Science, 20, 82–85. Nirjar, R.S., Jain, S., Paridar, M., Katiyar, V., S., Mittal, N.,. 2003. A Study of Transport Related Noise Pollution in Delhi, Institute of Engineering Kolkata. Pamanikabud, P., Tansatcha, M., 2003 .Geographical information system for traffic noise analysis and forecasting with the appearance of barriers. Environmental Modelling & Software, 18, 959– 973. Rau, J.G., Wooten, D.C., 1980. Environmental Impact Analysis Handbook .University of California at Irvine. Rochat, J. L., Reherman, C. N., U.S. DOT. 2005. FHWA Roadway Construction Noise Model (RCNM). Volpe Center Acoustics Facility Environmental Measurement and Modeling TRB ADC40 Summer Meeting Seattle, WA

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To, W. M., Rodney, C. W., Lam, G.C.K., Yau, C. T. H., 2002. A multiple regression model for urban traffic noise in Hong Kong. The Journal of the Acoustical Society of America 112, 551-556 . Van Leeuwen J. J. A., 2002. Noise Prediction Models to Determine the Effect of Barriers Placed Alongside Railway Lines, dgmr Consulting Engineers, Eisenhowerlaan 112, 2517 KM The Hague, Netherlands


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EVALUATION OF LAND USE CHANGE TREND IN TALEGHAN WATERSHED USING REMOTE SENSING AND GIS TECHNOLOGIES 1

A. Ahmadi1, H.R. Kohbanani2, E. Akbari3 & A. Keshavarzi4 member of scientific board of Islamic Azad university, Arak branch, 2&3, MSc. Student of GIS, university of Tabriz,4 MS.c student of soil science, university of Tehran Email: [email protected]

ABSTRACT Increasing change and deterioration of ecosystems in recent years make difficult the adaptation of living organisms with environment disturbances. The aim of this study was to determination of land use changes in Taleghan basin and explanation of effective factors on these changes, using remote sensing and GIS methods. For this purpose, the TM (1987) and ETM+ (2000) images were produced and then import to GIS with another data and layers of the region. Therefore, the progresses of preprocessing such as geo referencing of orthorectification and atmospheric correction upon the images were performed. After these processes, the production of check points was done using enhancement methods and application of pseudo color complex and also different data such as GPS outputs and topographical maps (with scale of 1/5000 and 1/25000). Then accuracy assessment was performed by check points to make certain about accuracy and precise of operation. The results were imported into GIS software's to determination of amount and kind of variances. Key words: RS, GIS, land use, TM, Taleghan

1. INTRODUCTION The Change in ecosystems in recent years has been so fast that the possibility of compatibility of living organisms with environmental changes have been too difficult and this phenomenon has been aroused from inattention to the time scale in utilization of basic natural resources (Sheikhhasani, 2001). Information from the land use and its changes over time is one of the most important cases in planning. With the knowledge of land use changes during time, we can predict future changes and make appropriate actions (Feyzizade et al., 2009). Land cover maps have vast application in environmental and natural resource management and recognition of land capacity and compatibility and used as an important source of information for policies and development programming. Land evaluation is the process of predicting the potential use of land on the basis of its attributes. It is necessary because land varies in its physical, social, economic, and geographic properties. It is essential to identify best land management practice as it is the key process for sound land use planning (Nedal et al., 2007). The conventional methods of detecting land use/land cover changes are costly, low in accuracy and present a picture of only a small area. Remote sensing, because of its capability of synoptic viewing and repetitive coverage, provides useful information on land use/land cover dynamics (Jaiswal et al., 1999). The changes in land use/land cover due to natural and human activities can be observed using current and archived remotely sensed data (Luong, 1993). Land use or land cover change is critically linked to the intersection of natural and human influences on environmental change. The constant growth of the human population increase the pressure on the natural resources, leads to its disequilibrium, its degradation and the lost of its biodiversity (Fotso et al., 2007). Usually the produce of land use maps of Taleghan watershed regarding to the mountainous and impassability and relatively high areas using field survey and aerial photo interpretation technique, is too time consuming and costly. The satellite data according to their super characteristics such as vast coverage and can be considered as reliable tool in this field (Shetaii et al., 2008). Many studies have been done with usage of satellite data such as Landsat, Spot and IRS for determination of land changes. Borri et al. (2005) used Aiconos images for studying of land cover changes in Altamurgia national park (located in the Italia). They assessed land change based on

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differences in spatial distribution. Feizizadeh and haj Mirrahimi (2007) used Landsat TM images and HDR of Spot satellite for evaluation of landscape changes of Tabriz using object-oriented classification method and reported that more than 46 percent of green space in Tabriz in a 16-year period has been destroyed. Khalaghi (2007) using TM and ETM + images and with application of object-oriented classification and pixel base of detection methods, produced changes detection map in two periods. The main objectives of this study were to analyzing and producing of land use map in two different years and also land use change detection in Taleghan watershed using GIS.

2. MATERIALS AND MATHODS 2.1. Study Area The Study Area located in Taleghan ( Qazvin province) between latitudes of 36° 3ánd 36° 23´ N and between longitudes of 50°10ánd 51°5É at west of Tehran city and has the area of 95575.5 hectares; The average height is 2656 meters from sea level.The Taleghan region restricted among Nowshahr Basin (from north) and Alamout Basin (from northwest) and Kordan Basin (from south). This region is very mountainous and its highest peak is Nazarkooh that located at North of Taleghan Basin with the height of 4300 meters from sea level. In this study, for detection of land use changes, the digital images from ETM+ (2000yr ) and TM (1987yr) Sensors were used and pre-processing stages include Atmospheric, Geometric and Altimetric corrections was done on the satellite images (Figure 1). After cropping of the study area from images, through of topographic maps with the scale of 1:250,000 and via field survey and visual interpretation, the training areas for each land use class in two stages (before and after classification) were selected. To determine the training areas, we try to select the areas that have suitable distribution. Considering the band's separability, appropriate bands for classification were 4, 5 and 7 respectively. Regarding to the algorithms of pixel-based classification were performed with matrix of variance and covariance, so minimum pixel that required for each class was n+1(n= The number of bands that were used in classification).but in the best form, the number of training samples must be between 10n and 100n (Lillesand et al., 2008). We tried to obtain classes with different spectral signatures. In this research, the Maximum likelihood classification method was used. This method is one of the best methods for pixel-based classification that has confirmed by many researcher such as feyzizadeh et al(2009). Using Envi 4.5 software and supervise classification in form of Maximum likelihood method, the classification map of both images was prepared (Figures 2&3). To determine the accuracy of classification, checking points were used. The overall accuracy of image classification for ETM+ imagery was estimated (table 1).

Figure 1. The algorithm of study process


Figure 2. ETM classified from Taleghan watershed

Figure 3. Land use trend from Taleghan watershed

Table 1: the results of the overall accuracy of image classification in both image Kappa coefficient 0.85 0.77

overall accuracy% 89.86 82.01

Image of sensor ETM TM

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3. RESULTS The results show that the dominant trend of the land use changes in this basin is negative in implicit period (Table 2). Degradation of some land use such as gardens is so considerable. Another point is that most degradation process is due to the changes of poor (class III) rangelands into barrens (bare lands) and then medium (class II) rangelands into barrens. This shows that the trend of degradation was increased with decrease of ecological potency. Changing of dry farming land into bare land allocated a considerable percentage. The next subject is land spectral that is stationary and maximum and minimum of stationary is related to bare land and farmland respectively. Indeed, whatever productivity potency decreases in every land use, the tendency to changes will decreases, too. Table 2. Type and percentage of land use changes occurred in Taleghan watershed during 1987 to 2000 Change type

Trend Percentage Change type Trend Percentage type type Agriculture to garden 0 0.32 Barren to range III + 077 Agriculture to barren 0.02 Range I to agriculture + 0.09 Agriculture to dry farming 0.10 Range I to garden + 0.25 Agriculture to range I 0.10 Range I to barren 2.24 Agriculture to range II 0.03 Range I to dry farming 1.08 Agriculture to range III 0.01 Range I to range II + 1.18 garden to Agriculture 0 0.23 Range I to range III + 2.58 garden to barren 0.9 Range II to agriculture + 0.00 garden to dry farming 0.45 Range II to garden + 0.07 garden to range I 0.26 Range II to barren 9.98 garden to range II 0.17 Range II to dry farming 2.71 garden to range III 0.18 Range II to range I 1.15 dry farming to garden + 0.26 Range II to range III 1.73 dry farm. to Agriculture + 0.08 Range III to agriculture + 0.01 dry farming to barren 6.04 Range III to garden + 0.25 dry farming to range I 0.35 Range III to barren 33.09 dry farming to range II 0.33 Range III to dry farm. 2.49 dry farming to range III + 0.69 Range III to range I + 1.19 Barren to agriculture + 0.00 Range III to range II + 0.85 Barren to garden + 0.03 Barren to range II + 0.16 Barren to range I + 0.16 Without change 0 26.61 (+): positive trend, (-): negative trend, (.): without trend Range class I: good rangeland, Range class II: medium rangeland, Range class III: poor rangeland

Figure 4. The percentage of stationary land in every land use


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4. CONCLUSION Overall we can conclude based on our finds that land degradation and change in Tsleghan watershed, has arisen due two principal causes, often in relationship with each other: overgrazing of livestock, and clearance of rangeland for cultivation and transform it to dry farming. These results should help the decision makers to develop and to improve the land use management concept in order to achieve a sustainable development in Taleghan area.

5. REFERENCES Borri, D, M, and Tarantino, C, 2005, Spatial Information Extraction from VHR Satellite Data to Detect Land Cover Transformations, polytechnic University of Bari, Italy. Feizizadeh, b. and M, Hajmirrahimi, 2008, Changes detection of landscape in Tabriz using object oriented method, proceedings of seminar of urban GIS, p 120-123. Feizizadeh, b. and M, Hajmirrahimi, 2009, Changes detection of land use in Shahrake Andisheh using object oriented method, proceedings of seminar of Geomatic, p 96-98. Fotso, L, m. Kappas and P. Propostin, 2007, Remote sensing base study on land use/land cover change in a high populated region in Bamileke highlands, Cameroon, conference on International agricultural research for development, university of Gottingen, Germany. Jaiswal, R., R. Saxena and S. Mukherjii, 1999, Application of Remote Sensing Technology For Land Use/Land Cover Change Analysis, Journal of the Indian Society of Remote Sensing, 27(2), p 123-128. Khalaghi, S, 2007, monitoring of changes in coastal line of Khazar lake, M.sc Thesis of geography, university of Tabriz. Lillesand, T., R. Kiefer, and J. Chipman. 2007. Remote Sensing and Image Interpretation, Wiley, 6th edition, 768 pages. Luong, P, 1993, The detection of land use/land cover changes using remote sensing and GIS In Vietnam. Asian-Pacific Remote Sensing J., 5 (2), p 63-66. Nedal, A, M., S. Mastura and J. Mat Akhir, 2007, Landuse Evaluation for Kuala Selangor Using Remote Sensing and GIS Technologies. Geografia, 4 (2). pp. 21-42. Sheikhhasani, H, 2002, Modeling of environmental programming using GIS and RS (case study: Taleghan area), Ph.D Thesis of natural geography, university of Tabiate Moddarres. Shetaii, s. and O, Abdi, 2008, Supply of land use maps in mountainous area of Zagros using ETM+ sensor (case study: Sorkhab watershed, Khorram Abad), J. of agriculture and natural resources science, 4(1), p 35-43.

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LAKE BIODIVERSITY AND ECO-STRUCTURE FOR SUSTAINABLE ECOTOURISM - A GIS based Comparative Assessment of two shallow lakes in Aligarh. Kamal Asif and Hifzur Rahman Department of Geography, Aligarh Muslim University, Aligarh Email- [email protected] ABSTRACT The paper envisages to describe the ecological structure and biodiversity of two wild swamps known by the name of ‘Patna Lake’ and ‘Sheikha Lake’ situated in the Aligarh region of western Uttar Pradesh, India. ‘Patna’ and ‘Sheikha’ are shallow lakes well known for their bird sanctuaries which are recognized as protected ecological spots. The biodiversity and the picturesque landscape of the lakes make them natural utopia suitable for ecotourism development. These wetland habitats have been favorite breeding centre for a huge number of local and migratory birds and other fauna. The relentless clustering and chirping of birds during winters attract a sizable number of ecotourists, naturalists, bird watchers, environmentalists etc. The scenic beauty of the sanctuaries with intertwined flora species clustered along the water body signatures an attractive atmosphere for Lake Ecotourism. The paper attempts to take a comparative study of the two eco-destinations with particular reference to their aquatic habitat and avifaunal community. It further tries to investigate the prospects of ecotourism for sustainable development in the area. There is need for diverting the concentration of limnologists, environmentalists, nature experts and planners who can play a vital role in protecting the basis of ecology and biodiversity of the lakes. Moreover, the intervention of NGOs is also a positive approach in creating awareness about the importance of natural resources and their genuine use, and can help in providing livelihood to the local populace. Therefore, ecotourism could be a prominent development strategy to achieve resource sustainability for economic development with cultural and environmental conservation in the region.

INTRODUCTION “All varieties of species have right to existence and every species survived on other species”, this would simply the essence of biodiversity. Biodiversity, a complex head covering aspects of biological variation, includes a range of living beings, the relationship among them and with the physical environment; and the sum total of their genetic makeup. Ecological system or ecosystem is an open space built by the physical and biological components of an environment. It is the result of an active interaction between living and non-living components. Ecosystem is where communities of plants, animals and their environment function as a whole, and there is a relationship between organisms and their environment thrive blissfully. Conserving the environment by enhancing culture and protecting ecology through tourism is the essence of Sustainable Tourism Development. Such strategy, in its purest sense, attempts to make a low impact on the environment and the local culture, while helping to generate income, employment, and the conservation of local ecosystems. Therefore, besides interaction with man, environment also interacts with plants and animals, all of which constitutes the subsystems of the global ecosystem. It could, for example, be a grain of soil, a pond, a forest, a river, the sea, a biome or the entire biosphere. When such ecological destinations are visited for their natural or cultural interest that strives to prevent ecological losses in a particular area we call it ecotourism. Shallow lakes are an important ecological and socio-economic resource. According to the estimates of the Ministry of Environment and Forest, India possesses about 4.1 million hectares of wetlands (excluding the paddy fields and mangroves) of which 1.5 million hectares are natural and 2.6 million hectares are manmade. The impact of human pressure on lakes and their catchments has precipitated a decline in the ecological status of many wetlands in the Gangetic plains of north India.


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Most of the lakes and wetlands in the region have been formed in low lying depressions, old river courses, oxbow lakes, canal seepage areas etc. Throughout the Indo-Gangetic plains, lakes and wetlands undergoes impulsive alterations due to global warming and climate change. This have resulted in greater flooding and erosion, reduced water quality and reduced populations of many plants and animals. Moreover, the underground replenishing of aquifers has also affected which results in many teething troubles like desertification and other geomorphologic hazards.

WORK STRUCTURE, DATA AND METHODOLOGY The general objective is to nurture, extend and consolidate sustainable environmental conservation and socio-economic development through ecotourism in the region. Following are the main objectives of the study: 1. To make a comparative assessment of the basis of ecological structure and biodiversity in the lakes and their catchment area. 2. To prepare eco- structural maps of the lakes and their catchment areas with the help GIS and RS Techniques. 3. To evaluate ecotourism in relation to the natural environment and contribution to sustainable socioeconomic and, community development through active participation of the local people. 4. To highlight some of the major problems/constraints in management and promotion of ecotourism in the sanctuaries and suggest ways how to overcome the constraints. 5. To make headway for improved management and conservation of avifauna and other natural resources. 6. The primary data has been generated through onsite observational survey and by making in-depth discussions, and interviews with the forest rangers, visitors and local residents. 7. The secondary data has been collected from the forest department of the district, the National Informatics Centre and various government websites.

NEED AND IMPORTANCE OF THE STUDY The ‘Patna’ and ‘Sheikha’ lakes are well known for their basis of ecology and biodiversity. But, unfortunately the natural/physical and anthropogenic disturbances prevailing in these areas have complicated the systematic functioning of the wetland ecosystems. Thus, limnological understanding is the foremost requisite to identify sound solutions for wise management and restoration of these aquatic ecosystems. Therefore, there are several topics to envisage and avert the losses of wetland resources. These are: Water- Temperature and Seasonal availability Aquatic and terrestrial biodiversity Associated avifaunal and faunal community Land degradation and Farm encroachment Soil quality and, use of chemical fertilizers and pesticides Over grazing and bird hunting Illegal cutting of trees. Community education and awareness The spotlight of the study is on the comparative assessment of biodiversity and ecological structure of the two lakes (‘Patna’ and ‘Sheikha’) for ecotourism potential and sustainable development. Insufficient efforts for promotion of tourism and biodiversity conservation in the areas affect the tourist arrivals in. Therefore, there is need to formulate essential plans for conservation of biodiversity and ecological structure for sustainable ecotourism and socio-economic development of the area.

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THE STUDY AREA The site of Patna Lake is positioned in Patna village near Jalesar town of Etah district. It lies at 27 31 39” N Latitude and 78o 18’ 55” S Longitude. While on the other hand, the Shiekha Lake is located in Panaithi village near Jalali town of Aligarh district. It lies 27o 51’ 25” N Latitude and 78o 13’ 17” E Longitude in the Ganga-Yamuna Doab region of Western Uttar Pradesh. Both of the ecological spots are situated near to the G.T. Road (N.H -91) which is well connected to the Aligarh city and the National Capital Delhi in the north, and Agra-Kanpur-Lucknow in the south. The climate of the region is semi-arid to sub-humid and the whole year can be divided into three main seasons, namely; winter (November to February), summer (March to June) and Rainy Season (July to October). In winter, the lowest temperature goes below 5oC while, during the summers the highest temperature remains around 46oC to 47oC. The average annual rainfall in the area is about 600 mm o

’

Figure 1 Google Image showing the location of Patna and Sheikha Lakes.


Figure 2 Google Image of Patna Bird Lake

Figure 3 Google Image of Sheikha Bird Lake

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Physiographic and Eco-Structure of the Patna and Sheikha Lakes: Physio-Cultural Asset

Patna Bird Lake

Sheikha Bird Lake

108 hectares 15.24 hectares Total area of the lake 950 x 600 meters 630 x 450 meters Maximum Length x Breadth 2.8 meters 2.5 meters Average depth of the lake 8.0 meters 3.0 meters Maximum land elevation 9 5 Nesting islands 8 2 Number of watch towers Rain and Irrigation canal Rain and Upper Ganga canal Source of water Date palms, acacia (babul), Arjun, jamun, acacia, doob, Floral community

Faunal community

Avifaunal community (winter and summer)

Other cultural assets

neem, semal, karanj, bakaim, bamboos, tall grasses, scrubs, hyacinth, lilies etc. Nilgai, jackals, wild pigs, fishing cats, fox, monkeys, bucks, antelopes, porcupines, rabbits, cobra, rattle snakes, variety of turtles and lizards.

moonj and sentha grasses, bamboos ferns, hyacinths, sarkanda, lilies etc. Nilgai, garihal, fox, monkeys, bucks, antelopes, scoliodon, porcupines, wolfs rabbits, cobra, variety of turtles, fishes and lizards.

Painted stork, Wood stork, Black headed stork, Siberian white crane, Brown pelican, Flamingoes, Pintail, War headed goose, Spoonbill, Indian cranes, Brahmani ducks, Swans, Water hens, Spot hills, Pied mynas, and Wading birds, Preybirds, Parrots, Peacocks, Crows, Kingfishers, Pigeons, Dominys, Cuckoos etc. Forest range office, ornithology center, museum, drive way, children park, restaurant, guest house, temple etc.

Open bill stork, Gralog goose, Purple murrah, Painted stork, Pelican, Flamingoes, Pintail, Indian cranes, Brahmani ducks, Swans, Water hen, Wading birds , Birds of prey, Parrots, Peacocks, Crows, Treepies, Kingfishers, Cuckoos, Pigeons etc

Chidren park, field office, lake side drive way and parking.

(Source: Survey and Forest Range Office)


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ECOTOURISM APPROACH FOR BIODIVERSITY CONSERVATION What is Ecotourism? The World Tourism Organization (WTO) has been defined it as “tourism that involves traveling to relatively undisturbed natural areas with the specific object of studying, admiring and enjoying nature and its wild plants and animals as well as existing cultural aspects (both of the past and present) found in these areas”. This is a conscientious form of tourism development, which encourages going back to natural products in every aspect of life and helps to preserve nature. It is also the key to sustainable ecological development.

Principles of Ecotourism The International Ecotourism Society (TIES) define ecotourism as “responsible travel to natural areas that conserves the environment and improves the wellbeing of the people”. This means that those who implement and participate in ecotourism activities should adhere to the following principles: Minimize the impacts. Build environment and cultural awareness, and respect. Provide positive experiences for both visitors and hosts. Provide direct financial benefits for conservation. Provide financial benefits and empowerment for local people. Raise sensitivity to political, environmental and social climate of the region.

Perspectives of Ecotourism The ecotourism approach, for sustainable development and biodiversity conservation, provides a viable means for the conservation of ecology and, protecting the social, cultural and economic wellbeing in a region. This approach has also been recognized by various international agencies viz. Global Lake Ecological Observatory Network (GLEON), The Ecotourism Society (TES) 1990, The International Ecotourism Society (TIES) 1990, and World Conservation Union (WCU) etc. The 12th World Lake Conference TAAL 2007 held in Jaipur, India, also called upon the importance of lakes for domestic and recreational uses through ecotourism. Sustainable ecotourism is a kind of approach to tourism, meant to make the development of tourism ecologically supportable in the long term. Conserving the environment by enhancing the culture is the essence of sustainable tourism development. Sustainable tourism is a responsible approach aimed at generating income and employment along with elevating a deeper impact on environment and local culture. Therefore, sustainable tourism development in its purest sense, attempts to make a low impact on the environment and local culture, while helping to generate income, employment and conservation of local ecosystems. The Conservation International (CI) 1989, formulated the application of ecotourism development programs as a tool for biodiversity conservation, and such ecotourism ventures have proved to be sustainable, both at ecological and economic grounds. The biodiversity status of the Patna Sanctuary is of such importance that it can contribute to sustainable ecotourism development in the area. Patna and Sheikha Lakes and their catchment fulfils the function of sustainable ecotourism spots because of the availability of rich ecosystems. Hence,the physical characteristics and wildlife resources with special emphasis on bird-life, rich culture and scenic beauty can contribute to ecotourism development of the region.

PROBLEMS AND CONSTRAINTS Successful ecotourism development of any destination is based on the development of a well documented developmental plan related to the issues and problems, which be set the area. In the study areas there are certain problems and constraints which were observed and reported by the researcher. These are as follows: Poor condition of access road to the lakes and inadequate infrastructure.

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Lack of adequate drinking water. No provision of health centre and first aid clinic. Improper methods conservation of wildlife resource. Lack of education and awareness creation, etc. Political constraints too are also impediments in the way of sustainable environmental development in the area such as: Poor political goodwill- lack of politeness. Land use pressure related problems. Community attitude- local authorities should strive to bring out changes through education. Governance- Participation of people and transparency. Manpower and employment.

PLANS AND RECOMMENDATIONS The preliminary suggestions and plans for the conservation of biodiversity and ecology in the Patna and Sheikha lakes for sustainable ecotourism development have been forwarded as follows: Improvement of existing link roads from NH. 91(G.T Road) and NH.2 (Delhi- Agra- Kanpur Road). The internal driveways and sub-paths are also need to be developed for access to various points in the lake catchments. Rejuvenation of the Children’s Park, restaurant, toilets, check posts, offices, museum and other infrastructural assets such as existing watch towers, and sightseeing points etc. Proper waste disposal and a health centre with first aid facility are also basic requirements. There is also need for a guest house in or near the sanctuary. To design an inventory of biophysical assets of the sanctuaries in order to provide easy information and data base to the researchers and visitors. Conservation and management of biodiversity, and natural resources with the help of local communities, NGOs and various stakeholders. Land use controls with the help of zoning, protection of the lake catchments from escalating pressure of agricultural farms and resolving the conflicts. Minimizing the reliance of local communities on the ecosystem and natural resource of the lakes and their catchments. Education and creation of public awareness in the region is very necessary for implementation of conservation plans. Arranging annual seminars to invite scientists, researchers, nature experts, ornithologists, academicians, environmentalists, government authorities, consultants, media persons and NGOs, etc., for their opinions and suggestions, solution of problems related with the implementation of developmental plans. Invitations to academic institutes like colleges, schools, universities and various other organizations may also help in the promotion of ecotourism and conservation of biophysical structure of the lakes. Governance through local, regional and national authorities, and other organizations with an interest in the area and adoption of Public Private Partnership (PPP) based approach.

CONCLUSION The sustainability of ecotourism venture in Patna Bird Sanctuary and Sheikha Bird Lake has proved on both ecological and economic grounds. However, much of the ecotourism potential lies in the harmonious compromise between the management authorities and local communities. Another priority is the management of resources for their genuine use and creating awareness among the people for the conservation of biodiversity. When the wants and needs of local community and ecotourism strategy are successfully completed, the goal of having sustainable environment is attainable. Therefore, ecotourism could be a prominent development strategy to achieve resource sustainability for economic development with cultural and environmental conservation.


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BIBLIOGRAPHY Asif, Kamal, “Ecological Basis and Prospects of Sustainable Ecotourism Development: a Study of Patna Bird Sanctuary, Etah District”, Conference on Resource Development and Environmental Change: Emerging Issues and Challenges, 27th-29th January 2009, A.M.U. Bhatnagar, Chhayanand, “Vanishing Habitats of Aquatic Birds in the City of Lakes, Udaipur: a Case Study”, The Indian Forester, Vol. 133, October 2007. Horochowski, Katerina; Moisey, R. Neil, “The Role of Environmental NGOs in Sustainable Tourism Development: a Case Study in Northern Honduras”, Tourism Recreation Research, Vol. 24, No. 2, 1999, Royal Geographical Society, pp. 19-29. Hunter, Peter D., “Remote Sensing in Shallow Lake Ecology”, E-Thesis, School of Biological and Environmental Sciences, University of Stirling, 2007. King Mahendra Trust for Nature Conservation(KMTNC) “Initiatives on Sustainable Development of Tourism”, Report in Tourism Recreation Research, Vol. 24, No. 2, 1999, pp. 115-118. Manning, Edward W.; Dougherty, T. David, “Planning Sustainable Tourism Destinations”, Tourism Recreation Research, Vol. 25, No. 2, 2000, pp. 3-14. Mathew, C.D.; Joseph, Kurian, “Relevance of OD Interventions in Ecotourism: An Empirical Study with Reference to Kerala”, Part-V Tourism and HR Issues, Conference on Tourism in India- Challenges Ahead, May 2008, IIMK Mittermeier R.A,; Mittermeier, C.G, “Wilderness and Biodiversity Conservation”, International Wilderness Leadership (WILD) Foundation, PNAS, Vol. 100, No. 18, September2003. “Patna Bird Sanctuary in Doldrums due to Scarcity of Water”, Article, the Hindustan Times, December 22, 2006. Raghwan, V.P., “Economy of Ecotourism in Kerala: a Perspective”, Kurukshetra, Vol. 55, No. 2, December 2006, pp.23-37. Ranade, P.S., “Managing Lake Tourism: Challenges Ahead”, Part XII-Tourism Other Sectors, Conference on Tourism in India-Challenges Ahead, May2008, IIMK. S, Narayan k., “Biodiversity Conservation should be the Mantra of the Century”, Kurukshetra, Vol. 55, No. 2, December 2006, pp.3-14. Sharma, B.L.; Sharma, N.K., “Plant Diversity in Context of Geography: a Case Study of Harauti Area (Rajasthan)”, Geographical Review of India,Vol. 66, No. 1, March 2004, pp.84-92. Sweeting,; McConnel, Mary Anne, “Tourism as a Tool for Biodiversity Conservation”, Tourism Recreation Research, Vol. 24, No. 2, 1999, pp. 106-108. Wood, Megan Epler, “The Ecotourism Society-An International NGO Committed to Sustainable Development’” (Founder and President, The Ecotourism Society, U.S.A), Tourism Recreation Research, Vol. 24, No. 2, 1999, pp. 119-123.

Webliography: www.ecotourism.org www.ecotour.org www.uptourism.org www.gujarattourism.org www.paradiselakes.co.uk www.pnas.org www.rajasthantourism.org www.geog.umn.edu www.nic.etah.in Wikipedia Online Encyclopedia. Microsoft Encarta Reference Library. Google Earth Images.

Emerging Pollutants


Emerging Techniques for the Removal of Sediment Nutrients in Lakes and Reservoirs V. Sudha* *

Corresponding Author, Research Scholar, Centre for Water Resources, Anna University, Chennai. Email: [email protected]

Dr. S. Ravichandran** **

Assistant Professor, Centre for Water Resources, Anna University, Chennai.

Dr. K. Karunakaran*** *** Director, Centre for Water Resources, Anna University, Chennai.

ABSTRACT Nutrient input to lakes and reservoirs includes external sources both from point and non point source of watershed and also internal sources from the bottom sediments. The vital impact of nutrients on water quality and the increased problem of eutrophication have led to extensive investments world wide to reduce the nutrient input to lakes and reservoirs. The external load of nutrients can be reduced by implementing the construction check dams, diversion of sediment rich water before entering the reservoir, water treatment techniques etc. But the nutrient already present in the bottom sediments of the system cannot be easily removed. The main focus is directed at phosphorus removal because it is a bio-growth limiting nutrient in aquatic environment and also it has the capacity to bind with sediments. This paper aims to discuss the different emerging techniques for the removal of phosphorus from the sediment in lakes and reservoirs. The techniques include physical methods includes diversion of bottom water in deep lakes and removal of sediment and also the catchment treatments and operation and maintenance such as bypassing, dredging, flushing, sluicing and upstream sediment trapping etc. and chemical methods such as the addition of aluminium / iron, nitrate treatment and oxidation of bottom water and the biological methods include biomanupulation and transplantation. Key words: Removal of nutrients, Sediment Phosphorus, Eutrophication, physical, chemical and biological methods

1. INTRODUCTION Every lake and reservoir is unique in nature. Most large Indian reservoirs were constructed over the last 50 years. India has a large number of reservoirs built behind dams to store monsoon flows for use during the dry season as dependable source of water for drinking, irrigation, hydropower, ecological use, industrial use, navigation etc., as well as providing flood moderation (Reddy 2006). These reservoirs are generally far from population centres and do not directly receive domestic effluents. Some are recipients of industrial effluents as well as nonpoint pollutants from irrigated agriculture. Reservoirs and lakes throughout India are experiencing varying degrees of environmental degradation, related mainly to encroachments, eutrophication and siltation. Indian reservoirs were surveyed and reported that they receive on an average about 200 percent more sediment than the design inflow. In brief 'misuse and mismanagement' of the catchment area are the causes for higher rates of sedimentation (Tejwani 1984). Nutrients such as phosphorus and nitrogen are the major contributions for non point source pollution. Rivers and streams are the major carriers of nitrogen and phosphorus with in the

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watershed. In aquatic ecosystems over-enrichment with P and N causes a wide range of problems, including toxic algal blooms, loss of oxygen, fish kills, loss of seagrass beds and other aquatic vegetation, and loss of biodiversity. Thus nutrient fouling seriously degrades our fresh water and marine resources and impairs their use for industry, agriculture, recreation, drinking water and other purposes. Phosphorus is the most limiting element. Phosphorus sediment flux has resulted in the enrichment of nutrients even when the external nutrient load is stopped. Phosphorus is an essential nutrient for living organisms. The dissolved fraction of phosphorus in aquatic systems contains mainly orthophosphates (PO4), polyphosphates and dissolved organic phosphorus. Only the forms of phosphorus that may be assimilated by algae play a direct role in eutrophication. However, some forms of phosphorus (not available directly) may be transformed to bio-available orthophosphate. If the concentration of orthophosphate is low, algae may metabolize dissolved forms of organic phosphorus. The exchanges of phosphorus between sediments and the overlying water are a major component of the phosphorus cycle in natural water. The phosphorus deposited into the sediments by sedimentation of phosphorus minerals, adsorption of P with inorganic matter and uptake of it from the water column by algal and other microbial community. Exchange across the sediment water interface is regulated by mechanisms associated with mineral water equilibria, sorption processes, and redox interaction and physiological and behavioral activities of many biotas associated with sediments. Stream and ditch sediments interact with P in the water column and as such play a pivotal ecological role in buffering water column P concentrations, and thus the P delivered downstream. Fig. 1 shows the mechanisms of phosphorus release and uptake from sediments to overlay water through pore water (Wetzel 2006). Nutrient enrichment problems in lakes and reservoirs can be managed by framing specific strategies on activities in the watershed and in-lake restoration techniques. Lake management approaches fall into two categories, the quick-fix and long-term management. The quick-fix gives a short-term solution such as the application of algaecides to kill unwanted algae. This approach treats the biological symptoms of a lake problem but does not address the fundamental causes of these symptoms. This paper attempts to present a comprehensive view of the different techniques for the removal of sediment phosphorous in lakes and reservoirs and a case study is discussed.

2. METHODS The study has drawn from both secondary data sources such as government documents and reports prepared by the NGO, as well as primary records through focus group discussion. Considerable data has been collected from secondary sources such as journals, research articles, text books, previous research papers, and many websites to frame the methodology for identifying the different techniques such as physical, chemical and biological methods for the removal of phosphorous from the sediments in lakes and reservoirs. The sediment of a lake -its muddy bottom layer -contains relatively high concentrations of nitrogen and phosphorus. These can be released to water, particularly under conditions of low oxygen concentrations. The nutrients in the sediment come from the past settling of algae and dead organic matter. The nutrients released from sediments are referred to as the lake’s internal loading. It is possible but very expensive to remove the upper nutrient-rich layer of sediment. Covering sediments with clay to seal them and thereby reduce internal loading has also been tried. Even when nutrients are removed in large amounts from wastewater, agricultural drainage water and rain, it often takes much time before nutrient concentrations fall in the upper sediment layer because they are still present in the water environment. Early reduction or elimination of


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nutrient sources is therefore very important. Fig. 1 shows the flow chart of the physical, chemical and biological methods for the removal of sediment nutrients.

Methods of Sediment Nutrient Removal

Physical Methods

Diversion of bottom water in deep lakes

Removal of Sediment

Biological Methods

Removal of nonpredatory fish

Catchment treatment and O & M

Predatory fish stocking

Transplantati on and protection of submerged macrophytes

Chemical Methods

Oxidation of bottom water in deep lakes

Nitrate addition to bottom water and sediment

Addition of Aluminium and Iron

Fig 1. Flow chart of different methods for the removal of sediment nutrients

2.1 Physical Methods The aim to use the physical method is to reduce the availability of phosphorus by physically removing phosphorus using different methods. 2.1.1 Diversion of bottom water in deep lakes The nutrient-rich bottom water from deep lakes can be diverted to increase the transport of phosphorus out of the lake in order to reduce the phosphorus availability in the water column (Sondergaard 2007). In Lake Jabel, North-east Germany the effect of phosphorus release and the simultaneous phosphorus removal by deep-water siphoning was studied proved for the faster deprivation of phosphorus from lake sediment (Kleeberg etal 2001). Various technical measures can be adopted based on the lake morphology (Klapper 2003). Results are available from Austrian and Canadian experiments (Tolotti and Thies 2002; Macdonald et al 2004). 2.1.2 Removal of Sediment Another physical method of reducing the nutrient is by removing the lake sediments. This type of method was performed in many small-sized Danish lakes, large –scale removal was conducted only in Lake Brabrand near the city of Aarhus. During a period of seven years 500,000 m3 of nutrient-rich sediment were removed from large parts of the lake at 0-90am depth (Jorgensen 1998). During the experimental period the average lake water phosphorus concentration declined from almost 1 mg Pl-1 to 0.3 mg Pl-1, but Secchi depth increased only marginally due to the still high concentrations of phosphorus. However, the impact of sediment removal on the quality of Lake Braband appeared to be only minimal.

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2.1.3 Catchment treatment and Operation & Maintenance Apart from the above mentioned methods the other methods which can be used to minimize the sediment inflow into lakes and reservoirs are discussed as follows. Different control measures to minimize the impacts in rivers and reservoirs Reservoir sedimentation is a natural process and is unavoidable. However, it can be controlled by certain good practices, works and measures. The controlling measures can be only achieved through good watershed conservation practices it includes agricultural practices. The major three methods are mentioned as follows: i) Reduction of sediment yield ii) Reduction of Sediment Inflow in Reservoirs iii) Reducing / Controlling sediment deposition in Reservoir Reduction of Sediment Yield This can be only achieved by adopting soil conservation measures in the watershed as it is the sources of generation of sediment. The climatic, topographic, soil and land use characteristics are the main factors in soil conservation practices. The soil conservation practices can be achieved through two major practices a) By means of structural measures such as check dams, contour bunding, gully plugging and bank protection. b) By means of Non-structural measures such as Agronomic and vegetative measures and Operational measures like timber harvesting activities. Reduction of Sediment Inflow in Reservoirs This can be achieved through a variety of hydraulic structures located in river system upstream of the reservoir as follows: i) Sediment trapping structures such as check dams, debris basin and buffer reservoirs. ii) River bank stabilization/protection works such as terracing, revetment and retaining walls. iii) Sediment bypassing structures such as canals and tunnels. Reducing / Controlling Sediment Deposition in Reservoir The deposition of sediment in the reservoir can be minimized by the operational methods such as i) Sluicing Venting density currents

2.2 Chemical Methods There are many chemical methods, all of which are designed to reduce phosphorus availability, either improving the existing binding potential, for instance via oxidation of bottom water and surface sediment (Muller ans Stadelmann 2004) or by increasing the binding potential via aluminium or iron addition (Boers etal 1994). In some instances when oxidizing bottom water may improve the living conditions for fish and bottom animals (Muller and Stadelmann 2004). In Denmark oxidation projects have been undertaken in five large-sized lakes, aluminium or iron addition in two lakes and nitrate addition in one lake (Sondergaard 2007). 2.2.1 Oxidation of bottom water in deep lakes The most ambitious oxidation project in denmark so far is that undertaken in Lake Hald near the city of Viborg in Central Jutland. The addition of oxygen to Lake Hald has not led to a significant increase in average oxygen concentrations in the bottom water, whereas nitrate concentrations in the bottom water have risen in consequence of ammonium nitrification (Rasmussen 1998). The internal phosphorus loading was decreased considerably from net release


of 1.5-3.7 t P per year to a net retention of 0.3-0.7 t P per year. Today oxidation is still performed during a sequence of months each summer. The possibility of limiting the sediment phosphorus release via bottom water oxidation may be debated. Based on 15-year oxidation record of Lake Sempach, Switzerland it was concluded that increased hypolimnetic dissolved oxygen concentrations neither led to reduced release of phosphorus from the sediment in summer nor to increase phosphorus retention. They concluded that oxygenation only leads to increased phosphorus retention if the sulphide production is lowered and more ferrous phosphate and less FeS are deposited in the anoxic sediment. 2.2.2 Dilution Dilution projects direct a low-nutrient water source into and through a lake as a means of diluting and flushing nutrients from the higher-nutrient lake water. Flushing may wash out surface algae and replace higher-nutrient lake water with lower-nutrient dilution water. Lowernutrient water may lead to fewer problem algae in the water. On the downside, dilution requires large volumes of low-nutrient water (which may be scarce or expensive) and does not eliminate sources of phosphorous from the sediments or the watershed. Green Lake in Seattle and Moses Lake in Grant County are examples of Washington lakes where dilution has been successfully used (32) 2.2.3 Nitrate addition to bottom water and sediment The nitrate was first used as a chemical method of treatment of sediment was first applied in Swedish lakes according to the “Riplox-method” developed in the 1970s (Ripl 1976). In this method addition of nitrate to the sediment was carried out to increase mineralization and improve the redox-sensitive binding of phosphorus to iron. The nitrate is added by stirring it into the upper 15-20 cm sediment layer. Subsequently, extra iron may be added if the natural concentration is low. The importance of nitrate for the accumulation of phosphate in bottom water is also illustrated by measurements made in 29 m deep Knud Danish Lake showing inter-annual variations in bottom water nitrate concentrations. In years with nitrate concentrations below .01 mg Nl-1 phosphate concentrations of 0.8-1.5 mg P l-1 were measured, whereas phosphorus concentrations did not exceeds 0.01 mg P l-1 in years with a nitrate level exceeding 1.3 mg N l-1 (Andersen 1994). 2.2.4 Addition of Aluminium and Iron Addition of iron (Yamanda et al 1986; Boers et al 1994) and aluminium salts (Sonnichsen et al 1997) has been used to enhance the binding potential of phosphorus and thus enhance the binding potential of phosphorus and thus reduce lake phosphorus concentrations. The phosphorus binding capacity of both iron and aluminium is good, but in contrast to the binding to iron that to aluminium is not redox dependent. Moreover aluminium has toxic effects at low alkalinity and pH values below 5.5(Cooke et al 1993). It has negative effects on Daphnia (Schumaker et al 1993)

2.3 Biological Methods Various biological methods can be used. Most are directed at the fish stock and intend either i) by selective removal of zooplanktivorous species to reduce the abundance of nonpredatory fish, or ii) to graze down the phytoplankton to increase the zooplankton potential, and thus create (Shapiro and Wright 1984; Benndorf et al 1988; Sondergaard 2007). 2.3.1 Removal of non-predatory fish A case study from Danish lakes has taken to analyse the effect of non-predatory fish removal. In Denmark the lake called Vaeng, Central Jutland showed an approximately 50% reduction of the non-predatory fish stock. It is the most well documented example. Over a period

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of 2-3 years, 2.5t fish were removed. The substantial changes in the overall environmental changes are decrease of phytoplankton abundance, the average size of zooplankton increased and Sechhi depth improved. The intervention into Lake Vaeng had strong positive effects on the water quality for approximately for the period of 10 years. The best effects of non-predatory fish removal were obtained when a large percentage of the total fish stock has been removed. If the portion removed is too small, there is a risk that the breeding and growth rates of the remaining stock will rise and thereby rapidly reach the same size as before. Hence, minimum 70-80% of the non-predatory fish stock should be removed, preferably within a relatively short period (Jeppesen & Sammalkorpi 2002). 2.3.2 Predatory fish stocking Predatory fish can also be removed as an alternative or supplement to the removal of zooplanktivorous fish species (Prejs et al 1994). One of the problems associated with stocking of zooplanktivorous fish fry, such as pike, is that an effect is only obtained during the year of the stocking and only for a brief period around the time of the stocking event. The sustainable stock of pike in a lake depends first and foremost on the extent of the littoral zone (Grimm and Backx, 1990), which means that an artificially high density of pike will be rapidly declined. If the density is high and the habitat opportunity poor, mortality due to cannibalism will be high (Skov et al 2003b). 2.3.3

Transplantation and protection of submerged macrophytes Submerged macrophytes shows a number of positive effects on the water quality of shallow lakes and play a central role for the maintenance of a clearwater state (Scheffer et al 1993; Jeppesen, 1998). Through a series of direct and indirect mechanisms submerged macrophytes affect strongly the phytoplankton communities of shallow lakes. Submerged macrophytes create a structure enhancing the abundance of sessile or plant-associated and pelagic zooplankton species and thereby generate a higher grazing pressure (Timms and Moss 1984; Lauridsen et al 1997). Table 1 shows the abundance of phytoplankton is lower in the presence of submerged macrophytes.

Table 1 Chlorophyll a concentrations (µg l-l) and phytoplankton biomass (mm3 l-l) day and night in enclosures with 50% plant coverage and without plants. Averages from three enclosures are shown (+SD in parenthesis) from 1-3 days of sampling. Source: (Sondergaard 2007)

The transplantation of submerged macrophytes was used to ensure a stable clearwater state (Donabaum et al 1999; Lauridsen et al 2003). This is particularly relevant in situations where immigration and spreading of plants are limited by lack of spreading potential or when herbivorous birds such as coot and mute swan diminish plant abundance and in some instances actively prevent plant establishment and spreading (Søndergaard et al 1996). The setting-up of a wire fence around existing or transplanted plants may be a means to improve plant conditions (Jeppesen et al., 1997a; Lauridsen et al., 2003).

3. Summary and Conclusion In this paper an attempt was made to review the various methods for the removal of sediment nutrients. Since the environmental and ecological impacts of sediment nutrients especially phosphorus is much higher than nitrogen. The data required to understand the problem of sediment nutrients and the different methods includes physical, chemical and biological


methods were collected from the secondary sources such as journals, research articles, text books and websites. When the sediments were carried by the rivers during flood events will get dumped in to the reservoirs, which resulted in the accumulation of more sediment nutrients in the reservoirs and forms deltas. Because of the binding capacity of the phosphorus with the soil, the accumulation of phosphorus in the bottom sediment will gradually take place. During the summer period when the external load decreases the phosphorus accumulated in the sediment will start releasing to the water column that will resulted in the various ecological and environmental effects like eutrophication, turbidity, depletion of dissolved oxygen, disturbances in the food chain and biotic community structures. Various authors were conducted different studies to identify the different methods to remove sediment nutrients. Each method has its own positive and negative effects which includes the sediment removal method. In this method it is possible but very expensive to remove the upper nutrient-rich layer of sediment. In chemical methods The phosphorus binding capacity of both aluminium is good, but it is not redox dependent. Aluminium has toxic effects at low alkalinity and a pH value below 5.5. It also has the negative effects on Daphnia. The biological method of removal also has its own limitation, especially in the predatory fish stocking method when the density of predatory fish is high and the habitat opportunity poor and the mortality due to cannibalism will be high. From the review of literature it was identified and concluded that sediment nutrient is one of the important problem which causes various environmental and ecological impacts in the lakes and reservoir. Literature also shows that there is a lacuna in the study of sediment nutrients removal in the tropical countries, especially in India. From this paper it was also identified that early reduction or elimination of nutrient sources is therefore very important. The scope of this study is to identify the study area which has the eutrophication and other environmental problems related to sediment nutrients in India especially in Tamil Nadu. The future study is aimed to investigate sediment nutrients and to conduct the experimental studies to remove the nutrients from the reservoir sediments. References 1. Andersen J. M, 1994, Water quality management in the River Gudenaa, a Danish lakestream-estuary system, Hydrobiologia, 275/276: 499-507. 2. Barnard, P, 1987, Learning and remembering interactive commands in a text-editing task, Behaviour and Information Technology, 1, p347-358. 3. Benndorf, J., Schulz, H., Benndorf, A., Unger, R., Penz, E., Kneschke, H., Kossatz, K., Dumke, R., Hornig, U., Kruspe, R. & Reichel, S, 1988, Food-web manipulation by enhancement of piscivorous fish stocks:long-term effects in the hypertrophic Bautzen reservoir, Limnologica: 97-110. 4. Boers, P., Vanderdoes, J., Quaak, M. & Vandervlugt, J, 1994, Phosphorus fixation with iron(iii)chloride – a new method to combat internal phosphorus loading in shallow lakes. Arch. Hydrobiol. 129: 339-351. 5. Chapanis, A, 1988, Some generalizations about generalization, Human Factors, 30, p253-267. 6. Cooke, G.D., Welch, E.B., & Newroth, P.R, 1993, Restoration and Management of Lakes and Reservoirs,2nd ed. Lewis Publishers, Boca Raton. 7. Grimm, M.P. and Backx, J.J.G.M, 1990. The restorationof shallow eutrophic lakes, and the role of northern pike, aquatic vegetation and nutrient concentration. Hydrobiologia, 200: 557-566. 8. Jeppesen, E. and Sammalkorpi, I, 2002, Chapter 14 "Lakes".In: M. Perrow & T. Davy (eds.): Handbook of Restoration Ecology, Cambridge University Press, Volume 2: 297324. 9. Jeppesen, E. 1998, Lavvandede søers økologi – Biologiske samspil i de frie vandmasser. Doktordisputats., Danmarks Miljøundersøgelser. Faglig rapport fra DMU 248: 59 s.

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10. Jorgensen ,T. B, 1998, Sedimentfjernelse: Brabrand Sørestaurering Danmark. Metoder, erfaringer og anbefalinger, Miljøstyrelsen, Miljønyt 28: 281-289. 11. Klapper, H, 2003, Technologies for lake restoration, J. Limnol. 62 (suppl 1): 73-90. 12. Kleeberg,A., Hammerling,R and Nixdorf,B., 2001, Effect of hypolimnetic discharge on the faster deprivation of phosphorus from lake sediment (Lake Jabel, north-east Germany), Lakes & Reservoirs: Research and Management, 6,p 289–295. 13. Lauridsen et al 1997). Table 1 shows the abundance of phytoplankton is lower in the presence of submerged macrophytes. 14. Lauridsen, T.L., Jeppesen, E., Søndergaard, M. & Lodge, D.M, 1997, Horizontal migration of zooplankton. Predator-mediated use of macrophyte habitat, Ecological Studies 131: 233-239. 15. Macdonald, R.H., Lawrence, G.A. and Murphy, T.P, 2004, Operation and evaluation of hypolimnetic withdrawal in a shallow eutrophic lake, Lake Reserv.Manage. 20: 39-53. 16. Muller, R. & Stadelmann, P, 2004, Fish habitat requirements as the basis for rehabilitation of eutrophic lakes by oxygenation, Fish. Manage. Ecol. 11:251-260. 17. Prejs, A., Martyniak, A., Boron, S., Hliwa, P. & Koperski, P, 1994, Food-web manipulation in a small, eutrophic Lake Wirbel, Poland - effect of stocking with juvenile pike on planktivorous fish, Hydrobiologia, 276: 65-70. 18. Rasmussen K, 1998, Iltning af bundvand Sørestaurering i Danmark. Metoder, erfaringer og anbefalinger, Miljøstyrelsen, Miljønyt 28: 259-268. 19. Reddy,M.S and Char,N.V.V., 2006, Management of lakes in India , Lakes & Reservoirs: Research and Management, Vol 11, pp 227–237. 20. Ripl, W, 1976, Biochemical oxidation of polluted lake sediment with nitrate: anew lake restoration method. Ambio 5: 132-135. 21. Scheffer M., Hosper S.H., Meijer M.-L., Moss B. & Jeppesen E, 1993, Alternative equilibria in shallow lakes. Trends Ecol. Evol. 8: 275-279. 22. Schumaker, R.J., Funk, W.H. & Moore, B.C, 1993,Zooplankton responses to aluminum sulfate treatment of Newman Lake, Washington. J. Freshwat. Ecol. 8: 375-387. 23. Shapiro, J. & Wright, D.I, 1984, Lake restoration by biomanipulation, Round Lake, Minnesota - the first small, eutrophic Lake Wirbel, Poland - effect of stocking with juvenile pike on planktivorous fish, Hydrobiologia, 276: 65-70. 24. Skov, C., Jacobsen, L. & Berg, S, 2003, Post-stocking survival of 0+year pike in ponds as a function of water transparency, habitat complexity, prey availability and size heterogeneity. J. Fish. Biol., 62: 311- 322. 25. Sondergaard ,M, 2007, Nutrient dynamics in lakes-with empasis on phosphorus, sediment and lake restoration, Doctor’s dissertation, National Environmental Research Institute, University of Aarhus, Denmark. 26. Sonnichsen, J.D., Jacoby, J. & Welch, E.B, 1997, Response of cyanobacterial migration to alum treatment in Green Lake. Arch. Hydrobiol. 140: 373-392. 27. Tejwani, K.G, 1984, Sedimentation of reservoirs in the Himalayan region-India, Water International, 9, Issue 4,p150 – 154. 28. Timms, R.M. and Moss, B, 1984, Prevention of growth of potentially dense phytoplankton populations by zooplankton grazing, in the presence of zooplanktivorous fish, in a shallow wetland ecosystem. Limnol. Oceanogr. 29: 472-486. 29. Tolotti, M. and Thies, H, 2002, Phytoplankton community and limnochemistry of Piburger See (Tyrol,Austria) 28 years after lake restoration. J. Limnol. 61:77-88. 30. Wetzel, R.G, 2006, Limnology Lake and River Ecosystems 3d edition Elsevier. 31. Yamada H, Kayama, M. Saito K & Hara M, 1986, A fundamental research on phosphate removal by using slag. Wat. Res. 20: 547-557. 32. http://www.ecy.wa.gov/Programs/wq/plants/algae/lakes/LakeRestoration.html


Investigating the Possibility of Residual Al and Iron Removal in Conventional and Enhanced Coagulation Using Phosphate Compounds

Mohammad Hadi Dehghani, Fazlollah Changani , Reza Ghanbari Tehran University of Medical Sciences, School of Public Health, Department of Environmental Health Engineering, Tehran, I.R.Iran

*Corresponding author: M.H.Dehghani, Tehran University of Medical Sciences, School of Public Health, Department of Environmental Health Engineering, Tehran, I.R.Iran, Tel. +98 21 6695 4237; Fax + 98 21 6641 9984; Email: [email protected]

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ABSTRACT Aluminum and iron salts are important chemical materials which are extensively used next to in water treatment processes. In natural circumstances, aluminum and iron may be changed into insoluble forms and consequently could be removed from water. But in other cases and especially in enhanced coagulation, some of them could be remained in soluble forms and in concentrations higher than of raw water. It was concluded that post coagulant addition of phosphate in rapid mixing could reduce the residual Al and iron. But required phosphate dosages, at pH=5.5 (in both conventional and enhanced coagulation) should be increased. In all stages residual phosphate in coagulation with ferric chloride in all stages was permanently lower than alum coagulation. In this research no significant correlations was seen between phosphate dosages and corrosion indexes (Langeliar and Riznar) and thus it could be concluded that anticorrosiblity of Phosphate compounds is due to the formation of a thin layer on the internal surface of tubes.

Key words: Conventional coagulation, Enhanced coagulation, Residual aluminum, Residual iron, Phosphate compounds INTRODUCTION High concentration of Al in drinking water may produce health problems. Beside Al and iron in high concentrations could be precipitated within distribution systems and make the water authentically unacceptable. Post coagulant addition of phosphate compounds could reduce the concentrations of residual metals without the need of installing new unit processes in existing water treatment plants [1-8].The purpose of this research was to examine the possibility of residual Al and iron removal in conventional and enhanced coagulation using phosphate compounds.

MATERIALS AND METHODS In this research, Jar tests were used for investigation of residual Al and iron removal by use of phosphate compounds in conventional and enhanced coagulation and also for determination of affecting parameters. Jar tests (coagulation, flocculation and sedimentation) were done by a standard Jar instrument which was consisted of six jars (volume of each was 1 liter). Jar tests were performed on sequences of rapid mixing (120 rpm in 2 minutes), slow mixing (20 rpm in 20 minutes) and sedimentation (30 minutes). All the containers had been washed and have been rinsed with acid and distilled water. Addition of Phosphate compounds had been accomplished during rapid mixing (one minute before coagulant dosing or one minute after that). Phosphate compounds Used in this research were sodium orthophosphate and sodium polyphosphate. Phosphate compounds were added to the jars in concentrations of 0.5, 1, 1.5, 2, 2.5, 3 and 3.5 mg/L. But in all of these tests, one jar remained phosphate free as the blank for investigating the true concentration of soluble metals in each condition. Dosages of alum and ferric chloride in conventional coagulation test were 10 mg/L and these tests had been accomplished in different temperatures (35, 22 and 5 centigrade) and pHs (8.5, 7.5, 6.5 and 5.5). For enhanced coagulation tests, dosages of alum and ferric chloride were 10, 20, 30, 40 and 50 mg/L which have been used in different pHs (5.5 and natural pH of water). All the samples had been filtered through 0.45 micron filters before analyses [9].


RESULTS Both of phosphate compounds in this research were effective in reducing residual metals and there was significant correlation between phosphate concentration and metal reduction. Significant differences (PValue 0.019 for Al and PValue 0.04 for iron) had been considered between these compounds and since sodium orthophosphate had proved to be more effective, it was chosen for the rest of research. There were no significant differences between points for phosphate addition, but post coagulation have been chosen because of higher residual phosphate. Concentrations of residual metals in conventional coagulation were different in various pHs and minimum and maximum concentrations of Al were in pHs of 6.5 and 5.5. Maximum removal of Al took place in pH=5.5 with 0.37 mg/L reduction. Concentration of residual iron in pH of 5.5, 6.5, 7.5 and 8.5 were 0.32, 0.15, 0.08 and 0.22 mg/L respectively.

DISCUSSION Maximum removal of iron was 0.27 mg/L which took place in pH=5.5. Maximum and minimum concentrations of residual phosphate were detected at pHs of 8.5 and 5.5 respectively. In natural pH Concentrations of Al in enhanced coagulation had been increased versus coagulant dose increase (from 0.21 mg/L to 0.35mg/l). Maximum removal of Al took place by alum dosage of 20 mg/L which reduce the concentration from 0.28 mg/L to 0.07 mg/L. Concentration of iron reached its maximum (0.18 mg/L) in coagulant dosage of 40 mg/L. Maximum removal of iron in this stage (0.1 mg/L) happened in coagulant dosages of 30 and 40 mg/L. Residual Al concentration in enhanced coagulation at pH of 5.5 increased from 0.55 mg/L to 2.4 mg/L with the increase of coagulant dosages from 10 to 50 mg/L. Maximum removal of residual Al happened in coagulant dosage of 50 mg/L. Concentrations of residual iron in this stage were 0.31, 0.72, 0.93, 1.2 and 1.68 mg/L which took place in coagulant dosages of 10, 20, 30, 40 and 50 mg/L, respectively. Maximum removal of residual iron was 0.35 mg/L which happened in coagulant dosages of 50 mg/L. Temperature increases permanently increased the concentrations of soluble metals and consequently removal efficiency. Orthophosphate reduced the soluble metals to the standard levels in the all temperatures of this stage. Residual phosphates in this stage were independent from temperatures.

CONCLUSION It was concluded that post coagulant addition of phosphate in rapid mixing could reduce the residual Al and iron. But required phosphate dosages, at pH=5.5 (in both conventional and enhanced coagulation) should be increased. In all stages residual phosphate in coagulation with ferric chloride in all stages was permanently lower than alum coagulation.

ACKNOWLEDGMENTS This research has been supported by Tehran University of Medical Sciences and Health Services, Grant 6142-27-03-86.

REFERENCES 1. Ammary, B.Y., J.L., Cleasby, 2004, Effect of addition sequence on dual-couagulant performance, AWWA, 96( 2): 29-34

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2. Budd, G.C., A.F., Hess, H., Shorney-Darby, 2004, Coagulation, application for new treatment goals. AWWA, 96(2): 32-39 3. Carroll, B. A., M. J., Hawkes, 1991, Operation experiences of converting from aluminium to iron coagulation at water supply treatment works. Water Supply, 9 (3 -4):353 -358. 4. Eikebrkk, B., T., Juhna, S.W., Qsterhus, 2006, Water treatment by enhanced coagulation: Operational status and optimization issues, TECHNEAU. 5. Judkins, E.T 1982, Process Chemistry for Water and Wastewater Treatment. Mc Graw- Hill. 6. Kastl, G., A., Sathasivan, I., Fisher, 2004, Modelling DOC removal by enhanced coagulation. AWWA, 96(2): 43-50 7. Nilson, R, 1990, Residual aluminium concentration in the drinking water after treatment with aluminium or iron salts. Chemical Water and Wastewater Treatment. 8. Nilson, R, 1992, Residual aluminium concentration in the drinking water after treatment with aluminium or iron salts or apatite-Health Aspects, Water Supply, 10 (4): 156-165 9. APHA, 2005, Standard Methods for the Examination of Water and Wastewater, 20th ed., American Public Health Association/ American Water Works Association / Water Environment Federation, Washington DC, USA.


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DENITRIFICATION OF WASTEWATER CONTAINING HIGH NITRATE USING A BIOREACTOR SYSTEM PACKED BY MICROBIAL CELLULOSE Hatam Godini1, Abbas Rezaee2, Ali Jafari1 1- Department of Environmental Health, Faculty of public Health, Lorestan University of Medical Sciences, Khoramabad, Iran 2- Environmental Health Dept., Faculty of medical sciences, Tarbiat Modares university, Tehran, Iran *Corresponding Author: Hatam Godini Environmental Health Dept., Faculty of public Health , Lorestan University of Medical Sciences, Khoramabbad, Iran Fax: +98 661 4208176 Email: [email protected]

ABSTRACT A Laboratory-scale packed bed reactor with microbial cellulose as the biofilm carrier was used to investigate the denitrification of high-strength nitrate wastewater with specific emphasis on the effect the nitrogen loading rate and hydraulic retention time. A 3.51-L bioreactor (50 cm packed height × 8 cm diameter) was used to evaluate the performance reactor in the removal of nitrate from synthetic wastewater. In this study the effect of feed solution nitrate content, which varied between 100 and 700 ppm, and feed solution flow rate, which was in the range from 834 to 2500 ml/h, on the nitrate removal performance of a microbial cellulose packed-attached biofilm-fixed bed reactor has been investigated. Ethanol was added as a carbon source for denitrification. As a result of this investigation, it was found that up to 500 mg/l feed nitrate concentration the present system is able to produce an effluent with nitrate content below 10 ppm at 3 h hydraulic retention time. High denitrification with low accumulation of nitrite-N (20 ppm). The highest observed denitrification rate was 4.57 kg NO3-N/ (m3 .d) at a nitrate load of 5.64 kg NO3N/(m3 .d), and removal efficiencies higher than 90% were obtained for loads up to 4.2 kg NO3-N/(m3 .d). A mass relation between COD consumed and NO3-N removed around 2.82 was observed. This continuous-flow bioreactor proved an efficient denitrification system with a relatively low retention time.

Keywords: Biological nitrate removal; Denitrification; Microbial cellulose; Packed-bed reactor

INTRODUCTION Nitrate released into environment can create serious problems, such as eutrophication of rivers, deterioration of water quality and potential hazard to human health, because nitrate in the gastrointestinal tract can be reduced to nitrite ions. In addition, nitrate and nitrite have the potential to form N-nitrous compounds, which are potent carcinogens (Yang et al. 2007; Bouchard et al., 1992, Boyd and Tucker, 1998). To address this problem, specific rules have been established globally. The European Community and the USA Environmental Protection Agency, set the 5.6 mg (NO3-N)/L and 10 mg (NO3-N)/L respectively (Aslan and Cakici 2007). This dangers necessitates the removal of NO3− from water reserves. Biological denitrification is an attractive treatment option, for the NO3− is converted by the denitrifying bacteria to inert nitrogen gas and the waste product usually contains only biological solids. Biological

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removal of nitrate is widely used in the treatment of domestic and complex industrial wastewaters (Delanghe et al., 1994; Sozen and Orhon, 1999; Kesseru¨ et al., 2003; Dong and Tollner, 2003). The denitrification could be achieved either in the suspended or attached growth systems. Attached growth reactors are the favoured bioreactors for denitrification because they may be made much more compact. The treatment of wastewater in packed bed bioreactors is attracting increasing interest with the application of a variety of carriers (Pujol et al, 1994; Eckenfelder et al, 1991; Borregaard, 1997; Henz, 2002). Several natural materials (agar, agarose, collagen, alginates and chitosan) and synthetic polymer materials (polyacrylamide, polyurethane, polyethylene glycol and polyvinyl alcohol) have been applied as media (Manohar and Karegoudar, 1998). Among the various matrixes that are available, the Microbial cellulose (MC) had been chosen for its ease of use, low cost, low toxicity, high operational stability (Son et al., 2003; Rezaee et al., 2005), biopolymer without lignin or hemicelluloses, high strength crystalline, light weight, selective porosity, and high surface-to-volume carrier capacity. The MC synthesized by Acetobacter xylinum is identical to that made by plants in respect to molecular structure. Because of these features there is an increasing interest in the development of new fields of application (Klemm et al., 2001; Rezaee et al., 2005). The microbial cellulose media provides a continuously high cell concentration in the bioreactor. To ensure complete denitrification, an external carbon source is often used that serves as the electron donor and facilitates the denitrification process (Grommen et al., 2006; Van Rijn et al., 2006). The usage of ethanol is common not only in experimental pilot plants (Fuchs et al., 1997; Æsøy et al., 1998; Mohseni-Bandpi and Elliott, 1998), but also in full-scale technologies ( Hallin et al., 1996; Hasselblad and Hallin, 1996). Saliling et al (2007) results indicate that wood chips and with straw can used as alternative biofilter media for denitrification of wastewater with high nitrate concentrations. In this study it is aimed to investigate performance of high nitrate removal in a microbial cellulose packedattached growth biofilm reactor. These parameters are nitrate concentration in feed solution and feed solution flow rate. The microbial cellulose is known to be effective in holding organic substances in water streams. Thus by the use of microbial cellulose bed it is aimed to minimise the contamination of the product water by residual organics. The aim was to attain a constantly high denitrification activity and a minimal NO2− concentration in the effluent with a low retention time.

2. MATERIAL AND METHODS 2.1. Microbial cellulose production In this study A. xylinum (ATCC 23768) was used. It was grown in SH medium at 28ºC under static culture conditions. Preinoculum for all experiments was prepared by transferring a single A. xylinum colony grown on SH agar into a 50 ml Erlenmeyer flask filled with liquid SH medium. After 5 days of cultivation at 28°C, the cellulose pellicle formed on the surface of the culture broth. Ten milliliters of the cell suspension was introduced into a 500 ml Erlenmeyer flask containing 100 ml of fresh SH medium. The culture was carried out statically for 72 h and the cell suspension derived from the synthesized cellulose pellicle was used as the inoculum for further cultures. The stationary cultures in Erlenmeyer flasks filled with different volumes of the medium lasted for 7 days. After cultivation, the cellulose sheets were removed and rinsed with distilled water and cleaned of bacterial and medium residues using 2% sodium dodecyl sulfate and 4% NaOH solutions in a boiling-water bath. The MC was cut into 5-10 mm pieces and used for cell immobilization, bioreactor media and carbon source.

2.2. The denitrifier bacteria and inoculation of bioreactor The Consortium microorganisms with high denitrification efficiency were isolated from effluent petrochemical industry taken from Razi in Iran. This industry produces Nitrogen fertilizer and have high nitrate. To inoculate the biofilter media with bacteria, the bioreactor was first filled up with nitrate-rich media and isolated bacteria for 48 h. After the static period, the waste storage tank was filled with more wastewater from the same source and circulated through the reactors in a closed loop, returning to the


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storage tank. This recirculation was continued until there was an indication of a substantial decline of the nitrate–nitrogen concentration of the wastewater in the storage tank. During this acclimation period, the wastewater in the storage tank was amended with the addition of nitrate and ethanol to improve bacterial growth. After recirculating the wastewater for 3 days, feeding of the synthetic wastewater began at an influent NO3 + NO2–N concentration of 100-700 mg/L. During this study, reactor was fed from a common source of synthetic wastewater.

2.3. Synthetic wastewater The synthetic wastewater was prepared using deionized water in addition to other chemicals. Potassium nitrate was added as the nitrogen source at a concentration of 100-700 mg NO3- - N/L. ethanol was added as the carbon source at a concentration of 300-2100 mg COD/L. The ratio of the nitrogen to COD was taken as 1:3 to keep the nitrogen as the limiting substrate. Trace mineral constituents essential to the bacterial growth added per liter were: 0.85 mg FeSO4.7H2O, 0.25 mg NaMO4, 0.157 mg MnSO4.7H2O, and 33 mg NaHCO3. Sodium Sulfite and cobalt chloride were added at concentration of 20 and 0.55 mg/L, respectively, to reduce the oxygen concentration to below 0.5 mg/L to ensure anoxic conditions in the reactors. Monobasic and dibasic potassium phosphate was added as a buffer system.

2.4. Bioreactor operation To increase the biological denitrification efficiency, packed-bed reactor was applied with microbial cellulose beads. In the long-term operation test, the synthetic wastewater was fed following as; 100700 mg/l of nitrate-N, 300-2100 mg/l of ethanol and the pH was adjusted to 7.2. The experimental set-up used in investigation was microbial cellulose packed bioreactor, a Plexiglas column has been used as reactor followed by a 5 liter sedimentation tank. The ends of the PVC column were covered with plastic screens to hold the biofilter media. The total volume of the reactor up to the top level was 3500 ml, with height 70 cm, and diameter 8 cm. which only 50 cm portion was filled with microbial cellulose. The synthetic wastewater was fed from the bottom of the reactor and left it from its top. Ethanol was used as carbon source which was added into the solution in such a quantity to give a COD/N ratio of 3. A constant flow rate was applied, at which the average HRT of the influent referred to the total volume of the reactor was 1-3 h. The wastewater influent was fed to the bottom of the reactor through 0.635 cm (1/4 in.) clear vinyl tubing. Similarly, vinyl tubing was used to carry effluent away from the top of the reactors for disposal (e.g. this was a flow through system). The vinyl tubing was cleaned at least once every 2 weeks to minimize biofilm and solids buildup inside the influent and effluent lines. This maintenance procedure was implemented to minimize denitrification in the influent and effluent lines. The reactor was operated at 30 °C. Samples were taken from the bioreactor every 24 h and the NO3−, NO2−, COD and alkalinity concentrations of the samples were determined to study the spatial separation of the NO3− and NO2− reduction steps of the denitrification process. The temperature of synthetic wastewater was controlled to 30 °C in the controller.

2.5. Analytical methods

Samples were collected at the influent and effluent ports. Liquid samples were centrifuged at 5 oC. Thus, obtained supernatant was used for nitrate and nitrite analysis. Samples were analyzed for NO3 , NO2–N, COD, and alkalinity using Standard Methods (APHA, 2005). The pH was measured routinely throughout the trials.

3. RESULTS AND DISCUSSION Table 1. summarizes the different average influent and effluent concentrations, the corresponding percent reduction in NO3 –N concentrations, and denitrification rates under pseudo steady-state conditions. This study showed that the nitrate removal efficiency was 90-100 % at COD:NO3−–N ratios of 3:1, with HRTs of 3 h. In this study a low nitrite was attained.

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Table 1. The different average influent and effluent concentrations, the corresponding percent reduction in NO3 –N concentrations, and denitrification rates (HRT= 3 h and T= 30 oC). Influent NO3–N Effluent NO3 –N Percentage Denitrification concentration concentration reduction (%) rates (mg/L) (mg/L) (kg N/(m3 .d)

99.98±4.76 0.95±0.35 98.06±1.36 0.78±0.08 201.27±5.86 0.596±0.25 99.70±0.2 1.610±.15 299.81±9.34 0.758±0.28 99.75±0.1 2.39±.123 399.541±10.84 5.63±1.29 98.59±0.12 3.15±.234 501.25±8.86 9.34±1.08 98.14±0.45 3.94±.245 599.63±10.89 69.68±3.89 88.38±0.89 4.23±.384 699.60±9.89 119.55±5.63 82.95±2.87 4.57±0.324 Dahab and Lee (1988) and Mohseni-Bandpi and Elliott (1999) reported that a nitrate removal efficiency of nearly 100% was achieved with HRTs of 9 and 8.8 h, respectively, using a bench-scale anoxic filter and the RBC system. Denitrification rates for the different NO3-N loading values are shown in table 1 and figure1. The highest observed denitrification rate was 4.57 kg NO3-N/(m3 d) for a nitrate load of 5.64 kg NO3-N/(m3 d). These values are comparative to those previously reported for high load studies (pujol et al, 1994; Borregaard et al, 1997). They Reported NO3-N loadings for up-flow packed-bed postanoxic denitrification reactors are in the range from 3 to 3.98 kg NO3-N/(m3 d) to achieve effluent NO3-N concentrations below 5.0 g/m3. Hirata et al. (2001) reported a maximum nitrogen volumetric rate of 0.24 kg NO3-N/(m3 day) by using an anaerobic aerobic circulating bioreactor system to remove ammonia and nitrate from two- to five-fold diluted industrial wastewater discharged from metal recovery processes. Denitrification rates increased when loading rates increased for reactor (Figure.1), ranging from approximately 0.72 to 4.57 kg N/(m3 d). As can be seen under low load conditions, the denitrification rate essentially equals the load, with removal efficiencies close to 100%. The critical nitrate load, that is, the lowest value that generates removal efficiencies lower than 100%, was about 3.5 kg NO3-N/(m3 d). 6

Denitrification rate (kg NO3-N/m3.d)

5 100 % Removal

4

3

2

1

0 0

1

2 3 4 Inlet load (kg NO3-N/m3.d)

5

6

Figure 1. Denitrification rate vs. NO3-N load of the synthetic wastewater (HRT= 3 h and T= 30 oC).


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The reactor gave essentially the maximum daily denitrification rate of 4.57 kg nitrogen removed/m3 media/day. Our calculated rates are in the high range of the rates reported by Suzuki et al (2003), Menasveta et al (2001), Kim et al (2002), Tal et al (2003), Gomez et al (2000), Park et al (2001), Kessreu et al (2002), for the other biological reactors. All studies referenced in the above focused on wastewater treatment with a variety of laboratory and pilot plant systems. This is the first paper to describe the use of microbial cellulose as a media and carbon source for nitrogen removal in a bioreactor system. For the nitrite accumulation, maximum 45 mg/l of nitrite- N was accumulated in the reactor with 1 h retention time and 700 mg/l initial nitrate concentration (Figure 2). However accumulated nitrite was decreased with increase of hydraulic retention time and decrease of nitrate loading rate. 50 Nitrite-N production (mg/L)

45 40 35 30 25 20 15 10 5 0 0

200

400

600

800

Initial Nitrate-N Concentration (mg/L) HRT=3 h

HRT= 2 h

HRT= 3 h

Figure 2. Nitrite accumulation at different hydraulic retention time and initial nitrate concentration There was a significant correlation with alkalinity gain and NO3–N reduced for bioreactor that shown in Figure.3.

g Alkalinity product (as CaCO3)/day

1600 1400

y = 2.4718x 2 R = 0.9001

1200 1000 800 600 400 200 0 0

100

200 300 400 g NO3-N removed/day

500

600

Figure. 3. Alkalinity gains of denitrification units supplemented with ethanol as carbon source

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Alkalinity in the effluent increased with increasing nitrate loading rates. In all cases, the amount of alkalinity produced was related to amount of NO3 –N removed. Alkalinity production averaged more than 2.5 mg CaCO3/mg NO3 + NO2–N removed at reactor. This values was in the lower than of amount of removed which would be predicted from stoichiometry with ethanol being used as carbon source (USEPA, 1993). The denitrification process caused a pH rise that cannot be buffered by the alkalinity of the synthetic wastewater. This effect was more relevant as the inlet concentration increased; it has been reported that pH values between 7.0 and 8.0 have no significant effects on denitrification rate (Metcalf and Eddy , 2002). In this study high removals were even possible for pH above 9.0. Effluent pH readings were between 7.32 and 9.17 confirming alkalinity production. Denitrification rate versus COD removal for rector (HRT=3 h and T=50oC) showed at table 2. These data imply that the reactors were not carbon limited, and were receiving enough carbon to facilitate the denitrification process. Effluent COD concentrations are kept between 19 and 126 g/m3. so the addition of ethanol should be adjusted in relation to the denitrification rate. Table.2. Average influent COD, COD removed and COD removed per nitrate–nitrogen reduced in each loading rate (value ± S.D.) Influent COD Concentrations (mg/L)

COD removed (mg/L)

Residual COD (mg/L)

COD removed/per NO3 –N reduced

300

281±8.35

19 ± 2.5

2.84 ± 0.2

600

560±21.8

40 ± 3.96

2.84 ± 0.16

900

846±19.78

54 ± 5.2

2.83 ± 0.12

1200

1128±35.47

72 ± 9.9

2.81 ± 0.13

1500

1410±33.41

90 ± 4.96

2.79 ± 0.16

1800

1692 ± 38.1

108 ± 4.6

2.79 ± 0.23

2100

1974 ± 31.9

126 ± 9.5

2.78 ± 0.17

USEPA (1993) estimated that a COD/NO3–N ratio of 3.75 is required for denitrification with methanol as carbon source. At this reactor requirement was below this stoichiometric estimate. The lower COD consumption per nitrate removed by this reactor may be attributed to the fact that microbial cellulose nature may have added some COD to the reaction, thus lessening the net COD requirement. Robertson et al. (2005) reported that at the early stages of use with their wood chip filters, the media leached carbonaceous COD (from tannic acid, etc.) out of the media. The microbial cellulose in this study may have also leached some carbonaceous COD, but it was likely minor compared to the ethanol contribution.

4. CONCULUSION Denitrification performance of attacked growth biofilm on microbial cellulose in a packed bed reactor system has been investigated as function of Nitrate concentration and others environmental factors.The denitrification reactor design used in this study was effective at significantly reducing nitrate concentrations within a relatively short timeframe. The spatial separation observed throughout the entire period of operation of the bioreactor is well represented by the average data. 90-100 % of the NO3− content of the influent had already been reduced. The reduction of the NO3− was followed by the


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accumulation of low NO2−. The maximum NO2−–N concentration at reactor was about 45 mg l−1 at 1 h retention time, and the concentration progressively decreased with increase of hydraulic retention time and decrease of nitrate loadings. Conclusion derived from this work showed that up to 500 mg/L of feed solution nitrate-N content, the present system is able to produce an effluent with nitrate content below allowed limits. The study showed that Microbial cellulose was suitable supporting bacterial growth to provide biological denitrification and can be used as biofilter media.

REFERENCES APHA, AWW, WPCF, 2005, Standard Methods for the Examination of Water and Wastewater, 21th ed, American Public Health Association, Washington, DC, USA. Aslan, S, Cakici, H, 2007, Biological denitrification of drinking water in a slow sand filter, J Hazard Mat, 148, p253-258. Astley, OM, Chanliaud, AM, Donald E, 2001, Structure of Acetobacter cellulose composites in the Hydrated State, Int J Biol Macromol, 29, p193-202. Borregaard, VR., 1997, Experience with nutrient removal in fixed-film system at full scale wastewater treatment plants, Water Sci. Technol, 36, p129–137. Bouchard, DC, Williams, MK, Surampalli, RY, 1992, Nitrate contamination of groundwater: source and potential health effects, Journal AWWA, 9, p85–90. Boyd, CE, Tucker, CS, 1998, Sustainability and Environmental Issues, Pond Aquaculture and Water Quality Management, p601–624. Dahab, M, Lee, YW, 1998, Nitrate removal from water supplies using biological denitrification, J. Water Pollut Control Fed, 60, p1670–1678. Delanghe, B, Nakamura, F, Myoga, H, Magara, Y, Guibal, E, 1994, Drinking water denitrification in a membrane bioreactor, Water Sci. Technol, 30, p157–160. Dong, X, Tollner, EW, 2003, Evaluation of Anammox and denitrification during anaerobic digestion of poultry manure, Bioresour. Technol, 86, p139–145. Eckenfelder, WW, Argaman, Y, 1991, Principles of biological and physical/chemical nitrogen removal. Lewis Publishers, New York , p 3–42. Æsøy, A, Ødegaard, H, Bach, K, Pujol, R, Hamon, M, 1998, Denitrification in a packed bed biofilm reactor (BIOFOR)-experiments with different carbon sources, Water Res, 32, p1463–1470. Fuchs, W, Schatzmayr, G, Braun, R, 1997, Nitrate removal from drinking water using a membrane-fixed biofilm reactor, Appl. Microbiol. Biotechnol, 48, p267–274. Gomez, M, Gonzalez-Lopez, J, Honotia-Garcia, E, 2000, Influence of carbon source on nitrate removal of contaminated groundwater in a dentrifying submerged filter, J. Hazard. Mater, 80, p69–80. Grommen, R, Verhaege, M, Verstraete, W, 2006, Removal of nitrate in aquaria by means of electrochemically generated hydrogen gas as electron donor for biological denitrification, Aquacult. Eng, 34, p33–39. Hallin, S, Lindberg, CF, Pell, M, Plaza, E, Carlsson, B, 1996, Microbial adaptation, process performance and a suggested control strategy in a pre-denitrifying system with ethanol dosage, Water Sci. Technol, 34(1), p91–99. Hasselblad, S, Hallin, S, 1996, Intermittent dosage of ethanol in a pre-denitrifying activated sludge process, Water Sci. Technol, 34, p387–389. Henze, M, Harremoes, P, Cour Jansen JA, Arvin, E, 2002, Wastewater Treatment. Biological and Chemical Processes (third ed.), Springer, Berlin. Hirata, A, Makamura, Y, Tsuneda, S, 2001, Biological nitrogen removal from industrial wastewater discharged from metal recovery processes, Water Sci. Technol, 44, p171–179. Kesseru, P, Kiss, I, Bihari, Z, Polyák, B, 2002, Investigation of the denitrification activity of immobilized Pseudomonas butanovora cells in the presence of different organic substrate, Water Res, 36, p1565–1571. Kessreu, I, Kiss, Z, 2003, Biological denitrification in a continuous-flow bioreactor containing immobilized Pseudomonas butanovora cells, Bioresour Tech, 87, p75–80.

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Kim, YK, Nakano, K, Lee, TL, 2002, On-site nitrate removal of groundwater by an immobilized phychrophilic denitrifier using soluble starch as a carbon source, J. Biosci. Bioeng, 93, p303–308. Klemm, D, Schumann, D, Udhardt, U, 2001, Bacterial synthesized cellulose - artificial blood vessels for microsurgery, Prog Polym Sci, 26, p1561-1603. Manohar, S, Karegoudar, TB, 1998, Degradation of naphthalene by cells of Pseudomonas sp. strain NGK 1 immobilized in alginate, agar and polyacrylamide, Appl Microbiol Biotechnol, 49, p785-792. Menasveta, P, Panritdam, T, Sihanonth, P, 2001, Design and function of a closed, recirculating seawater system with denitrification for the culture of black tiger shrimp broodstock, Aquacult. Eng, 25, p35–49. Metcalf and Eddy Inc, (Tchobanoglous, G, Burton, FL, and Stensel, HD, Editors), 2002, Wastewater Engineering-Treatment, Disposal and Reuse (fourth ed.), McGraw-Hill, New York. Mohseni-Bandpi, A, Elliot, D, Momeny-Mazdeh, A, 1999, Denitrification of ground water using acetic acid as a carbon source, Water Sci. Tech, 40, p53–59 Mohseni-Bandpi, A, Elliott, DJ, 1998, Groundwater denitrification with alternative carbon sources, Water Sci. Technol, 38, p237–243. Park, EJ., Seo, JK, Kim, MR, Jung, IH, Kim, JY, 2001, Salinity acclimation of immobilized freshwater denitrifiers, Aquacult. Eng, 24, p169–180. Pujol, R, Hamon, M, Kendel X, Lemmel, H, 1994, Biofilters: flexible, reliable biological reactors, Water Sci. Technol, 29, p33–38. Rezaee, A, Drayat, J, Mortazavi, SB, 2005, Removal of mercury from chlor-alkali industry wastewater using Acetobacter xylinum cellulose, Am J Environ Sci, 1, p102-105. Rezaee, A, Ansari, M, Zandi, F, 2005, Construction of a new shuttle vector for Acetobacter xylinum and Escherichia coli, J Biol sci, 5, p274-278. Robertson, WD, Ford GI, Lombardo, PS, 2005, Wood-based filter for nitrate removal in septic systems, Trans. ASAE, 48 (1), p121–128. Saliling, W J B, Westerman, PW, Losordo, TM, 2007, Wood chips and wheat straw as alternative biofilter media for denitrification reactors treating aquaculture and other wastewaters with high nitrate concentrations, Aquacultur Eng, 37(3), p222-233. Sozen, S, Orhon, D, 1999, The e ect of nitrite correction on the evaluation of the rate of nitrate utilization under anoxic conditions, J. Chem. Technol. Biotechnol, 74, p790–800. Suzuki, Y, Maruyama, T, Numata, H, Sato, H, Asakawa, M, 2003, Performance of a closed recirculating system with foam separation, nitrification and denitrification units, Aquacult Eng, 29, p165–182. Tal, Y, Nussinovitch, A, van Rijn, J, 2003, Nitrate removal in aquariums by immobilized denitrifers, Biotechnol. Prog, 19, p1019–1021 USEPA (US Environmental Protection Agency), 1993. Manual: Nitrogen Control. EPA/625/R-93/010. Environmental Protection Agency, Washington, DC. Van Rijn, J, Tal, Y, Schreier, HJ, 2006, Denitrification in recirculating systems: theory and applications, Aquacult. Eng, 34, p364–376. Yang, CY, Wu, DC, Chang, CC, 2007, Nitrate in drinking water and risk of death from colon cancer in Taiwan, Environ Int, 33, p649-653.


EUTROPHICATION STUDIES ON JEFFERY CANAL OF ALIGARH ABID ALI ANSARI* AND FAREED A. KHAN* *

Department of Botany Aligarh Muslim University, Aligarh-202002, U.P., INDIA (E-mail: [email protected]; [email protected])

ABSTRACT The growth of Eichhornia crassipes was studied in response to water samples collected from various sites of Jeffery Canal to know the trophic status of the canal. The dry weight, chlorophylla, nitrogen, phosphorus, potassium, peroxidase (POD), catalase (CAT) and malondialdehyde (MDA) levels in plants were determined. Optimum growth was recorded in plants grown in water samples from site S2 and S3. A significant reduction in growth and an increase in protective enzymes were recorded in lants grown in water samples from site S4. The growth pattern of Eichhornia crassipes showed all the selected sites of canal in eutrophic condition.

INTRODUCTION The nutrient input to waters from various sources causes eutrophication and are responsible for degradation of aquatic ecosystems (Ansari and Khan, 2007, Khan and Ansari, 2005) and plants biodiversty (Ansari and Khan, 2009b). The potential of Eichhornia crassipes (water hyacinth) for eutrophication studies has been determined (Mishra et al., 2007, Ansari and Khan, 2009c). Water hyacinth is reported for its efficiency to absorb about 60-80% nitrogen (Fox et al., 2008) and about 69% of potassium from water (Zhou et al., 2007). In the present study the growth responses of E. crassipes was investigated for eutrophication studies on Jeffery Canal of Aligarh, Utter Pradesh.

METERIALS AND METHODS Five sites of Jeffery Canal for the collection of water samples were selected at various locations of the canal for eutrophication studies. The sites located were S1 near Deprtment of Commerce, S2 near University Polytechnic, AMU, S3 near medical road, S4 near New Sir Sayed Nagar and S5 at Tayyab colony of Aligarh. Individual plants of E. crassipes were collected from waste water bodies on the Aligarh Muslim University campus, washed thoroughly in lab and cultured for two weeks in large earthen pots of size 40 x 25 cm (diam x depth) containing 15 liters of freshwater with Hoagland solution (1ml L-1). The experiments were conducted in flasks of 1 liter containing ordinary tap water (S0=control) and water samples from sites (S1-S5). The plants were disinfected by immersing them in NaClO (1%v/v) and then rinsed with distilled water. The final volume (1 liter) of water in the experimental flasks was maintained using distilled water. One young individual of E. crassipes with an average 3 leaves (approximately of equal size close to 4x6 cm) was transferred from the maintained stock to each experimental flask. The flasks of each water sample were maintained in triplicate. Plant growth was measured by placing pots inoculated with E. crassipes in a growth chamber maintained at 30o C temperature in a light of 36 µ mol m-2 s-1. The pH of all water samples were maintained at 7.0 using NaOH or HCl and measured regularly with a pH meter (Elico Limited, Hyderabad). The experiments were terminated after 15 days. The plants removed from the flask, fresh material was taken for chlorophyll estimation and rest of the plant dried at 80o C in order to obtain dry weight. Chlorophyll-a content in the plants was estimated following the method of Zhao (2000b). The nitrogen and phosphorus contents were determined using the method of Lindner (1944) and Fiske and Subba Row (1925) respectively. Potassium was determined with a Flame photometer

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(AIMIL). For peroxidase (POD) assay, the crude enzyme was extracted in a phosphate buffer (0.1 M, pH 7.0) following the technique of Kar and Mishra (1976) and the activity was determined as per Putter’s (1974) method. CAT activity was estimated following Lu (2002). MDA contents were estimated according to the method of Zhao (2000a). The data were analysed statistically following Dospekhov (1984).

RESULTS AND DISCUSSION Table.1 showed higher concentration of nutrients in water samples collected from various sites of Jeffery canal. Maximum concentarion was recorded in water from site S4, receiving water from housholds having direct water drainage system. The pH was alkaline except water at S4 site. Dissolved Oxygen contents were lowest at S4. Dry matter and chlorophyll-a accumulation were significantly higher in plants of water S2 and S3. (Table. 2). The optimum uptake of nitrogen, phosphorus and potassium was noted in water from S3. Growth responses of E. crassipes were studied as the primary productivity is considered to be a strong indicator of eutrophication (Smith 2007; Ansari and Khan, 2006). The water of site S4 significantly suppressed the nutrient uptake, dry matter and chlorophyll-a concentration. The POD, CAT activity and MDA contents were significantly higher in plants grown in water of site S4 site, showed plants in stressed condition due to low dissolved oxygen contents, acidic pH and very high nutrient contents in water from S4. The aquatic plants are found very sensitive to nutrients and are very efficient for eutrophication studies (Ansari and Khan, 2008, 2009a). This study indicated that E. crassipes is a very strong indicator of eutrophication and may be used for lowering high nutrient levels in eutrophic water. By removing the rapidly growing plants (having high nutrient contents taken up from the medium) and replacing old plants with fresh plants regularly, the quality of eutrophic water can be improved.

REFERENCES Ansari A. A. and Khan F. A. (2006). Studies on the role of selected nutrient sources in the eutrophication of fresh water ecosystem. Nature Environment and Pollution Technology 5, 47-52. Ansari A. A. and Khan F. A. (2007). Eutrophication studies in some freshwater ponds of Aligarh. Indian Journal of Applied and Pure Biology 22, 21-26. Ansari A. A. and Khan F. A. (2008) Remediation of eutrophied water using Lemna minor in a controlled environment. African Journal of Aquatic Science 33, 275-278. Ansari A. A. and Khan F. A. (2009a). Remediation of eutrophied water using Spirodela polyrrhiza L. Shleid in controlled environment. Pan-American Journal of Aquatic Sciences 4, 52-54. Ansari A. A. and Khan F. A. (2009b). Aquatic plant diversity in eutrophic ecosystems. Aquatic Sciences (submitted). Ansari A. A. and Khan F. A. (2009c). Nutrients phytoremediation of eutrophic water using Eichhornia crassipes in controlled environment. Water Science and Technology (submitted). Dospekhov B. A, 1984. Field Experimentation. Mir Publications, Moscow, pp 351. Fiske C. H. and Subba-Row Y. (1925). The colorimetric determination of phosphorus. Journal of Biological Chemistry 66, 375-400. Fox L. J., Struik P. C., Appletona B. L. and Rule J. H. (2008). Nitrogen phytoremediation by water hyacinth (Eichhornia crassipes (Mart.) Solms). Water Air and Soil Pollution 194, 199 207. Kar M. and Mishra D. (1976). Catalase, peroxidase and polyphenol oxidase activities during rice leaf senescence. Plant Physiology 57, 315-319. Khan F. A. and Ansari A. A. 2005. Eutrophication: an ecological vision. Botanical Review 71, 449-482.


Lindner R. C. (1944). Rapid analytical methods for inorganic constituents of plant tissues. Plant Physiology 19, 76-89. Lu S. Y. (2002). Determining the activities of several protective enzymes. In: Manual of plant physiology experiment, Chen J. X. and X. F. Wang (eds.), South China University of Technology Press, Guanzhou, pp. 119-121. Putter, J. (1974). Peroxidase. In: Methods of enzymatic analysis, Bergemeyer H.U. (eds.), Vol. II. Academic Press, London, pp. 685-690. Smith V. M. (2007). Using primary productivity as an index of coastal eutrophication: the unit of measurement matter. Journal of Plant Research 29, 1-6. Zhao S. H. J. (2000a). Detection of chlorophyll pigment. In: Manual of plant physiology experiment (in Chinese), Zou, Y. (eds.),. Chinese Agriculture Press, Beijing, pp. 72–75. Zhao S. H. J. (2000b). Detection of the activity of MDA in plant tissue. In: Manual of Plant Physiology Experiment (in Chinese), Zou, Y. (eds.), Chinese Agriculture Press, Beijing, pp. 173–174. Zhou W., Zhu D., Tan L., Liao S., Hu H. and David H. (2007). Extraction and retrieval of potassium from water hyacinth (Eichhornia crassipes). Bioresource Technology 98, 226231.

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Table 1: Physico-chemical characteristics of water samples collected from various sites of Jeffery Canal. Water Samples S0

S1

S2

S3

S4

S5

pH

7.2 ±0.2

7.8 ±0.3

7.5 ±0.3

8.0 ±0.2

6.4 ±0.2

7.3 ±0.2

Turbidity (NTU)

11 ±1.5

20 ±1.5

23 ±2.5

22 ±1.5

31 ±1.5

21 ±1.5

3

Dissolved Oxygen (mg/L)

7.3 ±0.54

5.9 ±1.1

6.3 ±1.3

5.5 ±1.4

4.1 ±0.6

6.6 ±0.65

0.5

Nitrates (mg/L)

0.73 ±0.07

9.4 ±1.84

12.9 ±1.83

34.4 ±4.46

43.7 ±7.27

7.2 ±1.70

4.5

Phosphates (mg/L)

0.23 ±0.07

2.7 ±0.18

4.41 ±0.82

3.79 ±0.69

6.42 ±1.61

2.55 ±0.79

0.97

Potassium (mg/L)

13.7 ±1.5

20.2 ±3.1

25.5 ±4.2

34.6 ±5.4

54.4 ±5.9

22.8 ±3.6

5.2

Table 2: Growth response of Eichhornia crassipes water samples from various sites of Jeffery Canal.

LSD at 5 % 0.3


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Water Samples

S0

S1

S2

S3

S4

S5

Dry weight mg g-1 FW

272.6 ±3.4

288.4 ±4.9

292.4 ±3.7

303.6 ±5.1

249.7 ±4.2

274.5 ±3.1

Chlorophyll mg g-1 FW

1.246 ±0.065

1.115 ±0.070

1.252 ±0.085

1.347 ±0.091

0.894 ±0.052

1.120 ±0.058

0.078

Nitrogen mg 100mg-1

6.245 ±0.195

6.621 ±0.187

6.711 ±0.144

6.976 ±0.210

5.557 ±0.128

6.256 ±0.124

0.219

Phosphorus mg 100mg-1

0.782 ±0.043

0.879 ±0.052

0.898 ±0.040

0.946 ±0.031

0.638 ±0.035

0.747 ±0.025

0.051

Potassium mg 100mg-1

3.015 ±0.075

3.222 ±0.052

3.214 ±0.054

3.335 ±0.062

2.652 ±0.047

2.944 ±0.065

0.085

POD mg -1protein min-1

442 ±3

438 ±2

431 ±2

428 ±4

455 ±3

434 ±3

4

CAT mg-1protein min-1

130 ±2

122 ±2

114 ±4

111 ±3

135 ±4

117 ±3

5

MDA µmol g-1 FW

3.349 ±0.082

3.268 ±0.068

3.046 ±0.059

2.911 ±0.055

3.624 ±0.073

3.242 ±0.075

0.091

(FW: Fresh weight, LSD = Least significant difference, % = level of significance)

LSD at 5 % 5.9

Wetlands


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CONSTRUCTED WETLANDS FOR IMPROVING WATER QUALITY OF UASB-REACTORS EFFLUENT NADEEM KHALIL Department of Civil Engineering, Aligarh Muslim University Aligarh 202002 India A K RAGHAV Department of Applied Mechanics, Indian Institute of Technology Delhi Hauz Khas, New Delhi -110016 India A K MITTAL Department of Civil Engineering, Indian Institute of Technology Delhi Hauz Khas, New Delhi -110016 India This paper presents the outcome of the study recently carried out in India (tropical climatic region) to investigate the applicability and efficacy of constructed wetlands (CWs) for UASB reactors (upflow anaerobic sludge blanket) effluent treating municipal sewage. The study was carried out at pilot scale level consisting five wetlands units which were installed at the full-scale UASB sewage treatment plant in northern Indian city, Faridabad. Four units were planted while one unit was left unplanted used as a ‘control’. Locally available macrophytes like Typha latifolia, Canna Flaccida, Sagittaria lancifolia, and Ipomea aquatica were planted in these units. The media used in this study was aggregates of half-burnt bricks. The performance of wetlands units under identical conditions was monitored for about two years at different hydraulic retention times (2 days, 4 days, and 8 days). The evaluated parameters reported in this paper are the removal efficiency of residual organic material and suspended solids. However other parameters were also investigated but reported in some different papers. The study demonstrated that CWs planted with canna, typha and ipomea can effectively treat UASB reactor effluent as they showed considerable reduction in organic matter, and solids. Sagittaria could not withstand with anaerobic effluent and died few days after its exposure with the UASB effluent. The results reported are expected to be useful in adopting an integrated approach for sewage treatment comprising UASB and CWs particularly in countries (tropical) where UASB is being widely. Keywords: Constructed Wetlands, UASB, Macrophytes, Tropical Climate

1. Introduction Full scale application of UASB (Upflow Anaerobic Sludge Blanket) technology for municipal wastewater treatment especially in developing countries like in India, Brazil, Columbia, Indonesia etc has demonstrated several advantages over other treatment technologies. Major advantages which led to its wide scale application are its simplicity, easy and cost-effective operation and maintenance, competitively low capital investments, resource recovery in the form of biogas, digestion of sludge within the same reactor, and no energy consumption to significantly reduce organic pollution and solids load. The use of UASB technology for sewage treatment in tropical

regions is a consolidated practice. Under appropriate operational conditions (retention time of 8 to 10 hours), UASB reactor can remove the organic and suspended solids loads with an efficiency of 70 – 80% (Khalil et al., 2006). Amongst the nation which favours conditions for UASB process, India has taken the lead in its application and today it has highest the number of UASB plants in the world. However, there has been growing concern about its effluent quality. Several posttreatment methods like polishing ponds, aerated lagoons, etc. have been tried and provided but still the effluent quality of UASB with these methods is of major concern.

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Polishing pond is very common post-treatment method for UASB plants in India (Sato et al., 2005). But two decades of Indian experience with respect to UASB demonstrates that ponds have not performed well after few years of operation. In most of these plants, the final effluent (after polishing ponds) usually exceed the maximum permissible level prescribed by the effluent standards in India (Sato et al., 2006). There are some other problems like scum of solids, formation of algae, odour, breeding ground for mosquitoes, etc. This paper summarizes the performance of constructed wetlands for UASB reactors effluent treatment under tropical climatic conditions using different macrophytes.

2. Materials and Methods 2.1. Study Site and UASB Effluent Source

The site where experimental system (pilot units) was located for this study was sewage treatment plant (STP) in Faridabad, Haryana, India. The city of Faridabad is situated approximately 25 Kms from national capital of India, Delhi. It is located at 28o 25' 16" North Latitude and 77o 18' 28" East Longitude. The climate is hot and dry in summer and cool and dry in winter with a rainy season in between. The temperature in summer ranges from 37oC to 46oC and in winters from 10oC to 1oC. Mean daily temperatures vary between 18oC and 33oC. The city receives an average annual rainfall of about 590 mm. Influent to the CWs was sourced from the UASB reactors of the STP which receives municipal sewage of Faridabad. This STP was commissioned in the year 1999-2000 which has a capacity of 20 MLD (20, 000m3.day-1). Figure 2.1 shows view of UASB Reactors of this STP and final effluent channel from where UASB effluent was collected for the study.

Figure 2.1: View of UASB Reactors and Final Effluent Channel at STP

2.2. Design and Layout of the Pilot Units The experimental system consisted of five units at pilot scale. All the pilot units were of same size, shape, flat bottom and equal aspect ratio (width-to-length) was kept. The schematic diagram showing experimental set-up is given in Figure 2.2. Major characteristics and constructive details of the wetlands units used in this study are given in Table 2.1. All the vegetated units were provided with baffles

dividing tank into three equal compartments. The idea behind providing baffles was to achieve maximum dispersion of water and minimum short-circuiting under plug flow conditions. Each bed had sampling ports (taps) located at the middle and bottom of each horizontal side and front vertical side (outlet position). The plants that were chosen and used for this study are Typha latifolia (cattails), Canna Flaccida (canna lily), Sagittaria lancifolia (arrowheads), and Ipomea aquatica (water spinach).


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Table 2.1: Major characteristics and constructive details of the wetlands units Material of the construction Plexiglass (10 mm thick) Number of beds Number of vegetated beds Number of control (s) Length Width Bed height (Effective Media Depth) Aspect ratio Bed surface area Filter media Size of media Porosity

05 04 01 1.35 m 0.45 m 0.50 m (SSF) 1:3 0.6075 m2 Half burnt bricks from local kiln 25 mm – 40 mm 0.43

Figure 2.2 Schematic diagram of pilot CW (type design)

2.3 Systems operational conditions In order to allow growth of vegetation and microorganisms to acclimatize, initially wetlands were operated at a low hydraulic loading rate (HLR) of approximately 40 Ld-1. Two months after start-up period, when wetlands were stabilized, the hydraulic loading was increased in accordance with retention time to be maintained. All the beds were operated in parallel on continuous basis under identical conditions for about two years (April 2007 to January 2009) to ensure similarity of performance. Beds were operated for 2 days, 4

3. Results and Discussions 3.1. Growth and response of macrophytes Through out the monitoring period, plants were observed for their appearance, growth patterns, survival and propagation. Typha exhibit good growth demonstrating a vigorous

days and 8 days under Sub-surface flow (SSF) conditions. Regular sampling was done and samples were analyzed in the Environmental Engineering Laboratory, IIT Delhi in accordance with guidelines prescribed in the Standard Methods for Water and Wastewater Examination (APHA, AWWA, WEF, 1998). The parameters monitored during this study were suspended solids (SS), bio-chemical oxygen demand (BOD5), chemical oxygen demand (COD), total coliforms (TC) and feacal coliforms (FC). Results are presented in the box-and-whisker plots and percentile curves. spread and was able to confluent and increased in root depth and shoots. They showed periods of dormancy in the growth of emergent vegetation throughout the study period. It covered 80% of the bed surface within weeks after plantation. Canna also grew well throughout the study period and showed no sign of poor health. Ipomea and sagitarria showed some visual signs of detrimental effects and therefore the growth was far less

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of fresh sagitarria was planted but again it could not survive with this nature of effluent.

than the typha and canna. But after two months period, new leaves occurred and active growth pattern was also observed in ipomea quite similar to other species (typha and canna). However, in case of sagitarria, initially there was some growth but when this bed was constantly fed with UASB effluent, it started showing some detrimental effects and finally termination. Few days later, not a single specimen could survive in the bed. Another set

Through out the monitoring period, the characteristics of UASB effluent was directly measured at the inlet of CWs. Table 3.1 presents the mean, standard deviation minimum and maximum concentration of the UASB effluent of the investigated constituents over the monitoring period.

Table 3.1 Mean, standard deviation, min. and max. concentration of UASB Effluent (n= 98) Parameter

BOD

COD

TSS

Average

82.39

135.62

113.97

14.55

25.88

31.03

Standard deviation Minimum

49.00

96

73.00

Maximum

114.00

202

232.00

3.2. The treatment performance of CWs BOD, COD and TSS Removal Figures 3.1 present the box-and-whisker plot of removal efficiencies for BOD, COD and TSS for all the planted and an unplanted beds (control) at different hydraulic retention times (HRTs) under two flow conditions (FWS and SSF). It can be observed from the plots that there is variation in the BOD removal with respect to vegetation type and HRT. At 8 days HRT, mean removal efficiency for CWs vegetated with typha was 63%, ipomea 57% and canna 59% whereas mean removal efficiency in unplanted bed for the same

retention time was 34%. Cumulatively, the average BOD reduction from all the vegetated beds is 50%. For COD removal, better trends are obtained. From the plots given in Figure 3.1, it can further be seen that under SSF conditions, average values of SS removal efficiencies of 49, 56, and 53% were obtained from typha bed at 2 days, 4 days and 8 days HRT respectively. Removal efficiencies from the unplanted bed at these HRTs were 46, 51 and 59%. Similar removal efficiencies were obtained in other beds. Comparing results in between planted and unplanted beds, there is not significant difference in the TSS removal efficiencies.

80

70

70

60 50 40 30 20

857

80

TSS Removal Efficiencies, %

80

COD Removal Efficiencies, %

BOD Removal Efficiencies, %


60 50 40 30

Planted Control FWS-4d

Planted Control SSF-2d


50 40

20



60

30

20 10

10

70








80

70

70

60 50 40 30 20

80


80



(a) Typha

60 50 40 30 20

70

60 50

40

30 10

10 Planted Control FWS-4d




Planted Control FWS - 4d

Planted Control SSF - 2d



20 Planted Control FWS-4d








(b) Ipomea 80

70 60 50 40 30 20


80



80

70 60 50 40 30





60

50

40

30

20 20

10

10

70





(c) Canna Figure 3.1: Removal Efficiencies of BOD, COD and TSS in different vegetated beds at different HRTs

4. Conclusions

5. References

Results of this study suggest that constructed wetlands have ability to effectively treat effluent from UASB reactors treating municipal sewage under tropical climatic conditions. This research has reaffirmed that in tropical climatic regions as prevailing in India, CWs provides great opportunities for their application to improve effluent quality as these regions have year-round favourable condition for macrophytes which influences on their performance.

1. 2.

Khalil. N, Mittal. A.K, Raghav. A. K, and Sinha. R, Env. Engg & Mgt. 5(5), 1059-1069 (2006). Sato. N. Okubo, T. Onodera, Agrawal L. K, Ohashi A, and Harada. H, Env. Mgt. 84, 447- 460 (2007).

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AQUATIC BIODIVERSITY OF WETLANDS OF “CITY OF HUNDRED ISLANDS” ON HILLS OF ARAVALI Dr. Seema Bhardwaj, Head of Department (Zoology), Sh. Govind Guru Govt. P.G College, Banswara 327001, Rajasthan, India, Lalit Choudhary, Research Scholar, Department of Zoology & Microbiology, Madhav Vigyan Mahavidhyalay, Vikram University, Ujjain 45601, Madhya Pradesh,

“Species generally become rare before extinct – to feel no surprise at the rarity of a species, and yet to marvel greatly when the species ceases to exist, is much the same as to feel no surprise at sickness, but, when the sick man dies, to wonder and to suspect that he died by some deed of violence”. - Charles Darwin

1. ABSTRACT Wetlands are cradle of aquatic biodiversity. Wetlands are ‘wet’ (partly or yearly) ‘land’ areas where availability of water during part or all of the year depends on their location. Wetlands are transitional between aquatic and terrestrial ecosystems. The importance of study of wetlands is increasing day by day because they provide habitats for aquatic life and water availability for surrounding fauna and flora. Wetlands are very productive aquatic ecosystems. They provide a good habitat platform to aquatic biodiversity. Wetlands are also useful in water storage, conservation, and recharge, recycling of nutrients, Research, Education, recreational opportunities, sacred values, and fisheries operations and reducing of flood risks. Wetlands are natural filtration plants therefore wetlands are usually known as kidneys of the landscape. Such valuable services of wetlands are really beneficial for humanity and usually wealth of biodiversity of any country. City of Hundred islands is situated in Southern Rajasthan on hills of Aravali, about 170 wetlands are found over here. This city is heaven and haven for migratory birds. In present study we observed some aspect of aquatic biodiversity in few wetland of this city. Wetlands are most threatened valuable habitats of the developing world. Wetlands are not delineated under any specific administrative jurisdiction. Primary responsibilities are in the hands of Ministry of Forest and Environment .The protection of such a valuable habitat is going on and the results of some work are also appreciable but effective coordination of other sectors also essential for these life-lines of biodiversity.

2. KEY WORDS - Wetland, Aquatic biodiversity, Contamination, Environment, Habitat.

3. INTRODUCTION “The City of Hundred Islands” is Banswara district of southern most part of Rajasthan. It lies between 23.1 ° N to 23.56 ° N latitudes and 73.58 ° E to 74.49° E longitudes. Its eastern part occupied by hills of Deccan trap. Banswara district lies in Mahi river basin. Mahi enters from the southeast and flowing north towards the northern end of Banswara and them turns southwest where it forms boundary between Dungarpur & Banswara finally Mahi reaches in to Gulf of Cambay. This district is supported by five rivers namely Mahi, Anas, Erav, Chanp and Haram. Mahi Bajaj Sagar dam has been constructed on river Mahi. A good number of wetlands are found in this city and they provide habitat platform to aquatic biocommunities. Aquatic biodiversity and wetlands are important for environmental health. In India about 1230 bird species are available out of them about 23% are mainly dependent on wetlands. Wetlands are among the most productive ecosystems in the world. A


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great variety of species depend on wetlands. Most of these wetlands are essentially natural ecosystems stabilized over the years, and have retained their natural characteristics. However, years of uncontrolled encroachment have degraded many wetlands. It is calculated that since 1990 nearly half of the world’s wetlands have been destroyed. In India, it is estimated that only 58 million ha of wetlands remain and many have been degraded requiring restoration (Sen 2009). Wetlands provide many services and commodities to humanity. Regional wetlands are integral parts of larger landscapes, their functions and values to the people in these landscapes depend on both their extent and their location. Each wetland thus is ecologically unique. Wetlands perform numerous valuable functions such as recycle nutrients, purify water, attenuate floods, maintain stream flow, recharge ground water, and also serve in providing drinking water, fish, fodder, fuel, wildlife habitat, control rate of runoff in urban area, buffer shorelines against erosion and recreation to the society (Prasad et al. 2002). Avifauna is available at Jamwa Ramgarh Lake of Rajasthan in India. More than 100 species of birds belonging to 38 families were recorded at lake during the year 2002, maximum species were sighted during the winter season. In the wetland most water birds were found to be migratory and few being resident. Some rare, endangered, uncommon, vulnerable, threatened and near threatened species of birds those already listed in Red Data Book were sighted in Jamwa Ramgarh Lake (Moundiotiya et al. 2005). Wetlands are well known for their aquatic flora and fauna, particularly rare plants and migratory bird species. The compositions of species in wetlands vary both in time and between wetland sites. The diversity and abundance of plant and animal species in different wetland ecosystems are discussed by earlier workers (Mitsch and Gosselink 1986, Williams 1990 and Ewel 1991). The presence and abundance of species living in a wetland depends on their life histories which are often short but complex and their specific adaptation to the environmental conditions of the wetland site. The wetland environment is in many ways a physiologically harsh habitat. There is significant sediment water exchange due to the shallow water in wetland. In general, physical and microbial processes are more important than vegetative uptake in controlling sediment and nutrient retention (Johnston 1991). Globally, forested wetlands occupy more than 330,000,000 ha (Matthews and Fong 1987). These wetlands are vital habitats that harbor high levels of floral and faunal biodiversity including critical bird and mammal habitat (Saenger et al. 1983). Wetlands contribute to fisheries productivity, and act as nursery sites for fish and crustaceans (Robertson and Duke 1987). They also regulate run-off quantity and quality (Lugo et al. 1988), mitigate flooding (Saenger et al. 1983), control erosion and modify geomorphological processes (Carlton 1974). The concept of wetland functions is relatively new in both the regulatory and scientific arenas. Wetlands are parts of a global network of water-dependent cross-frontier resources and processes. As such, water and wetlands are integral parts of a bigger picture whose constituents can not be managed in isolation (Jafari 2002). About 20 per cent of the known biodiversity in India found in freshwater wetlands alone (Deepa and Ramachandra 1999). Wetlands are continuously degraded in many parts of the world. One reason is the lack of the appropriate valuation of the multifunctionality of wetland (Gren et al. 1994). One important reason for serious concern about the loss of wetlands is that they are multifunctional and can be considered as very valuable capital assets. Under sustainable management regime they can produce a flow of functions such as nutrient purification, ground water buffering and biodiversity. This flow is generated by species, populations and communities dynamically interacting with their physical and chemical environment in what is referred to as life-support systems (Odum 1989). Humans derive many utilitarian benefits from the environmental services of biotas and ecosystems. This is often advanced as a prime argument to support conservation of biodiversity. Biodiversity often plays a key role, the services can also derive from biomass and other attributes of biotas (Norman1996). Biodiversity is helpful in assessing the condition and in preparation of Index of Biological Integrity (IBI) of any wetland. Environment Protection Agency has been worked on methods for evaluating wetland condition. The purpose of this study was to help states and tribes develop methods to evaluate ecological condition of wetlands using biological assessments and nutrient enrichment of wetlands which is one of primary stressors damaging wetlands (Helgen 2002). Northern Prairie Wildlife Research Center (NPWRC) has a long history of conducting high-quality, comprehensive wetlands research in the Great Plains and elsewhere in the United States and Canada. This will increase the probability of successful management and reduce long-term maintenance management costs. Scientists within the NPWRC wetland science program also recognize that decisions uniformly made at the Federal level years ago are now made with outside collaboration. This is evidenced by the active

860


participation of citizens in advisory committees and the proliferation of stakeholder groups and land trusts across the country (Euliss 2004).

4. METHODOLOGY The present study carried out in some wetlands of Banswara district namely Kagdi, Lodha, Mordi, Dilab, Baitalab, Patela, Bhagora, Arthuna, Loharia, Metwala, Survania, Nathelav, Senavasa Talab, Dandela Talab (Padoli village), Haro wetland (Ghatol), Vanela Talab, Kambua, Konia wetland. This study based of field, site observation and views of some viewers villagers. The informations and data collected through discussions with members of Forest Department, Irrigation department, Fisheries department and Panchyat of related area. Some data also collected through secondary sources. These include literature review, reports and records of related departments.

5. OBSERVATIONS & RESULTS


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We have observed different aquatic flora and fauna from study area (Table 1, 2 & 3). Malformations also have been recorded in some aquatic arthropods. Aquatic bio-diversity shows fluctuations in different wetlands. In this year water level of Patela, Baitalab, Kagdi wetland was very low in comparison with last some years. Due to this reason so many types of flora and fauna were not found in this year. Kagdi, Lodha, Mordi, Dilab, Baitalab, Barigama , Patela, Bhagora, Gangar Tali, Arthuna, Loharia, Metwala, Survania, Nathelav, Senavasa Talab, Dandela Talab (Padoli village), Haro wetland (Ghatol), Vanela Talab, Kambua, Konia wetland, support wintering populations of several species of aquatic birds and are good nursery sites for fish and other fisheries operations. In present study we have also observed that services and functions of some wetlands do not have direct market value but they have so many primary and secondary values. Primary values are related with structure of ecosystems while secondary values are related with other outputs such as recreation, ecotourism, migration of birds, crop pollination, pest control, fishing and other life support services. So many species of migratory birds are known in Banswara. Among them about fifty species are found in wetlands of this district. Environmental contamination (heavy metal, pesticides, insecticides, agricultural fertilizers, sewage) was also a future coming problem in some wetlands of study area. Agricultural waste cause excess nutrition in some wetlands and this extra nutrition is major cause of extra growth of plants and micro organisms. These bioagents suck oxygen from the water and decline of oxygen causes mortality of aquatic biodiversity. During a field trip of Bagidora Dr. D. Bhatt (R.O. of Bagidora range) has told us that the wetlands are helpful to fulfill the basic needs (Domestic, Agricultural, and for livestock) of inhabitants. Some wetlands of Banswara Kagdi, Lodha, Mordi, Dilab, Baitalab, Patela, Bhagora, Arthuna, Loharia, Metwala, Survania, Nathelav, Senavasa Talab, Dandela Talab (Padoli village), Haro wetland (Ghatol), Vanela Talab, Kambua, Konia are good shelter stations of migratory and resident birds, really wetlands are paradise of our landscape view.

862


6. DISCUSSION Wetlands are incredibly very important ecosystem. A major team of biodiversity agents spend their entire life or an important part of their life cycle in wetlands. These aquatic bodies provide a platform for nesting, nursery and resting stations for so many migratory birds. Wetlands help in maintenance of ground water quality and quantity. Marshes are well developed in some wetlands (Kagdi, Lodha, Nathelav, Patela, Metwala, and Dilab). These marshes are helpful in removal of excess nutrients and heavy metals from the water. Snails feed among the dead grass. Several other species of insects, crustacean and others animals of different phyla found feeding on the aquatic flora. Mixture of dead


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plants materials and other organisms is decomposed by bacteria, fungi and form detritus. Detritus is an important part of food chain and food web. So many species of arthropods, mollusks, worms, and fishes feed on this detritus. Therefore wetlands play a key role in ecological maintenance of environment. Wetlands can control flood and suspended nutrients and have good command over commercial fisheries. Wetlands also provide open space for recreational activities and tourism (Hunting, fishing, boating, canoeing, bird watching and hiking). Finding of values of wetlands of present study show similarities with earlier workers (Gren et al. 1994, Jafari 2009, Costanza et al. 1997, Saenger et al. 1983, Roberson and Duke 1987, Moundiotiya 2005). Environmental contamination was also noticed in some wetlands of study area (Lodha, Mordi, Kagdi and Dilab) due to pollution load. While measurement of contamination was not done in present study because it needs further studies but environmental conditions in some wetlands of Rajasthan was previously carried out and supported by a report on wetlands of India from Salim Ali Centre for Ornithology and Natural History (SACON). They observed that Lead (5.57± 1.18ppm); Zinc (34.26± 8.42 ppm) in fishes of Ramsagar wetland. Cu, Cd and Cr were also detected in same specimen but they were in safe limits.

7. CONCLUSION Wetlands of study area are very good shelter places of aquatic biodiversity but research base projects are needed for maintenance of these habitat shelters of biodiversity in study area. Practice and policies for conservation of wetlands are recommended. The location of wetland, its present legal status of conservation and its benefit to local population are some common inputs for conservatory values of wetlands of study area because socio economic statuses of wetlands are very important. Wetlands are multi-functional they provide services, such as water purification, regulation of water flows, fishery, habitats for plants, animals, micro-organisms, opportunities for recreation and tourism.

8. ACKNOWLEDGEMENTS I am deeply indebted to the Commissioner, College Education, Rajasthan, and to the Principal of S.G.G. Govt. College, Banswara for allowing me to present this paper. I wish express my sincere gratitude to Dr. D.C. Bhatt, Mr. Netra Pal singh Choudhary, (Forest Department), Mr. H.Mehara (Eng. watershed project of Pipalkhunt) for consultation and rendering me all sources of assistance for the completion of this paper. I would dutifully and sincerely express my thanks to organizer and convener of International Conference on Emerging Technologies in Environmental Science and Engineering who provided me a platform for this nice opportunity. In last but not in least I am thankful to authors and sources of all references for their direct and indirect help in preparation of this paper.

9. REFERENCES Bhatt, D, 2009, RFO, Bagidora Forest Range. ([email protected]). Carlton, J, M, 1974, Land-building and stabilization by mangroves, Environ. Conservation 1, p285– 294. Deepa, R, S , and Ramachandra, T,V, 1999, Impact of Urbanization in the Interconnectivity of Wetlands, Paper Presented at the National Symposium on Remote Sensing Applications for Natural Resources: Retrospective and Perspective (XIX-XXI 1999), Indian Society of Remote Sensing, Banglore.

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Euliss, N, H, 2004, Wetland and aquatic ecosystem studies, Wetland Science Program Northern Prairie Wildlife Research Center 8711 37th Street SE Jamestown, North Dakota 58401-7317. [email protected]. Ewel, K, C, 1991, Diversity in Wetlands, Evolutionary Trends in Plants 5, p90-92. Gren, I, M, Folke, C, Turner K, and Batemen, I, 1994, Primary and Secondary Values of Wetland Ecosystems, Environmental and Resource Economics 4, p55--74, Kluwer Academic Publishers. Printed in the Netherlands. Helgen, J, 2002, Methods for Evaluating Wetland Condition, Developing an Invertebrate Index of Biological Integrity for Wetlands, Office of Water, U.S. Environmental Protection Agency, Washington, DC. EPA-822-R-02-019. Johnston, C, A, 1991, 'Sediment and Nutrient Retention by Freshwater Wetlands, Effects on Surface. Lugo, A, E, Brown, S., Brinson, M, M, 1988, Forested wetlands in freshwater and salt-water environments, Limnology and Oceanography, 33, p 894–909. Matthews, E, Fong, I, 1987, Methane emission from natural wetlands, Global distribution area and environmental characteristics of sources, Global Biogeochemical Cycles 1, p 61–86. Mitsch, W, I, and Gosselink, I, G, 1986, Wetlands, Van Nostrand Reinhold, New York. Moundiotiya, C, Kulshreshtha, M, Bhatia, A,L , Sisodia, R,2005, Diversity of avifauna of Jamwa Ramgarh wetland of Rajasthan in India. J Environ. Biol. 2005 Jul; 26(3) p579-83. Norman, M, 1996, Environmental services of biodiversity, Proc. Natl. Acad. Sci. USA Vol. 93, p 2764-2769. Odum, E, P, 1989, Ecology and Our Endangered Life-Support Systems, Sinuaer Associates, Sunderland, Massachusetts. Prasad S, N, Ramachandra T,V, Ahalya, N, Sengupta, T, Kumar Alok ,Tiwari A, K,Vijayan V, S , and Vijayan, L,2002, Conservation of Wetlands of India, A Review Tropical Ecology, p 173-186. Robertson, AI, Duke, N, C, 1987, Mangroves as nursery sites: comparisons of the abundance and species composition of fish and crustaceans in mangroves and other near shore habitats in tropical Australia, Mar, Biol, 96, p193–205. Saenger, P, Hegerl E, J, and Davie, J, D, S, 1983, Global status of mangrove ecosystems, The Environmentalist, p1–88. Salim Ali Centre for Ornithology and Natural History (SACON), Deccan Regional Station, 12-13-588/B Nagarjuna Nagar Colony, Tarnaka, Secunderabad - 500 017 Andhra Pradesh, INDIA. Email: [email protected], [email protected] Sen, K, Sumit, 2009, Kolkata. E-mail: [email protected]. Williams, M, Ed, 1990, Wetlands, A Threatened Landscape, Basil Blackwell, and Oxford, UK.


Phytoplankton studies of Wular lake (Ramsar site) Jammu and Kashmir India Aijaz.R. Mir1 ; A. Wanganeo; A.R. Yousuf 2 and R. Wanganeo 3 1. Department of Limnology, Barkatullah University, Bhopal-462026 2. CORD, University of Kashmir, Srinagar-190006, Kashmir. 3. Department of Zoology, S.V. College, Bairagarh, Bhopal. Abstract The phytoplankton of Wular Lake was sampled from five stations from March 2002 to February 2004. All together 24 water samples were analysed with main emphasis on phytoplankton. A total of 100 species of phytoplankton were enumerated with Bacillariophyceae contributed 42 species, Chlorophyceae 43 species, Cyanophyceae 10 species, Euglenophyceae 3 species while, Dinophyceae and Chrysophyceae contributed 1 species each. The very high Nitrate and Phosphate concentration in the lake is the indication of pollution. Diversity values vary from (-0.66) – ( -0.53) site1, ( -0.59) - ( 0.27) site2 , (-0.57) – (-0.39) site3, ( -0.56) – (-0.46), site4, ( -0.45) – (-0.34) site5. Statistically positive correlation was found between phytoplankton counts and dissolved oxygen. While nitrate and phosphate showed the negative correlation (NO3-N = -0.34) and (PO4 –P = - 0.49). The shanon’s index indicates that the Wular Lake is eutrophic in nature. Key words: phytoplankton eutrophication Wular Lake: Introduction: No published record is available regarding the Wular lake so far due to the tumultuous conditions of the region nearly for about two decades so base line information is required due to the important geographical and ecological position and continuous changes in the lake. The lake has been declared as the wetland of national importance (1986) under wetland programme of Ministry of environment and forests Govt. of India and was designated as wetland of international importance under ramsar convention (1990). Wular lake located at 340 16/ N - 740 33/ E with present area of merely 2400 hac only as per recent records of revenue department jammu and Kashmir and is situated in Bandipur district of Jammu and Kashmir state. River Jhelum traverses through it and leaves at

865

866


Ningli Sopore. The recent investigations indicate lake area of 125 sqkms. Of which 61 sqkms are under willow plantation, 4 sqkms are under paddy cultivation and 1 sqkm under human inhabitation. This important international Ramsar site is under serious ecological threat, becoming shallower and shrinking day by day on account of siltation. The Catchment area is large, with the result accumulation of solid wastes and considerable part of its sediments entering the lake filling its basin, enrich its water and make it conducive for the growth of eutrophic aquatic weeds. The lake is wintering site for migratory birds, such as Common teal, Pintail, Shoveller and others. It is also the important habitat for fish and contributes 60% of the fish yield of Kashmir Valley. Presently large area of the lake enchoachments has resulted in converting vast catchment areas into agricultural land. Pollution from fertilizers, animal wastes and falling of untreated wastes into the lake had led to the deterioration of lake water and the siltation has resulted in the reduction of lake area with the mean depth not more than 3m.

Material and methods Five sites have been selected for the collection of ecological data. Site1 (Gurur) it represents the inlet of river Jhelum. The area is inhabited with the huge population lying close to the vicinity of the lake. Site 2 (Laharwal pur) lies at the distance of 8 kms from site1. The site lies close to the laharwalpur village. Site 3 (Ashtingoo) at the distance of 15 kms from site 2 and there occurs the huge agricultural intensification. Site 4 (Wutlab) lies close to the Shrine of Baba shakurdin. Site5 (Ningli) is surrounded by the huge population and represents the exit of river Jhelum from the lake lies at the distance of 10 kms from the site 4. Water samples were collected at each station in one litre polythene bottle for physicochemical analysis. Dissolved oxygen was assessed by wrinkler’s method, alkalinity and carbon dioxide was analyzed at the site, while the remaining parameters were analysed within 24 hours following the methods as given in (A.P.H.A 1998). For plankton analysis 1-5 litres of the lake water was sieved through the plankton net (mesh size 64µ). The filtered sample was preserved in 4% formaline. The samples were immediately brought to laboratory and were reduced to 15, 30 ml in the centrifuge. Enumeration of the plankton was done by taking 1 ml of the sub-sample in Sedgwick


rafter chamber and counting its entire contents to obtain the statistical accuracy. The results have been expressed as units / litre for phytoplankton (Wanganeo and Wanganeo 1991). Following works were consulted for identification: Heurck (1896), Smith (1950), Desikachary (1959), Randhawa (1959), Edmondson (1959), Ramanathan (1964), Philipose (1967). Species diversity indices was calculated using the Shannon formula: H/ = ∑s pi log 2 pi I=1 Where S is the number of species and pi is the proportion of the ith species in the sample (Odum 1971).

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Results: A total of 24 water samples were analyzed over two year study period. Table 1 showed the phytoplankton recorded in Wular lake during the investigation period. Table 2 depicted the mean depth of the sampling sites, while, Table 3 lists the phytoplankton species enumerated in the Wular lake along with their month of maximum occurrence and the number of times each algae was present (sampling situations).

Table 1. Classification of Phytoplankton recorded in Wular lake. Division

Bacillariophyta

Class

Bacillariophyceae

Order

Pennales

Family

Naviculoideae Amphiopleura pelicida Amphopra ovalis Astronella formosa Closteriopsis longisima Coconeis placentula Cyclotella sp Cymbella cistula C. tumida Diatoma elongatum D. vulgare Epethemia sorex E. turgida Eunotia sp Fragillaria crotonensis Frustulia rhomboides Gomphonema augur G. constrictum G. olevaceum

869

870


Hantzschia sp Leimophora sp Longissima elongatum Melosira granulata Meriodon circulare Navicula cuspidata N. formosa N. mutica N. oblonga N. obtusa N. radiosa N. smithi Nitzschia accicularis N. epiculata N. sigmoides Pennularia sp Pleurosigma angulatum Rhophalodia gibba Stauroneis anceps S. acuta Surirella biseriata S. robusta Synedra ulna Tabellaria sp. Division

Chlorophyta

Class

Chlorophyceae

Order

Volvocales

Family

Volvocaceae Volvox sp Pandorina sp Gonium pectorale


Order Family

Chlorococales Chlorellaceae Chlorella sp

Family

Coelastraceae Coalastrum microporum Goniochiloris mutica

Family

Hydrodictyaceae Hydrodictyon reticulatum Pediastrum biradiatum P.duplex P. muticum P.ovatum P. simplex P.tetras

Family

Scenedesmaceae Scenedesmus armatus S. bijugatus S. indicus S. obliques Tetraaedon trigonium T. incus

Family

Selenastraceae Dactylococus sp Dicellula germinata Selenastrum muticum S. gracile Kirchneriella sp.

Order

Ulotrichales

Family

Ulotrichaceae Ulothrix zonata

Order

Oedogonales

871

872


Family

Oedogoniaceae Oedogonium sp

Order

Cladophorales

Family

Cladophoraceae Cladophora sp Pithophora sp

Order

Chaetophorales

Family

Chaetophoraceae Stigeoclonium sp

Order

Zignamales

Family

Desmidiaceae Closterium acerosum Closterium gracile C. acutum C. monaliform C . probosideum Cosmarium ovale C.circulare C. gracile Eaustrum germinatum Mougetia sp Pleurotaenium trabeculae P. ehrenberii Spirogyra sp

Division

Charaphyta

Class

Charaphyceae

Order

Charales

Family

Characeae Scheroideria stigera

Division Class

Cyanophyta Cyanophyceae


Order

Oscillatorales

Family

Oscillatoraceae Oscillatoria limnetica O . princeps Lyngbya limnetica Phormedium sp Spirulina sp Anabaena sp Anabaenopsis sp

Order

Chroococales

family

Chroococaceae Merismopedia glauca

Order

Nostocales

family

Nostocaceae Nostoc sp

Order

Scytonematales

Family

Scytonemataceae Scytonema sp

Divisio

Euglenophyta

Order

Euglenales

Family

Euglenophyceae Euglena acus

Divisio

Dynophyta

Family

Dinophyceae Peridenium Sp

Family

Chrysophyceae Dinobryon sp

873

874


Table 2. Five sampling sites with their mean depths (m) S.No Station Mean depth 1 0.700417( m) Durur( where the river Jhelum enters the lake) 2 Laharwal pur 0.86625(m)

3 4 5

Ashtingoo Wutlab Ningli (where the river jhelum leaves the lake

0.840417(m) 0.303959(m) 1.7875(m)

and moves towards pakistan.

Table3. Monthly mean value of plankton collected during study period and their corrrsponding period of maximum occurance, their maximum percent of population (2002-2004).

Taxon Bacillariophyceae Amphiopleura pelicida Amphora ovalis Astronella formosa Closteriopsis longissima Coconeis placentula Cyclotella sp. Cymbella cistula Cymbella tumida Diatoma elongatum Diatoma vulgare Epithemia sorex Epithemia turgida Eunotia sp. Fragillaria crotonensis Frustullia rhomboides Gomphonema olevaceum Gomphonema constrictum Gomphonema augur Hantzchia sp. Leimophora sp. Longissima elongatum Melosira granulata Meriodon circulare Navicula cuspidata

Month of max occurance Jan - Feb / May Dec - feb/ Apr/ Jun Dec - Apr / Jun Dec - Feb/ Jun Dec - May Dec - Apr/ Jun Dec- Mar / Jun/ Nov Dec - Apr / Jun Jan - Apr / Jun Jan - Apr / Jun Dec - Apr / Jun Dec - Apr / Jun Jan - Apr / Jun Jan - Apr / Jun Dec - Feb / Jun Dec - Feb / Apr/ Jun/ Aug Dec - Feb / Apr/ Jun/ Aug Dec - Feb/ Jul Dec - Jun Dec - Feb / Jun Dec - Feb / Apr/ Jun Dec - Feb / Apr / Jun Dec - Feb / Jun Dec - Apr / Jun

Maximum % of population

sampling situations

1.05 0.84 1.04 0.99 0.99 0.86 0.79 0.89 0.96 0.95 0.77 0.92 0.90 0.84 0.99

22 32 24 21 22 21 30 35 21 22 36 34 20 23 22

0.72

29

0.94 1.17 0.87 0.99 0.84 0.87 1.10 0.92

31 29 22 28 21 18 20 34


Navicula formosa Navicula mutica Navicula oblonga Navicola obtusa Navicula radiosa Nitzschia sigmiodes Navicula smithi Nitzschia accicularis Nitzschia epiculata Penularia sp. Pleurosigma angulatum Rhophalodia gibba Surrirella robusta Stauroneis acuta Stauroneis anceps Surrirella bisseriata Synedra ulna Tabellaria sp.

875

Dec - Mar / Jun Dec - Feb / Apr/ Jun/ Sep Jan - Mar / May / Jun Jan - Mar / Jun Dec - Feb / Jul Dec - Mar / Jun Dec - Feb / Jun Dec - Mar / Jun Dec - Mar / Jun Dec - Apr / Jun Jan - mar / Jun Jan / Feb / Jun Jan - Feb Dec - Mar / Jun Dec - Mar / Jun / Nov Dec - feb / apr / Jun Dec - Feb / Jun Jan - Apr / Jun

0.94

32

0.87 0.87 0.89 1.00 1.00 0.87 0.90 0.95 0.77 0.94 1.02 1.07 0.79 0.95 1.02 1.12 1.04

30 28 21 33 20 25 22 28 33 21 22 20 23 24 25 21 21

May Ju - aug Ap - May / Oct Apr - May / Sep- Oct Apr - May / Sep Apr - May/ Oct May Apr - May/ Oct - Nov Feb/ May/ Sep - Nov May/ Sep - Oct Apr - May/ Sep- Oct Feb / Apr - May / Oct Jul - aug Jul - Aug Jul - Sep Aug - sep Jul - Aug Jul - Aug May - Aug Jul - Aug Jul - Aug Apr - May May / Sep May Mar - May Apr - Jun / Oct May/ Sep - Oct Aug Aug

0.94 1.15 1.02 0.94 1.00 1.00 0.21 0.97 0.86 0.91 0.87 0.86 1.04 1.25 1.09 1.36 1.09 1.12 1.25 1.32 0.99 0.90 0.79 1.13 1.04 0.81 1.02 1.40 0.53

30 14 19 22 21 20 7 23 29 28 27 23 9 14 14 6 10 11 29 13 12 26 24 25 25 22 25 12 8

Chlorophyceae Chlorella sp. Cladophora sp. Closterium acerosum Closterium acutum Closterium gracile Closterium monaliform Closterium probosideum Coelastrum microporum Cosmarium circulare Cosmarium gracile Cosmarium ovale Dactylococus sp. Dicellula germinatum Euastrum germinatum Gleocotheca sp. Goniochiloris mutica Gonium pectorale Hydrodictyon reticulatum Mougetia sp. Oedogonium sp. Pandorina sp. Pediastrum biradiatum Pediastrum duplex Pediastrum muticum Pediastrum ovatum Pediastrum simplex Pediastrum tetras Pithophora sp. Pleurotanium ehrenbergi

876


Pleurotanium trabeculae Scenedesmus armatus Scenedesmus bijugatus Scenedesmus indicus Scenedesmus obliques Scherioderia stigera Selenastrum gracile Selenastrum muticum Spirogyra sp. Stigeoclonium sp. Tetroedon incus Tetroedon trigonium Ulothrix zonata Volvox sp.

Aug Apr - May Apr - May Apr - May Apr - May May May Apr - May / Sep Oct / Dec / Jul - Aug Oct / Dec / Feb - May Jul Jun - Aug Mar/ May/ Jul - Aug Feb/ Apr - May / Oct

0.85 0.92 0.94 1.02 0.83 0.90 1.07 1.07 0.61 0.86 1.09 1.15 0.71 1.05

10 16 16 21 16 21 21 26 45 28 12 12 21 29

Aug Aug Jul - Aug Jul -Aug May - Aug Jul - aug Aug Jul - Aug Aug - Sep / Nov Jul - Sep

1.35 1.38 1.51 1.17 1.50 1.38 1.50 0.98 1.18 1.32

13 16 28 17 15 37 33 34 30 31

May Jan / May Feb - May

1.17 0.90 1.25

25 18 19

Dec - Jan

1.02

20

Jan - Feb / Apr

1.33

15

Cyanophyceae Anabaenopsis sp. Anabena sp. Lyngbya limnetica Merismopedia sp. Nostoc sp. Oscillatoria limnitica O princeps Phormedium sp. Scytonema sp. spirulina sp.

Euglenophyceae Euglena acus Phacus sp. Trachelomonas sp.

Dinophyceae Peridenium sp.

Chrysophyceae Dinobryon sp.

Bacillariophyceae contributed 42 sp, while as, the Chlorophyceae contributed 43 species. Total phytoplankton contribution at the five sites of the lake is represented in Fig 2. Fig.2 Total phytoplankton in Wular lake (2002-2004) 9000 8000

Site1

7000 Site2

Units/l

6000 5000

Site3

4000 3000

Site4

2000 1000

Site5

0 Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb


877

The phytoplankton density ranged from 3.2x 104 (site5) to 5.22x104 (site 4). The data showed that the majority of phytoplankton classes depicted unimodal seasonal peaks, Bacillariophyceae with winter peak ( Dec – Jan ) , Chlorophyceae with spring peak (March – May) and Cyanophyceae with summer peak (Jun – Aug) Fig 3 – 5.

7000

4000

Site3

3000 Site4

2000 1000

Se p O ct N ov D ec Ja n Fe b

Ju l Au g

M ar Ap r M ay Ju n

Fig.5. Unimodal summer peak of Cyanophyceae in Wular lake (20022004) 3500 3000

Site1

2500

Site2

2000

4000

Site2

3000

Site3

2000

Site4

1000

Site5

0 M ar Ap r M ay Ju n

Site5

0

Site1

5000

Site2

5000

U n it s /l

6000

Site1

Units/l

Units/l

6000

Fig.4. Unim odal spring peak of Chlorophyceae in Wular lake (2002-2004)

Ju l Au g Se p O ct N ov D ec Ja n Fe b

Fig.3. Unim odal Spring peak of bacillariphyyceae in Wular lake (2002-2004) 8000

Site3

1500

Site4

1000 500

Site5

0

Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb

The average cell count for the entire study period at all the five stations was 2.32x105 with each station having the mean standing crops : site1 (5.15x104 units/l) , site 2 (4.19 x 104) site3 ( 5.22 x 104) site4 ( 5.31x104) and site5 ( 3.27x104.). Based on the standing crop site 4 was recorded maximum standing crop, while site 5 recorded minimum standing crop of phytoplankton.

878


The seasonal variations in abundant species of the particular taxa are shown in Fig 6 –8. Fig.6. Seasonal variation of dominant bacillariophyceae in Wular lake (2002-2004)

800

Amphora ovalis

700

Cymbella cstula

600

Cymbella tumida Epethemia sorex

500

Epethemi turgida

400

G. constrictum N cuspidata

300

N. formosa

200

N mutica

100

N.radiosa Pennularia sp

0 mar Apr may Jun Jul Aug Sep Oct Nov Dec Jan Feb

U n it s /l

U n its /l

Fig.7. Seasonal variation of dominant chlorophyceae in Wular lake (2002-2004) Chlorella sp

900 800 700 600 500 400 300 200 100 0

C, circulare C, graclie C. ovale Mougetia Spirogyra Stogeoclonium mar Apr may Jun

Jul Aug Sep Oct Nov Dec Jan Feb

Fig.8. Seasonal variation of dominant cyanophyceae in Wular lake (2002-2004) 1400 1200

O limnetica

U n it s /l

1000

O.princeps

800 600

Phormedium

400 200

Scytonema

0 mar Apr may Jun

Jul Aug Sep Oct Nov Dec Jan Feb

The abundant diatoms include Amphora ovalis, Cymbella sp., Epethemia

sp.,

Gomphonema constrictum navicula sp., and Pennularia sp among diatoms, Chlorella sp., Cosmarium sp., Mougetia sp.,Spirogyra sp.,stegeoclonium sp., and Volvox sp., among chlorophyceae and Oscillatoria sp., Phormedium sp., and Scytonema sp., among cyanophyceae.

Volvox


Table 4. Shannon’s index of diversity in Wular lake (2002-2004). Index Month

Station1

Station2

Station3

Station4

Station5

March

-0.047

-0.0246

-0.0266

-0.0266

-0.0419

April

-0.058

-0.0345

-0.0326

-0.0409

-0.0395

May

-0.071

-0.0481

-0.0616

-0.0626

June

-0.0002 0.00004

-0.0005

-0.0005

-0.0105

-0.0005

July

-0.0001

-0.1934

-0.0243

-0.0294

-0.0007

August

-0.089

-0.0506

-0.0402

-0.0328

-0.0419

September

-0.0009

-0.0009

-0.0007

-0.0008

-0.0006

October

-0.0116

-0.0007

-0.0007

-0.0008

-0.0009

November

-0.0005

-0.0003

-0.0002

-0.0003

-0.0004

December

-0.0005

-0.0007

-0.0138

-0.0009

-0.0174

January

-0.026

-0.0534

-0.0555

-0.0511

-0.0047

February

-0.056

-0.0051

-0.0615

-0.0341

-0.0416

-0.02415

-0.0363

-0.0254

-0.0242

-0.0141

Avg.

Species diversity varied among the five sites with site 5 exhibiting the highest mean index (-0.0141), while on monthly basis lowest index was exhibited in June (-0.00004 site1), November (-0.0003 site2, site3, site4) and in August (-0.0419 site5) indicating that plankton density is inversely proportional to the Shanon’s index thereby revealing the pollution status of the water body so studied (Table 4). Discussion: Fresh water bodies in general record variations in their physico-chemical as well as the biological parameters. These parameters are responsible for the distribution of organisms in different water habitats according to their habitations which allow them to survive in that specific habitat. The results of the present study depicted the presence of diatoms and green algae and blue green algae though the diatoms and green algae were the dominant forms which is the characteristic of eutrophic conditions (Forsyth and McColl 1975). A remarkable feature is the very scanty representation of euglenophyceae, chrysophyceae and dinophyceae in the lake. The bacillariophtceae with winter peak depicted the negative correlation with water temperature (Table. 5) and the results are coinciding with

879

880


Raina (1980) and Wanganeo and Wanganeo (1991), who reported the abundance of diatoms in the weak light conditions. Table 5 . Pearson correlation

D,o Cal hard T, hard

Temp **0.88 **0.69 **0.50

D.o

Cal hard

T. hard

Sechi

pH

Contd

Nitrate

Phos

**0.80 **0.80

**0.87

**0.53

**0.49

**0.80 **0.34

**0.61 **0.49

**0.40

Sechi

**0.43

*0.21 **0.38

*-0.21

**-41

Depth

**0.41

Ns

**-0.88

**-87

**0.32

pH

**0.52

**0.74

Ns

Ns

Contd

(NS)

**0.64

Nitrate

**0.95

Phos bac

**0.85 **0.82

Ns **0.90 **0.68

Ns **0.68 **0.38 **0.53

**0.77

**0.67

Chl

**0.68

Cya

**0.77 **0.28

**-.53 **0.83 **0.28

Phyto

Depth

**0.86

**-0.60 **-0.71

*-0.17

**0.31 **0.85

**0.34

**0.23

**0.33 *-0.22

**-0.80

**0.52 **0.55

**0.42 **0.31

**0.23

**0.75

**-0.32

Ns

**0.26

Ns

*0.22

**0.38

Ns

Ns

** = significant at 1% * = significant at 5%

**0.31 **0.60 **0.50 **0.64 Ns **0.64 **0.42

Ns Ns Ns **0.59 *0.18 **0.25

N.s = non significant.

George, (1960) has reported the existence of diatom peak in winter in lentic waters at Delhi. Kant and Kachroo (1977) reported maximum development of diatoms in post autumn to winter in Dal lake Kashmir. Many others also have observed diatoms to be influenced by low temperatures (Zafar, 1967, Goldman et.al., 1968 and Wanganeo and Wanganeo 1991). In addition to that due to the less density of other plankton on account of incondicive environmental factors the diatoms take up more nutrients especially nitrate in weak light conditions owing to their development in winter season and hence depicted negative correlation with Nitrate. Phosphate also revealed the correlation with diatoms indicating its consumption to certain extent (Table 5), however Seenayya (1972) reported that the diatoms do not attain greater development in the polluted water. He further reported that even the higher concentration of nitrate and phosphate are not helpful in sustaining the rich diatom flora but the few species like Navicula cryptocephala, Nitzschia palea multiplied profusely in the polluted waters. In contrast Cymbella cymbiformis, Gomphonema gracile, Nitzschi amphibia and N.gracilis could be regarded


as the forms avoiding the pollution condition. Chlorophyceae depicted positive correlation with temperature, conductivity, Nitrate and phosphate as with the increase in water temperature due to the increase in solar intensity and due to the absence of macrophytic bloom in spring the chlorophyceae are able to absorb the nutrient easily especially the nitrate and phosphate and depicted the highly positive correlation with these nutrients (at 1% Table.5) so revealed the maximum population density in spring. The spring bloom of chlorophyceae was also recorded by Ulrich Sommer (1985). Furthermore there occurs increase in agricultural intensification in spring season (Marmay) which increases the nutrient input of lake and hence the population density of Chlorophyceae. The Chlorophyceae depicted the positive correlation with the water depth on account of shallow depth of lake the chlorophyceae are able to get nutrients readily (Table 5). However, during summer season the Cyanophyceae become the dominant one. The above results revealed that the Cyanophyceae are the thermophillic species as with the increase in the water temperature their population density gets increased. The results are coinciding with Mehmeet and Mustafa (2005). The Cyanophyceae also depicted positive correlation with Nitrate and phosphate (Table 5). The results are coinciding with Seenayya (1972), who reported the positive correlation of cyanophyceae with nitrate and phosphate and related the development of Cyanophyceae with the organic pollution. Over and above the Wular lake receives heavy load of domestic waste by means of river Jhelum which acts as the main feeding channel of the Wular Lake. However, the plankton population on the whole in the lake depicted the negative correlation with both the nutrients (phosphate =-0.49, Nitrate -0.34 at 1% level) as both these nutrients are taken up by the plankton on the whole. The results are coinciding with Nassar and hamid (2003). Taking into account of Shanon’s index value into consideration ( H = < 1 Table 4 ), it is clear that the lake is eutrophic in nature on account of high domestic load by means of river Jhelum which traverses through it and over and above due to the anthropogenic activities along the boundaries of the lake. Conclusion and recommendation: The shannon’s index revealed that the lake is eutrophic in nature and the results could be explained by prevailing the ecological conditions such as continuous flow of domestic load and discharge of agricultural and sewage waste as well as the human activities at the

881

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Wular lake. Our recommendation is to avoid discharge of sewage and the agricultural waste as well as the human activities in and around the Wular Lake.

Refrences : A.P.H.A. (1998):

Standard Methods for the examination of Water and Waste water. 20 Th Edition. American Public Health Assoc. Washington, D.C.

Desikacharya (1959): Cyanophyta, ICAR, New Delhi, 686 PP. D. J. Forsyth and R. H. S. McColl (1975): Limnology of lake Ngahewa, North Island, New Zealand. New Zealand Journal of Marine and Freshwater Research; 9 (3) : 311 – 332. Seenayya (1972) : Ecological studies in the plankton of certain fresh water ponds of Hyderabad India. Hydrobiologia ; 39 (247 – 270). George, M.G. (1960) : Comparative plankton ecology of five fish tanks in Delhi India. Hydrobiologia; 27 ( 1-2) : 81 – 108. Goldman, C.R. Gerletti, M. Javornicky, P. Meichiorri, S.U. Amezaga, E.D.(1968): Primary productivity, Bacteria, Phytoplankton and Zooplankton in lake Maggiore. Correlations and relationships with ecological factors. Mem. Ist. Ital. Idrobiol; 23 : 49 – 127. Heurek, H.V. (1896): A treatise on Diatomaceae. William Wisley and Son, Assex street, strand, W.C. Kant, S. kachroo, P. (1972) : Plankton Dyanamics and distribution of two adjoining lakes in srinagar. Macro flora and fauna in relation to phytoplankton. Proc. Nat.cacad. Sci. (India). 37 B (5) : 632 -645. Mehmeet Naaz and Mustafa Turkemen ( 2005) : Phytoplankton biomass and species composition of lake Golbolf (Haqtay – Turkey) Turk J . Bio; 29 : 49 -56. Nassar, M. Z and Hameed, M.A (2003) : Phytoplankton standing crop and species diversity in relation to some water characteristics of Suez Bay (Red sea) Egypt. Egyptian journal of aquatic biology and Fisheries; 7 (3): 25 -48. Odum, E.P. (1971) : Fundamentals of ecology. W.B. saunders, Philadelphia. 574pp. Philipose, M.T. (1967): Chlorococales, ICAR, New Delhi, 365 PP. Ramanathan, K.R. (1964): Ulotrichales, ICAR, New Delhi, 188 PP.


Randhawa, M.S. (1959): Zygnemaceae. ICAR Publ.PP. 91 – 437. New Delhi. Raina, R. (1981): Plankton dyanamics and hydrobiology of Bod –Sar Lake, Kashmir. phD. Theisis University of Kashmir. (Unpublished). Shannon weiner (1963). The mathehmatical theory communication. Univ.Illinois press, Urbana, USA. Smith, G.M. (1950): Fresh water algae of United states. McGraw – Hill Book Company, New York, Toronto, London. Ulrich Sommer (1985) : Seasonal succession of phytoplankton in lake Constance. Boisciences; Vol 35 No.6 : 351- 361. Wanganeo, A. and Wanganeo. (1991): Algal population of Kashmir Himalayas. Arch. Hydrobiol; 121 (2): 219 – 233. Zafar, A.R. (1967) : On the ecology of algae in certain fish ponds of Hyderabad, India III. The periodicity. Hydrobiol ; 13 (1) : 96 -112.

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Water quality assessment of lake water of Patna Bird Sanctuary with special reference to abiotic and biotic factors RAJEEV SHARMA1, AJAY CAPOOR1, RAKESH DAKSH1 AND MAHESH CHANDRA2 1 2

Ecotoxicology and Environmental Biology Lab., Deptt. of Zoology, Agra College, Agra Deptt. of Zoology, R.B.S. College, Agra

E-mail: [email protected]

ABSTRACT Study on limnobiotic status of the Patna Bird Sanctuary (PBS) water was made to assess the pot ability of water for all three seasons (winter, summer and rainy) of 2004 to 2005. PBS exhibits high alkalinity with pH ranging from 7.4 to 8.0, alkalinity from 131 to 428 mg/l, Phosphates from 0.02 to 0.11 mg/l and BOD from 18.00 to 44.07 mg/l. The population of zooplanktons varies with the change in climate of the PBS. The maximum population of Rotifers (1178 number/l) and Cladocers (851 number/l) were recorded in the month of May and June, respectively. However, Copepods and Ostracods were attained highest population (946 and 212 number/l, respectively) during the month of December. The observations revealed that the PBS water is inferior and not suitable for drinking purposes. The possible factors for its poor quality have been discussed. Key words: Physiochemical factors, Seasonal variation, Zooplankton, Patna Bird Sanctuary 1. INTRODUCTION The state government of Uttar Pradesh declared Patna as a full fledged Sanctuary in year 1990 by the special gazette notification (Ref. No. 2432/14-3-49/90 dated 22-12-1990). It tallies name from village Patna of Jalesar Tehsil in Etah district. It spread over an area of 108.86 hectare which is an important place for breeding of the birds. The accidental or infant mortality in aquatic and semi aquatic migratory birds, fish killing and the climination of desirable species as a result of oxygen depletion constitute a serious eutrophication problem in aquatic habitats of Patna Bird Sanctuary (PBS). Our knowledge on limnology of these lakes is quite meager. Therefore, the present investigation has been undertaken to investigate the physiochemical and biological factors of the lake for holding good population of fishes, and aquatic as well as semi aquatic migratory bird too.


887

2. MATERIALS AND METHODS Surface water samples were collected in clean polyethylene containers fortnightly from May 2004 to Jan 2005. The collected samples were brought to the laboratory for the estimation of various physiochemical parameters. The procedures were followed as per the suggestions of APHA, 1991. Temperature and pH were recorded on the same day at site. The dissolved oxygen was analyzed by using Winkler's modification method. On the other hand, potassium, chloride and phosphate were extracted by flame photometric method, argentometric method and stannous chloride method, respectively. However, the numerical estimation of zooplankton was done by using Sedgewick Rafter Cell. 3. RESULTS AND DISCUSSION The physiochemical study of PBS lake water revealed that the temperature varied from 17.10

0.087 to 26.06

0.096 ºC, pH from 7.46 0.043 to 7.86 0.096, DO from 6.05

5.056 to 482 0.876 mg/l and BOD from 15.2

0.175 to 44.04 0.026 mg/l (Table - 1). As

far as biotic factors (zooplanktons) were concerned, the maximum population (1178 number/l) of Rotifers was recorded in the month of May. However, the highest population (851 number/l) of Cladocers was found in the month of June. On the other hand, Copepods and Ostracods were attained maximum numbers (946 and 212 number/l, respectively) during the month of December (Table - 2). The recorded tropical ranges corroborated with other Indian lakes (Zingade 1981, Singh 2000, Shastri and Pendse 2001). The pH depicted alkaline nature varied between 7.46 to 7.83 mg/l. It recorded minimum in the month of January and maximum in the month of June. Alkaline nature of lake water in summer could be attributed to the increase of the photoperiod. The dissolved oxygen (DO) concentration fluctuated between 4.08 to 6.07 mg/l. The DO did not show any definite annual pattern but its higher concentration was recorded (482 0.876 mg/l) during winter and early monsoon. It showed an inverse correlation with water temperature which is in conformity with the findings of Bath and Kaur (1997). Biological Oxygen Demand (BOD) was ranged from 15.2 to 44.04 mg/l and the maximum value (44.04 mg/l) was recorded in rainy seasons, indicating contamination of organic wastes. The BOD is inversely correlated with DO, suggesting its consumption during aerobic degradation of organic wastes. The alkalinity fluctuated between 7.05 and 156.66 mg/l. The potassium was recorded from 1.06 – 3.01 mg/l, contributed to the hardness of water. The first three alkaline earth metals also depicted direct correlation with hardness of water. High concentration of chloride

888


(7.05 to 11.01 mg/l) in the PBS reflects the presence of high amount of organic pollutants (Jha and Verma 2000). Sharma et al. (1978) pointed out that chloride content also increase with the degree of eutrophication. Phosphate fluctuated between 0.02 and 0.10 mg/l. Its value is high because of continuous disposal of city sewage into the lake. The zooplanktons were represented by four groups namely Rotifera, Cladocera, Copepoda and Ostracoda (Table - 2). Rotifers contributed zooplankton richness in PBS accounting 52.38% followed by copepodes 26.5%. cladocerans 16.45% and ostracodans 4.67%. The rotifers and copepodes were found in the lake throughout the year, whereas cladocerans made their appearance in May, persisted up to November and disappeared in December. However, Ostracodes were remained in small number around the year. The annual range of zooplankton richness in PBS lake are higher than other lake as reported by Zutshi et al. (1980), Patil and Goudar (1985), Kaushik and Sharma (1994) and Patil and Karikal (2001). The present study depicted considerable variations in overall community structure within limonitic zooplanktons. Dominance of rotifers in the lake could be attributed to the continuous supply of food material, which in turn indicates eutrophic nature of the lake. The rate of eutrophication is increasingly and the necessary steps should be taken up to check the eutrophication of lake at Patna Bird Sanctuary. 4. REFERENCES APHA, 1991, Standard methods for examination of water and waste waters.16th Ed. American Public Health Association, Washington, USA. Bath, K.S. and Kaur, H. 1997, Crustacean population in relation to certain physico-chemical factors at Harike reservoir (Punjab), J. Environ. Ecoi, 15, p954-957. Jha, A.N. and Verma, P.K., 2000, Physico-chemical properties of drinking water in town area of Godda district under Santal Pargana (Bihar), India, Poll. Res., 19, p245-247. Kaushik, S. and Sharma, N. 1994, Physico-chemical characteristics and zooplankton population of a perenial tank, Matsya Sarowar, Gwalior, J. Environ. Ecoi, 1, p429434. Patil, C.S and Goudar, B.Y.M., 1985, Ecological study of fresh water zooplankton of a subtropical pond, Int. Revue. Ges. Hydrobiol., 70, p259-267.


889

Patil, H.S. and Karikal, S.M., 2001, Zooplankton diversity of Bhutnal water reservoir at Bijapur, Kamataka state. In: Water quality assessment and zooplankton diversity (Ed: B.K. Sharma), p236-249. Sharma, K.P., Goel, P.K. and Gopal, B., 1978, Limnological studies of polluted freshwater Physico-chemical characteristics, Int. J, Ecoi. Environ., 4, p89-105. Shastri, Y. and Pendse, D.C., 2001, Hydrobiological study of Dahikhuta reservoir, J. Environ. Biol., 22, p67-70. Singh, D.N., 2000, Seasonal variation of zooplankton in a tropical lake, Geobios., 27, p92100. Zingade, M.D., 1981, Base line water quality of river Narmada (Gujarat), Indian. J. Mar. Sci., 10, p161-198. Zutshi, D.P., Shukla B.A., Khan, M.A. and Wanganeo, A. 1980, Comparative limnology of nine lakes of Jammu and Kashmir Himalayas, Hydrobiologia, 80, p101-112.

890


Table 1. Seasonal variation in abiotic factors of lake water of Patna Birds Sanctuary (2004 - 2005)

Winter

Parameters December Water temp. (ºC)

17.10

0.087

Summer January

15.06

0.096

Rainy

May

June

August

September

25.10 0.148

33.06 0.096

26.06 0.096

24.10 0.096

pH

7.50 0.087

7.46 0.043

7.86 0.096

7.83 0.043

7.50 0.087

7.53 0.043

DO (mg/l)

6.05

5.056

6.07 0.043

380.33 1.332

482 0.876

148.33 0.499

150.33 0.499

BOD (mg/l)

15.2

0.175

18.04

39.01 8.764

44.04 0.026

40.72 0.508

38.02

0.017

Potassium (mg/l)

3.01

8.764

2.9

1.69 5.056

1.80

5.056

1.06

8.764

1.30

5.056

Chloride (mg/l)

7.06

8.764

10.04

8.764

9.02

8.764

11.01 8.764

7.05

8.764

8.08

8.764

Alkalinity (mg/l)

132.66 1.822

156.66 0.499

9.02

8.764

11.01 8.764

7.05

8.764

8.08

8.764

Phosphate (mg/l)

0.04 5.056

0.02 5.056

0.043 8.764

0.09 5.056

8.08 8.764

0.10 5.056

0.03 5.056


891

Table 2. Seasonal variations in the biotic factors (zooplankton’s unit number/l) in the lake water of Patna Birds Sanctuary (2004 - 05)

Winter

Zooplanktons

Summer

Rainy

December

January

May

June

August

September

Rotifera

989.00

884.00

1178.00

745.00

696.00

768.00

Cladocera

0.00

0.00

120.00

851.00

741.00

510.00

Cpepoda

946.00

726.00

348.00

102.00

456.00

526.00

Ostracoda

212.00

0.00

0.00

88.00

82.00

96.00

892


COMPARATIVE BATCH GROWTH KINETIC AND MORPHOLOGICAL STUDIES OF TRICHODERMA,ASPERGILLUS AND NEUROSPORA STRAINS UNDER SUBMERGED CULTIVATION Nitin Verma*, M.C.Bansal, Vivek Kumar Department of Paper Technology ,Indian Institute of Technology,Roorkee Saharanpur campus,Saharanpur,247001,India. *Corresponding author: [email protected]

Abstract The extent of solid waste production is of global concern and development of its bioenergy potential can combine issues such as pollution control and bioproduct development, simultaneously.The genus Trichoderma ,Aspergillus and Neurospora are the efficient producers and capable of synthesizing and secreting high levels of the cellulase complex enzymes.Cellulolytic enzymes are essential for the maintenance of the global carbon cycle ,since they initiate the degradation of cellulose, an almost inexhaustible raw materials is the most abundant and ubiquitous biopolymer on the earth.Fungal cellulases have proved to be a better candidate than other microbial cellulases, with their secreted free cellulases complexes comprising all three components of cellulases (endoglucanase, exoglucanase and β-glucosidase). Production of cellulases in large quantities by fungus requires the understanding the dynamics between growth and enzyme production. Trichoderma ,Aspergillus and Neurospora are highly useful in solid as well as liquid waste management.Morphological studies have been considered very important in fungal fermentation to correlate their growth and product formation rate. Morphology has a crucial effect on productivity and the supply of substrate for cultures of filamentous fungi.Therefore it is necessary to study the growth rate and pattern of these organisms.In the present comparative study we investigate the cell biomass growth in terms of cell dry weight (g/l) of Trichoderma reesei, Aspergillus niger and Neurospora crassa.Batch experiments were performed with T.reesei,A niger on a potato dextrose broth (PDB) and N.crassa on M2 cultivation medium at 300C and 180 rpm. Trichoderma reesei, Aspergillus niger and Neurospora crassa showed filamentous mycelial, pelleted and pulpy type of growth morphology respectively. The maximum cell dry weight attained by microbes in PDB medium was also investigated.This kinetic study may be helpful in knowing the growth rate, growth characteristic and the growth pattern of individual microorganisms for better industrial and environmental applications. Key Words : Trichoderma, Aspergillus , Neurospora, Cell dry weight, Cellulases 1.INTRODUCTION: Trichoderma, Aspergillus and Neurospora plays a vital and significant role environmental sectors.Trichoderma, Aspergillus and Neurospora have also been used in a wide range of commercial enzyme productions, namely, cellulases, hemicellulases, proteases, and β-1,3glucanase. The ability of fungi to secrete large amounts of proteins and the ability to invade substrate has motivated their extensive use for the production of industrial enzymes(Seidle and Huber 2005) .The genus Aspergillus is one of the most important filamentous fungal genera. Aspergillus species are used in the fermentation industry(Perrone et al. 2007). Aspergillus sp are known to be a good producers of β-glucosidase.Intensive agitation altered the morphology of Aspergillus strain and reduced β-glucosidase activity(Ong et al. 2004). Neurospora crassa (the common pink, red bread mould and mesophilic fungus) is a filamentous ascomycete and true cellulolytic producer, secrete high levels of all the three enzymes components involved in the cellulose degradation(Perkins and Davis 2000). Neurospora crassa was recently reported to produced high yields of CMCase and βglucosidase when grow in solid substrate(Macris et al.1989) . Cellulose is the world’s most abundant natural biopolymer and potentially important source for the production of industrially useful materials such as biofuels and chemicals (Li et al. 2005).Degradation of the cellulosic materials is achieved enzymatically by the action of cellulases(Rakshit and Sahai 1991). Cost of production and low yields of these enzyme are the major obstacles for industrial applications(Lo et al. 2005).Complete cellulase


systems can be produced by a large diversity of microorganisms. The best characterized and most widely studied organism for cellulase systems are the fungus Trichodermma reesei and Aspergillus niger .Cellulase produced by filamentous fungus have a high industrial interest. Therefore it is necessary to study the growth rate and their morphological pattern of cellulase producing fungus. The objective of this paper is to study the growth rate and pattern of Trichoderma, Aspergillus & Neurospora crassa on PDB and M2 medium respectively.

2.BACKGROUND INFORMATION: Due to the filamentous and non homogenous nature of the growth of moulds, the analysis of the growth characteristic and the growth curve is difficult. Although determining the rate of colony extension will provide us with the measure of fungal growth but it will not necessarily be equivalent to the increase in the biomass of the fungus because hyphae will be growing down and through the agar medium as well as across its surface. Due to this it is better to estimate growth (cell biomass) in terms of cell dry weight for fungal systems(W1).During the growth and development of Trichoderma reesei cells, several morphological and physiological changes takes place. These changes (long hyphae appearance, sporulation etc) influence cellulase production and need to be taken into consideration of batch model (Velkovaska et al.1997).A new two phase kinetic model including exponential and logistic models was applied to simulate the growth rate of fungi at various temperatures. The model can describe the whole growth curve including the lag phase and the cessation of growth in the latter stages of the cultivation with an adequate approximation (Hamidi- Esfahni et al.2007). The fungal morphological forms varies from mycelial pulpy to pellets structure. The filamentous growth characteristic creates a number of process engineering problems attributed to the morphological change accounted during the fermentation process in large scales. Rheology–morphology relationships are particular relevant in fermentations involving filamentous fungi and bacteria. Excessive hydrodynamic shear stresses are known to damage mycelial hyphae and form pellets. In such fermentations, the mass transfer of oxygen and nutrients is considerably better and the subsequent separation of the pellets from the medium is simpler. Since agitation and aeration is also much easier in such a system, the power input therefore the operating cost is lower(Kelly et al.2004)(Karns et al.1995)( Domingues et al.2004). In more intensely agitated stirred tanks (≥600 rpm; impeller tip speed of ≥2.03 m s−1), the stable pellet size was only about ≤900 µm. The biomass concentration and the pellet diameter were the main factors that influenced the flow index and the consistency index of the power-law broths (Parcel et al.2005).

3.MATERIALS AND METHODS: Trichodema reesei, Aspergillus niger and Neurospora crassa NCIM 1021 strains were procured from National Chemical Laboratory (NCL),Pune. Fungal spores from a stock, kept at 40 C in 20% (v/v) glycerol. Trichoderma and Aspergillus cultures were grown on potato dextrose agar (PDA) slants at 280 C for 4-5 days whereas Neurospora crassa was grown on M2 agar media containing slants. Slants were maintained at 40C and subcultured about monthly intervals. For the study of growth rate and morphology of cellulase producing cultures, two separate sets of experiments have been performed with each culture. First set of experiments have been carried out in a 250 ml Erlenmeyer flasks containing 150 ml of Potato Dextrose broth (PDB) (In g/l Peeled Potato,200;Dextrose,20; and Yeast extract,0.1) and M2 agar medium in which 5 loopfull cultures of fungal spores or mycelial conidia are added and shaken at 180 rpm at 300 C in an incubator shaker for 3-4 days (Domingues et al.2004) . While other sets of batch experiments were carried out in 250 ml Erlenmeyer flasks(total 16 flasks) containing 50 ml of PDB for Trichoderma reesei and Aspergillus niger and M2 media for Neurospora crassa .A definite volume of earlier prepared cultures in PDB or M2 broth suspension (containing 0.56 g/l cell dry weight) were added to each flasks containing their respective culture media. Samples ( As whole flask containing 50 ml, due to nonuniform nature of growth in fungal system) were taken at every 6 hr intervals till 84 hr .

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3.1Dry Cell Weight Determination: Samples of 50 ml were filtered on a dried and preweighted whatman no-1 filter paper and washed thoroughly with cold distilled water and 50 ml of 0.9% NaCl (saline) Solution. The filter with mycelium was than dried for 24 h at 1050 C and weighted. The determination of growth by dry weight were expressed as the mean of 3 independent readings.

4.RESULTS AND DISCUSSIONS: For the morphological and the growth kinetic studies

separate sets of batch experiments have been performed at 300C and 180 rpm. From the above experimental observations we found that Trichodermma reesei showed, growth with yellowish small filamentous mycelium (with branched active, inactive hyphae and hyphal tips) type of morphology, whereas Aspergillus niger grown in pellatized form of morphology. On the other hand Neurospora showed thick mycelial pulpy nature of growth.

1 2 3 Photograph:1.,2.,3. Growth of Trichoderma reesei , Aspergillus niger in Potato Dextrose Broth (PDB) media and Neurospora crassa NCIM1021 in M2 media at 300C and 180 rpm respectively. Photograph 1,2 and 3 showed the growth nature and morphological pattern of Trichoderma reesei ,Aspergillus niger and Neurospora crassa respectively. This morphological information might be helpful in knowing the mass scale production of these organisms and also on cellulase formation capability of these organisms. For the kinetic studies of cellulase producing organisms separate sets of batch experiments have been performed. Table 1: Cell dry weight (g/l) of Trichoderma reesei, Aspergillus niger in PDB and Neurospora crassa in M2 medium respectively. Time(hr)

0 6 12 18 24 30 36 42 48 54 60 66 72 78 84 90 96

Biomass in terms of cell dry weight(g/l) Trichoderma reesei

Aspergillus niger

Neurospora crassa

0.56 4.20 5.40 5.54 8.04 8.54 9.42 10.36 10.60 11.42 12.88 12.64 11.30 11.68 11.02 9.72 9.45

0.56 0.87 1.68 2.02 2.52 3.86 5.12 6.64 7.78 8.50 8.94 9.60 9.94 11.26 10.91 9.42 9.35

0.56 0.66 4.34 5.82 7.04 7.12 7.42 7.66 8.16 8.86 8.42 8.16 7.02 6.92 6.76 6.55 6.12


As the literature reported that the filamentous growth characteristic creates a number of process engineering problems attributed to the morphological change accounted during the fermentation process in large scales(Hermersdorfer et al 1988).Due to the thick and pulpy nature of growth morphology organisms suffers mass ,heat and O2 transfer limitation which might be affects the overall productivity of the product produced by fermentation using Neurospora crassa ,whereas in palletized forms heat transfer and mass transfer of nutrients and Oxygen is considerably better than other morphological forms(Parcel et al.2005) . It is evident from Table 1. and Figure 1. that lag phase observed upto 6 hr in case of Aspergillus niger and Neurospora crassa whereas for Trichoderma very short lag phase has been observed (approx 2-3 hr).As in the lag phase microbes acclimate to food and nutrients in their new habitat. The longer and stable lag phase in Neurospora crassa shows that this microbes takes much more time for reaching their active state .In Trichoderma after 2 hr a steep rise in the growth was observed till 24 hr and the exponential or lag phase( as in this phase substrate conversion and cell mass reached to their maximum values) was also started whereas in Aspergillus niger growth no sharp increment found only steady increment has been observed up to 70 hr, which indicates that growth rate was much slower in case of Aspergillus niger. In case of Neurospora crassa, growth was sharply increased till 12 hr(exponential phase )afterwards they showed steady increment with the progress of fermentation time upto 48 hr.

Figure 1:Batch growth kinetic curve of Trichoderma ,Aspergillus in PDB medium and Neurospora in M2 media at 180 rpm and 300C. The maximum cell dry weight (g/l) attained by Trichoderma , Aspergillus and Neurospora were 12.88,11.26,8.86 at 60h,78h and 54h respectively ,which indicates the growth and growth rate both was much faster in case of Trichoderma, afterthat there was no significant increment in cell biomass in each microbes probably due to the depletion of nutrients and carbon source in the media therefore booming growth stops.

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Figure 2: Comparative growth of Trichoderma ,Aspergillus and Neurospora in their respective culture media at 180 rpm and 300C . Whereas in case of Trichoderma slight increment in growth(11.30 g/l) has been observed during fermentation period between 72 h to 78h, this might be due to the formation of secondary mycelium. Secondary mycelia having much growing hyphal tips and has much more tendency for protein synthesis and enzyme production. After this time period cell growth was moves towards stationary and death phase .As in death phase toxic waste products build up, food is depleted and the microbes begin to die.It has been inferred from Table 1. and Figure 1. that the growth and rate both was much faster in case of Trichoderma and slower in case of Aspergillus niger whereas Neurospora crassa grown with faster growth rate. Figure 2. represents the comparative growth studies of Trichoderma ,Aspergillus in PDB and Neurospora in M2 medium respectively at every 6 h intervals.

5.CONCLUSION: The morphological pattern attained by the Trichoderma, Aspergillus and Neurospora in their respective cultures medium, might be helpful in knowing the growth patterns of microbes which ultimately beneficial for their mass scale production. The growth kinetic studies is also useful for gathering the important information about the microbes such as growth rate and maximum growth in terms of cell dry weight, which gives the detailed information about the nature of microbial growth .This useful information may be helpful in the industrial and environmental application of these industrial strains.

6.REFRENCES: Domingues, F C,Queiroz, J.A, Cabral, J.M.S, Fonseca, L.P,2004,The influence of culture conditions on mycelial structure and cellulase production by Trichodermma reesei RUT C-30 ,Enzyme & Microbial Technology ,26,p394-401. Hamidi- Esfahni, Z, Hejazi, P, Abbas-Shojaosadati, S,Hoogschagen, M,Vasheghani –Farahani, E & Rinzema, A,2007, A two kinetic model for fungal growth in solid state cultivation,Biochemical Engineering Journal.,36,p100-107. Hermersdorfer, H , Leuchetenberger, A , Wardsock, CH & Ruttloff ,H,1988,Influence of culture conditions on mycelial structure and polygalacturanase synthesis of Aspergillus niger,J. Basic Microbiol,27,p3409-315.


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Karns, G,Dalchow, E, Klappacha, G & Meyer, D,1995,Formation and release of βglucosidase by Aspergillus Highzinet 43746 in correlation to process operations .Acta Biotechnology,6, p355-359 Kelly,S,Grimmer, LH, Herysther, J, Schultheis, E ,Krull, R & Hempel, DC,2004, Agitation effects on submerged growth and product formation of Aspergillus niger.Bioprocess and Biosystem Engineering,26,p315-323. Li, X.L , Dien, B.S., Cotta, M.A., Wu, Y.V. & Saha, B.C,2005,Profiles of enzyme production by Trichodermma reesei grown on corn fiber fractions, Applied Biochemistry & Biotechnology,121124,p321-333. Lo, CM., Zhang, Q, Lee ,P & Ju, LK,2005,Cellulase production by Trichodermma reesei using saw dust hydrolysate,Applied Biochemistry & Biotechnology,121-124, p561-572. Macris, BJ, Kekos, D & Evangelidou, X,1989,Simple and inexpensive method for cellulase and βglucosidase production by Neurospora crassa .Applied Microbiology & Biotechnology,31,p150-151. Ong, LGA ,Aziz, SA ,Narini, S,Karim, MIA & Hassan, MA,2004,Enzyme production and profile by Aspergillus niger during solid substrate fermentation using palm kernal cake as substrate ,Applied Biochemistry & Biotechnology ,118,p73-79. Parcel, EMR, Lopez, JLC, Perez ,JAS, Sevila, JMF & Christi, R,2005,Effects of pellet morphology on broth rheology in fermentations of Aspergillus terreus.Biochemical Engineering Journal, 26 ,p139-144. Perkins, D & Davis,R,2000,Evidence for safety of Neurospora species for academic and commercial uses ,Applied Environment & Microbiology,66,p5107-5109. Perrone, G, Susca, A, Cozzi, G, Ehrlich, K, Varga, J, Frisvad, JC, Meijer, M, Noonim ,P, Mahakarnchanakul, W & Samson, R A,2007,Biodiversity of Aspergillus species in some important agricultural products,Studies in Mycology ,59,p53-66. Rakshit, S.K.& Sahai, V,1991,Optimal control strategy for the enhanced production of cellulase enzyme using the new mutant Trichodermma reesei E-12,Bioprocess Engineering,6 ,p101-107. Seidle, HF & Huber,RE,2005,Transglucosidic reactions of the Aspergillus niger family 3 βglucosidae qualitative and quantitative analyses and evidence that the transglucosidic rates is independent of pH. Archives of Biochemistry and Biophysics 436,p254-264. Velkovska, S, Marten, MR & Ollis, D F,1997,Kinetic model for batch cellulase production by Trichodermma reesei RUT C-30,ournal of Biotechnology,54,p83-94.

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Survey of Local Communities for Conservation of Miankaleh Wetland in Mazandaran Province Reza Tamartash 1,Mohammadreza Tatian 2, Maedeh Yousefian3 ,Sarah Sadat Amjadi Zanjani 4 1 Faculty Member of Sari Agricultural Sciences and Natural Resources University. Ph.D. Student of Natural Resources Science and Research Campus, Islamic Azad University of Tehran, 2, 3B.Sc. Student of Natural Resources, Sari Agricultural Sciences and Natural Resources University,4 B.Sc. Student of sana institute, sari

ABSTRACT One of the best ways for environment conservation is local community’s enrichment. Use of native people lead to sustainable development and conservation of natural ecosystem. Due to important of Miankaleh wetland ecosystem conservation, this area was selected in Mazandaran province of Iran. In this research, initially, study of finished projects about participation and enrichment carried out by field method in Miankaleh area. Then, data were collected with questionnaire quantitatively and finally analysis was done by Excel software. The result showed that performance of these projects, after two years, Has increased cause to ability of hunters, fishers and other marginal groups in these area. These projects lead to identification of problems, Grow up of hunters and fishers public knowledge actively participation of local communities in hunt and fishery management and conservation of Miankaleh Biodiversity. Key words: Miankaleh, diversity, local communities, Mazandaran

INTRODUCTION Nowadays, human has destroyed many of vegetation and animal in the entire of the world. Some of them can’t go back to the ecosystem cycle. Therefore, preservation of overthrow of them is necessary. For natural ecosystem conversation improve of knowledge in utilizers around it is needfull (2). This survety was a project for biodiversity conservation through community participation and management of sustainable hunting and fishing in two villages of Zaghmarz and Qareh-Tappeh. . The main objective of this project was to develop and implement a sustainable management plan based on the awareness raising for the local community. The coordination and cooperation between the governmental sectors and the local community will be enhanced for the sustainability of the project. The aim was to develop a successful model to be extended into the immediate Miankaleh Protection Area and possibly upcoming future national and international projects. Also the grantee will lobby for a loan from the Ministry of Agricultural Jihad to the local community. . The project will seek alternative livelihood methods as well. Finally, English and Farsi guide booklets will be produced on participatory management methods for drawing sustainable fishing and hunting plans by the community. The lessons learned will be documented as a report and a film in English and Farsi.

MATERIAL AND METHOD Study Area The study site is located in north of Iran. The Location in this region is between 36◦45' 30" --36◦49' 10"latitude and, 53◦40' 28"- 54◦ 1 ' longitude (Figure 1). The mean annual precipitation is 700 mm. The mean annual temperature in this area is i6.7oC and its climate is moderate. The elevation range is - 27 m a.s.l(3). mainly Vegetation is formed by punica, Ramnus, juncus (1).


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Figure1: The geographical position of Miankaleh in Iran (5).

RESEARCH METHOD

In this research, First, The data were collected with questionnaire quantitatively and then analysis was done by Excel software.

Results The sensitivity of local people mainly youths to environmental values of Miankaleh wetland. And Project team organized an environmental drawing contest among seven local schools. The methodology of community participation for local conservation of natural resources and the possibility of generating income through environmental friendly alternative livelihoods by the local community. (Figure2). . .

service 28% pollution 22%

port 39%

agriculture 11 11%

Other 33%

Figur2: alternative livelihoods with a view to local communities

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This was accomplished by conducting 52 weekly & biweekly meetings and workshops on the project site. Participants identified and prioritized twenty-eight environmental issues regarding Miankaleh ecosystem. Locals formed working groups to follow up the eco-tourist initiative as their first priority to reduce the pressure on environmental resources and follow up an economic activity.

labory 13% hunting 17%

Agriculture 47%

fishery 23%

Figure3: Income resource of local communities

percent

Fifty locals from surrounding communities participated in the first scientific tour for identification of endangered bird species.27 locals received certificates from Provincial Department of Environment for successfully completing short courses on identifying fourteen endangered bird species and environmental regulations. 50 45 40 35 30 25 20 15 10 5 0 population

building

increase of gun

population

unsafety

Factors

Figure4: The effective factors on reduction of hunting with a view to local communities Department of Environment issued the first official Environment Ranger Volunteer’s identification card in the name of a local activist of a newly formed NGO, House of Nature of Zaghmarze. Locals


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conducted independent workshops. Income Generation First ever-fishing tournament was organized on a local water reservoir. 60 50

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40 30 20 10 0 salinity

over prey

water polution

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Figure5: The effective factors on reduction of prey (fish) with a view to local communities

livelihoodrecreation 14%

recreation 27% livlihood 59%

Figur6: Goal of hunting with a view to local communities DISCOSION AND CONCLUSION Young literate women became active in project meetings and activities and started viewing the project as an opportunity for a healthy and respectful social engagement. As a result one local woman became elected as Member of Board of Directors of a newly established NGO. Documenting & sharing experiences School children’s drawings became a booklet with co funding of HSBC as a best awareness-raising document on Miankaleh ecosystem produced by locals. A film documenting project’s process and a brochure on endangered birds was produced (6, 7). Sustainability: Three local NGO’s were formed Local people kept the project’s local office open for their regular gatherings by searching for local resources.

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REFRENCES 1- Ahmadi, M.Z. & N.Safaian. (1995): A study of the relationship between watertable and salinity of soil and water with plant communities in Miankaleh region. –Research Report submitted to the University of Mazandaran. pp.20 2- Akhani, H. (1998): Plant Biodiversity of Golestan National Park, Iran. – Ph.D.Thesis, University of Munchen. 400p.. 3- Firouz, E. (2000): A Guide to the Fauna of Iran. – Iran University Press, 491p.inPersian.. 4- Kovach, W. (1985-2002): Institute of Earth Studies, – University college of Wales, ABERYSTWYTH, (Shareware)-MVSP Version 3.2, 1985-2002 Kovach Computing Services - http://www.kovcomp.com/MVPs/downl2.html. 5- Roo-Zielinska, E. (1996): Phytoindicative role of plant communities in a rural landscape. – Journal of Fragmenta et Geobotanica, 41:1,379-398. 6-] Safaian, N. & M. Shokri (1997): An introduction on one of Caspian sea BiosphereReserve. 2nd Congress of the Union of the Caspian Sea Region Universities.Gorgan. Iran. pp. 16 7- Shokri, M. & N. Safaian (1995): Ecological study of Biosphere Reserve“Miankaleh” in Iran. – 5th International Rangeland Congress, Salt Lake City, Utah,USA, p: 5


SUSTAINABLE ENVIRONMENTAND LIVELIHOOD IMPROVEMENT THROUGH RESTORATION AND CONSERVATION OF WATERBODIES –CASE STUDY A.Deivalatha* Dr. N.K.Ambujam** Dr.K.Karunakaran *** *

Senior Research fellow, Centre for Water Resources, Anna University, Chennai - 600025 ** Professor, Centre for Water Resources, Anna University, Chennai - 600025 ****Director, Centre for Water Resources, Anna University, Chennai – 600025

Management of Water bodies is not only increases storage capacity also protects and conserves the environment and also contributes to livelihood improvement. Water bodies are a profitable technology in economic, environment and social terms; under present conditions, management of water bodies deteriorating rapidly. Extent as well as reliability of this technology is decreasing. Degradation of water bodies and the environment is a common to some degree throughout the world, spanning different economic and political systems, and touching both rich and poor countries. It leads to loss of biodiversity that is a reduction in the variety of plant and animal species. However the loss of biodiversity itself can be considered a form of environmental degradation. In India, Many of the water bodies has been suffer the problems of siltation, decreases storage capacity and further reduces water flow, crop yields decline as soil fertility and moisture retention declines and some of the water bodies are used for dumping site of solid waste and garbage and also some of them are encroached by common utilities. In general, sustainable environment and

livelihood improvement requires better

performance of water bodies, which needs restoration and proper maintenance after the restoration of water bodies through people participation. This study is to develop a framework for assessing the economical and social issues of Water bodies’ and to assess the impact of Sustainable environment by restoration of Water bodies. It is useful to sustainability of environment and improvement of livelihoods and also improving effectiveness and efficiency of water bodies.

Key Words: Restoration, Degradation, Framework, Water bodies, Biodiversity, Environment

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INTRODUCTION General Tanks in the Indian context are inextricably linked to the socio-cultural aspects of rural life and have historically been an indispensable part of the village habitat, sustaining its socio-ecological balance. Tank systems, developed ingeniously and maintained over the centuries, have provided insulation from recurring droughts, floods, vagaries of the monsoon, and offered the much needed livelihood security to the poor living in fragile semi-arid regions. Conserving the tank eco-systems for multiple uses such as irrigation, domestic and livestock use and groundwater recharge is a way to provide a safety net to protect the livelihood of millions in a semi-arid India. (Sakthivadivel, 2004). These tanks have many special features. Tank Irrigation Surface structures or formations collecting and storing rainwater, runoff and seepage from the surrounding areas are known as tanks or ponds. Over the centuries, locally built water storage systems (e.g, tanks in South India, Johads in Rajasthan), have acted as insulation against droughts, helped in recharging groundwater, provided crucial irrigation for crop production, functioned as a source of multiple uses for the village community (drinking water, washing, bathing, water for livestock and wildlife, fishing, water for cultural and ritual purposes), and played a role in the maintenance of a good natural environment. Because of these benefits, the Indian kings, Jagirdars, religious bodies and philanthropists built a large number of tanks all over their domains (Tushaar shah and Vengama raju k, 1999). These rainwater-harvesting structures in various forms were known by different names in different parts of the country, e.g., kere in Karnataka, cheruvu in Andhra Pradesh, erie in Tamil Nadu, johad and bund in Rajasthan, ahar and pyne in Bihar.Tanks were meant not only for agriculture, but also served as a resourcebase for many other activities such as the collection of fodder, fuel, the making of bricks, pots, baskets, etc, with women offering their assistance in these processes. Tanks were also part of the socio-religious and economic system in villages. The location of the tank and its physical conditions were a matter of much significance to the people, particularly women, in carrying out their economic activities. The tank and its surroundings used to be the common property of the village and its people.The maintenance of natural resources through a continuous process of use and conservation meant not merely the assurance of livelihoods to the people of the village, but also the preservation of the ecological balance (Vaidyanathan, A, (2001). While the given social framework might have restricted women’s participation in community matters, their role in the conservation and maintenance of natural resources was implicitly acknowledged. The integral role of the tank in the livelihood of a village community is also clear from the fact that in the past the village functionaries received land grants (inam) in the tank's command area, in return for their services.


OBJECTIVES

¾ To develop a framework for improving sustainable development and livelihood improvement by restoration and conservation of irrigation tanks METHODOLOGY Study Area This Study was carried out in Avalur tank, located at Southern side of river Palar, Kancheepuram Block and Puliambakkam tank located on northern side of river Palar, Walajabad block, Kanchipuram district, in the state of Tamil nadu, India and also some tanks are taken from the some literatures. Avalur tank is located 40 km from Chennai and Puliambakkam tank is located around 42 Km from Chennai (Capital of Tamilnadu). Sociological survey: The prepared questionnaire comprises a) Respondent profile, farm extent, location, assets, income and cropping pattern, educational standards and experience of water distribution, village level organization and awareness of rehabilitation programme. b) General awareness of water user association c) Household profile, credit facilities and social participation. d) Tank problems Opinion surveys. An unofficial survey was done to find out the reaction, their participation and involvement in the programme, constraints and suggestions. Focus group discussion was carried out with the community members and observed information was thoroughly triangulated with relevant literatures in both the study areas. Most of the discussions and surveys focussed more on their perspective. FRAMEWORK OF DECISION MAKING WITH MULTI STAKE HOLDER FOR TANK RESTORATION There are many stakeholders in the tank and tank related programs, of which the government agencies, farmers and technologists are important. The government officials, institutions and farmers should be invited for the meeting to listen to each other’s views on the tank systems. The meeting should focus on the status of tanks, tank fed agriculture, tank improvement, tank administration and encroachment. Based on the aspects enabling solution was to be decided. Perspectives of technologist are important one which should get integrated in the decision making to increase farm productivity.

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Recent technologies have been used to improve the tank irrigation and also they have been used for maximizing tank productivity, ground water recharge and other tank services. Micro-irrigation encompasses drip and sprinkler technologies. Our framework considers the three key areas as equally important. Figure 1, shows the relationship among three key network of active stake holders (the technologist, the government and the farmers), as well as three objectives to be achieved (social equity, economic efficiency and environmental sustainability).The integration of these stakeholder in decision making is very important for achieving all the three objectives.

The Tank irrigation is mainly used to surface irrigate by gravity and to recharging surrounding areas in order to increase the water productivity and net returns to the farmers. Different Stake holders are involved in tank irrigation, so that any decision about tank renovation program should be taken after consultation among different stakeholders. Encroachments and siltation in water spread areas and the supply channels, catchments degradation, deterioration of the traditional irrigation institutions, improper water management at farm level are some of the major problems confront tank irrigation in the State.

Restoration program is carried out before understanding the general characteristics about tank system and perspectives of farmers, technologist and the Government. Any restoration program must start with identifying the problems of tank irrigation through perspectives of farmers, improvement of the tank water productivity, ground water recharge and other tank support services which should be collaborated by the perspectives of technologist and finally the government should allocate funds not only for infrastructure development but also for institution building and awareness programs. Integration of stake holder (Government, farmers and technologist) in decision making for rehabilitation /restoration/ renovation, modernization and desilting etc is very important for achieving long term sustainability. Lacking of any one of the stake holder participation, in decision-making may lead to immediate short-term benefit, but it will lead to long term un sustainability. Restoration of irrigation tanks not only increases


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storage capacity also protects and conserves the environment and contributes to village livelihood security. Multi stake Holder Decision making for Restoration of tanks

Farmer

Technologist

Maximising Tank water Productivity

Techniques of groundwater recharge

Change in surface water storages, Changes in ground water table (i.e. water table rise) Improvement in Bio -mass

Government

Status of tanks and its Improvement needed

Past uses of tanks Tank restoration and its need

Cattle production, changes in housing facilities, changes in farms and house hold assets, growth of social institution, Changes in farm and non farm activities and changes in migration pattern

Awareness Training

Cause

Performanc e Support Performanc e evaluation

Productivity (yield) of land, value of land and livestock holding, family income and Employment Effect

Social Development Economic wellbeing Environmental sustainability

Causes Effect

Figure .1- Multi-stake holder decision making Framework for tank restoration

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CASE STUDY IMPROVED PRODUCTIVITY OF WATER BEFORE AND AFTER TANK RESTORATION IN VENGAL VILLAGE The Vengal village is situated in Thiruvallur district in the northern part of Tamil Nadu. It is also easily accessible from Red Hills, Avadi and Chennai city suburban towns. Before abolition of Zamandari act in 1952, the Vengal village was under the control of Zamindars. Vengal has a population of 5523 constituting of 2786 males and 2737 females. The area under Vengal command is 178.045.5 ha and there are 252 members in Water users Association. It is a rainfed tank which is fully depending on it own catchment’s for water. Tank capacity is 1.11 Mm3.In vengal tank, any decision are taken about renovation consulted with stakeholders. Water Acquisition The outcome of tank restoration could be apprehended with the following documented results. Before rehabilitation the supply channel was full of vegetation and the cross section of the channel was not uniform. So farmers required to remove the vegetation and made proper sectioning of the channel to facilitate smooth inflow into the tank. After rehabilitation supply channel is improved in terms of water acquisition. Water Storage Tank bund was strengthened and brought to standards by providing the maximum required free board. Sluice number three was in a damaged condition. RF (rear front) weir was also in a damaged condition with the disturbed Apron, broken coping concrete and with cracked abutments through which leakage was possible. In the After rehabilitation phase the damages were rectified. Water Distribution The earthen field channels were having mild bottom width lots of undulations that caused heavy silting up and stagnation problems in the channels. But after rehabilitation phase the main distributory channels are lined. And hence the conveyance, field channel, field application and irrigation efficiency got increased to 16.36%, 12.49%, 0.81%, and 19.28% respectively. Not only that, the percentage of loss of flow in study tank also reduced to 2.39%. Table 1 . Crop yield and efficiencies related to water use Sl.no 1

Description Crop yield average kg/ha

Pre project

Post project

3980

4100


2 3 4

Water use efficiency kg/ha cm Relative water supply * Rainfall during the crop calendar year (mm)

22 1.51 1256.40

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23.97 1.42 1087.80

Increase in Relative water supply is 0.09. Up to RWS value of 1.12, the WUE increases and reaches the maximum value of 27.20-kg/ha cm. Potential socio-economic benefits of restoration of irrigation tanks Improved production and higher income Improved nourishment (through fisheries development) Increased opportunity for gainful employment. Reduction in seasonal migration by landless and poor households. Increased family income. Improved quality of life. Improved interaction and cordial relationship among different communities. Improved livestock and milk production. Increased availability of water in terms of storage days for livestock and humans.

Drinking water problem is solved in Vengal village through drilling bore in tank bed itself. Water extracted is stored in 6 overhead tanks of 60,000 litres capacity helps to meet their drinking water demand. Moreover the excess water was used for kitchen garden like vegetables and orchids. Thereby women can get a small amount for their home needs and their nutritional value was also improved when they consumed it. Due to the dugout pond work, the cattle are getting sufficient drinking water through out the year. Cattle drinking water source is created and was full with water even in summer. Fodder cultivation on the farm pond bunds and near the plot of farm ponds in 13 acres were introduced. Additionally 160 liters of milk/day has been produced from the watershed area due to the project works. The villages of South India, which are mostly located on the banks of the tanks, enjoy the water from the tank for their use in livestock rearing, drinking and for domestic use. Historically, some marginal groups for grazing livestock, growing trees and for undertaking seasonal cultivation use the water-spread area. Even today the Thiruvellore district has one of the highest populations of livestock such as sheep and goats, which require vast area of grazing. Apart from the above, tank restoration helps in growing more fodder. The most remarkable fact is that the women are the utmost beneficiaries of the above. Migration from this village has stopped in the last two seasons and it is reported that the people from the surrounding villages are coming to work as labourers to this village

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Improved recharge in the command area wells Puliambakkam tank and Avalur tank was selected for case studies under this research. In formations were collected regarding the general status of tanks and their previous management histories, rehabilitation programs undertaken, farmers’ participation, tank encroachments and tank productivity. Avalur village have 50% of marginal farmers (below 2.5 acres), 30% of small farmers (2.5 acres to 5 acres) and 20 % of large farmers (above 5 acres) and Puliambakkam village have 40% of marginal farmers, 30% of small farmers and 30% of large farmers .Primary occupations of these villages are agriculture and agriculture labor work and secondary occupations are brick making work, rearing livestock and food fuel collection. In Puliambakkam village 75% farmers are mainly depending upon the tank water and marginally dependent on well water as a supplementary source for irrigation. Farmers are cultivating paddy and sugarcane as major crops and also go in for different types of vegetables like ladies finger, cucumber, pumpkin etc. Since the village is located nearer to the city they are selling their produce at wholesale rate which is highly remunerative for them. The farmer community under the leadership of councilor undertook desilting a small portion of the tank during the year 2004.Water stored in the desilted area had helped the farmers to recharge their wells located in the command area, which increased the command area water table level significantly. Even in peak summer, these wells are having water to a level of about 7 feet which was completely dry before partially desilting this tank. Since the desilted soil was more suitable to prepare brick, it was taken away by the near by villagers on payment. The amount charged for the silt was again invested in tank development works by the councilor. With this encouraging experience, farmers from Puliambakkam village prepared a proposal and received a fund of Rs. 3 lakhs from National Rural Employment Guarantee Scheme (NREGA). Partial desilting was again done in the same Puliambakkam tank near deeper sluice with 416 pits (each pit size is 10mX3mX0.3m) and shown in picture 1

Picture 1 After desilting portion of Puliambakkam tank


Avalur tank, located in southern side of river Palar, Kancheepuram district of Tamilnadu is facing lowering water table in command area wells due to sand mining in the river bed. Paddy and Sugarcane are cultivated as main crop with the available tank water from the middle sluice. Water user association is well functioning in this village, especially women involvement is high in irrigation management at the sluice level. (Picture 2 and Picture 3 ) .Farmers from Avalur village received a fund of Rs. 3 lakhs from National Rural Employment Guarantee Scheme (NREGA) and done in channel desilting the channel and increasing the water level of wells in the command area and also directly using the channel water for to improve the productivity.

Picture 2 Woman participation in Avalur tank

Picture 3 Farmers involvement in decision For tank renovation

Verma (1999) presented the following picture 4 and picture 5 shows the Regupalem Irrigation tank before renovation situation and after renovation. After renovation regupalem tank improve the water storage leads to sustainable development.

Picture 4 Before renovation of Regupalem irrigation tank

Picture 5 After renovation of Regupalem irrigation tank

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SUMMARY AND CONCLUSION Tanks provide direct as well as in direct irrigation benefits through recharge of groundwater and hence safeguard the economic and ecological sustainability of these districts. Conserving the tank eco-systems for multiple uses such as irrigation, domestic, livestock use and groundwater recharge is a way to provide a safety net to protect the livelihood of millions in semi-arid India. Hence conserving and proper management of tank and its water will make the tank ecosystem sustainable. Today Tank irrigation development has become a part of natural resource management. Restoration of traditional tanks not only increases storage capacity also protects and conserves the environment and also contributes to village livelihood security. Any tank restoration program must start with identifying the problems of tank irrigation through perspectives of farmers for improvement of the tank water productivity, ground water recharge and other tank support services which should be wetted and corroborated by the perspectives of technologist and finally by the government for allocating funds not only for infrastructure development but also for institution building, capacity building and awareness creation. In case studies, many of the tanks in Tamilnadu has been affected the problems of siltation, decreases storage capacity and further reduces water flow, crop yields decline as soil fertility and moisture retention declines, and income and food supplies decrease.. Hence this paper concludes, support of stakeholder participant is much need to restoration of irrigation tanks for improving Rural Livelihood and sustainable development. .

REFERENCE . Centre for Water Resources (2000) “Monitoring and Evaluation: Phase II and Phase II- Extension, Tank Modernization Project with EEC Assistance: Final Report Volumes I and II, Anna University, Chennai, November. Janakarajan, S (1996) Note on Irrigation Experience of Tamil Nadu, Proceedings of the Seminar on Conservation and Development of Tank Irrigation for Livelihood Promotion, July 12, Madurai, Conservation and Development Forum Gainsville, USA. Sakthivadivel R, gomathinayagam P and tushaar shah (2004) “Rejuvenating Irrigation Tanks through Local Institutions” Economic and Political Weekly. Sakthivadivel R and Gomathinayagam P (2006) “Rehabilitation and management of tanks in India” Asian Development Bank. Shah, Tushar and K V Raju (1999): Rajasthan Minor Irrigation Tank Rehabilitation Project: Socio-Ecological and Organizational Assessment for Swedish International Development Agency, New Delhi.


Sivasubramaniyan, K (1997): ‘Irrigation Institutions under Two Major System Tanks in Tamil Nadu’, Review of Development and Change, Madras Institute of Development Studies, Chennai. Tang, Shui Yan (1992): Institutions and Collective Action: Self Governance in Irrigation, ICS Press, Sanfrancisco, pp 151. Tushaar Shah and K Vengama Raju (2001): ‘Rethinking rehabilitation: socioecology of tanks and water harvesting in rajasthan, north-west India’, Raju International Food Policy Research Institute, Washington, D.C. Vaidyanathan, A (ed) (2001): Tanks of South India, Centre for Science and Environment, New Delhi.

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Global Warming Carbon Capture and Sequestration


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ORGANIC CARBON STOCKS ESTIMATION IN BEESH HAZAR LAKE: A RAMSAR SITE OF THE NEPAL LOWLANDS Shalu Adhikari1, Roshan M. Bajracharya, Saurav Silwal and Sony Pun Department of Environmental Science and Engineering, Kathmandu University, Nepal Abstract Wetlands are dynamic ecosystems characterized by water logged or standing water conditions during at least a part of the year. Wetland characteristics lead to the accumulation of a high amount of organic matter in its sediment serving as a carbon (C) sink and making them one of the most effective ecosystems for sequestering C. Occupying about 5% of the earth’s land area, wetlands store about 15%-35% of the total C globally in its sediments. Carbon fluxes and pools vary widely in different wetlands. A study was conducted during April 2009 to estimate organic C stocks in “Beeshhazar lake” a Ramsar designated wetland of lowland Nepal. Organic C in the form of biomass and sediment were estimated based on dry weight basis following Fernander-Alaez et al., 1999 and Loss on Ignition (LOI) method following Heiri et al., 2001, respectively, with eight replications; four each on shallow and deep areas taken over an area of 150 ha. Macrophytes collected from 1m x 1m quadrat were air dried till a constant weight was reached and further burnt at 600oc for an hour in muffle furnace. Sediment samples were taken by means of a UWITEC- corer (60mm diameter) with a one-way check valve that created a vacuum inside the core liner as pushed into the sediment, and when pulled out it created a suction force that retains the sample into the tube without compaction, distortion and disturbance and finally sectioned with a blade into samples of 2cm thickness. The C in biomass ranged from 24.74 gm/m2 to 77.85gm/m2. However, average C in macrophytes was found to be around 55.51 gm/m2. Organic C in sediment was found to have ranged from 4% to 30% in shallow areas and from 3.6% to 40.2% in deeper areas. High C value for 0-2cm (surface) could be due to greater accumulation of organic matter at the top in recent years. The influence of water temperature, pH, water levels and management practices upon C storage in wetland needs further study on seasonal and long-term annual basis. If trading of emission certificates as envisaged in the Kyoto Protocol could become an established norm, then this mechanism can be applied to wetlands with high carbon sequestration potential. Keywords: wetlands, organic carbon, biomass, sediment, pH, temperature, water levels, Kyoto Protocol, sequestration ___________________ 1

Corresponding author: [email protected], Mobile: 009779841212266

INTRODUCTION Wetlands are among the most important natural resources on earth. Occupying about 5% of the earth’s land area, wetlands are dynamic and natural ecosystems characterized by water logged or standing water conditions during at least part of the year. In most wetlands, water levels fluctuate seasonally instead of being stable, a property that accounts for making wetlands highly productive environments. Productivity among wetlands varies depending on the type of the wetland, climatic condition and vegetation communities. Along with productivity, decomposition is another complicated process that involves both aerobic and anaerobic processes. The rate of decomposition is a function of climate (temperature and moisture enhanced microbial activity) and quality (composition) of organic matter entering the system (Schlesinger, 1997). In general, wetland characteristics lead to the accumulation of organic matter in the soil and sediment serving as carbon (C) sinks and making them one of the most effective ecosystems for storing soil carbon (Schlensinger, 1997). It has been estimated that different kinds of wetlands contain 350-535Gt C, corresponding to 20-25% of world’s organic soil carbon (Gorham, 1998). Tropical wetlands store 80% more carbon than temperate wetlands according to findings based on the studies conducted to compare ecosystems in Costa Rica and Ohio (Bernal, 2008). As estimated by Lal (2007), the

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total soil organic pool is 1550Pg and the wetlands are responsible for 150Pg, one third of this pool, despite the fact that they cover a very small portion of the total earth’s surface. Wetlands occupy approximately 5% of the total area of Nepal ranging from high altitude glacial lakes to hot springs, ponds, ox-bow lakes to river flood plains, swamps to marshes. In view of the significance of wetlands on various aspects like biodiversity richness, livelihood of the wetland dependent people and its contribution on the purification of water sources, Nepal became signatory to the Ramsar Convention on Wetlands on 17th April 1988. Presently, Nepal has nine wetlands of International Importance. Although Nepal has shown its commitment to wetland conservation, problems of over-exploitation, illegal harvesting, over hunting, fishing, encroachment and pollution, among others, are still prevalent. The role of these wetlands as carbon sink locally as well as globally are still not realized and no scientific database on the stock of organic carbon deposited has been maintained (Adhikari, et al., 2009). Therefore there is a need to assess and analyze sediment C and biomass C in wetlands of Nepal.

OBJECTIVES The main aim of the study is to estimate the organic carbon stocks in Beesh Hazar Lake, a Ramsar site of Nepal lowlands with the following specifice objectives: ¾ Estimate organic carbon in different increments in different areas of wetland sediments ¾ Estimate organic carbon in macrophytes of the lake

MATERIALS AND METHODS Study Area A Ramsar site spreaded over in 3200ha area, Beesh Hazar Lake (150 ha.) and the surrounding landscape system (avg. altitude 172m asl) is situated within the Barandabhar Forest Corridor (BFC) south to Mahendra Highway in Chitwan district of central Nepal (see figure 1). It is an extension of the buffer zone of Chitwan National Park supporting an appreciable assemblage of rare, vulnerable and endangered flora and fauna. The presence of dead trees and stumps lying around in the lake area suggests that it is a newly formed lake in the depression area locally called ghol, which was impounded due to the construction of levee built along the Khageri Irrigation Canal, which was constructed during mid 1960s to the south (Bhandari,1998). Khageri Irrigation Canal and rain accumulation are its main source of water. The lake has many ramifications. Most of the branches have already undergone succession and others are on the verge of succession.


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Figure 1: Nepal’s map showing sampling area and sites within the lake

Field Methods Field visit was conducted during the month of April 2009. Reconnainance visit was done prior to sampling days to get adjusted with the field situation. Sediment and macrophytes sampling were done within a few days of time. Physical parameters analysis-Physical parameters viz temperature and pH were determined in the field using a multi-parameter probe (ORION). Sediments with the help of the Corer were also taken from different replications for textural analysis. Sediment Sampling- Sediment Cores were taken in two representative sites i.e. shallow and deep areas of the wetland. Four replications were taken in each area. Sediment samples were taken from UWITEC- Corer (60mm diameter), as it was carefully inserted into the soil and pushed down as deep as possible. The corer has a one-way check valve that created a vacuum inside the core liner as pushed into the sediment, and when pulled out it created a suction force that retains the sample into the tube without compaction, distortion and disturbance and finally sectioned with a blade into samples of 2cm thickness. Sectioned samples were packed and brought to laboratory for further analysis. Sediment could not represent all ramifications of the lake as shown in the above figure as most of the area is in the verge of succession due to invasive species. Macrophytes Sampling-Macrophytes were also sampled in two representative sites i.e. shallow and deep areas of the wetland. Four replications were taken in each area. Destructive sampling was done as they were taken from 1m x 1m quadrat and brought to laboratory for further analysis.

Laboratory Methods Sediment textural analysis-Sediments of each replication were air dried for a week, grinded and passed through 2mm size sieve to make a homogenous sediment sample and further analyzed based on Hydrometer Method following Gee and Bauder, 1986. Sediment Organic Carbon analysis- Organic Carbon in sediments was estimated based on Loss on Ignition (LOI) Method following Heiri et al., 2001. Determination of weight percent organic matter in sediment by means of LOI is based on sequential heating of samples in a muffle furnace. After oven-

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drying of the sediment to constant weight (usually 24 hour at 105 oC) organic matter is combusted to ash and carbon dioxide at a temperature 550 oC for about an hour. The LOI is then calculated using the following equation: LOI 550 = ((DW105__DW550)/DW105)*100 Where LOI550 represent LOI at 550 0C (as a percentage), DW sample after heating to 550 oC (both in grams).

105

represents the dry weight of the

Macrophytes analysis- Organic Carbon in macrophytes was estimated based on Dry Weight Method following Fernandez-Alaez et al., 1999. Macrophytes were air dried till a constant weight was reached and further burnt at 600 oC for an hour in a muffle furnace. It is then expressed as gm/m2.

RESULTS AND DISCUSSION Physical Parameters -The values of basic physical parameters observed at the time of sampling are given in Table 1. Table 1. Physical parameters of lake water.

Parameter

Observed Value 250C

Temperature pH 8.7 The physical parameters are considered the most important principles in the identification of nature and type of water for any aquatic ecosystem. This study done during premonsoon (April) found the pH to be 8.7 while it was found to be 7.5 during monsoon (June) and 6 during postmonsoon (September) as observed by Bhattarai et al., 2007. In shallow lakes, water temperature tracks air temperatures closely (Brasch, 2005). Water temperature affects organisms as well as chemical and physical characteristics of water (Abdo, 2005). The textural class of the sediment was found to be sandy clay loam (60.66% sand, 22.4% clay, 16.94% silt). Clearly, the high sand content is washed in from the Khageri River which is the main source of water to the lake.

Organic Carbon in Sediment - Organic C in sediment was found to have ranged from 4% to 30% in shallow areas and from 3.6% to 40.2% in deeper areas as shown in figure 2.

Figure 2: Chart showing % of organic C in two areas of various segments


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% of organic carbon

25 20

R2 = 0.6818

15

Series1 Linear (Series1)

10 5 0 0

5

10

15

Sediment increments Figure 3: Regression model between organic C and sediment increments

Using linear regression model fit of the data, a negative correlation was observed between percent of organic carbon and different sediment increments (figure 3). It can be deduced that as the depth of sediment increased the organic carbon concentration decreases. It may be due to the higher deposition of organic matter in the top few centimeters of the sediment during recent years. Macrophytes- A total of nine different species of macrophytes were recorded within the given area in all replications. The most dominant species was Echhornia crassipes (Jalkumbi in Nepali) followed by Leersia hexandra (Karaude in Nepali) and Trapa natans(Pani singada in Nepali) . The C in biomass ranged from 24.74 gm/m2 to 77.85gm/m2 (figure 4). However, average C in macrophytes was found to be around 55.51 gm/m2 (average C -78.25%). This result was presumably due to high nutrient in water and sediment which led to the massive growth of macrophytes in the lake, in turn leading to high organic carbon concentration (% dry weight) in them.

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Figure 4: Percentage of organic carbon in macrophytes from various replications of wetland.

CONCLUSIONS This preliminary study revealed that wetlands could serve as a carbon sink. The average percentage of C in macrophytes was found to be higher than sediments. Carbon storage in wetlands depend on several factors such as the topography and the geological position of wetland; the hydrological regime; the type of plants present; the temperature and moisture of the soil; pH and the morphology. Therefore, it is difficult to evaluate the net carbon sequestering role of wetlands because decomposition of organic matter, methanogenesis and sediment fluxes are extremely complex and there exists a huge gap in scientific quantification and knowledge. Nonetheless, wetland mechanisms can facilitate a low cost approach to the Kyoto Protocol for lowering net emission of GHGs, while at the same time can help to advance the goals of Convention of Biological Diversity (Adhikari et al., 2009) One of the major problems existing in the lake is the problem of invasive species playing a major role in succession. Collection of edible fern species were seen to be very common in the periphery of the lake area. Illegal firewood collection from the adjoining forest was also observed during the study. Although a management plan of the lake has been prepared by the Department of National Park and Wildlife Conservation, there are major gaps in implementation of the plan.

RECOMMENDATIONS The influence of water temperature, pH, water levels and management practices upon C storage in wetland needs further study on seasonal and long-term annual basis. If trading of emission certificates as envisaged in the Kyoto Protocol could become an established norm, then this mechanism could be applied to wetlands with high carbon sequestration potential.


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ACKNOWLEDGEMENTS The study would not have been possible without the assistance of many people directly and indirectly. We would like to thank HIMUNET (NUFU) for the financial support to carry out the study. Thanks also go to Dr. Chhatra Mani Sharma, Visiting Faculty, Kathmandu University for all support during sample collection. Mr. Bal Bahadur Lama and Mr. Binod Lama, field assistants are also thanked for their necessary support. Lastly, we would like to thank National Trust for Nature Conservation, Sauraha for providing boat for sample collection during the study.

REFERENCES Abdo, M. H. 2005. Physico-chemical characteristics of Abuza’baal Ponds, Egypt. Egyptian Journal of Aquatic Research 31 (2): 1-15. Adhikari, S., Bajracharaya, R.M., and Sitaula, B.K. 2009. A Review of Carbon Dynamics and Sequestration in Wetlands. Journal of Wetlands Ecology, (2009) vol.2, pp 41-45. Bernal, B.2008. Carbon Pools and Profiles in Wetlands Soils: The effect of climate and wetland type. M.S. thesis, presented in partial fulfillment of the requirements for Master’s degree in the Graduate School of the Ohio State University. Bhandari, B. 1998b. A Study on Conservation of Beesh Hazar Tal. IUCN-Nepal. Bhattarai, B. and Acharya, P.M. 2007. Water Chemistry and Trophic Status of Shallow Macrophyte- Dominated lakes (Beeshazar Tal Complex), a Ramsar Site in Chitwan. Nepal Journal of Science and Technology 8: 119-127. Brasch, R. 2005. A report on Mckusick lake water quality assessment. Project File No.510-05-418, Minnesota, U.S.A. Fernandez-Alaez, M., Fernandez-Alaez, C., and Becares, E. 1999. Nutrient content in macrophytes in Spanish shallow lakes. Hydrobiologia 408/409: 317-326. Gee, G.W., and Bauder, J.W. 1986. Particle Size Analysis, pp: 383-411. Methods of Soil Analysis Part1. 2nd SSSA, Madison, WI. Gorham, E. 1998. The biochemistry of Northern Peatlands and its possible responses to global warming. Pp. 169-187. In Biotic Feedbacks in the Global Climatic Systems. G.M. Woodwell and F.T. Mackenzie, Eds. Oxfors University Press, NY. Heiri, O., Lotter, A.F., and Lemcke, G. 2001. Loss on ignition as a method for estimating organic and carbonate content in sediments: reproducibility and comparability of results. Journal of paleolimnology 25: 101-110. Lal, R. and Pimental, D. 2007. Biofuels from crop residues. Soil & Tillage research. Vol.93, no.2: 237-238. Schlensinger, W.H. 1997. Biogeochemistry: An Analysis of Global Change. Second edition. Academic Press. San Deigo. California. Thapa, S. T. 2004. Wetland Resources and Livelihood of Local Ethnic Communities (A Case Study from Beesh Hazar Tal, Chitwan, Ramsar Site of Nepal). A Dissertation Submitted in partial fulfillment for the Masters Degree in Environmental Science in the Department of Biological Sciences and Environmental Science of the School of Science at Kathmandu University.

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OCEAN FERTILIZATION FOR CO2 SEQUESTRATION. Avdesh Bhardawaj, Anand Kumar Gupta, Shukti Tomar School of Energy & Environmental Studies, Faculty of Engineering Sciences, Devi Ahilya Vishwavidhyalaya, Indore.

ABSTRACT Ocean Fertilization is the concept for CO2 sequestration in which infertile waters are seeded with iron or other nutrients to enhance the growth of plankton and consequently increase the uptake of CO2 into the ocean waters. Iron is highly insoluble in sea water and is quickly lost in sinking particles. Addition of trace amounts of iron to these waters, whether from natural sources or by artificial iron fertilization results in rapid algal growth leading to development of phytoplankton blooms that grow by taking up CO2 dissolved in sea water and converting the carbon into biomass. The fate of the bloom biomass determines how long this CO2 is retained in the ocean. If the organic matter is recycled by bacteria and zooplankton and the iron selectively lost, then the CO2 taken up is returned to the atmosphere within months. The organic particles in the form of phytoplankton cells and zooplankton faecal material that settle out of the surface layer sequester CO2 for longer time scales depending on how deep they sink. Carbon transported in particles that sink below 3,000 m is sequestered for centuries and the portion buried in the sediments for much longer. Previous experiments in the Southern Ocean have created phytoplankton blooms but only in the previous experiments EIFEX and LOHAFEX carried out from Polarstern was it possible to actually follow the rain of particles sinking through the underlying deep water column because the experiment was carried out in the closed core of a stationary, rotating eddy. Although nascient in stage, Ocean Fertilization should be tried more experimentally to evolve a consistent and longlasting solution for higher levels of CO2 by sequestration. Keywords : Ocean Fertilization, Sequestration, Phytoplankton, Seeding, Redfields ratio, Blooms

1. INTRODUCTION Ocean Fertilization is the concept for ocean sequestration in which infertile waters are seeded with iron or other nutrients to enhance the growth of plankton and consequently increase the uptake of CO2 into the ocean waters. The CO2 content of the atmosphere has increased from about 280 ppm to about 365 ppm during the last 60 years. During the 1980's the rate of increase of CO2 in the atmosphere, in terms of carbon metric tons, was about 3.3 gigatons of carbon per year (GtC/yr). Fossil fuel emissions were about 5.5 GtC/yr (20 Gt CO2/yr) and terrestrial emissions were about 1.1 GtC/yr during that period, so about 3.3 GtC/yr, 60% of fossil fuel emissions, were sequestered naturally. Of this, about 2.0 GtC/yr was absorbed by the oceans and 1.3 GtC/yr by the land. The remaining 40%, 2.2 GtC (8.1 GtCO2)/yr, contributed to the increasing atmospheric CO2 concentration. This increase in the CO2 content of the atmosphere has led to concerns that this increase will result in global climate change, which, over time, can have adverse effects on weather, sea level and human survival. This concern led to the 1992 Rio


Treaty, the IPCC Working Group and the Kyoto Protocol of 1997, which call for a reduction of emissions of 34% by 2050 and a reduction of 70% from the then-expected emissions from the industrial nations by 2100. These reductions, if put into effect, would have serious adverse effects on the world economy. 1Gt Carbon = 3.67 Gt CO2 Iron fertilization is the intentional introduction of iron to the upper ocean to stimulate a phytoplankton bloom. This is intended to enhance biological productivity, which can benefit the marine food chain and sequester carbon dioxide from the atmosphere. Iron is a trace element necessary for photosynthesis in all plants, however it is highly insoluble in sea water and is often the limiting nutrient for phytoplankton growth. Large phytoplankton blooms can be created by supplying iron to iron-deficient ocean waters. A number of ocean labs, scientists and businesses are exploring it as a means to sequester atmospheric carbon dioxide in the deep ocean, and to increase marine biological productivity which is likely in decline as a result of climate change. Fertilization also occurs naturally when upwellings bring nutrient-rich deep-water up to the surface, as occurs when ocean currents meet an ocean bank or a sea mount. This form of fertilization produces the world's largest marine habitats. Fertilization can occur when weather carries soil long distances over the ocean, or iron-rich minerals are carried into the ocean by glaciers, rivers and icebergs. The maximum possible result from this technique, assuming the most favourable conditions and disregarding all practical considerations,is 0.29W/m2 of globallyaveraged negative forcing, which is almost sufficient to reverse the warming effect of about 1/6th of current levels of anthropogenic CO2 emissions. It is notable, however, that CO2 levels will have risen by the time this could be achieved.

2. BASIC PRINCIPLE: When tonnes of dissolved iron sulphate is thrown in ocean the iron is expected to stimulate a rapid blooming of phytoplankton,a microscopicalgae that grows on the ocean surface. Like all plants, phytoplankton takes up CO2 from air and converts it to carbon compounds like carbohydrates. The plant quickely dies and starts sinking, taking the carbon with it. What happens thereafter is the key to the technique’s efficacy: If it sinks well below the ocean surface, the carbon would effectively been put away for a long period. If the entire southern ocean were fertilized by iron and a sizable fraction of the phytoplankton sank well below 1,000 m, then about 1 Gt of Carbon would be isolated for centuries. Water at depths below 500 m takes about 100 years to come to the surface. But Ocean Iron Fertilization remains controversial, with many environmentalists saying it amounts to major tinkering with the marine eco-system. If done on the scales proposed in the future, it could have unforeseen consequences.

3. HISTORY : Martin's famous 1991 quip at Woods Hole Oceanographic Institution, "Give me a half a tanker of iron and I will give you another ice age", drove a decade of research whose findings suggested that iron deficiency was not merely impacting ocean ecosystems, it also offered a key to mitigating climate change as well. Perhaps the most dramatic support for Martin's hypothesis was seen in the aftermath of the 1991 eruption of Mount Pinatubo in the Philippines. Andrew Watson analyzed global data from that eruption and calculated that it deposited approximately 40,000 tons of iron dust into the oceans worldwide. This single fertilization event generated an easily observed global decline in atmospheric CO2 and a parallel pulsed increase in oxygen levels.

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4. THE ROLE OF IRON: THE REDFIELD RATIO The Redfield ratio describes the relative atomic concentrations of critical nutrients in plankton biomass and is conventionally written "106 C: 16 N: 1 P." Recent research has expanded this constant to "106 C: 16 N: 1 P: .001 Fe" signifying that in iron deficient conditions each atom of iron can fix 106,000 atoms of carbon, or on a mass basis, each kilogram of iron can fix 83,000 kg of carbon dioxide. The 2004 EIFEX experiment reported a carbon dioxide to iron export ratio of nearly 3000 to 1. The atomic ratio would be approximately: "3000 C: 58,000 N: 3,600 P: 1 Fe". Therefore small amounts of iron (measured by mass parts per trillion) in "desolate" HNLC zones can trigger large phytoplankton blooms. Recent marine trials suggest that one kilogram of fine iron particles may generate well over 100,000 kilograms of plankton biomass. The size of the iron particles is critical, however, and particles of 0.5~1 micrometre or less seem to be ideal both in terms of sink rate and bioavailability. Particles this small are not only easier for cyanobacteria and other phytoplankton to incorporate, the churning of surface waters keeps them in the euphotic or sunlit biologically active depths without sinking for long periods of time.

5. ANALYSIS AND QUANTIFICATION Evaluation of the biological effects and verification of the amount of carbon actually sequestered by any particular bloom requires a variety of sophisticated measurements. Methods currently in use include a combination of ship-borne and remote sampling, submarine filtration traps, tracking buoy spectroscopy, and satellite telemetry. However, unpredictable ocean currents have been known to remove experimental iron patches from the pelagic zone, invalidating the experiment. If phytoplankton converted all the nitrate and phosphate present in the surface mixed layer across the entire Antarctic circumpolar current into organic carbon, the resulting carbon dioxide deficit could be compensated by uptake from the atmosphere amounting to about 0.8 to 1.4 gigatonnes of carbon per year. This quantity is comparable in magnitude to annual anthropogenic fossil fuels combustion of approximately 6 gigatonnes. The Antarctic circumpolar current region is only one of several in which iron fertilization could be conducted - the Galapagos islands area being another potentially suitable location.

6. COMMERCIALIZATION Since the advent of the Kyoto Protocol, several countries and the European Union have established carbon offset markets which trade certified emission reduction credits (CERs) and other types of carbon credit instruments internationally. In 2007 CERs sell for approximately €15~20/ton CO2e and European analysts project these prices will nearly double by 2012. Since scientists have reported a minimum 6~12% decline in global plankton production since 1980, this suggests that a full-scale international plankton restoration program could regenerate approximately 3~5 billion tons of carbon sequestration capacity worth €75 billion or more in carbon offset value. Iron fertilization is a relatively inexpensive carbon sequestration technology compared to scrubbing, direct injection and other industrial approaches, and can theoretically generate these credits for less than €5/ton CO2. The cost of sequestering CO2 on a commercial scale is expected to be about $1.00 per ton of CO2. The sales price for CO2 sequestering credits, should they become tradable, would be about $2.00 per ton of CO2, to include the cost of verification, overhead and profit. It is expected that these credits would be highly valued since they would not suffer from the problems of fire hazard, leakage and additionality the forest projects for CO2 sequestering face. Such credits could be produced within a few years of a


successful technology demonstration. Alternately, technology development could be continued with the objective of eventual large-scale CO2 sequestration to address major climate perturbations.

7. PRECAUTIONARY PRINCIPLE Critics apply the precautionary principle: the possible side effects of large-scale iron fertilization are not yet known; and that sufficient research has not yet been done. Significant, unknown, unforeseen, and unforeseeable risks may be involved. Creating blooms in naturally iron-poor areas of the ocean is like watering the desert: it is, in effect, completely changing one type of ecosystem into another. Critics argue that the risk of iron fertilization on the scale needed to affect global CO2 levels or animal populations is not an acceptable one. While advocates argue that iron addition would help to reverse a supposed decline in phytoplankton, this decline may not be real. One study (Gregg and Conkright, 2002) reported a decline in ocean productivity between the period 1979–1986 and 1997–2000, but another study (Antoine et al.., 2005) found a 22% increase between 1979–1986 and 1998–2002. Gregg et al.. 2005 also reported a recent increase in phytoplankton.

8. OCEAN FERTILIZATION The best approach is to sequester CO2 in the deep ocean by causing a bloom of plant life that then sinks to the deep waters where it remains for about 1600 years, as measured by the 14C to 12C ratio of upwelling of deep ocean water off of Peru. This process is possible because large areas of the oceans have excess, unused plant nutrients and much less than expected phytoplankton biomass, the so-called HNLC waters. The difference is that the HNLC waters are deficient in one or more of the micronutrients required for plants to grow. While several essential metals may be involved in the limitation of growth in HNLC areas, iron has been shown to be the major micronutrient. Generally, 100,000 moles of carbon biomass require 16,000 moles of fixed nitrogen, 1,000 moles of soluble phosphorous and one mole of available iron. The main difficulty is the iron. Since surface ocean waters are highly oxygenated, any soluble iron is converted to Fe+++ with a half-life of about one hour and precipitates as Fe(OH)3. A shovel full of earth is about 5.6% iron on the average. The ocean, on the other hand, has 0.0000000001 or less moles per liter of iron, too little to sustain plant growth. The first problem, then, is how to add iron to the ocean so that it will be available to the phytoplankton (plants). The phytoplankton themselves exude organic chelating compounds into the ocean that protect some of the iron that is there from precipitation. Adding iron in the form of a chelate so that it does not precipitate but remains available for plant fertilization can mimic this natural process. An essential element that may be in short supply in nutrient-depleted, tropical ocean waters is phosphorous. Most phosphates are soluble and can be added directly to the ocean. Since the phosphate may attack the iron chelate, it may be necessary to keep the concentrations of both fertilizers low. This can be done by adding them to the ocean separately in the form of small floating pellets that release the fertilizing element slowly over a period of days. This process has been tested by GreenSea Venture, Inc. (GSV) in the Gulf of Mexico with good results. The remaining required essential element is fixed nitrogen. Bluegreen algae or, as they are more properly called, cyanobacteria, have the ability to fix nitrogen, so inducing a bloom of nitrogen fixers might supply this requirement. When the fertilizer mixed with water is added to the tropical ocean surface it mixes rapidly in the warm waters (the mixed layer) and starts the phytoplankton

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bloom. The plants, mostly diatoms, multiply rapidly, increasing their numbers by two to three times per day, until they run out of one of the required nutrients. They then cease growing, lose the ability to maintain buoyancy and sink through the thermocline at a rate of about 75 feet a day. The sinking biomass is trapped in the cold, dense waters where it is eaten by animal life and bacteria. This slowly converts the biomass back to CO2 in the deep waters. Where high concentrations of biomass are generated and reach the ocean floor they may be covered by mud and debris, leading to anoxic digestion. The methane produced is converted to methane hydrates by the high pressure of the deep ocean. It has been estimated that there is twice as much carbon in the methane hydrates of the deep ocean floor than all the terrestrial fossil fuels combined. It is worth noting that the addition of CO2 in this low concentration, natural process is not expected to have any adverse environmental impact on the ocean, which now has about 85 times as much dissolved inorganic carbon as the atmosphere. To sequester CO2 to the deep ocean it is important that to minimize the proportion of the biomass produced that is processed by animal life and bacteria in the mixing layer above the thermocline. This can be done by fertilizing in pulses, so that the slowergrowing animal life cannot multiply effectively before the diatoms have bloomed, died and gone below the thermocline, a period of less than 20 days. The fraction of the biomass produced that is sequestered below the thermocline has been measured. It depends principally on the amount of animal life available to eat the biomass and convert it back into CO2 in the highly oxygenated surface waters. Where the ecosystem is in balance with large amounts of animal life the sequestered carbon is about 10% of primary production and consists mainly of animal parts, scales, bones and fecal pellets. Where animal life is absent the ratio may go as high as 80% sequestered. Measurements made in the tropical Pacific Ocean off of Peru produced a ratio of 53% sequestered beneath the thermocline. This measurement is used in calculations. The waters intended to fertilize must be tested in order to add the correct amount and mix to produce the optimum result. To achieve this a strong, shallow thermocline, tropical sunshine and high nutrient, low chlorophyll (HNLC) conditions are selected for fertilization. These waters can be found in the tropical Pacific near the equator west of the Galapagos Islands. The cool wind-driven currents go directly to the west before reaching the Line Islands of Polynesia. The 3,000,000 square miles of these HNLC waters can sequester about 0.4 GtCO2/yr. Recent studies have shown that, because of the rapidly growing forests and verdant agriculture, North America has an uptake of 1.7 GtCO2/yr and an emission of 1.6 GtCO2/yr. While this rough balance is variable, depending on weather-stimulated growth it illustrates that sequestering capability such as that of the Pacific Equatorial Current can be significant in affecting the c content of the atmosphere.

9. TECHNOLOGY EXPERIMENTS TO DATE The first voyage in the equatorial Pacific, IronEx I, spread 880 lbs. of Fe as FeSO4 on a 25 square mile patch resulting in an increase in phytoplankton, but no measurable decrease in the CO2 content of the water. This was due to the sinking of the patch under an intrusion of barren warmer water. A second voyage in the same area of the equatorial Pacific, IronEx II, spread 990 lbs. of Fe as FeSO4 on 28 square miles of the ocean surface.11 In order to mitigate the effect of iron precipitation, the iron was added in three infusions, half on day zero, one-fourth on day three and one-fourth on day seven. This resulted in a bloom of diatoms. The chlorophyll increased by a factor of 27 times, while the CO2 partial pressure was reduced by 90 µatm in the patch. Ocean


Farming, Inc. (OFI), now renamed GreenSea Venture, Inc., has undertaken two voyages in the nutrient-depleted tropical waters of the Gulf of Mexico. Voyage 1 was carried out in theGulf of Mexico in early January 1998. Three, 9 square mile, patches were fertilized: one with iron, only; one with iron and 6.35 times the molar ratio of phosphorous to iron; and one with iron and 63.5 times the molar ratio of phosphorous to iron. The iron was in the form of a chelate to protect it from precipitation and the phosphorous was in the form of phosphoric acid. The ocean and weather conditions, including a very deep thermocline and high winds, caused the fertilizer to mix much more rapidly, both vertically and horizontally, than planned. The result was a bloom of large diatoms to 4.3 times their initial concentration in a little over one day. After that, the mixing diluted the signal to about 1.5 times the initial chlorophyll concentration. These results, while giving a positive indication of a large bloom were not definitive and did not provide a verifiable measure of phytoplankton increase over the period of the expected bloom of about two weeks. Voyage 2 was carried out in the Gulf of Mexico in early May 1998. One 9 square mile patch was fertilized using the enhanced chelated iron-containing pellets. The ocean conditions were much more benign (no one got seasick) and we were able to follow the patch for six days. The floating pellets acted as expected, discharging the chelated iron over a period of four days. The result was a bloom of large diatoms that averaged five times background and reached seven times background. Further increase in phytoplankton was restricted by the absence of the next required fertilizing element, probably phosphorous, nitrate or both. However, extrapolating over the increased size to the patch gave an estimated 600 tons of diatoms per ton of fertilizer pellets, or 1,800 tons of diatoms per ton of chelated iron added to the waters. Both voyages in the Gulf of Mexico were in low nutrient, low chlorophyll (LNLC) waters, which are not favorable to the production of large blooms. A fifth voyage, SOIREE, has been conducted in the Southern Ocean south of New Zealand. Iron sulfate was added to the 20 mi2 patch on days 1,3,5 and 7 to keep the concentration of dissolved iron at about 1.0 _molar versus a background of 0.08 _molar. The chlorophyll concentration went up by a factor of six and biomass by a factor of three with a preponderance of diatoms in the bloom. The increase in biomass was slower in these frigid waters than at the equator and the bloom concentration was less. However, the bloom lasted for about one month, as measured by satellite imagery. These experiments have added greatly to our knowledge of the biodynamics and chemistry of the ocean. Other recent measurements have further increased our understanding. These have included the tethered buoy systems (TAO buoys) as well as the SeaWiFS satellite, instrumented buoys and drifter systems. These systems have, for the first time, provided continuous measurements of the ocean surface as well as at depth, instead of isolated measurements from intermittent ship cruises. This great increase in data has provided enough understanding that we can now design a technology demonstration aimed at proving the CO2 sequestration potential of ocean fertilization. All the voyages are listed: Ironex II, 1995. SOIREE (Southern Ocean Iron Release Experiment), 1999. EisenEx (Iron Experiment), 2000 .SEEDS (Subarctic Pacific Iron Experiment for Ecosystem Dynamics Study), 2001. SOFeX (Southern Ocean Iron Experiments - North & South), 2002. SERIES (Subarctic Ecosystem Response to Iron Enrichment Study), 2002. SEEDS-II, 2004. EIFEX (European Iron Fertilization Experiment), 2004 . CROZEX (CROZet natural iron bloom and Export experiment), 2005. LOHAFEX, 2009. Despite widespread opposition to this experiment, clearance was given on 26 January 2009 for fertilization to commence. The experiment was carried out in waters low in silicic acid which is likely to affect the efficacy of carbon sequestration. A large phytoplankton bloom was triggered, however this bloom did not contain diatoms because the fertilized location was already depleted in silicic acid, an essential nutrient for diatom growth. In the absence of diatoms, a relatively small amount of carbon was sequestered, because other phytoplankton are vulnerable to predation by zooplankton and do not sink rapidly upon death. These poor sequestration results have caused some, including members of the LOHAFEX research team, to suggest that ocean iron fertilization is not an effective carbon

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mitigation strategy in general, however prior ocean fertilization experiments in high silica locations have observed much higher carbon sequestration rates because of diatom growth. LOHAFEX has just confirmed that the carbon sequestration potential depends strongly upon careful choice of location.

10. DISCUSSION OF THE TECHNIQUE Artificial iron fertilization is carried out by releasing a solution of ferrous sulphate (the same substance used to treat patients suffering anaemia) in the ship’s propeller wash along a track about 2 km apart over an area depending on the hydrodynamics of the region and the intended duration of the experiment.Short-term experiments (1-2 weeks) in calm, warm seas need be only a few tens of km2 in area, longer-term experiments in stormy seas such as the Southern Ocean (57 weeks) will have to fertilize a few 100 km2. Plants, in this case the unicellular algae of the phytoplankton, increase their growth rates whereby the same species of phytoplankton are stimulated by iron addition as commonly occur in natural blooms in the region. Their growth results in stimulation of other components of oceanic ecosystems including zooplankton and bacteria. The amount of carbon eventually sequestered in the deep ocean by the biological pump depends on how much algal biomass is recycled in the surface layer by zooplankton and bacteria and how much sinks to depth. Previous experiments have not been able to adequately record this phase of the bloom because they have been too short or otherwise restricted. However, they have all demonstrated that OIF experiments simulate natural processes and that their environmental impact is hence benign.

11. RESULTS The expected impacts of a successful demonstration of the technology and the measurement of significant sequestration response by the ocean to the planned chelated iron addition could be significant. The costly early actions now being contemplated to counteract possible future impacts of increased CO2 content of the atmosphere would no longer be needed and instead all responses could be tied to measured consequences, which could then be reversed. This would open new options, avoid the unnecessary use of scarce resources and refocus attention on actual problems rather than seeking to deal with possible future scenarios. Many entities, both governmental and industrial may decide to do very useful things based on these concerns, such as improved energy efficiency and the exploration of new energy resources. This is to the good of society where they make economic sense and should be implemented in any case. A CO2 credit system may be instituted that will allow trading of credits to generate the lowest cost. Credits from sequestering CO2 in the oceans should be a part of this effort so as to take early advantage of this lower cost, environmentally benign, low human impact and robust capacity approach to solving the global warming concerns, should this become necessary.

12. CONCLUSION Although in its nascient stage, Ocean Fertilization for must be encouraged to open up new avenues for CO2 Sequestration


ACKNOWLEDGMENTS Dr. S.P.Singh, Prof. R.L Sawhney, Dr. Rubina Chaudhary from School of Energy & Environmental Studies, Faculty of Engineering Sciences, Devi Ahilya Vishwavidhyalaya, Indore.

REFERENCES Boyd, Philip W, et al, “A mesoscale phytoplankton bloom in the Southern Oean stimulated by iron fertilization”, Nature 407, 12 October 2000, pp 59-61. De Baar H.J.W.,Gerringa, L.J.A., Laan, P., Timmermans, K. R., 2008.Mar Ecol Prog Ser. 364: 269-282 Fan, S., et al, “A large terrestrial carbon sink in North America implied by atmospheric and oceanic carbon dioxide data and models”, Science 6 Oct 1998, Vol. 282, pp 442-446. Frost, W.F., “phytoplankton bloom on iron rations”; Nature 10 Oct. 1996, pp 495, 508, 511, 513 & 475. Hansell, et al, “Predominance of vertical loss of carbon from surface waters of the equatorial Pacific Ocean”, Nature 386, 6 March 1997, pp 240-243 Markels, Jr., Michael, US Patent No. 5,433,173, Method of Improving the Production of Seafood, 18 Jul 1995 Markels, Jr., Michael, US Patent No. 5,535,701, Method of Improving the Production of Seafood in the Ocean, 16 Jul 1996 and US Patent No. 5,967,087, Method of Improved Seafood Production in the Barren Ocean, 19 Oct 1999 Markels, Jr., Michael, US Patent No. 6,056,919, Method of Sequestering Carbon Dioxide, 02 May 2000 Schiermeir, Q. (2003) The oresmen, Nature 421, 109-110 Watson, A.J. (1997-02-13). "Volcanic iron, CO2, ocean productivity and climate" (PDF). Nature 385: 587–588. doi:10.1038/385587b0. Weier, John. “John Martin (1935-1993)”. On the Shoulders ofGiants. NASA Earth Observatory. http://earthobservatory.nasa.gov/Library/Giants/ Martin/printall.php. W. G., and S. A. Huntsman, 1995. Mar. Chem. 50: 189–206, Iron uptake and growth limitation in oceanic and coastal phytoplankton. Wigley, T.M.L., R. Richards and J.A. Edmonds “Economics and Environmental Choices in the Stabilization of Atmospheric CO2 Concentrations” Nature 379, 18 Jan 96, pp. 240-243 Williams, P. M. and E. R. M. Druffel (1987). "Radiocarbon in dissolved organic carbon in the central North Pacific Ocean" Nature, 330, 246-248.

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CONTRIBUTION OF COMPUTERS HEAT IN GLOBAL WARMING Virender Kumar Asst .Prof IIMS Bareilly [email protected] Sunil Kumar Sharma Lecturer INC Bareilly [email protected]

ABSTRACT Computers convert electricity in to heat as they operate. As they switch on and off, transistors produce heat, this heat must be dissipated in order to keep these components within their safe operating temperatures Components which gain heat are susceptible to performance loss and damage. These components usually includes integrated circuits such as CPUs, chipset and graphics cards, along with hard drives. Hence to encounter this heat at least equal amount of cooling is required by some external source such as Air Conditioners or Coolers, which too in turn release abundant amount of heat which is ultimately transferred to environment. The exponential rates at which computers are increasing world wide have raised concerns of environmentalist. According to a survey conducted by Forrester Research marketing company, the number of personal computers in the world has reached one billion already by the end of 2008, and it will reach two billion - by 2015. Forrester Research’s forecast is based on the assumption, that from 2003 to 2015 the total number of personal computers in the world will annually increase by 12 percent. In this paper we will present a model that will show contribution of computers heat to global warming in current year (2009) also, on the bases of research conducted by Forrester Research marketing company, we’ll also show the contribution of computers heat in global warming world wide by 2015 .Beside this we have also generated an equation which will calculate heat generated by computers world wide and their subsequent contribution in global warming in any year. Keywords: Green Computing, Global Warming, Computers Heat,

1. INTRODUCTION We love our computers for all the ways they make our lives (and the world) better, and easier. Any work which earlier seems to be impossible is now possible and that too by a single click of mouse. Performancewise, computer design has progressed staggeringly well and astonishingly fast but looking at it from a green perspective, the work has barely begun. Computer consumes a good amount of energy, and major fraction of this energy is dissipated in the form of heat. Hence, these computers are also contributing very actively in Global Warming like any thing else. By the law of conservation of energy, all the electricity coming into the computers has to go out somehow. It does so as heat. Obviously, the largest by-product of power is heat. This means that there should be a close correlation between watts of power consumed by the CPU and the heat it releases. Normally, heat (which is just a form of energy) is not measured in watt-hours, but in units such as calories or joules or BTUs. (A BTU (British Thermal Unit) is the amount of energy (heat) required to raise the temperature of 1 pound of water 1 degree Fahrenheit). The conversion from watt-hours is straightforward and is defined as:

1 watt-hour = 3.41 BTUs


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Now if we knew how much amperage a CPU was consuming by use of a multi-meter in line with the CPU, we can calculate the wattage it is consuming by the formula P(watts) = I (current[amps]) x E (electromotive force [volts]) and by that could calculate the theoretical CPU heat released. As a matter of fact all microprocessors are about 10% energy efficient, this means of all the electricity that we pump in, 10% does the job (like running a program), while the rest of the 90% is dissipated as heat. Let us take 2 examples to calculate heat dissipated firstly in case of 100 watt bulb than in case of a P4 processor: Case 1 – 100 w light bulb For example, a 100 watt light bulb that is on for 1 hour consumes 100 watt-hours of electricity and generates about 100 watt-hours of heat (assuming 100%(total) conversion of power in to heat energy ) Now we have 1 watt hour = 3.41 BTUs Hence; heat generated = 100 watt-hours x 3.41 BTUs/watt-hour Heat generated = 341 BTUs Case 2 – Intel Pentium IV 672 For example, a Intel Pentium IV 672 processor consumes 115.0 w of power, if this is working for one hour than it will consume 115.0 w of electricity and generates about 103.5 watt-hour of heat (assuming 10 % energy efficiency) Now we have 1 watt hour = 3.41 BTUs Hence; heat generated =103.5 watt-hour * 3.41 BTUs/watt-hour Heat Generated = 352.935 BTUs

2. MODEL FOR CALCULATING -TOTAL NUMBER OF COMPUTERS IN THE WORLD In general we can calculate the total number of computers in the entire world, (2008 onwards) on the basis of general formula (model) Total number of Computers = 1,000,000,000(1+r/100) t Where r = rate of growth, which is evidently 12% as per Foresters survey t = time t = 0, for 2008 t = 1, for 2009 By applying above model total number of computers in various years (2008-onwards) comes out to be: 2008 = 1,000,000,000 2009 = 1,120,000,000 2010 = 1,254,400,000 2011 = 1,404,928,000 2012 = 1,573,519,360 2013 = 1,762,341,683 2014 = 1,973,822,685 2015 = 2,210,681,407 And so on, these results are represented clearly, Figure 1.0 represents the results by using a bar diagram, whereas Figure 1.1 represents same results by using a line

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The total heat emitted in Btu/hr, can be further calculated by multiplying average heat emitted from a single CPU to the total number of CPU in the world.

3 .MOORE’S LAW AND CPU HEAT DISSIPATION “The numbers of transistor, incorporated in a chip will approximately double every 24 months“ (MOORE’S LAW). This law is clearly demonstrated in Figure 2.0 .Moore’s law shows one side of the coin. Technology advancements focus on output performance CPUs, despite advancements, consume more power and subsequently dissipate more heat. Heat dissipated is mainly affected by the CPU utilization Heat dissipation is linear to the CPU utilization [Impact-2008] P = a U+ b As the number of transistors with in a chip increases and physical size of the chip is reduced , clock speed is increased all these has boosted the heat dissipation across the chip to a dangerous level , these increased number of transistors results in a good power consumption, which in turn releases abundant heat. This is the basic reason for Intel Pentium 75 requiring as low as 6.0 w for its functioning whereas Pentium D 840 requiring 130 w for its functioning. However the heat dissipated does not strictly follow Moore’s law, this is evident from various types of processors and their subsequent power consumption (Figure 2.1) in which even though the number of transistors are increased manifold, even than power consumption and heat dissipation has subsequently reduced.

Power and performance relationship Increase in power consumption has occurred despite dramatic and revolutionary improvements in process technology and circuit design. The primary reason behind the increase in power has been the continued emphasis on higher performance[Shameen Akhter-2006].As complexity and performance of processors has increased over the year to provide unprecedented level of performance the power required to supply these processors has increased steadily too. A simplified equation that demonstrates power performance relationship for the CMOS circuits on which all modern processors are based is:


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P=ACV2f The first component in the equation captures dynamic power of charging and transistor circuits from which basic functional blocks of processor are built. The power is directly proportional to switching frequency (f), square of the supply voltage (V), and total capacitance(C).Since not all functional blocks are used at any given time by a processor workload and not all gates are switched ,’ A’ represents activity factor or the number of switched transistors on a die. The equation above demonstrates the tradeoff between performance and power. As processor frequency increases so does power consumption. As processors architecture becomes more complex to support greater levels of instruction level parallelism and increased performance, capacitance of system increases and so does dynamic power. Another and more subtle point in that concurrent processing can also lead to significant power reduction. Splitting the workload in to multiple threads and running them in parallel can significantly increase processor power efficiency .This is the basic reason why a subsequent power reduction has been observed in multi core and other advanced processors.

4 HEAT DISSIPATED BY A SPECIFIC PROCESSOR The waste heat also causes reliability problems, as CPU's crash much more often at higher temperatures. The central processing unit is the most significant source of heat in a modern PC. Heat dissipated by a specific processor depends on many factor, with in a specific category of CPU(say Pentium II), the power consumption varies to a great extent, for example: some model of Pentium II takes as low as 14.0 w where as other model of Pentium II consumes 34.5 w.

Heat Dissipation in year 2009 and in 2015: Average heat dissipated globally by all PC’s is dependent primarily on many factors such as, the type and model of processors used, operation time, idle time etc. Hence by calculating the power consumption of that specific processor one can easily calculate heat dissipated. This calculation is possible only in situations when we are aware about the fact that what fraction of world’s population is using which type (model) of processor. Once these figures are available calculation of heat dissipated in any year is an easy

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task. And on the basic of our model discussed in section 2 of this paper we can easily calculate the global heat in any year. Table 1.0 shows average heat dissipated by a specific category of processors. We have taken average power consumption of majority of Intel processors. Within a specific group (such as Pentium Core 2 duo) there are various models whose power consumption is variable to a great extent (for Pentium core to duo it is from 5.5 w to 150 w) hence average power is taken. Now as 10 % of power is used by system, for running programs etc, therefore if we subtract this 10 % power from total power of a CPU (or average here), than we will get the power that will be converted in to heat. Table 1 shows total heat generated globally (per hour for year 2009 and 2015). This is only applicable if we consider that world is using a specific type of processor. Global heat Average Power as generated(2009) Power(w) heat consumed dissipated 11.25*3.41*1,254,400,000 Pentium 12.49 11.25 =48121920000 Btu/hr 24.53*3.41*1,254,400,000 Pentium 27.25 24.53 II =104927173120 Btu/hr 22.98*3.41*1,254,400,000 Pentium 25.53 22.98 III = 98297041920 Btu/hr 74.31*3.41*1,254,400,000 Pentium 82.56 74.31 IV = 317861322240 Btu/hr 94.67*3.41*1,254,400,000 Pentium 105.17 94.67 IV Ex. = 404951303680 Btu/hr Ed 92.57*3.41*1,254,400,000 Pentium 102.77 92.57 D = 395968545280 Btu/hr 47.7*3.41*1,254,400,000 Pentium 53 47.7 Dual =204036940800 Btu/hr Core 44.1*3.41*1,254,400,000 Pentium 49 44.1 Core 2 =188637926400 Btu/hr Duo

S.No Processor Type 1 2 3 4 5

6 7

8

Global heat generated(2015) 11.25*3.41*2,210,681,407 = 84807265476 Btu/hr 24.53*3.41*2,210,681,407 =184917530855 Btu/hr 22.98*3.41*2,210,681,407 =173232974279 Btu/hr 74.31*3.41*2,210,681,407 =560180257557 Btu/hr 94.67*3.41*2,210,681,407 =713662562010 Btu/hr 92.57*3.41*2,210,681,407 =697831872454 Btu/hr 47.7*3.41*2,210,681,407 =359582805618 Btu/hr 44.1*3.41*2,210,681,407 =332444480666 Btu/hr

Table 1

5. HEAT DISSIPATION IN IDLE AND IN MAX USE STATE In reality, processors in mobile desktop and server platforms spend a significant amount of time doing nothing or being idle. Ensuring that processors power consumption is minimal in this state is critical for overall power efficiency. Heat dissipated in idle and max used(100% load) state (Figure 3.0 and 3.1 respectively) can be easily calculated if we have the power consumption reading .To determine the maximum power consumption of our review sample, we stressed all four cores using Prime95. Compared to its direct quad-core predecessor with the Kentsfield core (Conroe), the new Penryn-based CPU with its High-K Metal Gate technology draws 39.25% less power. This is because of the fact that the Penryn processor is able to signal the


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motherboard when it is idling. The motherboard then switches off parts of the voltage plane in order to conserve power further.

6. HEAT DISSIPATED WHEN A CPU IS NOT FULLY USED All CPU’s are not always utilized to the max state, neither they remain idle always, hence in these situations when CPU is used to a fixed percentage [Green grid (2008)] (say 10%,20% etc) than calculating heat dissipated in that situation require some alternative model. For n% CPU utilization, the power used Pn can be calculated using the following formula Pn = Pidle + (Pmax – Pidle) / 100 * n So for an example where Pidle= 200W and Pmax = 300W at 10% CPU utilization P10 = 200 + (300 - 200) / 100 * 10 = 210W Now once we have calculated the power than by subtracting 10% of the power (which is used eg.. for running a program), we can get the rest of the power as heat dissipated. Figure 4.0 shows heat dissipated v/s CPU utilization; it is evident that heat dissipated increases with CPU utilization .

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7. SOLUTION FOR REDUCING GLOBAL WARMING BY COMPUTERS Computer dissipates a good amount of heat. In fact a major cost of running an organization comes from supporting the PC infrastructure. Virtual desktop computing based on NComputing saves money up front and over time. NComputing consumes less power, generates less heat, lasts longer, and produces less ewaste. Ultimately, the NComputing green advantage helps organizations pursue their missions while they lessen their environmental impact. According to latest researches over 850 million PCs are turned on every day. If NComputing systems were used instead (at a ratio of six access devices to each PC) there would be substantial immediate and longterm environmental benefits. The impact on the environment of adopting NComputing solutions would be enormous. Energy use would decline by a good amount (83%). The electricity usage decline would save nearly approx 15 million metric tons of coal each year and would eliminate the need for 120 megawatts of coal power capacity. CO2 emissions would decrease by 96 million metric tons. This is equivalent to planting nearly 460 million trees. Disposing of NComputing devices (0.33 lb each), rather than disposing of an equal number of PCs (21 lbs each) would save over 6.7 million metric tons of e-waste. Heat Dissipation can be reduced to minimum level And that is just for the PCs in use today. There are another billion users who will join the digital world by 2015, than this ill effect will be clearly visible.

8. CONCLUSIONS Power is a challenge to the entire semiconductor industry and nothing new to CPU. Smaller transistors consume less power, but as transistor density and speed rise, the overall chip consumes more power and generates more heat. People seldom count this heat, and its contribution to global warming. But as the entire world has already crossed 1 billion PC in count, and this count will reach more than 2 billion in 2015, hence this area cannot be neglected. Processors manufacturers should focus on the development of processors which consumes less power and dissipates less heat. Intel and AMD have already enrolled in


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this mission with the introduction of multi core processors. Beside this NComputing can also be adapted as a good measure to reduce global warming by computers

9. ACKNOWLEDGEMENTS I acknowledge all those who have played a major role in this research paper; firstly I would like to start of with the co–author Mr. Sunil Kumar Sharma, who has played a major role in completion of this paper. I would like to thank Mr. Umesh Gautam Chancellor “Invertis University” for his continuous motivational and financial support at every level. I would like to acknowledge Dr.YDS Arya Director IIET Bareilly, as well as Prof. Arpan Khastagir, Director IIMS for sharing valuable experiences with me. At last I would also like to acknowledge my Father, Mother, Brother, My Wife and my Kids- “Gunjan and Vansh”, and of course my valuable friends without whose support this work would have been daunting task. For any one I may have missed please accept my apologies.

10. REFERENCES: [Impact-2008] Georgios Varsamopoulos, Sandeep Gupta “Thermal-Aware Task Placement in Data Centers” [Shameem Akhter-2006]Shameem Akther , Jason Roberts, Multi Core programming increasing performance through software multithreading ,Intel Press -ISBN-09764832-4-6 [Green grid(2008)]Five Ways to Save Server Power Mark Blackburn, 1E Operations Work Group-green grid(2008) [Cluster 2007]“Thermal Aware Task Scheduling for Datacenters through MinimizingHeat Recirculation” [GreenCom2007 A]“Thermal Aware Task Scheduling for Datacenters through MinimizingHeat Recirculation”, [GreenCom2007 B]“Thermal Aware Task Scheduling for Datacenters through MinimizingHeat Recirculation”,

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TECHNICAL SOLUTION TO COMBAT CLIMATE CHANGE Sunil Kumar and A.K. Rai Deptt. of Civil Engg M.I.T. Muzaffarpur

ABSTRACT Climate Change is a global phenomenon and it needs global solution. Climate Change has become a serious threat to society affecting environment, eco-system and biodiversity. Ever increasing consumption of fossil fuels is the major cause of global warming and climatic change. Efforts have been made to suggest various technical solutions to combat climate change. Energy efficient and green building, sanitary landfill, UASB and other anaerobic technologies and water hyacinth as well as other similar aquatic plant based waste water treatment system are some effective technical solutions to prevent global warming/ climate change. Green buildings are being constructed all over the country which not only take care of energy conservation but also look into water and waste management, environmental impact, minimum destruction of natural resources and various other aspects in an integrated way. Keywords: green building, anaerobic technology, sanitary landfill, water hyacinth. INTRODUCTION : Perhaps the biggest challenge before India today is how to provide energy to its people-energy to light their homes and hearth, energy to run the wheels of development, energy to maintain the spectacular growth rate achieved in recent years. The ends of our fossil fuel reserves is on the horizon. Generation of electricity from renewable sources like the sun and wind is proving to be expensive, yet we know that our commitment towards arresting global warming and the ill effects of climate change means that we must rapidly move towards green and cleaner energy sources. How we obtain and use energy is likely to play a crucial role in our environmental future. Burning fossil fuels, making cement, cultivating rice paddies, clearing forests and other human activities release carbon dioxide and other so called green house gases which trap heat in the atmosphere. Over the past 200 year, atmospheric CO2 concentrations have increased about 30 percent. Climatologists warn that by 2100, if the current trends continue, mean global temperature will probably warm between 1.50 and 60 C. Global climate change is already affecting a wide variety of biological species. Further warming is likely to cause increasingly severe weather events, including droughts in some areas and floods in others. Melting alpine glaciers and snowfields could threaten water supplies on which millions of people depend. Rising sea levels already are flooding low lying islands and costal regions while habitat losses and climate change are affecting many biological species. Global climate change is really a greater threat than terrorism because it could force hundreds of millions of people from their homes and trigger economic and social catastrophe.


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GREEN HOUSE GASES AND EEFECTS OF GLOBAL WARMING : Climate change has become serious threat to society affecting environment, ecosystems and biodiversity. The ever increasing consumption of fossil fuels is the major cause behind climate change. The earth is a self balanced thermal system. The minor changes in atmosphere are adjusted themselves due to large mass of earth and surrounding atmosphere. The man’s activity on the earth is easily digested, but it has been found in past two decades that man’s activity has changed considerably and brought the world on the brink of environmental disaster. Our dependency on carbon based fuels has resulted in rapid increase of atmospheric concentration of green house gases and the outcome is global warming resulting in more frequent severe weather conditions. Since the onset of industrial age, the green house effect has been enhanced rapidly adding the large amount of GHGs (Green House Gases) to atmosphere. The USA leads in per capita emission of green house gases. Three GHGs- Carbondioxide, Methane and Nitrous Oxides are together responsible for approximately 88% enhancement of GHGs. The rate of increase is 20% since 1990. CO2 is the most important among GHGs and most of it is due to burning of fossil fuels such as coal, oil and gas. Rising of CO2 is also related to deforestation. According to energy information administration per capita emission of CO2 from fossil fuels in 2004.

Table- 1: Per Capita Emission of CO2 from Fossil Fuels Country North America USA Europe Russia Africa China Japan India

Total Emission (million metric tons) 688688 591221 465343 168484 98655 470728 126210 111284

Emission per capita (metric tons) 15.99 20.18 7.96 11.70 1.13 3.62 9.91 1.04

The four major sinks of carbon are atmosphere, the terrestrial bio-sphere (trees and fresh water systems) oceans and sediments. Currently the atmosphere contains approximately 370ppm of CO2 which is the highest concentration in 4,20,000 years and perhaps as long as 2 million years. Estimates of CO2 concentration at the end of 21st century is 490 to 1260 ppm or 75% to 350% increase above pre-industrial concentrations. This confluence of speed and quantity of emission has created unprecedented climate change. The effect of global warming on earth could be enormous. It is a slow moving problem. We can not wait and see. If we wait it may become unsolvable. The climate shift will be unstoppable. Growing food may become difficult. The frequency of storms may increase and the sea level may rise. Flooding of the Kosi rivers over the past two years has driven millions from their homes in Bihar and Nepal. Cyclones Alia and Narges have killed thousands and displaced millions more in Burma, Bangladesh and West Bengal. Terrestial rains have caused terrible land slides across the Himalayas. And now a weakened monsoon is causing a drought which threatens hundreds of millions of farmers all over India, Bangladesh and Nepal. Once again, the number of farmer suicide is increasing. While none of these natural disasters can be directly attributed to climate change, scientists predict that they will become more frequent and more severe unless we act. A study conducted by Geological survey of India in the year 1999 revealed that glaciers in the Himalayas are retreating at an average rate 50 feet (15 meter) per year since 1970’s. Average glacial retreat in Bhutan is 100-130ft (30-40m) per year3.

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Similarly a number of glaciers of Himalayas has disappeared leaving the naked rock of the mountains and after subsequent heating landslides has been common phenomena because of melting of ice of the inner crust. According to Media news broadcast at 8 PM on 22nd of August 2009 on Aaj Tak channel the mountains of Himalayas are cracking. A major complication as reported by the channel is the imbalance of the weight of the two hemisphere of the globe because of melting of glaciers in one part and deposition of water on the other part which is resulting in the bending of the angle of inclination of the globe which is 23 0. Such a change in the angle of inclination may have far reaching effect on length of days and night, weather and climate. The rivers of India are retreating at rate of 10 – 15 meters per year1.

TECHNICAL SOLUTIONS : Our biggest challenge is how to control green house gases. However, Scientist & Engineers have developed many ways to control green - house emissions. Substitute natural gas for coal, promote energy efficiency in homes and industry. Nuclear power also is being promoted as an alternative to fossil fuels. It is true that nuclear reactions don’t produce green house gases, but security worries and unresolved problems of how to store wastes safely make this options unacceptable to many people. Many people believe renewable energy sources offer a better solution to climate problems. There are many options for conserving energy and switching over to renewable sources such as solar, wind, geothermal, biomass, and fuel cells. In India MNRE, Public and Private sector organizations have done tremendous work on field scale on renewable sources of energy. Denmark, the world’s leader in wind power, now gets 20 percent of its electricity from windmills. There are plans to generate half of nations electricity from offshore wind forms by 2030. Even China reduced its CO2 emissions 20 percent between 1997 and 2005 through greater efficiency in coal burning and industrial energy use. There are other options for capturing and storing CO2 available in the atmosphere. Dr. Klam S. Laclmer2 of Columbia University has proposed building synthetic trees to capture CO2 from the air. In this process, a solution of calcium hydroxide solution is trickled across the leaves which would absorb CO2. A structure with 2500m2 of collecting area could remove 90,000 tones of CO2 per year from the air ie. 1000 times more than a natural tree. Although critics claim that synthesizing the hydroxide needed for this reaction and disposing of vast amount of calcium carbonate, it would create may take more energy than the fuel that produced the CO2 released. The first of these trees is now being built in Arizona. Another way to store CO2 is to inject it into underground strata or deep ocean water. It might also be possible to pump liquid CO2 into deep ocean trenches where it would form lakes contained by enormous water pressure2. However there are worries about what this might do to deep ocean fauna and what might happen if earthquakes or landslides caused a sudden release of this CO2. In Canada an Alberta power plant is injecting CO2 into a coal seam too deep to be mined. The CO2 releases natural gas which is burned to produce electricity and more CO2. All such projects are called carbon managements projects. However, scientists argue that it may be cheaper to clean up fossil fuel effluents than to switch over to renewable energy sources. Our attention is mainly on CO2 because it lasts in the atmosphere, on an average, for about 120 years. Methane and other green house gases are much more powerful infrared absorbers but remain in the air for a much shorten time. Methane from landfills, oil wells and coal mines is simply vented into the air. Now it is being collected and used to generate electricity. Methane is produced as a result of anaerobic decomposition of organic waste lying hither and thither. Refuse should be carried and dumped into low lying areas under an engineered operation designed and operated according to the acceptable standards as not to cause any nuisance or hazard to public health or safety. Such engineered disposal of solid wastes are called sanitary land filling. Sanitary


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Landfill is the engineering solution for the disposal of solid waste and a systematic ventilation system is provided at the site to collect and use methane and other gases. Methane is important green house gas which absorbs heat 25 times more than that of CO2. For a country like India where there is acute power crisis, anaerobic treatment technology of solid waste and liquid waste like Upflow Anaerobic Sludge Blanket (UASB) system and others must be encouraged. Many UASB plants for the treatment of municipal waste water and industrial waste water had been commissioned in U.P., Haryana and in other parts of the country successfully. UASB technology is a self sufficient, clean and green technology which treats liquid waste very efficiently and at the same time it gives methane gas, a source of energy to run the plant. Encourage water hyacinth and other aquatic weed based waste water treatment technology which will enhance photosynthetic activity consuming CO2 and releasing oxygen in the atmosphere. Green Building : Buildings have major environmental impacts over their entire life cycle. Resources such as ground cover, forests, water and energy are depleted to give way to buildings. A green building depletes’ the natural resources to the minimum during its construction and operation. The aim of a green building design is to minimize the demand on non-renewable resources, maximize the utilization efficiency of these resources, when in use, and maximize the reuse, recycling and utilization of renewable resources4. In sum, the following aspects of the building design are looked into in an integrated way in a green building. 1. Site Planning 2. Building Envelope Design 3. Building System Design (HVAC) heating ventilation and air conditioning, lighting, electrical and water heating. 4. Integration of renewable energy sources to generate energy on site. 5. Water and Waste Management 6. Selection of Ecologically sustainable materials (with high recycled content, rapidly renewable resources with low emission potential etc.). 7. Indoor environmental quality (maintain indoor thermal and visual comfort and air quality). 8. The government has decided to make it mandatory for new building to undertake energy efficient measures, rainwater harvesting and use recycled construction, material in parts under the sustainable habitat mission of the national action plan on climate change. Energy efficient solar buildings are constructed based on the techniques of solar passive design with a view to provide comfortable living and working conditions, both in winter and summer. These buildings can be integrated with renewable energy and energy conservation devices and systems, and can save over 30% to 40% of conventional energy that is used for lighting, cooling or heating. Such buildings have been tried out in few states as a result of initiatives taken by the MNRE. Finding the concept of solar building useful, the state governments of Himachal Pradesh, Punjab, Haryana and Nagaland have already made it mandatory to construct all new buildings in the government and public sectors with this concept. Bio-fuel or fuel derived from non fossil plant sources is being seen today as a cleaner alternative to diesel. Bio-fuel development in India centers mainly around the cultivation and processing of Jatropha plant seeds to give bio-diesel and producing ethanol from sugarcane. Ethanol can be blended with petrol for auto mobiles. Similarly, bio-diesel can be blended with high speed diesel for transport vehicles, generators, railway engines, irrigation pumps etc. Large volume of such

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oils can also substitute imported oil for making soap. In its National bio-fuel policy the government of India has set a target of a minimum 20% ethanol blended petrol and diesel across the country by 2017. Bio-diesel plantations would be encouraged only on waste community/government/forest lands, and not on fertile land. The issue of the 4 ‘R’s : The four ‘R’s are reduction of waste, reuse of materials, recycling of waste and resource recovery. Adoption of such principle would improve our environment as a whole in addition to helping fight climate change. Engineering fraternity has a special role to play to neutralize the adverse effects on the climate. Scientists and engineers have been continuously working on many fronts to save the environment. Conservation of water, efficient management of solid wastes and generating wealth from them by recycling process are becoming the key areas where engineers are putting emphasis. India is an energy deficit country. It is felt that engineering solution to combat climate change needs to put more emphasis on renewable sources than non renewable sources of energy. Renewable or nonconventional sources of energy like wood energy, wing energy, solar energy, tidal energy, hydropower, biomass energy, bio-fuels, geothermal energy and hydrogen energy are some important options where on scientists and engineers are working and getting success. Use of low emission technologies in various sections of application is the need of the day.

Conclusion : Climate change is one of the most important global environment challenges that need global solution. Deforestation, depletion of ozone layer and green house effect are major causes of climatic change. To solve the climate crisis, we must make a whole scale shift to renewable energy technologies as soon as it becomes technically efficient and commercially viable. Energy efficient and green building, sanitary landfill, UASB and other anaerobic technologies and water hyacinth and other similar aquatic plant based waste water treatment system are some effective technical solutions to prevent global warming/climate change. At the same time we have to use advance technology to reduce green house gases emerging out from burning of fossil fuel. Better design and proper maintenance of pollution control devices are equally important in reducing green house gases and to combat climate change. Engineers need to come up with a solution that people will actually use while at the same time be beneficial to the earth’s ‘health’. In other words, they need to find the light at the end of the tunnel.

REFERENCES : 1. Aaj Tak Tv. Channel 8PM Special Report on 22.07.09 Climate change. 2. Cunning Ham, William P., and Mary Ann, 2007, Principles of Environmental Science Inquiry and Applications, Tata Mc Graw-Hill Publishing Company Ltd., Fourth Edition. 3. Kaul, M.K. et.al. (ed. 2002), Geological Survey of India, 1999, Inventory of the Himalayan Glaciers: Contribution to the International Hydrological Programme, Special Publication No. 34. Effect of global warming on snow ablation pattern in the Himalaya, Current Science, 83, 2: 120-123. 4. Mehrotra, Minni, March-April 2008, Mainstreaming green building in India, Akshay Urja, vol. 1, pp. 31-34.


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GLOBAL WARMING: SOME CONTROVERSIAL ISSUES

Syed Murtuza Abbas B.Tech III, Civil Engineering Department, Zakir Hussain College of Engineering and Technology, Aligarh Muslim University, Aligarh. e mail: [email protected] Phone no. : +919956563554

Naman Kumar B.Tech III, Civil Engineering Department, Zakir Hussain College of Engineering and Technology, Aligarh Muslim University, Aligarh. e mail: [email protected] Phone no. : +919997526409

Abstract: In the present scenario, the phenomenon of Global Warming is of utmost concern. It is the process by which absorption and emission of infrared radiation by atmospheric gases warm a planet's lower atmosphere and surface. Over the years, the unnatural human activities have been held responsible for the said change. But several environmentalists have provided contradictory facts which indicate that Global Warming is a part of cyclic events which have continued over 1000s of years, even before mankind evolved. There are pools of data, which can be used to support both sides of the debate or most of the inferences can be straightforwardly disputed by another rival school of thought, to draw contradicting conclusion. Keeping these facts in view, it may be mentioned that everyone in the humansociety should take precautionary measures to adopt a type of life-style to achieve the goal of sustainable development for protection of the life on the Earth in longer run.

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1. INTRODUCTION Global warming is the process by which absorption and emission of infrared radiation by atmospheric gases warm a planet's lower atmosphere and surface. Existence of the greenhouse effect as such is not disputed. The question is instead how the strength of the greenhouse effect changes when human activity increases the atmospheric concentrations of particular greenhouse gases, mainly CO2. Global releases of carbon have been rising steadily since late eighteenth century and more rapidly since 1950s. In fact, yearly emissions at present have quadrupled since 1950 (Earth Policy Institute, 2004). CO2 levels have increased significantly since the Industrial Revolution and are supposed to continue like this in near future also. It is logical to consider that activities of the mankind has been mainly accountable for much of this enhancement because the mankind is liberating carbon from beneath the Earth's surface and putting it into the atmosphere.

Fig: Showing the Earth’s Green House Effect After Industrial Revolution, composition of the atmosphere has been undergoing significant changes in terms of both, quality and quantity. One of the first indications that human beings have led to modifications in composition of the global atmosphere comes from measurements of the atmospheric carbon dioxide at Mauna Loa, Hawaii, USA; which have indicated an increase in the CO2 level from 316 ppm in 1959 to 373 ppm in 2002. This rise in CO2 concentration is closely associated with enhancement in consumption of fossil fuels (Keeling and Whorf, 2004).

2. POTENTIAL OUTCOME 2.1 Rising Temperatures The average surface temperature of the earth has increased by about 1°F in the past century. To many, a 1°F temperature change may seem trivial. However, consider "the year without a summer" - 1816. Atmospheric ash from a volcanic eruption in Southeast Asia decreased solar radiation reaching the earth's surface, lowering the global mean temperature. As a result, frost occurred in July in New England and crop failures occurred throughout the world. Yet the temperature change caused by this eruption was less than 1°F (Stommel et al. 1979).


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Surface temperature increases are projected to increase 1.8-6.3 °F in the next century, with scientists' best guess being about 3.5 °F. Scientific modeling suggests that the surface temperature will continue to increase beyond the year 2100 even if concentrations of greenhouse gases are stabilized by that time. However, if carbon dioxide emissions continue to increase at present rates, a quadrupling of pre-industrial CO2 concentration will occur not long after the year 2100. Projected temperature increases for such an atmospheric concentration are 15-20 °F above the present day mean annual global surface temperature.

2.2 Sea Level Rise Increasing global temperatures causes the thermal expansion of sea water and the melting of icecaps which will result in rising sea level. Sea level has risen 4 to 10 inches this century and is predicted to rise another 6 to 37 inches in the next century. A doubling of pre-industrial CO2 concentration (550 ppm) is predicted to result in a sea level rise of greater than 40 inches. A sea level rise of 80 inches is projected for an atmospheric CO2 concentration of 1100 ppm, a quadrupling of pre-industrial levels. Sea level rise increases the vulnerability of coastal populations to flooding and causes land to be lost to erosion. There are currently 46 million people around the world who are at risk due to flooding from storm surges. With a 50 cm sea level rise (approx. one and ½ feet), that number will increase to 92 million. Raise sea level 1 meter (about 3 feet) and the number of vulnerable people become 118 million. A 1 meter increase in sea level will be enough to flood 1% of Egypt, 6% of the Netherlands, 17.5% of Bangladesh, and 80% of the Majuro Atoll in the Marshall Islands. Rising waters might force the occupants of numerous small island nations to migrate elsewhere; as many of them lack the coastal defense systems to cope with higher water levels.

2.3 Intensification of the Hydrologic Cycle Warming will likely result in an increase in the amount of water exchanged among the oceans, atmosphere, and land. Increasing rates of evaporation will likely result in drier soils. An accelerated hydrologic cycle means greater amounts of precipitation in some areas and will probably result in more frequent and severe droughts and floods. This prediction has rung true already. In the early '90's, two 100year floods occurred in less than 5 years in the Midwestern United States. Significant changes in water volume, distribution, and supply are predicted and will likely have a dramatic impact on regional water resources.

2.4 Health Effects A warming earth will most likely have a spectrum of largely negative impacts on human health. The predicted decrease in the difference between day and night temperatures will result in more thermal extremes. Therefore, an increase in mortality from heat stress is likely (e.g. 465 deaths in Chicago during the summer of 1995). As a result of warming, the area of the earth's surface experiencing "killing" frosts will probably decline. As a result, there will likely be an increase in the geographical range of vectorborne (e.g. mosquito carried) diseases such as malaria, dengue, yellow fever, and encephalitis. Currently, 45% of the world's population is within the zone of potential malaria transmission. With predicted temperature increases, there will likely be an additional 50 to 80 million cases of malaria worldwide, bringing the percentage of the world's people within the susceptible zone to 60%. It is also likely that increasing temperatures will result in a decline in air quality due to increases in the abundance of air pollutants, pollen, and mold spores. An increase in the number of cases of respiratory disease, asthma, and allergies is likely to follow. The change in the frequency and intensity of extreme weather events (e.g. floods and droughts) combined with warmer atmospheric temperatures will probably

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result in a host of adverse health effects, among them, exposure to contaminated water supplies and death from diseases.

2.5 Dramatic Effects on Ecosystems Both plant and animal species are sensitive to climate. Due to global warming, ideal temperature and precipitation ranges suitable for present life forms may shift dramatically and rapidly, more rapidly than the species that depend upon them can adapt to, naturally. A decline in biodiversity and in the goods and services provided by most ecosystems is a likely result. However, a lengthening of the growing season is also predicted for some high latitude regions. This means that these regions will likely experience an increase in potential for agricultural production.

2.6 Forests Within the next 100 years many forest species may be forced to migrate between 100 and 340 miles in the direction of the poles. The upper end of this range is a distance typically covered by migrating forests in millennia, not in decades. A decline in species composition is predicted and some forest types may disappear from the earth, while new ones may be established.

2.7 Rangelands Changes in growing seasons and shifts in the boundaries between grasslands, forests, and shrub lands are projected results of changing temperature and precipitation regimes. Increased levels of carbon dioxide in the atmosphere may result in a decline in food values of grasses for herbivores.

2.8 Deserts Desert regions are likely to be more extreme, becoming even hotter than they are presently. The process of desertification will be more likely to become irreversible due to drier soils and land degradation through erosion and compaction.

2.9 Cryosphere In the next 100 years between one third and one half of the world's mountain glaciers could melt, affecting the water supply to rivers and thus hydroelectric dams and agriculture. As is already being observed in Alaska, the aerial extent and depth of permafrost are projected to decline, resulting in adverse effects on human infrastructure. A decrease in the extent and thickness of sea-ice will likely improve the navigability of the Arctic Ocean.

2.10 Mountain Regions Warming temperatures will probably induce a shift in the distribution of vegetation to higher elevations. Living creatures that exist only at high elevations will possibly become extinct due to the disappearance of habitat or the decline in migration potential. Recreational industries (e.g. ski industry) are likely to be disrupted, having a severe adverse effect on the economies of some regions. The high elevation populations of developing nations will probably suffer from a decline in the abundance of food and fuel.


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2.11 Lakes, Streams, Wetlands Climate change is predicted to alter water temperatures, flow regimes, and levels. Such changes will likely cause an increase in biological productivity at high latitudes, but may result in extinctions for low latitude, cool and cold water species. Increased variability in flow, which will result if the frequency and duration of large floods and droughts increases, will tend to reduce water quality, biological productivity, and the habitat in streams.

2.12 Coastal Systems Climate change and sea level rise, or changes in storms or storm surges could cause the erosion of shores and associated habitat, an increase in the salinity of estuaries and freshwater aquifers, a change in tidal ranges in rivers and bays, a change in sediment and nutrient transport, a change in the pattern of chemical and microbiological contamination in coastal areas, and an increase in coastal flooding. The ecosystems at risk are salt water marshes, mangrove ecosystems, coastal wetlands, coral reefs, coral atolls, and river deltas.

2.13 Oceans Changing atmospheric temperatures will change patterns of ocean circulation, vertical mixing, wave climate, and quantities of sea-ice cover. These changes will affect nutrient availability, biological productivity, and the structure and function of marine ecosystems. Paleoclimate (past climate) data and models show that major changes in ocean circulation can be caused by freshwater additions to the oceans from the movement and melting of sea ice or ice sheets and can result in rapid and dramatic changes in climate. Abrupt shifts in climate have had adverse effects on human civilizations in the past. Paleoclimate data suggest that the collapse of the Mesopotamian Empire about 4,200 years ago (2,200 BC) corresponds to a sharp cooling event (Alley & deMenocal, 1998).

2.14 Fisheries Rising temperatures are not predicted to change the global average production; however, significant regional changes are likely. Production is projected to increase in high latitudes, in freshwater and from aquaculture. Warmer climates should increase the growing season, decrease natural winter variability, and improve growing rates in high latitude regions. However, these beneficial results may be counterbalanced by changes in reproductive patterns, migration routes, and ecosystem relationships.

2.15 Food Production Total global food production is not expected to change substantially as a result of climate change, but production will probably change dramatically regionally. Some areas will have increasing crop yields. Others will decline, especially in tropical and subtropical regions. The flexibility in crop distribution is predicted to decline. Developed countries may be able to adapt to these circumstances. Developing countries that currently struggle with these issues will suffer even more.

3. CONTROVERSIAL ISSUES The rise (still controversial in terms of magnitude) in average surface temperature of Earth is due to a phenomenon, commonly referred to as green house effect (GHE). This process is also supposed to be resulting in various changes in climate of this planet, though such changes have been characteristic

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features of the Earth for quite long in geological time-scale. As a matter of fact, Europe has suffered something like Ice Age from 1500 to 1800 AD. For long, GHE has caused desirable warming of the globe due to which water exists on it at triple point, i.e., in all three phases of matter – solid, liquid and gas. Due to this reason only, the life on Earth could originate or/and evolve up to the present state of existence. Without such a phenomenon, the Earth might have been a totally frozen ball of different rocks. At present, a big controversy also lies around as to what extent anthropogenic activities can lead to alterations in climate. The gaseous culprits, being named at present responsible for this phenomenon, are CO2, CH4, N2O, tropospheric O3, water vapour and various chlorofluorocarbons. It has been observed that atmospheric level of CO2 has continued to increase in historic times and keeps on following the same trend with enhanced rate prevailing now. It is also noticed that water level in sea has gone up as recorded in (at least) the past two centuries. But, it is yet to be proved beyond doubt that the increase is not due to natural land movements. Many glaciers, located in different continents, have also either totally disappeared or been retreating for a long time. In about the last 150 years of measurements, temperature of the Earth’s surface has been recorded to rise significantly from 1920-1940 (20 years period) and from 1979-1994 (15 years). Whether this rise still continues, will persist or not is also a matter of central controversy? Very complex general circulation (computation) models (GCMs) include data regarding concentration of green house gases, their sources and sinks, atmospheric and ocean circulation, etc. Huge number of variables (most of which are beyond human control) can lead to many types of uncertainties related to various intriguing issues involved in global warming and the consequent climate changes. GCMs have been employed to make a forecast that the temperature rise should have been about 0.25°C every decade, but actually observed increase has been about 0.09°C per decade. This difference may be supposedly due to release of huge quantities of SO2 in the atmosphere from natural as well as man-made sources. This SO2 is ultimately converted into sulfate-aerosol, which reflects the incoming sun-light to Earth and consequently, helps in bringing down the temperature. Some contentious issues regarding global warming and climate changes may be mentioned in brief as below (Anderson and Andrews, 1999; Comisco, 2000; Joughin and Tulaczuk, 2002; Lin, Curry and Martinson, 2004; Lomborg, 1998; Parkinson, 2002; Thompson and Solomon, 2002; Vyas et al, 2005). (i) Atmospheric CO2 levels have not invariably been higher during the recorded inter-glacial periods. (ii) Increased evaporation due to global warming will lead to higher cloud cover and consequent counteractive action to temperature-rise. Other group of scientists is of the opinion that enhanced cloudcover may also aggravate the global warming. (iii) Skeptics point out that the GCMs which have been employed to forecast global warming are developed with very little data. They believe that the rise in temperature will be slower than the predicted results and so, it will be gradual enough even for higher forms of life to undergo adaptation successfully. (iv) A large number of climatologists have the opinion that 0.3-0.6°C increase in temperature (observe to date) may be due to natural variability and may not be related to enhancements in concentrations of different GHGs, specifically CO2. (v) Some scientists argue that making major changes (before conclusive evidence) may be very expensive and even, counter-productive. (vi) Other groups of scientists have the opinion that another Ice Age (thousands of years away in future) will be preceded by significant warming in the coming centuries. (vii) Many experts believe that if afforestation is carried out at a large scale around the melting glaciers, their retreating trends may be reversed. (viii) From 1986-2000, Central Antarctic valleys have undergone cooling at a rate of 0.7°C per decade and it has led even to an ecosystem-damage from cold. It has also been observed that in a relatively small geographical region known as Antarctic Peninsula, melting of ice and calving of huge iceberg has been continuing for a long time. Measurements at ground-stations and also data from satellites reveal that there is a mild cooling at Antarctic for more than about the last 20 years. But, the latest reports have revealed a frightening fact that western part of the continent has also started warming up.


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(ix) Some radar measurements have exhibited that in West Antarctic, ice has been increasing at the rate of 26.8 gigatons (GT) every year. Enhancing quantitative trend in sea-ice-mass at Antarctic is being observed since 1979 and the rate may even be accelerating in near future. It presents a reversal of trends, observed in the last 6000 years. Though ice shelves at Antarctic have retreated, sea-ice has been increasing. (x) During the last four interglacial periods (in about 4,20,000 years), the Earth has been warmer than it is at present and relatively less amount of ice has melted now than what has happened earlier. (xi) Larger part of Antarctic undergoes a longer (about 21 days) sea-ice season than that occurred in 1979. (xii) It is commonly believed that as a consequence of climate changes, there may be ever increasing occurrences of extreme weather-conditions, hurricanes, tornadoes, tsunamis and cyclones in near future.

Thorough scientific studies have demonstrated that there is no evidence for such claims. On the other end, it has been observed that there has been no rise in the number of hurricanes recorded so far in the United States of America. Rise in average temperature of Earth’s surface has been recorded since early 1880s and may be continuing from the last Ice Age. Thus, industrialization which is held responsible for increasing carbon dioxide levels can not be considered solely responsible for all this because it seems to be also a part of the natural trend. It is noticed from 1940 to 1970 that the carbon dioxide levels have increased continuously, but the temperature has decreased to the extent of causing damage due to incidence of frost in summer and also resulting in some European glaciers to move forward. Moreover, data from satellites (in orbit about five miles high) recorded since 1979 have revealed that upper atmosphere is warming much less in comparison to surface of the Globe. In addition, other sets of data reveal that there has been no abnormal rise in South Pacific sea levels for over the last thirty years. The sea level has definitely been going up, but this has been taking place for about the last 6000 years, dating from the Holocene era. The sea level has been increasing at a rate of 10 to 20 centimeters in a period of every hundred years and no irrefutable proof exists to ascertain that the present rate of increase in sea-water level is faster than that observed earlier. At present, there are about one hundred sixty thousand glaciers in the world. There are extensive massbalance records extending for a time-span of five years or more for only seventy nine glaciers on Earth. Some glaciers like that at the mountain of Kilimanjaro have been quickly receding since the 1800s, earlier than the recorded global warming. This has happened despite a constant temperature at the altitude of the mountain. This has happened because the rain forests at base of the mountain has been destroyed and consequently, the air blowing upward carries very little moisture-content with it at present. Many experts feel that if afforestation is done, the glacier may start growing again. To complicate the phenomenon of temperature-rise further, there may be another significant feature, popularly recognized as ‘heat-island’ effect. This is a phenomenon which makes croplands and villages, towns or cities warmer than the nearby forest areas. Mostly, human settlement or urbanization and related activities lead to a rise in temperature. Consequently, at most of the weather-stations, relatively higher

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temperature has been being recorded due to this effect in comparison to the (earlier) situation, when the same stations were located in rural areas and presently, these are surrounded by various structures in urban areas. If one compares the prevailing trends of the temperature records in case of cities with those areas where no urbanization has occurred, e.g., Death Valley, one can observe that the regions without urbanization have demonstrated practically no significant enhancement in temperature. As a matter of fact, certain smaller cities have even shown cooling trend on the whole.

Comparison of meteorological variables for urban and rural areas Variable Daily temperature minima Relative humidity, summer Total wind movement Solar radiation Total precipitation Cloud cover, all types Frequency of fog, winter

Urban value related to rural value, average 2.5°C higher 8% lower 25% less 15% less 10% greater 10% greater 100% greater

To bring down the impact of various hazards which may arise on account of particularly the global warming, Kyoto Global Warming Treaty has identified a number of actions to be taken. This Treaty has been opposed by both the USA and Australia. As a matter of fact, the 1997 Leipzig Declaration described this Protocol as ‘dangerously simplistic, quite ineffective and even economically destructive to jobs and standards-of-living’. Some forecasts have exposed that the effect it would have produced, had it have been provided total cooperation, would have been to decrease the warming by only 0.04°C in the year 2100 AD, but this might have been accompanied with an exceptional economic cost (Henriques, 2006).

4. CONCLUSION Present level of understanding in the realm of climate-related sciences can enable none to conclude exactly as to what is going on currently at large and what may come in future, near or far. There are pools of data, which can be used to support both sides of the debate or most of the inferences can be straightforwardly disputed by another rival school of thought, to draw contradicting conclusion. Keeping these facts in view, it may be mentioned that everyone in the human-society should take precautionary measures to adopt a type of life-style to achieve the goal of sustainable development for protection of the life on the Earth in longer run. Even though there are many uncertainties and controversial issues related to global warming and the ensuing climate changes, many steps being proposed to mitigate these phenomena are worth taking at the earliest because measures like improved fuel-economy, maintaining and re-establishing the forests, stabilizing the world population etc. have many other desirable consequences, which may be directly unrelated to global warming.

REFERENCES Howard S. Peavy, Donald R. Rowe and George Tchobanoglous (1985), Environmental Engineering, 509. Ankit Mathur, Mariyam and Ankana Dey, Global Warming, Proceedings, National Conference on Recent Advances in Civil Engineering, Shilp’09, IT BHU. Devendra Mohan, Global Warming: Some Contentious Issues, Proceedings, National Conference on Recent Advances in Civil Engineering, Shilp’09, IT BHU. Lars Hagen (2007) http://www.roanokeslant.org/GlobalWarmingThoughts The science of climate change, contribution of working group 1 to the second assessment report of the Intergovernmental Panel on Climate Change, UNEP and WMO, Cambridge University Press, 1966.

Sustainable Environment


Paper Presentation:

International Conference On Emerging Technologies in Environmental Science & Engineering October 26-28, 2009 At Aligarh Muslim University

Abstract Title of the Paper: Protection and Preservation of the Marine Environment-Role of National and International Legislations Submitted by: Benjamin.E Senior Lecturer in Management De Paul Institute of Science & Technology De Paul Nagar, Angamaly South Kerala-683573 Phone (College) 0484-2454336, 2459122 Phone: Mobile: 09846516081

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ABSTRACT Title of the Paper: Protection and Preservation of the Marine Environment-Role of National and International Legislations The oceans had long been subject to the freedom of the sea doctrine—a principle put forth in the seventeenth century essentially limiting national rights and jurisdiction over the oceans to a narrow belt of sea surrounding a nature’s coastline. The remainder of the sea was proclaimed to be free to all and belonging to none. While this situation prevailed into the twentieth century, by mid-century there was an impetus to extend national claims over offshore resources. There was growing concern over the hill taken on coastal fish stocks by long distance fishing fleets and over the threat of pollution and wastes from transport ships and oil tankers carrying noxious cargoes that piled see routed across the globe. The hazard of pollution was ever present, threatening coastal resorts and all forms of ocean life. Pollution of the marine environment includes the introduction by man, directly or indirectly of substance or energy into the marine environment, including estuaries which results in harm to living resources and marine life and also hazard to human health. The health of the world’s oceans is degrading as a result of human activities. Furthermore, as the human population continues to grow and extend the range of its activities, as well as increase its demands for marine goods and services, the world’s oceans and coasts will be increasingly stressed In order to protect and preserve the marine environment global and regional cooperation is desirable. The states shall cooperate on a global basis and appropriate on a regional basis, directly or through an international organization in order maintain standards to protect and preserve the marine environment. Marine pollution prevention and control arising from land-based sources, sea-bedactivities subject to national jurisdiction are covered quite extensively under the United Nations Convention on the Law of the Sea. States are bound to prevent and control marine pollution from any source and are liable for damage caused by violation of their international obligations to combat pollution. The United Nations Convention on the Law of Sea provides for the protection of marine environment in a diverse manner. The convention delegate the member nations to protect the marine environment with the help of national legislation This paper reveals the role of national and international legislation to protect and preserve the marine environment. Key words: Marine Pollution, National marine law, preservation,

Benjamin.E


Title: PROTECTION AND PRESERVATION OF THE MARINE ENVIRONMENT-ROLE OF NATIONAL AND INTERNATIONAL LEGISLATIONS Author Benjamin.E Senior Lecturer in Management De Paul Institute of Science & Technology De Paul Nagar Angamaly, Ernakulam Kerala -683 573

INTRODUCTION Our oceans remain as one of the final frontier: unexplored, unknown and in some places, unreachable. Every second breath we take comes from the oceans. We rely on them for food, for recreation and the very life we all too often take for granted. In return, we are choking them with pollution and destroying the marine environment that enables us to live rich and enjoyable life. Since the days of ancient Phoenician mariners, sea goers have been dumping their trash at sea. Back on those days, the oceans could easily handle the waste, but today both the nature and the quantity of trash have changed greatly.

THEORETICAL BACKGROUND At least two reasons allow us to consider pollution as the main, most widespread, and most dangerous factor of anthropogenic impact on the hydrosphere. First, pollution accompanies most kinds of human activities, including offshore oil and gas production and marine oil transportation. Second, in contrast with land ecosystems, in the water environment, pollutants quickly spread over large distances from the sources of pollution. In the freshwater and inland ecosystems, the effects of pollution are obvious. They literally appear right in front of our eyes. In contrast, the World Ocean has a large inertia of response to all forms of external impact. It requires a long hidden (latent) period to manifest the evidence of non-obvious consequences of this impact. The danger of the situation is complicated by the fact that when it happens, it will be too late to do anything

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The Structure of the Sea-(Legal)

Pollutant input into the marine environment Among all the diversity of human activities and sources of pollution, we can distinguish three main ways that pollutants enter the marine environment:


direct discharge of effluents and solid wastes into the seas and oceans (industrial discharge, municipal waste discharge, coastal sewage, and others); land runoff into the coastal zone, mainly with rivers; atmospheric fallout of pollutants transferred by the air mass onto the seas' surface. Certainly, the relative contribution of each of these channels into the combined pollution input into the sea will be different for different substances and in different situations. Quantitative estimates of these processes are difficult because of the lack of reliable data and the extreme complexity of the natural processes, especially at the sea-land and sea-atmosphere boundaries. For a number of pollutants (metals, nitrates, phosphates, oil and some other hydrocarbons), this task is even more complicated. They are distributed in the marine environment in the background of natural biogeochemical cycles of the same substances. There are numerous examples when extremely high concentrations of oil and gas hydrocarbons, heavy metals, radio nuclides, nutrients, and suspended substances are not connected with human activity at all. It can happen as a result of such natural processes as volcanic activity; oil and gas seepage on the bottom; splits and breaks of the earth's crust; algae blooms; mud flows; river flooding; and many others. These phenomena should be taken into consideration in order to get the objective assessment of anthropogenic impact and its consequences in the hydrosphere. Recognizing these complications explains why many earlier conclusions about the levels, flows, and balance of many substances in the hydrosphere are currently under revision. Developing new approaches and more precise analytical methods to determine trace amounts of contaminants allowed to get more reliable estimates of the contribution of different channels into the total contamination of the marine environment. The data show that land-based and atmospheric sources account for about two-thirds of the total input of contaminants into the marine environment, constituting 44% and 33%, respectively. The main pollution press undoubtedly falls on the shelf zones and especially on the coastal areas.

Sources, composition, and degree of hazards of pollution components We need to mention the extreme diversity of marine pollution components, variety of their sources, scales of distribution, and degree of hazards. These pollutants can be classified in different ways, depending on their composition, toxicity, persistence, sources, volumes, and so on. In order to analyze large-scale pollution and its global effects, it is common to distinguish a group of the most widespread pollutants. These include chlorinated hydrocarbons, heavy metals, nutrients, oil hydrocarbons, surface-active substances, and artificial radionuclide. These substances form the so-called background contamination that exists at present in any place in the hydrosphere. Depending on the type of impact on the water organisms, communities, and ecosystems, the pollutants can be grouped in the following order of increasing hazard: substances causing mechanical impacts (suspensions, films, solid wastes) that damage the respiratory organs, digestive system, and receptive ability;

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substances provoking eutrophic effects (e.g., mineral compounds of nitrogen and phosphorus, and organic substances) that cause mass rapid growth of phytoplankton and disturbances of the balance, structure, and functions of the water ecosystems; substances with saprogenic properties (sewage with a high content of easily decomposing organic matter) that cause oxygen deficiency followed by mass mortality of water organisms, and appearance of specific microphlora; substances causing toxic effects (e.g., heavy metals, chlorinated hydrocarbons, dioxins, and furans) that damage the physiological processes and functions of reproduction, feeding, and respiration; Substances with mutagenic properties (e.g., benzo (a) pyrene and other polycyclic aromatic compounds, biphenyls, radio nuclides) that cause carcinogenic, mutagenic, and teratogenic effects. Some of these pollutants (especially chlorinated hydrocarbons) cause toxic and mutagenic effects. Others (decomposing organic substances) lead to eutrophic and saprogenic effects. Oil and oil products are a group of pollutants that have complex and diverse composition and various impacts on living organisms - from physical and physicochemical damage to carcinogenic effects. To estimate the hazard of different pollutants, we should take into account not only their hazardous properties but other factors, too. These include the volumes of their input into the environment, the ways and scale of their distribution, the patterns of their behavior in the water ecosystems, their ability to accumulate in living organisms, the stability of their composition, and other properties.

Global and regional aspect of Marine pollution It is significant that at the regional and local levels, the intensity of anthropogenic press on the marine environment generally increases. The number and diversity of pollution components is growing as well. The contaminants with global distribution are combined here with hundreds and thousands of ingredients of local and regional distribution. Most of these substances are wastes and discharges from different local industries and activities. Often they are not included in the sphere of chemical-analytical control and monitoring. We usually get to know about their existence in the water environment from various signs of environmental trouble. These include the decline of abundance and various pathologies among fish and other organisms, poisoning or diseases among people, degradation of coastal ecosystems, fouled beaches, unusual algae blooms, and so forth.

Plastic pollution threat to marine environment Every day, more and more plastic is accumulating in our oceans. Recreational boaters improperly dispose of plastic refuse at sea. Plastics also enter the marine environment from sewage outfalls, merchant shipping, commercial fishing operations and beach goers. The world wide fishing industry dumps an estimated 150,000 tons of plastic into the oceans each year including packaging, plastic nets and buoys. A growing threat to the health of our oceans is plastic pollution. Such pollution can linger for years affecting marine environments far from where it


entered the oceans. Plastic poses a serious enough threat to the marine environment that, in 1987, Congress enacted the Marine Plastic Pollution Research and Control Act. This law prohibits the dumping of plastics in all US water bodies and applies to all watercrafts from the smallest recreational boat to the largest commercial ship. Plastic acts like a sponge for poisons such as PCBs, concentrating them at levels a million times higher than in sea water. It fatally contaminates sea water, sea floor and the marine environment as a whole. Careless disposal of plastic in ocean can have dire consequences on marine biodiversity. By discarding plastic thoughtlessly especially fishing gear and packaging, people are accidentally causing the death of millions of mammals, birds, reptiles and fish every year. Plastic can affect marine wildlife in two important ways: by entangling creatures, and by being eaten. Scientists estimate that plastic products are killing up to a million seabirds and over 100,000 sea animals a year. Turtles are particularly badly affected by plastic pollution, and all seven of the world's turtle species are already either endangered or threatened for a number of reasons. Plastic pollution is highly mentionable one. Turtle gets entangled in fishing nets and many sea turtles have been found dead with plastic bags in their stomachs. It is believed that they mistake these floating semi-transparent bags for jelly fish and eat them. The turtles die from choking or from being unable to eat. Under these circumstances, the issue of protecting the world's oceans from plastic pollution has become a burning question to the world community for the conservation of the largest water body and ecosystem of the world. Here one key way to reverse the destruction is a global net work of marine reserves. Currently less than one percent of the world's ocean is protected. Protecting large areas of ocean is necessary to give marine life time to recover from over fishing, plastic and other pollutions, other destructive practices as well as protecting vital habitats.

Marine pollution protection –national legislations The Indian Constitution Under article 297 of the Constitution, all lands, minerals and other things of value underlying the ocean within the territorial waters or the continental shelf of India vest in the Union to be held for the purposes of the Union. India has sovereign rights over the resources of the exclusive economic zone and is entitled to exercise jurisdiction in respect of certain other matters. It is proposed to amend article 297 of the Constitution so as to provide that all lands, minerals and other things of value underlying the ocean within the exclusive economic zone of India and all other resources of the exclusive economic zone of India shall also vest in the Union and be held for the purposes of the Union. At present, the limits of territorial waters and the continental shelf are determined by Proclamation issued by the President. It is proposed that the limits of the territorial waters, the continental shelf, the exclusive economic zone and the maritime zones of India shall be as specified from time to time by or under law made by Parliament.

The Territorial Waters, Continental Shelf, Exclusive Economic Zone and other Maritime Zones Act, 1976, Act No. 80 of 28 May 1976 The Government of Indian is having the liberty to make rules, regulations and can implement within the maritime zones as per the provisions of the Act The Indian territorial waters is the line every point of which is at a distance of twelve nautical miles from the nearest point of the appropriate baseline. Thus sovereignty of India extends and

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has always extended to the territorial waters of India and to the seabed and subsoil underlying, and the airspace over, such waters. The contiguous zone of India is an area beyond and adjacent to the territorial waters, and the limit of the contiguous zone is the line every point of which is at a distance of twenty-four nautical miles from the nearest point of the baseline, the Central Government may, whenever it considers necessary so to do having regard to international law and State practice, alter, by notification in the Official Gazette, the limit of the contiguous zone. In the exclusive economic zone, the Union has, (a) Sovereign rights for the purpose of exploration, exploitation, conservation and Management of the natural resources, both living and non-living as well as for producing energy from tides, winds and currents; (b) Exclusive rights and jurisdiction for the construction, maintenance or operation of artificial islands, off-shore terminals, installations and other structures and devices necessary for the exploration and exploitation of the resources of the zone or for the convenience of shipping or for any other purpose; (c) Exclusive jurisdiction to authorize, regulate and control scientific research; (d) Exclusive jurisdiction to preserve and protect the marine environment and to prevent and control marine pollution; and such other rights as are recognized by International law

Marine pollution protection-International Legislation Protection and preservation of the marine environment under UN Convention of Law of Sea 1982 General Provisions of UNCLOS In the preamble of UNCLOS the importance of establishing a legal order for the oceans that promotes, among other things, the protection and preservation of the marine environment is recognized. At the same time, the preamble recognizes the tension that exists between these and other objectives designed to protect the common interest in the oceans on the one hand, and State sovereignty on the other. The preamble specifically urges Parties to adopt a holistic approach to ocean issues. UNCLOS Article 1 includes the following definition of “pollution of the marine environment”: The introduction by man, directly or indirectly, of substances or energy into the marine environment, including estuaries, which results or is likely to result in such deleterious effects as harm to living resources and marine life, hazards to human health, hindrance of marine activities, including fishing and other legitimate uses of the sea, impairment of quality for use of sea water and reduction of amenities. Article 293 of UNCLOS specifically opens the door to a progressive interpretation of UNCLOS obligations by bringing in other sources of international law not inconsistent with UNCLOS. Taking this into account, it is suggested that a broader interpretation of pollution is more consistent with the plain wording of Article 1and its purpose at the time it was negotiated. It is also one that commentators have advocated in the context of Part XII for example suggested even before the completion of UNCLOS that the general provisions on the marine environment in UNCLOS had to be read to include an obligation to protect threatened species and ecosystem. At the same time some others argued that these provisions include an obligation to protect the fauna and flora of the sea floor from harm. Part XII of UNCLOS deals generally with State obligations with respect to the marine


environment. As early as 1991, Part XII was characterized by academics as constitutional in character, reflecting in part existing customary international law, but at the same time providing the first comprehensive statement on the protection of the marine environment in international law. The starting point for Part XII is the general obligation under Article 192 to “protect and preserve the marine environment”, balanced with a reaffirmation of the right of States to exploit their natural resources “in accordance with their duty to protect and preserve the marine environment”. Pursuant to Article 194, States are obligated to take all measures consistent with the Convention necessary “to prevent, reduce and control pollution of the marine environment from any source, using the best practical means”. Article 194 is central to any analysis of State obligations under UNCLOS to mitigate climate change as it provides the foundation for the following specific obligations that provide some further guidance on what a State may be expected to do to protect and preserve the marine environment: • an obligation for States to act individually or jointly as appropriate; • an obligation to take all measures necessary to prevent, reduce and control pollution of the marine environment; • an obligation for States to use best practical means at their disposal; • an obligation for States to act in accordance with their capabilities; • an obligation to endeavor to harmonize policies with other States; • an obligation for States to control activities under their control or jurisdiction so as to not cause damage by pollution to other States and their environment; • an obligation to prevent pollution from spreading to areas outside of a State’s jurisdiction of control; and • a specific obligation for the preservation and projection or rare or fragile ecosystems, and the habitat of species at risk. Article 195 directs States in taking measures to prevent reduce and control pollution of the marine environment, to prevent the transfer of harm from one type or area to another. While the exact scope of this provision is not clear, it does, at a minimum, introduce the concept that mitigation measures must be designed so as to not result in other environmental damage, an issue that has been the subject of considerable controversy in the context of climate change. In so doing, UNCLOS may have been ahead of its time by providing a simple, yet potentially very effective tool to require States to take a holistic approach to addressing environmental issues. Article 212 is another provision of UNCLOS that, while not drafted with climate change in mind, can now be reasonably interpreted to apply to the issue. Article 212 obligates States to adopt laws and regulations and take other necessary measures “to prevent, reduce and control pollution of the marine environment from or through the atmosphere”. It essentially obligates States to prevent or control pollution from or through any air space over which a State has jurisdiction. Similarly, Article 207, dealing with pollution from land-based sources, is sufficiently broad to cover GHG emissions. It requires States to endeavor to establish regional and global rules to prevent, reduce, and control marine pollution from land-based sources. In determining a Party’s contribution to such efforts, economic capacity and need for economic development are to be taken into account. Article 213 requires States to enforce domestic laws passed in accordance with Article 207 and any other international obligation to address land-based sources of marine pollution. Overall, these provisions appear to be weaker than Articles 192 to 195 in that they only require States to endeavor to control pollution, and are, therefore, less likely to play a significant role in determining State obligations to mitigate climate change.

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Regional approach in ocean governance Ocean regionalism can be generally defined as the management of the oceans and their resources at the regional level. Environmental problems of ocean are as diverse as the ocean themselves. Certainly, different regions face different problems. Generally there are some issues such as land-based pollution, dumping and environmental protection by regional actions. The suitability of regional actions for the protection of marine environment as follows 1. First, a global approach to combat some types of pollution, such as that from land-based sources, is inappropriate because of the nature of the problem 2. second the heterogeneity of the oceans requires taking into account regional differences 3. third, regionally organized anti-pollution mechanisms can be more readily made available in case of emergency 4. Fourth, the regional approach encourages maximum participation by the regional nations, especially less developed countries which might otherwise stay away from a globally organized and technologically advanced system. Regional cooperation may thus favor cost effectiveness and transfer of technology to the developing nations 5. finally, a regional arrangement can serve as a forum for consultation and might even contribute to developing habits of cooperation eventually transcending matters to the protection of the marine environment Findings and Suggestions In accordance with the United Nations Convention on the Law of the Sea (UNCLOS) and global and regional instruments, all States have an obligation to prevent, combat and control marine pollution. The polluter pays principle is rapidly receiving global acceptance and requires further expression in international and national laws and regulations. The precautionary principle calls for anticipatory management actions, particularly for substances that are toxic, bio-accumulative and persistent, and this should find strong expression in national laws and regulations. In addition to States, NGOs should be allowed standing in international tribunals regarding environmental matters, in order to provide representation and assistance to victims of pollution and to seek appropriate compensation on their behalf. Act to encourage and assist United Nations (UN) members to draft and ratify a convention to discourage transboundary pollution in marine waters that identifies liability procedures so that nations adversely affected by transboundary pollution will be compensated for loss and the costs of clean-up Encourage and assist governments to regulate and monitor marine ecosystems and river systems that empty into marine waters for persistent toxic substances with the aim of achieving zero discharge levels. Encourage and assist the International Maritime Organization (IMO) in developing international laws to regulate actions to minimize marine pollution in international waters

CONCLUSION Failure to prevent pollution can be considered a violation of Parties’ UNCLOS obligations to protect and preserve the marine environment. There is an issue of causation respecting the extent to which the contribution to climate change by a particular Party or number of Parties can be isolated, how much higher the contribution of that country is relative to other countries, how relevant is the capacity to reduce emissions, and the effect of the historical contribution to the problem in determining whether a Party has failed to take sufficient action to mitigate its climate change impact on the marine environment.


The conclusion that there may be a breach of UNCLOS obligations and that the claim of a breach may be brought under the UNCLOS binding dispute settlement process raises a number of questions. Who can bring such a claim, and against what countries could such a claim be brought? What is the likelihood of such a claim? What would be the implications of such a claim for the climate change regime and international relations more generally? To what standard would a Party be held? Finally, there are questions about possible remedies. Would remedies be limited to a finding that a Party was in violation of its obligations, or would they extend to an order to reduce GHG emissions, either generally or by a specific amount. Furthermore, could remedies include an award of damages or perhaps even an order to as0sist other Parties in adapting to climate change? Most likely a claimant State would be a developing country with low GHG emissions, a high vulnerability to climate change, and a high social and economic reliance on the marine environment. The defending Party would most likely be a developed state, with high per capita or total GHG emissions.

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FAO-Fisheries Department ‘Information on the Fisheries Management in the Republic on India’ (2000), available online at http:/ / www.fao.org/fi/fcp/en/IND/body.htm

Haynes D, Carter S, Gaus C, Mueller J & Dennison W. 2005 Organ chlorine heavy metal concentrations in blubber and liver tissue collected from Queensland (Australia) dugong (Dugong dugon). Marine Pollution Bulletin; . Hiscock, K. & Oakley, J.,. 2005, English Channel towed sledge seabed images. Phase 2: Analysis of selected tow images. Report to the Joint Nature Conservation Committee from the Marine Biological Association. Plymouth,:Marine Biological Association. JNCCcontractF90-01-784 J.P. Riley ed, 1989, Chemical Oceanography Volume 9. Marine Pollution Chapter 50 by M.R. Preston Academic Press, John H. Bates UK1985 Marine Pollution Law, Lloyd's of London Press, MARPOL 73/78, 1991, 1992Consolidated Edition, , International Maritime Organization, Oakley, J.. A Rockpool Ramble. 2007, Vale of Glamorgan Biodiversity Matters Newsletter (Summer2007).

Oakley, J. 2008, The solitary marine biologist. JMBA Global Marine Environment. Spring Issue 7. Marine Biological Association of the United Kingdom R.M. Harrison 1996, Pollution: Causes, Effects & Control, Royal Society of Chemistry, (3rd Edition), R.B. Clark, 1987, The Waters Around the British Isles: Their Conflicting Uses, Clarendon Press, Oxford, Sewell, J., Jefferson, R. & Oakley, J.A. 2006. Marine life Topic Note. Commercial Fishing. Marine Life Information Network: (on-line). Plymouth: Marine Biological AssociationUK

W., Bayne, B.L., Duursma, E.K. and Förstner, U. Springer Verlag, 1988, Pollution of the North Sea: An Assessment Salomons,


International Conference on Emerging Technologies in Environmental Science and Engineering

October 26 – 28, 2009 Organized by Department of Civil Engineering Z.H.College of Engineering & Technology, A.M.U., Aligarh in conjunction with

THE UNIVERSITY OF TOLEDO OHIO, U.S.A Venue Zakir Husain College of Engineering & Technology Aligarh Muslim University Aligarh-202002 PAPER on Environment and ICT: “enemies or friends”? Authors

Raval Ajay A.

Buddh Mitesh Dineshchandra

(H. O. D.) Shree SPKM BCA & PGDCA College, Computer Science Dept., (Saurashtra University Affiliated) JETPUR- 360 370. Mobile: +91-98 251 63674 Email: [email protected]

(Lecturer) Shree G.K. & C.K. Bosamia College, BCA / PGDCA Dept., (Saurashtra University Affiliated) JETPUR – 360 370 Mobile: +91-94 264 70889 Email: [email protected]

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¾ Abstract:


The paper presented by me is for ICT is to show the impact of ICT on Environment. It has three types of impacts: 1) First order Impact: which is directly related to the production and use. 2) Second Impact: which are indirect impacts related to the effects of ICT on the structure of economy, production and distribution. 3) Third order impact: which are indirect effects on environment thought the stimulation of consumption and economy growth. All impacts give its positive and negative impacts on the environment. In my paper I also show you various examples about ICT Activity like ICT activities for disaster Management, ICT Activities for sustainable growth. Whatever, it is “friend or enemies?” two questions. I will also explain ICT in the environment sector is often used to. In conclusion, both should be typically understood at two levels: global and local. Both perspectives are critical, and both should be understood independently, as well as in conjunction with each other, to approach the subject. ICTs can indeed be critical in providing the dual perspective, while facilitating knowledge sharing at both levels simultaneously.

¾ Keywords: Impacts of ICT on Environmental Sustainability ICT Activities Environment and ICT

¾ Introduction: The issue of Information and Communication Technologies (ICT) and Environment is a complex and multifaceted one. ICT can play both positive and negative roles in environmental sustainability. This feature aims to show that the positive impact of ICT on the environment is greatly high and so, outweighs its potentially negative impact.

¾ Impacts of ICT on Environmental Sustainability: Speculations and Evidence: This report summarizes recent literature on the environmental impact of information and communication technologies (ICTs) and the Internet. Three main types of effects identified are: 9 First order impacts: direct environmental effects of the production and use of ICTs (resource use and pollution related to the production of ICT infrastructure and devices, electricity consumption of ICT hardware, electronic waste disposal). 9 Second order impacts: indirect environmental impacts related to the effect of ICTs on the structure of the economy, production processes, products and distribution systems; the main types of positive environmental effects are dematerialization (getting more output for less resource input), virtualization (the substitution of information goods for tangible goods) and "demobilization" (the substitution of communication at a distance for travel). 9 Third order impacts: indirect effects on the environment, mainly through the stimulation of more consumption and higher economic growth by ICTs ("rebound effect"), and through impacts on life styles and value systems.

The report concludes that ICTs are having profound environmental impacts, both positive and negative. While there are large opportunities for environmental and resources gains through the diffusion of ICTs, many of these opportunities will lead to incremental changes over the longer term (general labour, capital and resource productivity improvements). Technological and organisational changes enabled by the Internet and other ICT networks may also have profound environmental impacts, but evidence on the sign and magnitude of these effects is still sparse. The implications for policy, in particular technology and innovation policy, are manifold. In general, we would expect policy to influence most easily first-order effects by setting technology standards, by encouraging energy pricing taking into account environmental costs, and by facilitating the creation of robust systems for retrieving and recycling equipment at the 'end of life'. The influence of policy on second- and third-order effects is more difficult to foresee. Indeed, some commentators argue that policy can represent a significant obstacle to the efficient diffusion and use of ICTs (and by implication, the realisation of potential environmental benefits).

International Emerging Technologies in Environmental Science and 971 On the "supply side", Conference there is a on role for policy in encouraging innovation thatEngineering promise real substitutions of information for October 26–28, 2009 Aligarh Muslim University, Aligarh, India resources and mobility, and in setting ambitious long-term targets for their widespread adoption.

On the "demand side", there is an important role for government in shaping telecommunications and "hard" (transport, utilities, buildings, urban form) infrastructures that will determine whether opportunities for radical improvements in resource productivity will arise from the diffusion of ICTs. Government also has a role as a "consumer" through public procurement of de-materialized 'solutions' and in the delivery of government services. Imaginative use of ICTs also allows governments to associate consumption with their true environmental costs, and to create greater transparency about the relative environmental performance of alternative means of providing a good or a service. Many of the information gaps endemic to environmental policy making can be reduced through the intelligent use of intelligent systems. Effects

Positive Impacts Environmental ICT applications e.g. environmental monitoring

Negative Impacts Environmental impacts of production and use of ICTs e.g. electronic waste

Dematerialization structural change

Incomplete substitution

e.g. electronic directories

e.g. ‘white vans’ in addition to private shopping trips

Life style changes

‘Rebound effect’

e.g. green consumerism

e.g. growth of long distance travel

First Order

Second Order

Third Order

Table 1 : ICT impacts on the environment

¾ ICT Activity Examples: 9 ICT activities for Disaster Management

9 ICT 972 Activities for Sustainable International Growth Conference on Emerging Technologies in Environmental Science and Engineering

October 26–28, 2009 Aligarh Muslim University, Aligarh, India

9 ICT Activities for Sustainable Growth Unit (Summarized)

International Conference on Emerging ¾ Environment and ICT: enemies orTechnologies friends?:in Environmental Science and Engineering October 26–28, 2009 Aligarh Muslim University, Aligarh, India

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Now the above analysis, I will try to answer questions I have raised with colleagues. These questions are: 9 Environment and ICT: enemies or friends? 9 What are good examples of the positive roles that ICTs can play in assuring environmental sustainability? 9 What are the examples of the negative impacts? ICTs are a powerful tool for civil society in protecting environment. But more is needed to streamline ICT work of different groups and communities. Environmental Information Systems (EIS) are the core of modern urban environment management systems, and a prerequisite for proper and timely dissemination of information to the public. “Technological advances require systems that can make optimum use of informatics and telecommunications infrastructures to address environmental management needs. Yet these can be open, flexible, modular and inexpensive to implement and operate. On this basis, a number of existing EI components for wireless, mobile phone and web-based applications are presented. Overall, the right of access to information related to the quality of the environment that citizens live in, appears to be well matched with the concept of open source” (Aarhus Convention) (Sands P., (2003)). This type of service addresses today’s needs concerning EI (Environmental Information) access and supports an active participation of citizens in decisionmaking. Sometimes the relationship between ICT and the environment might seem distant or its nature may not seem clear. Environmental issues relate to natural resources and their complex dynamics, including water, soil, forests, flora, fauna, climate, and so on, and the world of ICTs is premised on a virtual construct of the world. One is "as real as it gets" and the other quite ‘short-lived’. What then is the link between ICTs and the environment? Perhaps this is where the power of ICTs lies and this can have a great bearing on virtually every aspect of human life and the rapidly expanding surroundings of human habitats. Like any other area, an understanding of the environment is deeply dependent on correct, relevant, and recent information being available to all those people, whose decisions and actions affect this field. In a larger perspective, however, ICTs and the environment have a much deeper connection. “Environment relates to the profound relationship between matter, nature, and society, and in such a context ICTs bring new ways of living in a more interconnected society, all of which reduces our dependency on matter and affects our relationships with nature” (Hargroves K. C. and Smith H., (2005)). Today the impact of ICT on the Environment is one of the broadest issues. It relates to one of the Millennium Development Goals (MDG), as ICT in national and international efforts assures environmental sustainability.

¾ “ICT in the environment sector is often used to: 9 Communicate traditional forms of environmental knowledge to communities and to o facilitate the citizen monitoring of environmental issues 9 Make a valuable contribution to sustainable environmental management by improving o monitoring and response systems, facilitating environmental activism and o

enabling more efficient resource use

9 Reduce the consumption of energy, water and other essential natural resources through o more efficient agriculture and industrial procedures 9 Play an important role in the fight against pollution—not only by providing more o useful metrics and information, but also by enabling population o

decentralization and large-scale telecommuting

9 Provide an ideal platform for local voices to be heard, overcoming physical and social o barriers, and for allowing special-interest groups and virtual communities to be formed” (http://www.opt-init.org/framework/pages/2.2.5.html)

International Conference on Emerging in Environmental and Engineering ICT is also 974 being organized extensively to monitor and respond to Technologies environmental disasters Science in developing countries and not October 26–28, 2009 Aligarh Muslim University, Aligarh, India only, they also worn and predict disasters.

“ICT in the environment sector is often used to communicate traditional forms of environmental knowledge to communities and to facilitate the citizen monitoring of environmental issues” (http://www.wsis.ethz.ch/). The power of ICT as an information and networking medium can also enable citizens to act as environmental enforcement agents, alerting decision makers to infringements of all kinds and leveraging the power of ICT to reach and influence public opinion. At a higher level, ICTs enable greater participation and involvement of human beings with activities that are critical to protecting the environment at several levels. At the institutional level, they enable less use of paper and better resource management, networking, and information exchange. For researchers, they provide tools that are critical in observation, simulation, and analysis of environmental processes; and for educators, they make learning and teaching more effective, while extending educational resources to a larger community. At the individual level, ICTs can be critical in equipping a new generation of people who are more informed, more sensitive, and more involved in the formulation of policies that affect their communities, nations and the world. ICTs have proved critical in environmental monitoring and the associated information management systems; for the exponential growth and integration of data and information on the environment at national and international levels; for knowledge sharing and community building around general and specialized environmental issues across borders; for enabling remote sensing and constant mapping of natural resources; for environmental research; and for raising public awareness about environmental issues and policy implications. Perhaps the most visible area of a positive impact of ICTs on the environment is their potential to reduce consumption of paper through paperless government, paperless office operations (e.g. via electronic document flows, reduced bureaucracy and paper work). As with other not fully recyclable products of technological progress, ICTs can also increase the burden on the environment, as is in the case of toxic e-waste polluting the environment in both developed and developing countries.

International Conference on Emerging Technologies in Environmental Science and Engineering ¾ Conclusion: October 26–28, 2009 Aligarh Muslim University, Aligarh, India

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In conclusion, I want to add that when we speak of the environment or ICT, both should be typically understood at two levels: local and global. Both perspectives are critical, and both should be understood independently, as well as in conjunction with each other, to approach the subject. ICTs can indeed be critical in providing this dual perspective, while facilitating knowledge sharing at both levels simultaneously.

¾ Reference: Hargroves K. C. and Smith H. (Eds.). (2005). The National Advantage of Nations: Business Opportunities, Innovation and Governance in the 21st Century. Section 3: The regulatory measure response. London: Sterling, VA, (182-188). Sands P. (2003). Principles of International Environmental Law (2nd ed.). Cambridge University Press. (200-211). Markle Foundation. Creating a Development Dynamic. 2.2.5 ICT for the Environment. United Nations Development Programme. Final report of the digital opportunity initiative. July 2001, from http://www.optinit.org/framework/pages/2.2.5.html Strong M. (2003). The Environment and ICT Working Group. 2 September 2006, from http://www.wsis.ethz.ch/

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Concepts of Industrial Ecology: A Review Srinivasan, A. Environmental Systems Engineering, University of Regina, Regina, SK, Canada Dhanushkodi, S.R. Chemical Engineering, University of Waterloo, Waterloo, ON, Canada

ABSTRACT Industrial ecology is a strategic environmental approach that provides economic, environmental and social benefits. This cooperative approach to address business-environment issues is a key aspect of sustainable development. Growing industrial demand, increasing pollution and pressure on natural resources have led to eco-industrial development approaches. This article presents a review of the existing literature on industrial ecology. We introduce industrial ecology's primary concepts, and analyze the approach involved in assembling an eco-industrial park. We also discuss the needs and potential for linking industrial ecology to policy studies. These initiatives of industrial ecology indicate the potential for collective endeavors to address sustainability at all levels.

Keywords: industrial ecology, eco-industrial parks, waste to product, sustainable development, policy studies. 1. INTRODUCTION The term “industrial ecology” was first coined by Robert A. Frosch and Nicholas E. Gallopoulus (1989) in a special issue of Scientific American. Frosch (1992) later defined industrial ecology system as one, which “would maximize the economical use of waste materials and of products at the ends of their lives as inputs to other processes and industries”. Industrial ecology has emerged as a process to fulfill the objectives of sustainability, with respect to industrial development. It aims to mimic the processes operating in natural ecosystems emphasizing material and energy cycling. The webs of firms mimic the activities of producers, consumers and decomposers in a natural ecosystem. The basic premise of industrial ecology is that industrial activities should not be considered in ‘isolation’, but rather in terms of industrial ecosystem functioning within the natural ecosystem. At the most basic level, industrial ecology describes a system where one firm’s wastes (outputs) become another’s raw materials (inputs). Within this ‘closed loop’, fewer materials would be wasted. The terms ‘industrial ecosystem’ and ‘industrial symbiosis’ as well as the term “eco-industrial network” are usually used as an umbrella for a number of co-operation structures (Fleig, 2000). The key terms and concepts that have become established in the literature are as follows: 1) Industrial Ecosystem: Industrial ecology’s greatest realization is the development of the industrial ecosystem. It is defined as “a system in which the consumption of energy and materials is optimized, waste generation is minimized and the effluents of one process . . . serve as the raw material for another process” (Frosch and Gallopoulus, 1989). 2) Industrial Metabolism: Industrial metabolism is concerned with the flows and fluxes of materials and energy primarily within a technical or anthropogenic system recognizing the importance of understanding natural limits and environmental capacities (Cote, 2003). 3) Industrial Symbiosis: One perspective on industrial ecology is “industrial symbiosis” where a group of industries work collaboratively through exchanges to reduce natural resource consumption and pollution. In this network, “industrial symbiosis engages traditionally separate and collective approaches to competitive advantage involving physical exchanges of materials, energy, water, and by-products” (Chertow, 1999). Industrial symbiosis involves linking separate companies so that the byproduct of one company may be used as a feedstock to the other company. With a network of these linkages, one can


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achieve a closed loop system where waste is eliminated or drastically reduced (Hollander and Lowitt, 2000). The other main element to industrial symbiosis is energy cascading. Energy cascading involves the use of residual heat in liquids or steam from one process to provide heating, cooling, or pressure for another process (Gertler, 1995). 4) Eco-industrial Parks: Eco-industrial parks are one of the strategies to implement the concept of industrial ecology by inter-company collaboration (Fleig, 2000). An eco-industrial park is “a community of manufacturing and service business seeking enhanced environmental and economic performance through collaboration in managing environmental resource including energy, water, and materials. By working together, the community of businesses seeks a collective benefit that is greater than the sum of individual benefits each company would realize, if it optimized its individual performance only” (Lowe et al., 1998). 5) By-product Synergy: By-product synergy is also referred to as “green twinning”, “zero waste/zero emission” and “cradle to cradle eco-efficient manufacturing” (Mangan, 1997). The Business Council for Sustainable Development-Gulf of Mexico (BCSD-GM) and the U.S. Environmental Protection Agency (EPA) has defined by-product synergy as “The synergy among diverse industries, agriculture, and communities resulting in profitable conversion of by-products and wastes to resources promoting sustainability”.

1.1 Cyclical Loop Systems and Co-Operation Moving from linear throughput to closed-loop material and energy use is a key theme in industrial ecology (Allenby, 1992). This process, described as a change from a Type I to a Type III System is seen as the evolution towards industrial ecosystems. Allenby describes a Type I System as a linear constellation, where energy and resources enter the system and products and wastes leave it. Many early stages of industrial development show characteristics of a Type I System. However, this concept could only work in a situation with unlimited resources to feed the system and unlimited space to deposit wastes and used products leaving it. The characteristics of a Type II system are: reduced input of resources, limited amount of waste leaving the system, and collaboration of ecosystem components exchanging energy and materials. This type represents high-technology industrial systems with a certain degree of pollution prevention and waste recycling. A Type III system represents the dynamic equilibrium of ecological systems, where energy and wastes are constantly recycled and reused by other organisms and processes within the system. This is a highly integrated, closed system. In a totally closed industrial system, only solar (or other renewable) energy would come from outside, while all by-products would be constantly reused and recycled within. A Type III system represents a sustainable state and is an ideal goal of industrial ecology (Garner and Keoleian, 1995). While the Type III System seems to be an ideal goal at a higher level (as discussed by Allenby), a closed cyclical loop system is not achievable at the level of Eco-Industrial Parks. "The goal is not hermetically sealed "biospheres" but real world solutions to improving business and environmental performance simultaneously" (Cohen-Rosenthal, 1996).

1.2 Assembling an Eco-Industrial Park In a case where there is some existing industry at a site, Lowe (1997) outlined the steps to create an ecoindustrial park. The first step is to determine energy, material, and water flows. Then, a network flow strategy is devised and synergies between existing and proposed industries at the site are examined. Where synergies are identified, those businesses are matched up and the benefits of exchanges are discussed. In the meantime, customers for existing energy/material/water flows are sought. As data are collected from new businesses at the park, a database is assembled to further promote exchanges. The final step is to adjust the network flow strategy as companies’ come and go. Industrial symbiosis involves linking separate companies so that the byproduct of one company may be used as a feedstock for the other company. With a network of these linkages, one can achieve a closed

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loop system where waste is eliminated or drastically reduced (Hollander and Lowitt, 2000). The other main element to industrial symbiosis is energy cascading. Energy cascading involves the use of residual heat in liquids or steam from one process to provide heating, cooling, or pressure for another process (Gertler, 1995).

1.3 Benefits of Industrial Symbiosis Most experts consider industrial symbiosis as one of a number of strategies that could lead to sustainable industrial development (Cote, 1998) and as a very helpful tool towards implementation of industrial ecology ideas, resulting in much more environmental protection and, simultaneously, creating a new model for local economic development (Chertow, 1999). Most authors put emphasis on the positive effects of eco-industrial development at the local and regional level — in terms of social and environmental improvement as well as in terms of the advantages for the collaborating companies (Cohen-Rosenthal, 1999). Table 1 lists the benefits of industrial symbiosis. Once communicated and discussed, these advantages would appear to be very promising incentives for companies to enter into the process of improving environmental performance and joining an industrial symbiosis. The prospects for local development encourage communities to invest in such development designs. Table 1. Benefits of industrial symbiosis (Cohen-Rosenthal, 1999) Communities Expanded local business opportunities Larger tax base Community pride Improved environmental health

Environment Continuous environmental Improvement Better resource use Reduced waste Increased protection of ecosystems

Improved health for employees and community Reduced waste disposal costs Innovative environmental solutions Less impact on infrastructure Partnership with businesses Enhanced quality of life near eco-industrial development Improved environment and habitat Improved tax base Recruitment of higher quality More efficient use of natural companies resources

Business Higher profitability Enhanced market image High performance workplaces Access to financing

Higher value for developers Improved environmental efficiency Income from sale of byproducts Reduction in disposal costs Improved public image Reduction of operating costs (energy, materials and water) Less environmental liability Regulatory flexibility

2. THE PRACTICE OF INDUSTRIAL SYMBIOSIS - EXAMPLES Some examples of industrial symbiosis projects implemented in different parts of the world are described (Table 2). As a detailed description is not possible in this context, references for further information are added.


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Table 2. Examples of Industrial Symbiosis Site Kalundborg, Denmark

Features Highly evolved industrial symbiosis, characterized by a network of inter-firm material exchanges and energy cascades - developed during the past 25 years without influence from outside (Lowe, 2001) Burnside Industrial Research and development subject of a university; large site; creation of Park, Nova Scotia, materials and energy cycles, imbedding into the natural environment, renewable Canada energy use, information centre (Cote & Cohen Rosenthal, 1998) Bruce Energy Centre, Park organized around a nuclear power station in order to use its waste heat and Ontario, Canada steam generation capacity for processes such as dehydration, concentration, distillation etc. (Cote & Cohen Rosenthal, 1998) Development of an industrial cluster around a brewery with the goal of Tsumeb, Namibia achieving zero emission of pollutants to the surrounding environment (Cote, 2003) Fujisawa Factory Combination of industrial, commercial, agricultural, residential components, including technologies in energy conservation, waste water treatment, industrial Park, Japan conversion of wastes into cement and ceramics, etc. (Marikowa, 2000) Brownsville, Texas Riverside, Vermont Chattanooga, Tennessee

Regional/virtual approach to waste material exchange, marketing (BCSD, 1997) Urban Agricultural industrial park, bio-energy, waste treatment (CohenRosenthal et al., 1999) Redevelopment of inner city and former military manufacturing facilities, green areas, environmental technology (Cohen-Rosenthal et al., 1999)

Resource Recovery Eco-Industrial Park project; advanced waste-to-energy and materials recovery Park, Puerto Rico plant as anchor (Chertow, 2000) Chaparral steel, Texas Midlothian Texas company; Rely on recycled steel as feedstock; implemented project STAR that reduced resource consumption, enhanced value of byproducts, reduced waste (BCSD, 1997) Research triangle Industrial Symbiosis between 90 facilities; 46 categories of inputs/byproducts Park, North Carolina identified and partnerships implemented (Kinciad, 1999) Naroda Industrial Huge estate of about 30 km², hosting approximately 1,200 companies(Chiu, Estate, India 2001) Hoara Foundries, 500 foundries in Hoara study showed that industry could adapt to use coke oven Calcutta, India gas, an easily available waste by product in the region (Ramaswamy, 2003) Tirupur town, Resource flow analysis undertaken for 4000 small units; A water recycling Tamilnadu, India system using waste heat from boilers was developed; solid waste found to replace 500,000 tonnes of firewood (Ramaswamy, 2003)

2.1 Example of Industrial Symbiosis at Kalundborg, Denmark The first and oldest example of industrial symbiosis project is in Kalundborg, Denmark. In addition to several companies that participate as recipients of materials or energy, this ecosystem today consists of six main partners are listed below:

Asnaes power station - part of SK Power Company and the largest coal-fired plant producing electricity in Denmark

Statoil - an oil refinery belonging to the Norwegian State oil company

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Novo Nordisk - a multi-national biotechnology company that is the largest producer of insulin and industrial enzymes in the world.

Gyproc - a Swedish company producing plasterboard for the building industry

The town of Kalundborg, which receives excess heat from Asnaes for its residential district heating system

Bioteknisk Jordrens - a soil remediation company that joined the Symbiosis in 1998

The Asnaes coal-fired electric power plant supplies steam to the Novo Nordisk pharmaceutical plant and the Statoil refinery, and low grade heat to a district heating system serving 3,500 homes. The refinery removes sulfur from its natural gas, selling it to Kemira, a sulfuric acid manufacturer, resulting in a cleaner gas that is in turn bought by Asnaes. Asnaes sells fly ash to a cement plant and produced gypsum from sulphur capture to a wallboard plant, and uses still more waste heat in the greenhouses and fish farms it operates. Sludge from Novo Nordisk becomes fertilizer for local agriculture, and refinery wastewater feeds the power plant. The eco-industrial symbiotic approach has led to the numerous environmental benefits (Erkman, 1998). Reduction in consumption of resources include, Oil 45,000 tons/year, coal 15,000 tons/year and water 600,000 m3/year; Reduction in waste emissions such as, carbon dioxide 175,000 tons/year and Sulfur dioxide 10,200 tons/year; and Valorization of "wastes" such as sulfur 4,500 tons/year, calcium sulfate (gypsum) 90,000 tons/year, fly ash (for cement etc) 130,000 tons/year. Financial gains have also resulted from reduced waste disposal costs, generation of new revenue from selling waste and saving on input costs such as energy and material. By the end of 1980’s the partners had established a formal and long-term relationships. Still successfully operating today, the Kalundborg is viewed as a classical example of industrial symbiosis approach (Lowe et al., 1998).

2.2 Examples in Canada Canada has a few industrial projects underway representing ecological characteristics with the potential for many more across the country. Burnside is an example of modifying an existing industrial park to improve environmental performance. The park is extended over 2,500 acres with more than 1,200 businesses employing 18,000 people. Researchers from Dalhousie University have explored ideologies and approaches that would help promote reconstruction of an existing industrial park into an industrial ecosystem. A similar study has been in progress in the Portlands Industrial District in Toronto, Ontario since 1995. This industrial area holds the potential for waste and energy exchanges comprising various facilities in manufacturing and services. In Nova Scotia, one business organization has connected several industries which highlight the recycling of waste paper, cardboard and oils. Other possibilities exist within the corporation but are limited due to distance between the industrial locations. A study was initiated in Alberta by The Business Council on Sustainable Development and the IISD with the participation of public agencies and private companies. Through the cooperation of the companies, large quantities (in excess of 1000 tonnes) of by-products were identified including bottom ash, fly ash, sulfur, lime, sawdust, sulfur dioxide and miscellaneous organic chemicals. In Sarnia, Ontario, symbioses exist between oil refineries, a synthetic rubber plant, petrochemical facilities and a steam electrical generating station. Table 3 provides details on some potential eco-industrial park sites in Canada. Although, currently there are only a few examples of materials exchange, other participants that support material cycling functions within the park have been identified. There are a number of sites in Canada where some degree of industrial ecosystems are in function.


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Table 3. Potential Eco-industrial Parks in Canada (Cote and Cohen-Rosenthal, 1998) Province Vancouver, British Columbia Fort Saskatchewan, Alberta Sault Ste.Marie, Ontario Nanticoke, Ontario Cornwall, Ontario Becancour, Quebec Montreal East, Quebec Saint John, New Brunswick Point Tupper, Nova Scotia

Key industries Steam generator, paper mills, packaging, industrial park Chemicals, power generation, styrene, PVC, biofuels Power generation, steel, paper mill, flakeboard mill, industrial park Thermal generating station, oil refinery, steel mill, cement, industrial park Power and steam generation, paper mill, chemical, food, electrical equipment, plastics and concrete products Co-generation plant, chemical plants (H2O2, HCl, Cl, NaOH, Alkylbenzene) magnesium, aluminum Co-generation plant, petrochemicals, refineries, compressed air, gypsum board, metal refinery, asphalt Power plant, paper mill, oil refinery, brewery, sugar refinery industrial parks Generating station, pulp and paper, building board, oil refinery

3. LINKING INDUSTRIAL ECOLOGY TO POLICY STUDIES The attraction of industrial ecology as a theoretical approach towards sustainable development has resulted in several program in Canada, United States, Europe and Asia for eco-industrial development at national as well as regional levels. Korhonen et al (2004) has identified three themes to be considered for linking traditional industrial ecology research to management and policy studies. The themes are (i) interorganizational management, (ii) development and management of industrial ecosystems and (iii) industrial ecology as a vision and source of inspiration for management strategy. Inter-organizational environmental management theory extends beyond practice such as ISO 14001 and focuses on many different firms and organizations. Specific approaches and tools include life cycle management, which develops a strategic environmental business policy using the information derived from life cycle analysis, supply chain management and integrated chain management. Industrial ecology can be a source for new kinds of cooperative networks between private firms and public organizations. To realize an industrial ecosystem in practice, a combination of active government policy and voluntary, proactive actions by private firms are needed (Korhonen et al., 2004). One of the potential policy approaches already being considered is extended producer responsibility (Ehrenfeld, 2004), which extends the manufacturer’s responsibility for the environmental effects of the product over the life cycle including after-use waste management, disposal, recovery and recycling. This policy is an example of an approach that couples public policy mandates and private incentives. Some authors have highlighted the importance of cooperation of public and private actors and have stressed the central role of local authorities in ecoindustrial development (Burstrom and Korhonen, 2001). Local authorities can serve as institutional anchor tenants by initiating the network as well as providing political, managerial, and informational and infrastructure supports for the participants of the industrial ecosystems. Regional and local policy frameworks may provide opportunities for experimenting with the concepts of industrial ecology such as eco-industrial parks. 4. CONCLUSION The case studies described above have considered industrial symbiosis strategies to make existing strategies more viable and to attract new businesses. Many more examples of industrial symbiosis exist worldwide. Many communities are also investigating the potential for adopting such approaches. These initiatives indicate the potential for collective endeavors to address sustainability at all levels. Success

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could be achieved by integrating social, economic and environmental considerations in to policy decisions.

ACKNOWLEDGEMENT The authors like to thank Dr. Malcolm Wilson, Director, Office of Energy and Environment, University of Regina, Canada and Dr. R. Nagendran, Professor, Centre for Environmental Studies, Anna University, India for their support and constructive comments in the improvement of this manuscript.

REFERENCES Burnsrom, F, and Korhonen, J, 2001, Municipalities and industrial ecology: reconsidering municipal environmental management, Sustainable Development, 9(1), p36-46. Chertow, M, 2000, Economic and Environmental Impacts from Industrial Symbiosis Exchnages: A Guayama, Puerto Rico, Yale School of Forestry and Environmental Studies, USA. Chiu, A, 2001, Eco Industrial Networking in Asia, International Conference on Cleaner Production, September, Beijing, China. Cohen – Rosenthal, E, 1999, Eco Industrial Development : The case of US, Cornell University, USA. Cote, R, and Cohen-Rosenthal, E, 1998, Designing eco-industrial parks: a synthesis of some experience, Journal of Cleaner Production, 6, p181-188. Cote, R, and Ellison, R, 1994, Designing and Operating Industrial Parks as Ecosystems, School for resource and Environmental Studies, Dalhousie University, Halifax, Canada. Cote, R, 2002, Eco Industrial Networking: A typology with example, School of resource and Environmental Studies, Delhousie Universtiy, Halifax, Canada. Cote, R, 2003, A Primer on Industrial Ecosystem – A strategy for Sustainable Development, Dalhousie University, Canada. Ehrenfeld, J, 2004, Industrial ecology: a new field or only a metaphor?, Journal of Cleaner Production, 12(8-10), p825-831. Ehrenfeld, J, and Gerler, N, 1997, Industrial Ecology in Practice – The evolution of Interdependence at Kalundborg, Journal of Industrial Ecology, 1(1), 67-79. Erkman, S, 2001, Industrial Ecology: a brief introduction New Strategies for Industrial Development, An International Conference and Workshop, April 2-6, Manila, Philippines. Erkman, S, and Ramaswamy, R, 2001, Industrial Ecology: An agenda for long term evolution of Industrial System, Industrial Ecology Workshop, August 27, Geneva. Fleig, A, 2000, Eco-Industrial Parks: a strategy towards Industrial Ecology in Developing and Newly Industrialised Countries, Working paper etc.-11, GTZ group 4454, Eco efficiency in Business and Industry. Frosch, R, and Gallopoulus, N.E, 1989, Strategies for Manufacturing, Scientific American, p144-152.


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Garner, A, and Keoleian, 1995, Industrial Ecology: An introduction, National Pollution Prevention Centre for Higher Education, University of Michigan, USA. Hollander, J, and Lowitt, P, 2000, Applying Industrial Ecology to Devens, Devens Enterprise Commission, Devens, USA. Kinciad, J, 1999, “Industrial Ecosystem Development Project Report”, Triangle J council of Government, Research Triangle Park, North Carolina, USA. Korhonen, J, von Malmborg, F, Strachan, P.A, and Ehrenfeld, J.R, 2004, “Management and policy aspects of industrial ecology: an emerging research agenda, Business Strategy and the Environment, 13, p289-305. Lowe, E, 1997, Regional resource recovery and Eco-Industrial Parks in integrated strategy, Indigo Development Center, Canada. Lowe, E, 2001, Eco Industrial Park Handbook, Indigo Development Centre, Canada. Mangan, A, 1997, Byproduct Synergy: A strategy for Sustainable Development a Primer. The Business Council for Sustainable Development, Gulf of Mexico, USA. Mangan, A, and Thomas, R, 2000, Byproduct Synergy: Cross Industry coloboration to achieve100% product manufacturing, Austin, Texas, USA. Ramaswamy, R, 2003, Industrial Ecology – A New Platform for Planning Sustainable Societies, Technology Exchange Networks, Bangalore, India.

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BACTERIAL BIOCONTROL AGENTS AS ALTERNATIVE FUNGICIDES FOR MANAGEMENT OF TWO FOLIAR DISEASES OF MULBERRY P. M. Pratheesh Kumar, M. D. Maji1, S. M. H. Qadri and B. Saratchandra2 1

Central Sericultural Research & Training Institute, Mysore, Karnataka 560 008 Central Sericultural Research & Training Institute, Berhampore, West Bengal 742 101 2 Central Silk Board, Madivala, Bangalore 560 068

ABSTRACT Studies were conducted with bacterial strains isolated from various sources of compost and mulberry phylloplane to evaluate their efficiency to control powdery mildew (Phyllactinia corylea) and leaf spot (Myrothecium roridum). In vitro studies with twenty strains of bacteria isolated from compost sources revealed significant (PMBBT>MBST Among the compounds investigated in the present study MBCT has been found to give the best performance as corrosion inhibitor. This can be explained on the basis of the presence of an additional π-bond between carbon atoms (-C=C-) in conjugation with aromatic ring. These extensively delocalized π-electrons favour greater adsorption on the metal surface as compared to other compounds, The corrosion inhibition tests at different times were also carried out under similar conditions using 500 and 1000 ppm concentration of all the inhibitors to investigate the effect of duration Figure 1(a,b). It was found that IE increases with increase in immersion time from 1 minute to 10 minute. This showed the persistency of the studied heterocyclic compounds on the metal surface over a longer time.

Potentiodynamic polarization studies The electrochemical corrosion parameters such as corrosion current density (Icorr),corrosion potential (Ecorr) and % IE obtained from Potentiodynamic polarization curves Figure 2(a,b) of mild steel in 20% H2SO4 at 280±50C in absence and presence of various inhibitors are given in Table 3. It was found that Icorr value decreases significantly in presence of compounds indicating that the compounds were

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effective corrosion inhibitors. It was found that these compounds did not cause any significant change in corrosion potential values except MBBT suggesting that they were mixed type inhibitors i.e. they inhibit corrosion by slowing down both anodic as well as cathodic corrosion processes. MBBT at 500 ppm showed predominantly anodic behaviour. The effectiveness of a compound as a corrosion inhibitor depends on the structure of organic compounds. All of the compounds exhibited excellent IE (>98%) at a concentration of 500 ppm. High IE of these compounds may be attributed due to the presence of extensively delocalized πelectrons on the phenyl rings, planarity and presence of lone pair of electrons on N- and S- atoms, which favour greater adsorption of these compounds on the metal surface.

CONCLUSIONS All the compounds behaved as excellent corrosion inhibitors in 20% hot sulphuric acid. All the compounds showed mixed behaviour except MBBT which showed predominantly anodic at 500ppm concentration. The inhibitors reduce corrosion by being adsorbed on the metal surface. Development of more environmentally acceptable corrosion inhibitors is a challenge. .

REFERENCES 1. 2. 3. 4.

A.Rahman,P. Labine, Rev. on Corros. Inhi.Sci.and Technol.1.11(NACE,TX,(1986)20. B.A.Abd-El-Nabey,E.Khamis,G.E.Thompson,J.L.Davson,Surf.Coat.Technol.28(1986)87. I.Singh,Corrosion,49(1993)473 M.A.Quraishi and R.Sardar. Indian Journal of Chemical Technology, Vol.11,( 2004) 103-107. 5. M.A.Quraishi and R.Sardar, Journal of Applied Chemistry 33(2003) 1163-1168. 6. M.A.Quraishi and R.Sardar,S.Khan.Anticorrosion Methods and Material Vol.55, no.2 (2008)60-65. 7. G .Moretti, G.Quartarone,A.Tassan,A.Zingales,Brit.Corros.J.31(1996)49. 8. A. Singh, R.S.Chaudhary, Brit.Corros.J.31(1996)300. 9. M.A.Quraishi,M.A.W.Khan,M.Ajmal,S.Muralidharan,S.V.Iyer, Brit.Corros.J.32(1997)72. 10. D.Stankovic, M.Vukovic,Electrochim.Acta41 (1996)2529. 11. A.Frignani,C. Monticelli,G.Trabenelli,Corrosion34(1999)214. 12. W.W.Frineir, F.B.Growcock,”Inhibitors for cleaning solvents”, Rev.on Corros. Inhib.Sci.andTech.,Ed.A.Rahman and P.LabineNACE,Vol.I,TX,Houston,(1993)1-28. 13. G.Schmidt,Brit.Corros.J.19(1984)165. 14. ASTM: Standard Practice for Laboratory Immersion Corrosion Testing of MetalsG31-72 Philadelphia,PA.(1990)401. 15. S.N Dubey and Beena Kaushik,Ind.J.Chem.24A(1985)950.


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Table 1. Name and structures of the inhibitors used. S.No.

Structure

N

Designation & Abbreviation

N

1.

5-mercapto-3-butyl-4salicylidineimino-1, 2, 4-triazole (MBST)

HO N SH N CH

H9C4

N

N

2.

H9C4

N

SH N CH

N

3.

H9C4

5-mercapto-3-butyl-4benzylidineimino-1, 2, 4-triazole (MBBT)

N

5-mercapto-3-butyl-4cinnamylidineimino-1, 2, 4-triazole (MBCT)

N

SH N CH CH CH

Table 2 - Corrosion parameters for mild steel in 20% H2SO4 solution in absence and presence of 500 ppm and 1000 ppm of various inhibitors at different immersion time from weight loss measurements at 900C Inhibitor 1 Minute 10 Minutes Concentration (ppm) Weight IE CR Weight loss IE CR loss (%) (mmpy) (%) (mmpy) (mg) (mg) 20% H2SO4

MBST 500 1000 MBBT 500 1000 MBCT 500 1000

169.3

-

3145.42

1828.3

-

3382.35

2.0 1.6

98.81 99.05

37.14 29.71

6.3 5.4

99.65 99.70

11.65 9.99

1.7 1.4

99.00 99.17

31.56 25.99

5.7 4.8

99.68 99.73

10.54 8.88

1.1 0.7

99.35 99.58

20.42 12.99

5.1 2.6

99.72 99.85

9.43 4.81

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Table 3 – Electrochemical Polarization Parameters for Corrosion of mild steel in 20% H2SO4 solution in absence and presence of 500 ppm and 1000 ppm concentrations of various inhibitors at 280±50C 500 ppm

Inhibitors

1000 ppm IE (%)

IE (%)

Ecorr

Icorr

(mV)

(mA/cm2)

-

-400

5.60

-

0.84

85.00

-394

0.76

86.42

-370

0.24

95.71

-380

0.37

93.39

-391

0.17

96.96

-397

0.067

98.80

Ecorr

Icorr

(mV)

(mAcm-2)

20% H2SO4

-400

5.60

MBST

-380

MBBT MBCT


Figure 1 Variation of inhibition efficiency with immersion time at (a) 500 ppm and (b) 1000 ppm in 20% H2SO4 (1, MBST; 2,MBBT; 3,MBCT)

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Figure 2 - Potentiodynamic curves for Mild Steel (MS) in 20% H2SO4 in the presence and absence of various inhibitors at, (a) 500 ppm and (b) 1000 ppm: of various (1, 20% H2SO4 ; 2, MBST; 3,MBBT; 4,MBCT)


GREEN APPROACH TOWARDS CORROSION INHIBITION BY SOME GREEN INHIBITORS AND VCI’S Farhat A Ansari* & Mumtaz A Quraishi Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi-221005 U.P., India and Farah Yasmin Department of Mechanical Engineering, Shivdan Singh Institute of Technology & Management, Aligarh-202002, U.P., India

ABSTRACT Corrosion inhibition phenomena have been dealt from decades. Among the several methods of corrosion control and prevention, the use of corrosion inhibitors is very popular. Large numbers of organic compounds were used and are being studied to investigate their corrosion inhibition potential. But, unfortunately most of these compounds are not only expensive but also toxic to living beings. These toxic effects have led to the use of natural products as anticorrosion agents which are eco-friendly and harmless. Plant extracts have become important as an environmentally acceptable, readily available and renewable source for wide range of inhibitors. Some green inhibitors are also used as VCI’s (volatile corrosion inhibitors). VCIs can be used in cases where other protection methods are not feasible or when protection could be very expensive. This article gives a vivid account of natural products which are used as corrosion inhibitors as well as VCI’s for various metal and alloys in aggressive media. This article serves dual purpose; firstly it establishes the effectiveness of green inhibitors as corrosion inhibitors and next attempts in deduction of the inhibition mechanism and possible adsorption modes of the extract active components through a number of experimental observations. Keywords: Metals, natural products, natural volatile corrosion inhibitors, green inhibitors

1. INTRODUCTION A great number of scientific studies have been devoted to the subject of corrosion and its inhibition for metals in various aggressive environments. Atmospheric corrosion, a form of corrosion, known by some researchers as vapor phase corrosion (VPC), is due to the individual and combined action of oxygen, moisture, and atmospheric pollutants. Additional contributors to VPC are rain, snow, dust, soot, ash, wind, and radiation (light, heat, etc.). The rate of VPC may be accelerated by both acids and bases, depending upon the metal. Classical methods of protecting equipment from atmospheric attack includes using coating materials or paints and by alloying the metal to increase its -resistance to corrosion. The use of corrosion inhibitors and volatile corrosion inhibitors (VCI) is usually the most appropriate way to prevent electrochemical corrosion. The majority of well-known inhibitors are organic compounds containing heteroatoms, such as O, N or S, and multiple bonds. The inhibitors function by adsorption of ions or molecules onto metal surface. Four types of adsorption may take place by organic molecules at metal/solution interface: (a) electrostatic attraction between the charged molecules and charged metal, (b) interaction of uncharged electron pairs in the molecule with the metal, (c) interaction of p-electrons with the metal and (d) combination of (a) and (c) (Ostovari et al. 2009). However, the stability of the inhibitor film on the metal surface depends on some physicochemical characteristics of the molecule, related to its functional groups, aromaticity, possible steric effects, electronic density of donors, type of corrosive medium, structure, charge of metal surface and nature of interaction between the p-orbital of inhibitors with the d-orbital of iron (Machnikova et al. 2008). Although many synthetic compounds show good anticorrosive action, most of them are highly toxic to both human beings and environment. These inhibitors may cause temporary or permanent damage to organ system such as kidneys or liver, or to disturb a biochemical process or to disturb an enzyme system at some site in the body (Raja et al. 2008). The toxicity may manifest either during the synthesis of the compound or during its applications. These investigations lead to focus on the use of naturally occurring substances in order to find lowcost and non-hazardous inhibitors. Green corrosion inhibitors, are organic compounds which act as environmentally friendly corrosion inhibitors. These compounds show good inhibition efficiency and low environmental risk. In recent days many alternative eco-friendly corrosion inhibitors have been developed, they range from rare earth elements (Arenas et al. 2002) to organic compounds (Sanna et al. 2001; Cano et al. 2003). In continuation, plant extracts have also

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became important as an environmentally acceptable, readily available and renewable source of materials for wide range of corrosion prevention. The natural inhibitors are often easy to apply and offer wide range of advantage without causing any significant disruption to the process. However, there are several considerations when choosing a green inhibitor: The part of the plant and its location. The yield of the natural products will determine its selection and if yield is low, the inhibitor becomes often expensive. Specificity of corrosion inhibiting compounds as one compound effective in a certain medium with a given metal may be ineffective for the same metal in another medium. In the present review a detailed account of green inhibitors used as corrosion inhibitors and volatile corrosion inhibitors (VCI) is given. The recent trends used to measure their inhibition efficiencies and the aspect of mechanism of corrosion inhibition by adsorption is also discussed.

2. NATURAL CORROSION INHIBITORS Since 1930, various parts of plants – seeds (Saleh et al. 1983), fruits (Farooqui et al.1999), leaves (Kliskic et al. 2000), and flowers (Hosary et al. 1972; Minhaj et al. 1999) were extracted and used as corrosion inhibitors. Animal proteins (by products of meat and milk industries) were also used for retarding acid corrosion. The additives used in acid, included flour, bran, yeast, a mixture of molasses and vegetable oil, starch and hydrocarbons (tars and oils). “Antra” made by sulphonating anthracene or anthracene oil and “TM” consisting of heavy oils obtained in the fractionation of coal tar were used in Russia (Sanyal 1981). The first patented corrosion inhibitors used were either natural product such as flour, yeast etc., (Baldwin, 1895) or by products of food industries for restraining iron corrosion in acid media (Putilova et al. 1960).

2.1 Natural corrosion inhibitors for steel in various corrosive media 2. 1. .1 Corrosion inhibitors for steel in acidic media A mild steel corrosion phenomenon has become important particularly in acidic media because of the increased industrial applications of acid solutions. Molasses treated in alkali solution inhibit the corrosion of steel in HCl used in acid cleaning (Cabrera et al. 1977). Peels of certain fruits and vegetables are likely used as corrosion inhibitors. Orange and mango peels give adequate protection to steel in 5% and 10% HCl at 25 and 40 °C (Saleh et al. 1982). Peel of pomegranate (Saleh et al. 1972) and Beet root (El-Hosary et al.1982) as corrosion inhibitor for mild steel in acid media. Leaves extract are used as common corrosion inhibitors. The application of extracts of henna, thyme, bgugaine and inriine was investigated for their anticorrosion activity (Hammouti et al.2003). The anticorrosion activity of Embilica officianilis, Terminalia chebula, Terminalia belivia, Sapindus trifolianus and Accacia conicianna was also investigated (Sanghvi et al. 1996). Corrosion inhibition has also been studied for the extracts of Swertia angustifolia (Zakvi et al. 1988). Similar results was also shown by Eucalyptus leaves, Eugenia jambolans, Pongamia glabra, Annona squamosa (Sakthivel et al. 1999), Accacia Arabica (Verma et al. 1999), Carica papaya, Azadirachta indica and Vernonia amydalina was used for steel in acid media. Nypa fructicans wurmb leaves were studied for the corrosion inhibition of mild steel in HCl media (Orubite et al. 2004). Ricimus communis leaves were studied for the corrosion inhibition of mild steel in acid media by (Sathiyanathan et al. 2005). The use of herbs (such as coriander, hibiscus, anis, black cumin and garden cress) as used as new type of green inhibitors for acidic corrosion of steel (Khamis et al. 2002). Seeds are of great concern for corrosion inhibition studies. Tobacco, black pepper, caster oil seeds, acacia gum and lignin can be good inhibitors for steel in acid medium (Srivastava et al. 1981). Papaia, Poinciana pulcherrima, Cassia occidentalis and Datura stramonmium seeds are efficient corrosion inhibitor for steel (Zucchi et al. 1985). The extract of Khillah (Ammi visnaga) seeds, on the corrosion of SX 316 steel in HCl solution was also studied (El-Etre et al. 2006). The anticorrosion activity of onion, garlic and bitter gourd for mild steel in HCl media showed good results (Parikh et al. 2004) studied. Oil extracts of Ginger, jojoba, eugenol, acetyl-eugenol, artemisia oil and Mentha pulegium are used for corrosion inhibition of steel in acid media (Hammouti et al. 2006). Berberine an alkaloid isolated from Captis was studied for its anticorrosion effect for mild steel corrosion in H2SO4 medium (Yan et al. 2005). Saps of certain plants are very useful corrosion inhibitors. Calotropis procera, Azydracta indica and Auforpio turkiale sap are useful as acid corrosion inhibitors. The extract of Datura metel was used as corrosion inhibitor for mild steel in acid medium (Sethuraman et al. 2005). Quinine has been studied for its anticorrosive effect of carbon steel in 1 M HCl (Awad 2006). The inhibitive effect of Occium viridis extract on the acid corrosion of mild steel was studied (Oguzie 2006). The inhibition effect of Zenthoxylum alatum extract on the corrosion of mild steel in aqueous orthophosphonic acid was investigated (Chauhan et al. 2004). The inhibitive effect of lupine (Lupinous albus L.) extract on the corrosion of steel in aqueous solution of 1 M H2SO4 and 2M HCl


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was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques (Abdel-Gaber et al. 2009). Potentiodynamic polarization curves indicated that the lupine extract acts as a mixedtype inhibitor. EIS measurements showed that the dissolution process is under activation control shown in Figure 1(a) & (b).

2. 1. 2. Corrosion inhibitors for steel in neutral/ alkaline media The performance of caffeine and nicotine was investigated in the inhibition of steel corrosion in neutral media (Srivastava et al. 1973). The aqueous extract of Hibiscus and Agaricus flower as corrosion inhibitor for industrial cooling system was very well studied (Minhaj et al. 1999). The extensive study on the effect of caffeine as chloride corrosion inhibitor of carbon steel was further examined by potentiodynamic polarization technique (Anthony et al. 2004). The structure of various corrosion inhibitors used for steel in various corrosive environment is given in Table 1. Table 1: Structures of green inhibitors used for mild steel

H

OH HO

N

OH H

H3CO

OH

HO

Caffeic acid

Quinine sulphate

OH

OCOCH3

OMe

OMe

CH2CH=CH2

CH2CH=CH2

Eugenol

Acetyl eugenol

OCH3

H3C

O

H3C

O

O

OCH3

O

O

O

Khellin

Visnagin N

N

N

N

O

Sparteine

Lupaine N

O N

Multiflorine

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(a)

(b) Figure 1. Electrochemical measurements of steel in 1 M H2SO4 in the absence and presence of different lupine extract concentrations (a) Tafel curve (b) Nyquist plot

2. 2. Natural corrosion inhibitors for aluminum 2. 2. 1. Corrosion inhibitors for aluminium in acidic media Opuntia extract was investigated for the corrosion of Aluminium in acid medium (El-Etre 2003). The inhibitive action of Vernonia amygdalina on the corrosion of Aluminium alloys in HCl and HNO3 was also studied (Avwiri 2003). The inhibitive effect of Sansevieria trifasciata extract showed good effect on both acidic and alkaline corrosion of Aluminium alloy (Oguzie 2007). The list of inhibitors used for retardation of aluminium corrosion is shown in Table 2.

2. 2. 2. Corrosion inhibitors for aluminium in neutral/ alkaline media Inhibition of aluminium corrosion in 2M NaOH solution in the presence and absence of 0.5M NaCl using damsissa (Ambrosia maritime, L.) extract has been studied employing different chemical and electrochemical techniques (Abdel-Gaber et al. 2008). The analyzed aqueous extract of Rosmarinus officinalis (Kliskic et al. 2000) was analyzed as corrosion inhibitor for Aluminium alloy corrosion in chloride solution. The effect of saccharides [reducing sugars—fructose and mannose] was investigated on the corrosion of Aluminium and Zinc in alkaline media (Muller 2002). Natural compounds rutin and quercetin (Berković et al. 2005), which are strong antioxidants are also used as corrosion inhibitors for aluminium in 3% sodium chloride solution. The corrosion inhibition of Aluminium and Zinc in HCl using Hisbiscus subdariffa (El-Hosary et al. 1972) extract was also examined. Figure 2. shows the inhibition efficiency of various inhibitors used for aluminium in various corrosive media.


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Table 2: Structures of some natural inhibitors used for Aluminium corrosion inhibition CHO

OH

OH

CHO OH

HO

CH3 H3C

HO H3C

CH

OH HC

CH3

H3C

CH3

Gossypol OH

HO

O OH

OH OH

Cdl(IE)

Wt. loss(IE)

2MNaOH

2MNaOH+0.5MNaCl

2MKOH

2MHCl

leaves

seeds seeds

100

2MHCl

(+) Catechin

Inhibition Efficiency (%)

80

60

40

20

0 O. ficus

-- G.hirsutum -- S.Trisfasciata -- A. maritime --Tapioca Starch--

Figure 2. The inhibition efficiency of inhibitors used for aluminium in various corrosive environments

2.3. Natural corrosion inhibitors for copper Effect of vegetal tannin (Mabrour et al. 2004) on anodic copper dissolution was studied in chloride solutions. The tannin was extracted from Takaout galls (Tamarix articulata). The gallic acid has been used as a representative of the tannin species. The tannin behaved as anodic inhibitors. The inhibition efficiency of the tannin evaluated from impedance measurements is about 98% for a tannin concentration of 3 g/l and 97% for gallic acid. The application of natural honey (El-Etre 1998) was studied as corrosion inhibitor for copper in aqueous solution. The structure of the components of vegetal tannins is shown in Table 3.

2. 4. Natural corrosion inhibitors for zinc Zinc corrosion inhibition was studied in alkaline media by saccharides [reducing sugars—fructose and mannose] (Muller 2002). The corrosion inhibition of Zinc in HCl was studied by using Hisbiscus subdariffa (El-Hosary et al. 1972)extract.

2. 5. Natural corrosion inhibitors for tin The influence of natural honey (chestnut and acacia) and natural honey with black radish juice (Radojcic et al. 2008), on corrosion of tin in aqueous and sodium chloride solutions was studied using weight loss and polarization techniques. The inhibition efficiency of acacia honey was lower than that of chestnut honey, while the addition of black radish juice increased the inhibition efficiency of both honey varieties.

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Table 3: Structures of green inhibitors used for copper OH HO

OH HO

O

O

C

C

O

OH

OH OH

O

OH

OH

3,4-Flavandiol

Ellagic acid

OH HO

OH

COOH

Gallic acid

3. NATURAL VOLATILE CORROSION INHIBITORS Thyme extract of (Premkumar et al. 2008) Thymus vulgar L. plant was used as volatile corrosion inhibitor for mild steel in sodium chloride environment with 100 % relative humidity. It was found that both powder and impregnated craft paper have significant inhibitive effect. The inhibition efficiency increases with increase in concentration from 250 to 1000 mg for the powder and 250 to 1000 mg/sq.ft for impregnated craft paper. It has also been found that thyme powder of concentration 1000 mg and impregnated craft paper of concentration 1000 mg/sq.ft offered maximum inhibition efficiency of 80.49 and 78.64 %, respectively, shown in Figure 3. Some beta-amino alcohols compounds are examined as green volatile corrosion inhibitor for brass (Gao et al. 2007). Wood bark oils were used as vapour phase corrosion inhibitor for metals in NaCl and SO2 environments by (Poongothai et al. 2005). Biodegradable volatile corrosion inhibitors were tested for offshore and onshore installations (Chandler 2001). 100 90

Inhibition Efficinecy (%)

80

80.49

78.64

70 60 50 40 30 20 10 0 1000 mg

--

1000 mg/sqft impregnated paper

Thymus vulgaris

Figure 3. Performance of Thymus vulgaris extract as powder and impregnated in paper

4. CONCLUSION The natural products of plant origin have been found to exhibit corrosion inhibiting properties. The significance of this area of research is primarily due to the fact that natural products are environmentally friendly and ecologically acceptable. The safe handling, cost affectivity and simple extraction process made the use of green inhibitors very easy. It is certain that natural compounds emerge out as effective inhibitors of corrosion in the coming years due to their biodegradability, easy availability and non-toxic nature. Careful perusal of the literature clearly reveals that the era of green inhibitors has already begun.


5. REFERENCES Abdel-Gaber, A M, Abd-El-Nabey, B A, Saadawy Abdel-Gaber, M, 2009, The role of acid anion on the inhibition of the acidic corrosion of steel by lupine extract, Corrosion Science, 51 p 1038-1042 Ananda, R, Sathiyanathan, L, Maruthamuthu, S, Selvanayagam, M, Mohanan, S, Palaniswamy, N, 2005,

Corrosion inhibition of mild steel by ethanolic extracts of Ricinus communis leaves, Indian Journal Chemical Technology, 12 p 356-360 Anthony, N, Malarvizhi, E, Maheshwari, P, Rajendran, S, Palaniswamy, N, 2004, Corrosion inhibition by caffeine Mn2+ system, Indian Journal Chemical Technology, 11 p 346-350 Arenas, M A, Conde, A, Damborenea, J D, 2002, Cerium: a suitable green corrosion inhibitor for tinplate, Corrosion Science, 44 p 511-520 Avwiri, O, Igho, F O, 2003,Inhibitive action of Vernonia amygdalina on the corrosion of aluminium alloys in acidic media, Material Letter, 57 p 3705-3711. Awad, M I, 2006, Eco friendly corrosion inhibitors: Inhibitive action of quinine for corrosion of low carbon steel in 1M HCl, Journal Applied Electrochemistry, 36 p 1163-1168 Baldwin, J, 1895, British Patent, 2327

Berković, K., Kovač, S, Vorkapić-Furač, J, 2004, Natural compounds as environmentally friendly corrosion inhibitors of aluminium, Acta Elementaria, 33 p 237-247 Bouyanzer, A, Hammouti, B, Majidi, L, 2006, Pennyroyal oil from Mentha pulegium as corrosion inhibitor for steel in 1 M HCl, Material Letter, 60 p 2840-2843. Cano, E, Pinilla, P, Polo, J L, Bastidas, J M, 2003, Copper corrosion inhibition by fast green, fuchsin acid and basic compounds in citric acid solution, Materials and Corrosion, 54 p 222-228. Cabrera, G, Ramos, E, Perez, J, Santhomas, J,1977, Cuba Azucar (patent),(April–June), p13–20 Chandler C, 2001, Biodegradable volatile corrosion inhibitors for offshore and onshore installations Material Performance, 40 p 48-52 Chetouani, Hammouti, B, 2003, Bulletin of Electrochemistry, 19 p 23 El-Etre, A Y, 2006, Khillah extract as inhibitor for acid corrosion of SX 316 steel, Applied Surface Science, 252 p 8521–8525 El-Etre, A Y, 2003, Inhibition of aluminium corrosion using Opuntia extract, Corrosion Science, 45 p 24852495 El-Etre, A Y, 1998, Natural honey as corrosion inhibitor for metals and alloys. i. copper in neutral aqueous solution, Corrosion Science, 40 p 1845-1850 El-Hosary, A A, Saleh, R M, Sharns El Din, A M, 1972, Corrosion inhibition by naturally occurring substances—I. The effect of Hibiscus subdariffa (karkade) extract on the dissolution of Al and Zn, Corrosion Science, 12 p 897904. El-Hosary, A A, Salah, R M, El-Dahan, H A, 1990, Proc. 7th European Symposium on Corrosion Inhibitors, University of Ferrara, Ferrara, Italy, 1 p 725 El-Hosary, A A, Gowish, M M, Saleh, R M, 1980, Proceedings 2nd International Symposium and Oriented Basic Electrochemistry, SAEST, IIT, Madras,Technical Session, 7 paper 6.24

Farooqi, I H, Quraishi, M A, Saini, P A, 1999, Corrosiosn prevention of mild steel in 3% NaCl by some naturally occurring substances Corrosion Prevention Control, 46 p 93-96 Fodor G E, 1985,The inhibition of vapour-phase corrosion inhibition: A review, Interim Report Bflrf No. 209, Materials, Fuels and Lubricants Laboratory, Fort Belvoir, Virginia, p 5-51 Gao, G, Liang, C, 2007, Some –amino alcohols compounds as green volatile inhibitors for brass, Journal of Electrochemical Society, 154 p C144-151 Khamis, E, Al-Andis, N, N. 2002, Herbs as new type of green inhibitors for acidic corrosion of steel, Materials and Corrosion, 33 p 550-554.

Kliskic, M, Radosevic, J, Gudic, S, Katalinic, V, 2000, Aqueous extract of Rosamarinus officinalis L. as inhibitor of Al-Mg alloy corrosion in chloride, Journal of Applied Electrochemistry, 30 p 823-830 Li, Y, Zhao, P, Liang, Q, Hou, B, 2005, Berberine as a natural source inhibitor for mild steel in 1 M H2SO4, Applied Surface Science, 252 p 1245- 1253 Mabrour, J, Akssira, M, Azzi, M, Zertoubi, M, Saib, N, Messaoudi, A, Albizane, A, Tahiri, S, 2004, Effect of vegetal tannin on anodic copper dissolution in chloride solutions, Corrosion Science, 46 p 1833–1847 Machnikova, E, Whitmire, K H, Hackerman, N, 2008, Corrosion inhibition of carbon steel in hydrochloric acid by furan derivatives, Electrochimca Acta, 53 p 6024–6032.

Minhaj, A, Saini, P A, Quraishi, M A, Farooqi, I H, 1999, A study of natural compound as corrosion inhibitors for industrial cooling system, Corrosion Prevention Control, 45 p 32-38

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Muller, B, 2002, Corrosion inhibition of aluminium and zinc pigments by saccharides, Corrosion Science, 44 p 1583-1591 Oguzie, E, E, 2007, Corrosion inhibition of aluminium in acidic and alkaline media by Sansevieria trifasciata extract, Corrosion Science, 49 p 1527-1539. Orubite, K O, Oforka, N C, 2004, Inhibition of the corrosion of mild steel in hydrochloric acid solutions by the extracts of leaves of Nypa fruticans Wurmb, Material Letter, 58 p 1768-1772. Ostovari, A, Hoseinieh, S M, Peikari, M, Shadizadeh, S R, Hashemi, S J, 2009, Corrosion inhibition of mild steel in 1 M HCl solution by henna extract: A comparative study of the inhibition by henna and its constituents (Lawsone, Gallic acid, a-D-Glucose and Tannic acid), Corrosion Science, 51 p1935–1949 Parikh, K S, Joshi, K J, 2004, Trans. SAEST, 39 p 29.

Premkumar, P, Kannan, K, Natesan, M, 2008, Thyme extract of thymus vulgar L. As volatile corrosion inhibitor for mild steel in NaCl environment, Asian Journal of Chemistry, 20 p 445-451 Poongothai N, Rajendran P, Natesan M, Palaniswamy N, 2005, Wood bark oils as vapour phase corrosion inhibitors for metals in NaCl and SO2 environments, Indian Journal of Chemical Technology, 12 p 641-647 Putilova, N, Balezin, S A, Barannik, V P, 1960, Metallic Corrosion Inhibitors, Pergamon Press, Oxford, London, Raja, P, Sethuraman, M G, 2008, Natural products as corrosion inhibitor for metals in corrosive media — A review, Material Letter, 62 p 113–116 Radojcic, I, Berkovic, K, Kovac, S, Vorkapic-Furac, J, 2008, Natural honey and black radish juice as tin corrosion inhibitors, Corrosion Science, 50 p 1498–1504 Saleh, R M, Ismail, A A, El Hosary, A A, 1983, Corrosion inhibition by naturally occurring substances-IX. The effect of the aqueous extracts of some seeds, leaves, fruits and fruit-peels on the corrosion of Al in NaOH,

Corrosion Science, 23 p 1239-1241 Saleh, R M, Ismail, A H, El. Hosary, A A, 1982, British Corrosion Journal, 17 p 131 Saleh, R M, El-Hosaray, A A, 1972, Proceedings 13th Seminar on Electrochemistry, CECRI, Karaikudi,. Sanaa, El-Sawy, M, Yosreya, M, Abu-Ayana, F, Abdel-Mohdy, A, 2001, Some chitin/chitosan derivatives for corrosion protection and waste water treatments, Anticorrosion Methods Materials, 48 p 227-235. Sanghvi, M J, Shukla, S K, Mishra, A N, Padh, M R, Mehta, G N, 1996, Trans. MFSI, 5 p 143. Sanyal, B, 1981, Organic compounds as corrosion inhibitors in different environments — A review, Progress in Organic Coating, 9 p 165-236 Sakthivel, P, Nirmala, P V, Umamaheswari, S, Antony, A A, Kalignan, G P P, Gopalan, A, Vasudevan, T, 1999, Bulletin of Electrochemistry, 15 p 83-. Sethuraman, M G, Bothi Raja, P, 2005, Corrosion inhibition of mild steel by Datura metel, Pigment Resin Technology, 34 p 327-331 Srivatsava, K, Srivatsava, P, 1981, British Corrosion Journal, 16 p 221 Srivatsava, B C, Sanyal, B, 1973, Proceeding Symposium of Cathodic Protection, Defence Research Laboratory, Kanpur, India, Paper 1.2 Srivatsava, K, Sanyal, B, 1973 Proceeding Symposium of Cathodic Protection, Defence Research Laboratory, Kanpur, India, , Paper 1.4 Verma, S, Mehta, G N, 1999, Bulletin of Electrochemistry, 15 p 67 Zakvi, S J, Mehta, G N, 1988, Trans SAEST, 23 p 4 Zucchi, F, Omar, I H, 1985, Plant extracts as corrosion inhibitors of mild steel in HCl solutions, Surface Technology, 24 p 391-399


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TRIPLE BOTTOM LINE: A STUDY OF M/S. CHANDERIYA SMELTING COMPLEX, HZL R.K. Bansal Asso. Vice President, HZL, Chittorgarh Tauseef Zia Siddiqui Environmental Cell, HZL, Chittorgarh

Abstract: Since the introduction of Cleaner Production (CP) to industrial sectors in India, much effort and resources from various stakeholders have been to speed up its implementation. CP took a slow but steady start with quite a few demonstration projects, followed by capacity building activities. Even though the industries were convinced to use CP for productivity improvement, it has not been really sustained in companies and the multiplier effects are slow. The lack of a human dimension probably is a significant hindrance in making CP self-sustained in Indian industries. A few organizations took the initiative to test this hypothesis, supporting a demonstration project on financial, environmental and social issues which is called “Triple Bottom Line (TBL)”. The thrust of this TBL project was to use CP as a baseline and extend its concepts to cover social issues also. The demonstration industries undertook TBL assessment including CP and social issues like employee work hrs, compensation & benefits, freedom of association, health & safety, harassment & abuse, discrimination, use of child or bonded labor etc. The TBL assessment of CSC has provided breakthrough opportunities of improvement in non-ferrous sector. Out of these several opportunities were implemented. Preliminary results suggested that both manager and employee of CSC were satisfied with results of the project and can be depicted from the Award given by Hewitt’s for Best employer also. Results indicated that not only did management enjoy the savings in each case, but also the employees got a more enjoyable working environment. Thus we can conclude that a key factor to keep CP momentum is the social and environmental bottom line, which has direct impact on employees, who are the actual implementers of CP.

Keywords: Cleaner Production (CP), Triple Bottom Line (TBL), Environnemental Botton Line 1.0 INTRODUCTION 1.1 What is TBL? TBL is the process of evaluating company performance in three dimensions: financial, environment and social using a set of indices to identify problem/focus. Consequently, systematic measures to prevent or alleviate the problem following CP procedures were applied, considering not only the economic and environmental aspects but also social issues. The three sets of indices are: Financial Bottom Line: The primary concern of the financial bottom line in the TBL context is not the accounting figures but the indicators reflecting the long term economic value of investing in the company. The indicators employed also represent efficiency and effectiveness of resource utilization, i.e. those relating to purely finance, resource utilization efficiency, resource utilization

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indicator, turnover and overall effectiveness. The key figure in TBL is “Value Added”, which in this context means revenue minus cost of raw material and energy. This allows us to visualize operational performance in all three dimensions, which traditional terms such as profit cannot. Environmental Bottom Line. The fundamental principle here is to minimize waste generation per functional unit. As a result, production cost decreases and environmental impact is prevented at source. Indicators employed for this bottom line are production related environmental indicators, which includes both generic parameters and those specific to each industry. In other words, CP should be employed to address environmental issues in the company. Social Bottom Line. This new area is all about labor and the quality of life in the work environment. There are eight areas of major concern, i.e., hours of work, payment and compensation, freedom to communicate, health and safety, harassment and abuse, discrimination, child labor, and bonded labor. The criteria for this bottom line are to act in accordance with national laws and registration and international labor standards.

1.2 Methodology of TBL Demonstration: Methodology of TBL consisted of five steps, i.e. gap analysis, in-house training, brainstorming, follow- up, and conclusion. Each company’s TBL team assessed the condition of their business in three dimensions. Then CP procedures were used to improve existing conditions from TBL options.

1.3 Application of TBL concept: The primary purpose of TBL approach is to bring enterprises to see international pressures as a positive driving force to encourage management to look more closely at the operations of the business and to make it more successful and sustainable over the long-term. Once a company like HZL recognize by evidence that TBL is not a cost but a concrete help in planning and tracking environmental and social improvements that bring financial benefits, they can then be engaged in the virtuous cycle of continuous improvement. The two primary building blocks of improvement methodology in TBL approach are the Cleaner Production Process (CP), and the Social/Human Resource Development Process (HR). These two processes are very similar and are compared in the table below:

PROJECT PHASE

CLEANER PRODUCTION

HR DEVELOPMENT

Preparatory Phase

Stage 1: Getting Started

Stage 1: Getting Started

• Designate a Cleaner Production / HR Improvement Team • Team Training Stage 2: Analysing Process Steps Stage 2: Analysing HR Performance • List Process Steps / Departmental Units • Identify & Select Wasteful/Polluting Processes and HR problem areas • Baseline Data Collection • Gap Analysis Stage 3: Generating Cleaner Stage 3: Generating HR Improvement Application Phase Production Opportunities Opportunities Stage 4: Selecting HR Improvement Stage 4: Selecting Cleaner Production Solutions Solutions Assess options on technical, financial, environmental and HR criteria Stage 5: Implementing HR Improvement Stage 5: Implementing Cleaner Production Solutions Solutions


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Table 1.1 Main Stages in the Cleaner Production and Social/ Human Resource Development Process for TBL As shown in the table the TBL approach involves different stages but it is essentially made up of two key phases:

(a)Preparatory Phase: The environmental indicators cover air emissions, water effluents and solid wastes. In particular, the indicators considered are: Water Consumption; Energy Consumption; Waste Generation; Releases of key Water Pollutants and Releases of key Air Pollutants. An additional indicator is compliance with all applicable environmental rules, regulations and standards. The social indicators address the need to change the social consciousness of the companies’ management and to provide decent working conditions, while others refer more to the productivity of the employees. They cover the following issues: Hours of work; Compensation & benefits; Freedom of association; Health & safety; Harassment & abuse; Discrimination; Use of child labour and Use of forced/bonded labour.

Once the baseline data have been collected the TBL teams compare them to a set of benchmarks that are set for each of the TBL indicators. The benchmarks can be either external or internal. External benchmarks may be drawn from a variety of sources. These will include national legislative or administrative standards, national industry averages or best practice, international norms or best practice or technical optima. For instance, environmental benchmarks can refer mainly to national effluent or emissions standards while the social benchmarks will often refer to both national and international regulations and codes of conduct. Internal benchmarks are likely to reflect either management targets or goals. The result of this comparison between the actual situation and the benchmarks is a “gap analysis”, which prepares the ground for the following phase of the TBL approach. The Leading Indicators (or benchmarks): consist of the policies, systems and procedures that a company management should have in place to eliminate or at least minimise the risks of negative social and environmental “outcomes”. They “lead” in the sense that they aim to prevent a problem happening in the first place. The Lagging Indicators (or benchmarks) consist of standards of performance for a range of TBL issues. They “lag” in the sense that they are based on measures of “outcomes” or “outputs”. They typically include environmental efficiency and emission standards as well as those relating to the treatment of the workforce.

(b)Application phase: In This phase, the TBL teams evaluate the results of the gap analysis. The teams first assess what improvement options exist to close the gaps that have been shown to exist between the actual situation and the chosen benchmarks. Then they assess the options for technical feasibility and financial viability in the light of the priorities of the enterprise, and submit to management their recommended set of improvement options to be implemented. Once the management has accepted the recommendations, the teams can then take on the task of implementing them. Social and environmental improvements like better housekeeping, raw materials and energy conservation, reuse and recycling, a better working environment and better working conditions all can reduce operating costs; they have proved to also increase product value added and product quality and to reduce product rejection rates.

Gap analysis: Once the baseline data were collected, the TBL teams performed their gap analysis, i.e. they assessed their enterprises’ current performance with respect to the benchmarks chosen for the three dimensions of TBL performance.

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TRIPLE BOTTOM LINE REPORTING STUDY OF CHANDERIYA SMELTING COMPLEX

2.0 People Dimension: Social Bottom Line 2.1 Profile of the employees: People empowerment - We influence and get influenced for betterment On account of expansion of Hindustan Zinc Limited there is large scale recruitment of professional from different discipline on regular basis from premier institutes and once they are exposed to basic training these individuals are deployed on various assignments in different units.15% women are contributing effectively & efficiently for the growth & development of this location. Always there is an attempt to ensure balanced amalgamation of young & experienced professionals to achieve the organization goals. In order to provide ample growth opportunities to Non-Executives, the company has devised a Junior Executive Training Process (JET Process), to promote these Non-Executives into Executive cadre. To further enhance their qualification. Management has also launched a scheme whereby these individuals absorbed in to executive cadre are provided another opportunity to pursue their education by joining a Bsc Engineering course conducted in collaboration of BITS Pilani in CSC Colony Campus HZL ensures its compliance to employee welfare related activities. Some of the benefits offered to employees are listed below: Personal Accident Insurance, Mediclaim Insurance, Annual medical checkup, Medical Bill Reimbursement. HZL is following group HR policy in providing services, benefits to employees. Food allowance is provided to all employees. Refreshments, Transport, uniform are provided free of cost to employees. “Zinc Nagar” - HZL Township is provided with Swimming pool, Gym, Shuttle court, Children’s Park, Indoor games etc., to enhance quality of life of employees. We have a programme called Employee Contact Programme (ECP) in which couple of members of the HR team interacts with the employees at shop floor and give feedback on their problems at work place and solutions thereof.

We grow together- Support of Key Communities 2.2 SOCIAL POLICY At HZL/CSC, we believe in sustainable development and are committed to raise the quality of life and social well-being of the communities where we operate. Towards this, we will be guided by following: (a) Our community development initiatives will be prioritized based on local needs. Broad areas of focus will be Social Investment – Health, Education, Livelihood, Social Mobilization & Infrastructural Development Bio Investment – Water harvesting, agriculture and animal husbandry. Environment Conservation- Social forestry (b) All operating locations will incorporate CSR activities as an integral part of their business plan and have an appropriate organization to implement the same. (c) We will be open to working with like minded associates, Government bodies and other volunteer organization in pursuit of our mission. (d) We will measure and report progress as per social accounting systems and encourage third party reviews for effective delivery and measurable impact. (e) We regularly communicate with all our stakeholders on the progress and performance on social management.


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2.3 Social Vision a part of Business Vision. Driven by this philosophy, Hindustan Zinc has been planning, designing and implementing CSR Projects on a sustainable basis. We work in partnerships with local communities whereas positively impacting their quality of life and contributing to their sustainable development, avoiding long term dependency on our operations. We also take care of human rights, respecting cultural considerations and diversity across all units in the country. At the outset of each Community Development project we adopt a mechanism which incorporates deliverance of sustained benefits to the community. Stakeholders feedback are taken into account in the process of decision making and business planning and provide lasting benefits for the local communities through our corporate social involvement and community development programmes. We believe in the stake holder’s willingness to transform through continuous communication. Our determination is driven by the community’s commitment in owning our projects with a common goal and interests which would eventually facilitate our graduation. We also measure and report the progress as per social accounting system for that we appoint third party/ reputed external agency for review, study and audit of our social projects. The outcome of the study helps in applying timely corrective measures and documenting measurable impact. Right from planning to execution as well as monitoring of all the social projects we involve the Panchayat, Govt. Bodies, Community as well as other likeminded NGO’s in view of our philosophy to play a role of catalyst in social initiatives as a whole.

3.0 Planet Dimension: Environmental Botton Line 3.1 Signifiant Environmental Initiatives DCDA Tech. with cesium based V2O5 catalyst at all Acid Plants Tail Gas Treatment (TGT) Plant – based on Japanese Tech. (Mescon) at all smelters. Cansolv Technology to concentrate lean & varying SO2 gas at Ausmelt. Integrated ETP with Storm Water Ponds having auto sampler, online pH and water level indicators & GSM network. Reverse Osmosis Plant (298 m3/hr) – largest in Rajasthan. Achieving Zero Discharge. Dry Fog Dust Suppression Systems at Material Handling Areas De-dusting and Ventilation Systems in each plant. Building Ventilation & Column Ventilation systems at refinery plant Full fledged Environment Management Cell & sophisticated laboratory. 3 Online AAQM Stations Online Multi Parameter Analyzers Online Stack Analyzers MoEF approved Agency for Environment monitoring & analysis. Intranet based website on HSE We are committed to efficient resource utilization through environment conservation and protection. We were a signatory to a voluntary initiative named Corporate Responsibility for Environment protection, (CREP) in 2003.Initiated by the ministry of MoEF. We have developed a very strong CREP compliance comprising a significant reduction in Sulphur dioxide emissions and zero waste water discharge. Secured

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Land Fill & Jarofix Process for disposal of eco- friendly waste. We are the first in Asia and Third in world to adopt this state of art technology.

3.2 Waste Management Reduce: Notable among these projects are increasing the cycle of concentration in cooling tower of power plant in CSC, standardisation of slag granulation operation in CSC, leak arresting drives in all units, etc. Rainwater harvesting schemes are being implemented in new projects. Reuse: Waste water is utilized in plant operations, greenbelt and de-dusting operations. Used oil and waste oil are reused by disposing to registered recyclers. Recycle: Entire fly ash is disposed to cement industries. Permission has been taken permission from State Pollution Control Board to use slag in cement manufacturing. About 3 lac MT of ISF slag (CSC) was given to the cement industry to use as raw material in cement making. In a major development, Indian Road Congress (IRC) has directed NHAI to prepare test bed of sub layer and embankment by using ISF slag.

3.3 Sustainable Development at CSC 100% EOHS Compliance Aspire 10% reduction in water and Energy consumption every year Encourage to discover and innovate ideas for CDM Credits Find beneficial use of solid waste like Jarosite and Slag Accelerate social development initiatives around CSC Operational excellence Bottom-up Improvement Methodology At least two improvement projects for all Green belt training for all (Six sigma) 5S at CSC location Online Tracking System Management employee engagement and facilitation framework Bench Marking and best practice implementation

4.0 Economic Dimension: Profit One of the key drivers of sustainable development i.e. financial performance is well taken care and same is depicted through following tables and graphical presentation. Financial aspects are planned, managed & reviewed at unit levels but same are prepared in an integrated manner at corporate level for the organization as a whole. There is an impressive performance of CSC/HZL during last five Years as this has enhanced by four & five folds respectively. The exciting increase in revenue and profit is on account of increase in production, hike in LME price of Zinc & Lead, higher realization against acid sale and operational excellence. HZL has achieved record Zinc & Lead Metal Production in FY 2007-08 of 426323MT & 58247Mt respectively, an increase of 22.4% and 30.7% as compared with the previous year. The increase in production was primarily on account of production from the newly commissioned Hydro-2 smelter and the improved performance of the existing smelting units. We sold 338000MT of Zinc metal during FY 2007-08 an increase of 65.7% as compared to FY 2006-07, by improving sale to major domestic customer and during above period there was export of 88000 MT of Zinc metal.


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Every organization is having a potential risk and HZL is also not an exception as in the recent past there was adverse impact of lowering of Zinc LME price and appreciation of rupee against U.S dollar but it was a sound conceptualization of situation which help us to overcome the adverse effect of the above by increasing the volume through operational excellence and expansion.

PBDIT (Rs . Crore s )

Turnove r (Rs . Crores)

6639

7000

10 0 0 0

8560

6230

6000

7878 5000

8000

4000

6000 4000 18 4 1

2 4 18

3000

3877

2000

2202

2000

1000

0

0

10 18

660

2003- 04

2003- 04

2004- 05

2005- 06

2006- 07

Table 4.1 Turnover of HZL for 5 years

2005- 06

2006- 07

2007- 08

Table 4.2 PBDIT of last 5 years Capital Em ployed (Rs. Crores)

PAT (Rs. Crores) 5000

2004- 05

2007- 08

4442

4396

14 0 0 0 118 4 9 12 0 0 0

4000

10 0 0 0

3000

8000

2000

6000

10 0 0

14 72 405

4000

6 55

76 2 7

3988 2060

2625

2003-04

2004-05

2000

0

0 2003- 04

2004- 05

2005- 06

2006- 07

Table 4.3 PAT for 5 years

2007- 08

2 0 0 5- 0 6

2006-07

2 0 0 7- 0 8

Table 4.4 Capital Employed

5.0 CONCLUSION From the experiences in the TBL Demonstration Project in CSC, we can conclude that the results of the demonstration project have proven the importance of promoting TBL among non ferrous metal sector to improve their environmental performance and make their practices more acceptable in a manner that is financially advantageous. The TBL approach leads to continuous improvement and the implementation and maintenance of options that create benefits in all three bottom lines. The demonstration project provides good examples of financial savings (e.g. reduction in water, electricity and raw material consumption), environmental improvements (e.g. reduction in solid waste generation and improvement in waste water quantity/quality), social improvements (e.g. risk reduction, improvement in working/health conditions) and product improvements (e.g. better quality, increased yield, rejections reduction). TBL approach represent a starting point to move forward and provide to Indian metallurgical sector a simple and practical tool to respond to national or international pressures on their environmental and social performance in a proactive manner. Thus the social dimension helps to sustain CP in companies. This is because it has direct impacts to employees, who are the actual implementers of CP in the firms. The Triple bottom line (TBL) approach introduces the concerns relating to the environment and society alongside the usual business concept of profitability (the economic bottom line). However, the TBL concept suffers from at least four main intricacies: 1. Companies cannot simply put profitability on the same level as social and environmental considerations, as a company cannot survive by behaving in a socially or environmentally responsible manner while making losses.

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2. Social and environmental benefits tend to be long-term before impacting on stakeholder value. 3. TBL equates social with environmental, whereas social clearly encompasses environmental as one among many other concerns. 4. Therefore, let corporations focus on creating stakeholder value as measured by profits, but in a socially responsible manner. Let us not add on a “surplus fewer deficits” approach based on environmental or social considerations. A company that does poorly on one line, namely profits, but wonderfully on the environment or social component of TBL, is not going to last long in a competitive world!

5.1 Linkages between CP Process and the Social/Human Resource Development Process: Since the CP process and that of HR Development have been designed in TBL approach to have many methodological similarities, it is useful to review how the two processes work together, especially since typically a common team will manage the two processes. Possible types of options generated by the CP process on the one hand and the HR Development process on the other, and how these might evolve over time, are shown in the table below: TBL Stage “Compliance”

“Efficiency”

CP Improvement Options Better Housekeeping Better process control (“Low hanging fruit”) Changes in capital equipment Process re-engineering Cycle time reduction options

“Differentiation” Product Analysis Life Cycle Analysis

HR Improvement Options Policies & Procedures in place Improved worker facilities First Aid, fire & HS facilities and training Reducing absenteeism Reducing labour turnover, improving retention Reducing accidents and excessive overtime Improving take home pay Worker empowerment Ongoing HR investment

Table 5.1.1 CP and HR options at different stages in TBL implementation The balance of emphasis that a team will give between CP and HR issues will be determined in large part by the operational characteristics of the company. For example, companies with labour intensive operations with limited use of process chemicals, energy or water focus more on HR issues than CP, as small improvements in the former would probably give a greater payoff, at least in the short term. The balance would be more even in companies which are quite labour-intensive but also use significant quantities of toxic materials such as tanning.

6.0 REFERENCES 1. Pitsamai Eamsakulrat, Surachai Leewattananukul, Benja Jirapatpimol, Nungruthai Juntraget, Benjaporn Vachirasrisoontra and Sineenat Srisanan, Beyond CP: Triple Bottom Line – Thai Experience 2. Joshi Manoj, SAMA ,Corporate Social Responsibility: Global Perspective, Competitiveness, Social Entrepreneurship & Innovation . 3. Thomas Wiedmann and Manfred Lenzen, Sharing Responsibility along Supply Chains A New Life Cycle Approach and Software Tool for Triple Bottom Line Accounting, The Corporate Responsibility Research Conference 2006, 4-5 September 2006 Trinity College Dublin, Ireland 4. Dr. A K Saxena and Rajat Gupta National Productivity Council, New Delhi, Triple Bottom Line: An Approach for Small Business Sustenance. 5. Triple Bottom Line Demonstration Project in Four Asian Countries, UNIDO REPORT Vienna, January 2003 6. Siddiqui Tauseef, A Review on Triple Bottom Line Reporting, Paper Presented in International Convention on Climate Change, 14-16 June 2009, Palampur, India.


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GENETICALLY ENGINEERED PLANTS AND ENVIRNMENTAL HAZARDS 1. Dr. A.K. Srivastava and 2. Prof. Dr. D.N. Saxena SVN Institute of Engineering, Research and Technology Barabanki, U.P., India 1. Email-ID [email protected] Fax No. 0522-2355661 Mobile No. 9335838268 2. Email-ID [email protected] Fax No. 0522-2355661 Mobile No. 9450453476

ABSTRACT World population is increasing very fast. Population explosion causes hunger. Approximately more than 45% crops are destroyed by various diseases etc. So plant genetic engineering is a boon for whole world for increasing crop production very fast with desired characteristics. Agrobacterium tumefaciens is used for transfer of desired characteristics coding genes in development of genetically engineered plants for drought resistance, for frost resistance from antifreeze coding gene of fish, viral resistance, bacterial disease resistance, fungal disease resistance, production of recombinant vaccines in plants for various dangerous diseases, for more sugar content, for more protein and for insect resistance in crops etc. First of all, leaf discs are prepared of specific plant-in which new genes have to be introduced. Then these leaf discs are infected with Agrobacterium tumefaciens. Leaf discs infected with Agrobacterium turnefaciens are grown on MS medium containing phytohormones and glucose as carbon source. Phytohormones help in development of shoots and roots from plant callus. Tumour inducing (Ti) plasmid plays very important role in gene transfer. Ti plasmid contains genes coding for antibiotic resistance which are very much hazardous if these are leaked accidently from Recombinant DNA and Gene Cloning Laboratory. Then these highly hazardous antibiotic resistance DNA can combine with DNA of weeds and the monster weeds may develop in agricultural field or in forest. These monster weeds can not be destroyed easily because these contain genes coding for antibiotic resistance while ordinary weeds can be destroyed with help of herbicides and weedicides. These antibiotic resistant weeds will reduce crop production because they will cover maximum agricultural field. These genetically modified (GM) weeds can also cause dangerous diseases in human beings. These GM weeds can also destroy rich biodiversity flora & fauna of various ecosystems. Recombinant DNA safety guidelines and expert supervision are must for development of genetically engineered plants safely in Genetic Engineering Lab. Key words: DNA work station, Gene Cloning, Fish anti freeze gene, protocol, genetically engineered plants

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1. INTRODUCTION Shortage of food specially for under developed & developing countries is assuming a serious situation due to population explosion (Deswal & Deswal, 2009) (Gupta 2009). More than 45% crops are destroyed by various dangerous plant diseases. The plant genetic engineering therefore can be a boon for increasing crop production with desired characteristics.There are useful methods for introducing desired characteristics coding DNA into various crop plants.

2. DNA AND DESIRED CHARACTERISTICS Bacterium Agrobacterium tumefaciens is useful for transferring desired characteristics coding genes for development of genetically engineered (transgenic) plants e.g. for frost resistance from antifreeze coding gene from fish, for drought resistance for bacterial disease resistance, for plant viral resistance, for fungal disease resistance, for production of recombinant vaccines in plants for various dangerous diseases, for more protein content, for more sugar content and for insect resistance in crops etc (Newell, 2000).

3.

AGROBACTERIUM TUMEFACIENS AS AN EFFICIENT CLONING VECTOR

The use of Agrobacterium tumefaciens in transgenic (genetically engineered) plant production has arisen from the need to find an effective vector system to successfully integrate the gene of interest into the correct area of plant genome (Hooykass & Shilperoot, 1992). Agrobactrium tumefaciens can be used as a vector system to transfer foreign DNA into a plant genome with a higher degree of success than is currently seen with other methods like electroporation (Chowrira et al, 1995), gene gun mediated transformation – through particle bombardment (Luthra et al, 1995), silicon carbide whiskers, (Wang et al 1995), direct microinjection etc. (Crossway et al 1986). Agrobacterium tumefaciens is a gram negative motile, rod shaped bacterium which is non-sporing and is very closely related to the nitrogen-fixing rhizobium bacteria which form small root nodules on leguminous (pulses) plants (Binns & thomashow 1988). The Agrobactrium tumefaciens bacteria is surrounded by peritrichous flagella. Virulent bacterium-Agrobacterium contains plasmids, one of which carries the genes for tumor induction and is known as the Ti (Tumor inducing) plasmid. The Ti plasmid also contains the genes that determine the host range. Agrobactrium tumefaciens is a vey useful gene delivering system because this bacterium is able to carry any specific gene within the T complex and insert the gene into the desired plants DNA with a very high degree of success. (Hiei et al, 1997) The main reason for this is because unlike other mobile genetic elements such as transposons & retroviruses, the T-DNA strand does not encode functions required for movement and integration of DNA. Therefore T-DNA strand can be replaced by gene


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of interest which will be inserted automatically into the host plant nucleus resulting a great success. This process of gene delivery system is much more efficient than other methods of genetic modification.( Hooykaas & Shilperoot 1992) Successful Agrobacterium mediated genetic transformation has been done in medicago (Trieu et al 2000), rice (Hiei et al, 1997), sunflower (Grayburn & Wick, 1995), carnation (Zuker et al, 1999), Arabidopsis (Clough & Bent, 1998) (Feldmann & Marks, 1987), sugarcane (Enriquer-obregase et al, 1997), (Arencibia et al, 1998). Good result has been also achieved by combining the best characteristics of Agrobactrium- mediated genetic transformation (high efficiency, low copy number & stable integration) with the species independent transformation characteristics found while using gene gun mediated genetic transformation (particle bombardment). In Agrobacterium transformation, first of all, leaf discs are prepared of specific plant in which new genes have to be introduced. Then these leaf discs are infected with Agrobacterium tumefaciens. These leaf discs are grown on MS medium containing Phytoharmones and glucose as carbon source. Phytohormones help in the development of shoots & roots from plant callus. Tumor inducing (Ti) plasinid plays very important role in gene transfer, Ti plasmid contains genes coding for antibiotic resistance which are very much hazardous if these are leaked accidently from recombinant DNA and gene cloning laboratory. Then these highly hazardous antibiotic resistance DNA can combine with DNA of weeds and as a result monster weeds may develop in agricultural field or in forest. These monster weeds can not be destroyed easily because these contain genes coding for antibiotic resistance while ordinary weeds can be destroyed with help of herbicides and weedicides.

4. DNA SAFETY GUIDELINES Recombinant DNA safety guidelines and expert supervision are necessary for development of genetically engineered (transgenic) plants safely in genetic engineering laboratory. Details of recombinant DNA safety guidelines are as follows 1. 2. 3. 4. 5. 6. 7.

Make protocol of DNA experiment before starting DNA experiment. Never change or modify protocol at any cost while doing DNA experiment. Sterilize DNA workstation before starting DNA experiment. Never leave DNA experiment in middle. Never leave DNA laboratory while doing DNA analysis experiment otherwise through gloves, DNA can spread outside of genetic engineering lab. Before starting DNA experiment, sterilize hands properly & wear sterilized gloves. After electrophoresis of DNA in agarose gel and its visualization in ultraviolet light, don's discard agarose gel (containing DNA) without autoclaving.

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8

Carry on only one DNA experiment at one time. Otherwise for managing DNA experiments more than one at one time, accidently DNA can spread outside of the genetic engineering lab.

5. CONCLUSION All the genetic engineering laboratories should invariably follow the recombinant DNA safety guidelines and expert supervision during development of genetically engineered plant (transgenic plant) so that crop production can be increased. Chances of development of dangerous diseases in humans which can be caused by spread of antibiotic resistance weeds are minimized. Moreover there will be also no danger of destruction of rich bio-diversity flora and fauna of various ecosystems by these antibiotic resistant weeds.

6. REFERENCES 1.

2.

3.

4.

5.

6. 7.

8.

9.

Arencibia A.D., Carmona E.R., Tellez P., Chan M.T., Yu S.M., Trujillo L.E. and Oramas P. (1998) An efficient protocol for sugarcane (Saccharum spp.L) transformation mediated by Agrobacterium tumefaciens. Transgenic Research 7:1-10. Binns A.N. and Thomashow M.F. (1988). Cell biology of Agrobacterium infection and transformation of plants. Annual Review of Microbiology 42:575-606. Chowrira, G.M., AkeIla, V. and Lurquin, P.F. (1995) Electroporationmediated gene transfer into intact nodal meristems in plants. Molecular Biotechnology, 3, pp. 17-23. Clough, S.J. and Bent, A.F. (1998) Floral dip: a simplified method for Agrobacterium –mediated transformation of adult Arabidopsis thaliana plants by vacum infiltration. The Plant Journal, 16, pp. 735 - 743. Crossway, A., Oakes, J.V., Irvine, J.M., Ward, B., Knaut V.C. and Shewmaker, C.K. (1986) Integration of foreign DNA following microinjection of tobacco mesophyll protoplasts. Mol Gen Genet 207, 179-195. Deswal S and Deswal A, 2009. Environment and Ecology. Dhanpat Rai & Co. Pvt. Ltd., New Delhi, 1.1 – 7.38. Enriquez Obregón G.A., Vázquez-Padrôn R.I., Prieto-Sansonov D.L., De la Riva G.N., Selman- G. (1998). Herbicide resistant sugarcane (Saccharum officinarum L) plants by agrobacterium mediated transformation. Planta 206:20-27. Enriquez - Obregón G.A., Vázquez-Padrôn R.I., Prieto-Sansonov D.L. Perez M. and Selman – Housein G. (1997) Genetic transformation of sugarcane by Agrobacterium tumefaciens using antioxidants compounds. Biotecnologia Aplicada 14:169 – 174. Feldmann, K.A. and Marks, M.D. 1987) Agrobacterium-mediated transformation of germinating seeds of Arabidopsis thaliana: a non-tissue culture approach. Molecular Gen. Genet., 208, pp. 1-9.


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10.

Grayburn, W.S. and Vick, B.A. (1995) Transformation of Sunflower (Helianthus annus L.) following wounding with glass beads. Plant Cell Reports, 14, pp. 285-289.

11.

Gupta K.M., 2009, Environment & Ecology, Umesh Publications, New Delhi, 1-380 Hiei, Y., Komari, T. and Kubo, T. (1997) Transformation of rice mediated by Agrobacterium tumefaciens. Plant Molecular Biology, 35, pp. 205-218. Hooykaas P.J.J. and Shilperoort R.A. (1992). Agrobacterium and plant genetic engineering. Plant Molecular Biology 19:15-38. Luthra, B.., Varsha, R.K.D., Srivastava, A.K. and Kumar, S. (1995) Microprojectile mediated plant transformation: A bibliographic search. Euphytica, 95, pp. 269-294. Newell, C.A. (2000) Plant Transformation technology; Developments and Applications. Molecular Biotechnology, 16, 53-65 Trieu,A.T., Burleigh, S.H., Kardailsky, I.N., Maldonado-Mendoza, I.E., Versaw, W.K., Blaylock, L.A., Shin, H., Chiou, T, Katagi, H., Drewbre, G.R., Weigel, D. and Harrison, M.J. (2000) Transformation of Medicago truncatula via infiltration of seedlings or flowering plants with Agrobacterium. The Plant Journal, 22 (6), pp. 531-541. Wang, K., Drayton, P., Frame, B., Dunwell, J. and Thompson, J. (1995) Whisker-mediated plant transformation: an alternative technology. In vitro Cell Developmental Biology , 31, pp. 101-104. Zuker, A., Ahroni, A., Tzfira, T., Ben-Meir, H. and Vainstein, A. (1999) Wounding by bombardment yields highly efficient Agrobacterium-mediated transformation of carnation (Dianthus caryophyllus L.) Molecular Breeding, 367-375

12. 13. 14.

15. 16.

17.

18.

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APPLICATION OF GREEN ENGINEERING CONCEPTS FOR SUSTAINABLE DEVELOPMENT Dr. K. SUKUMARAN PRINCIPAL King College of Technology Namakkal-637020 [T.N] Email: [email protected], [email protected]

ABSTRACT

Planet Earth is endangered by the depletion of resources due to consumption of resources by humans for their needs and necessities for living and survival. The consumption of resources like materials, pro ducts, air, water, energy, etc., generates wastes, pollution and causes environmental degradation, ecological disorder, which contribute towards climate change, global warming, natural hazards, etc., that lead to future unsustainable world. This type of precarious conditions would affect the future generation a n ensured safer living. To overcome and manage these predicaments, it is essential that the products, materials and consumables shall be designed and manufactured taking into consideration of reuse , recycle, remanufacturing concepts such that sustainability is achievable to safeguard the world by minimizing the pollution. The green engineering principles or concepts should be adapted in all the stages of design, manufacturing, consumption, usage an d disposal. The paper highlights the significance of adhering to green engineering principles and its application in product design, process design and system design to achieve sustainability. Engineers, scientists, technocrats, policy makers and the governments should foresee the need of using green engineering in every act and deed of a venture in maintaining the sustainability. Discussion and conclusions are drawn on emphasizing that in all the spheres of design and manufacturing of industrial product s, energy generation, development of infrastructure, etc., application of green engineering has become relevant and essential to adhere to it in all the domains. Keywords: Sustainable World, Green Engineering Principles, Metal Working Fluid, Micro -reactors, Life Cycle.

1. INTRODUCTION

Global sustainability is based on the energy consumption, pollution control and its mitigation, food and health security, resources availability, population control , etc., which all the governing factors for its drift from safer to hazardous for all the life on the planet Earth. Human needs , expanded the consumption and utilization of various materials, energy sources, food, industrial products, which all generate pollution, release of CO2 greenhouse gases leading to enviro nmental degradation and ecological disturbance. The possible proposition to check such a precarious, hazardous and dangerous conditions shall be countered by adopting green based principles of engineering, designs, manufacture, products, processes developments, implementations, executions, constructions and in operations that would ensure world the sustainability for its safer future. The green concepts / principles awareness should be adapted in all the engineering designs, executions, and operations in optimization of resources consumption to achieve sustainability. The sustainability is defined as “meeting the needs of the current generation without impacting the needs of future generations to meet their own needs, aiming at the goals of global prosperity, environment and society” (Julie Beth Zimmerman). The over population and its growth in


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developing countries pose a great danger on world depleting resources, where as population growth i s stagnant or declining in case of developed countries as shown in Fig.1.

population

10000000

7500000

5000000

2500000

0 1950

1975

2000

2025

2050

Year

More developed regions Less developed regions World

Figure 1: Projected population of the world, more developed regions and less developed regions where more developed regions comprises all regions of Europe plus Northern America, Australia/New Zealand and Japan and less developed regions comprises all regions of Africa, Asia (excluding Japan), Latin America and the Caribbean plus Melanesia, Micronesia and Polynesia (UNDESA, 2004).

The quality of life is depends on food, health, education, habitation, available resources, cultural norms, governance and adhered polices, etc. The relationship between population and environment can be analysed in terms of resource depletion and dimensions of environmental quality such as land use, water quantity and quality, energy demand and related pollution generation, bio -diversity and climate change. Sustainable development of world could be achieved by practicing green eng ineering principles in all the domains with concepts of less polluted, recycle and re -use measures. Attaining the sustainable world can be evolved by adapting the twelve principles of green engineering, which provide a framework for scientists, engineers and technocrats in designing new materials, products, processes and systems that are concern with human health, life security, and environmental safeguards.

2. GREEN ENGINEERING PRINCIPLES / CONCEPTS

Green engineering is the use of measurement and control techniques to design, develop and improve products, technologies and processes that result in environmental and economic benefit. Green engineering encompasses common measurements such as power quality and consumption, emissions from vehicle and factories such as mercury, and nitrogen oxides and environmental data that include carbon, temperature and water quality ( www.ni.com). Green engineering aims at lowering of emissions in product manufacturing, developing devices t hat consume less energy and creation of viable, renewable energy technologies. Green engineering focuses on how to achieve sustainability through science and technology. The twelve principles of green engineering are shown in Table.1, which provide a

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framework for scientists and engineers to engage in designing new materials, products, processes and systems that are favourable to human health and environment (Paul T et al.). The materials and energy that enter each life cycle stage of every product and p rocesses have their own life cycle. For instance, a product or processes is energy efficient or even energy generating (e.g. photovoltaics) but its manufacturing process consumes more energy to a degree that offsets energy gains which does not offer sustainable advantage. Accordingly, designers should consider the entire life cycle, including the inputs of materials and energy. The twelve principles of green engineering provide a structure to create and assess the elements of design relevant to maximizin g sustainability. Engineers and scientists adapt these principles as guidelines to ensure that the design of products, processes or systems shall include the fundamental components, conditions and circumstances necessary to be more sustainable (Paul T et al.). The twelve themes of green engineering principles are as listed below (Paul T et al.): Principle 1: Inherent rather than circumstantial Principle 2: Prevention instead of treatment Principle 3: Design for separation Principle 4: Maximize mass, ener gy, space and time efficiency Principle 5: Out-put pulled versus Input pushed Principle 6: Conserve complexity Principle 7: Durability rather than immortality Principle 8: Meet need, maximize excess Principle 9: Minimize material diversity Principle 10: Integrate local material and energy Principle 11: Design for commercial ‘afterlife’ Principle 12: Renewable rather than depleting

3. USE OF GREEN ENGINEERING IN PRODUCT DESIGN In the product design process, the designer has the option to influence the t ype of materials and energy that will be used, but not just in manufacture of the product and throughout the life -cycle (Principle No. 10). By designing products based on inherently advantageous (Principle No.1), renewable materials and energy (Principle No.12) as explained in the principles of green engineering, the designer plays a significant role in preventing the exposure of toxic or hazardous materials to the end -user and also associated in the manufacture, assembly, distribution, maintenance or repa ir of the product (Julie B. Zimmerman and Paul T. Anastas ). Life-cycle consideration is critical to the implementation of the principles of green engineering in designing products to maximize environmental benefit. A life -cycle approach will facilitate to highlight any potential trade -offs that arise from applying the principles to the design of a product for the use phase rather than across the entire product cycle. In the design of an industrial product, a metalworking fluid (MWF) used in machining ope rations. The MWFs cool and lubricate during metal forming and cutting processes increasing the productivity and quality of manufacturing operations. Adopting green principles, human health and environmental impacts associated with MWFs can be eliminated by discontinuing or limiting the use of metalworking fluids or designing new MWFs products with improved health and environmental characteristics. In practice four types of MWFs are used in various machining operation viz., straight oils, oil -in-water emulsions (soluble oils, semi-synthetics) and true solutions (synthetics). The emulsifiable MWFs are defined by the ratio of water to oil in the formulation, which represents the balance of cooling to lubrication desired for a given machining process. Recen tly, a semi-synthetic MWF product was manufactured incorporating the principles of green engineering with the substitution of MWF components by oil and nonionic surfactants that can be produced from renewable, bio -based resources (Principle No.12), which i s less toxic than


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conventional emulsions. This fact is based that conventional MWF has anionic surfactant of LC 50 of 0.4 mg/l after 48 hours and for new MWF the value is 14.1 mg/l after 48 hours (Julie Beth Zimmerman). . By including anionic surfactants in the formulations, the emulsions can be destabilized by the addition of a simple salt, allowing oil separation (Principle No. 3) and also recovery of oil and reuse (Principle No. 6 and 10) in the new MWF formulation. The newly developed MWFs are more h ard water stable, a common cause of traditional MWF disposal and subsequent environmental impacts. This stability is achieved by designing the formulations based on a twin -headed anionic surfactant that has twice as many of moles of anionic head groups to provide electrostatic repulsive than the traditional surfactant. The improved hard water stability is achieved with the removal of two components found in current MWF formulations to improve emulsion stability – ethylenediaminetetraacetic acid (EDTA), a chelating agent and butyl carbitol, a coupler. By eliminating these two components from the formulation, the overall life cycle environmental impact is likely to be reduced (Principle No. 9). The disposal of MWFs containing EDTA cause concern as it does not readily biodegradable and once introduced in to the general environment, EDTA can remobilize heavy metals and allow them to re-enter and re-circulate in the food chain. Also EDTA can mobilize heavy metals in tool coatings, providing a route for meta ls to enter the environment.

4. USE OF GREEN ENGINEERING IN PROCESS DESIGN The design of processes used in the manufacture, repair, maintenance, operation and distribution of materials and energy has a significant impact on the environment and human hea lth. It is important to separate the byproducts from the matrix that occur during the production. Separation and purification tasks are often critical process steps in generating the desired product for deriving pure feed materials and for recovering ingredients for recycle (Julie Beth Zimmerman). The Principles of green engineering describe mechanisms to reduce the materials and energy necessary for separation and to minimize the formation of byproducts as a design goal. The green engineering principles address the need to maximize mass, energy, space and time efficiency upfront for increased environmental benefit. Principle 5 is a key concept in the process design such that the desired outcome can be derived by pulling rather than pushing through the material and energy in process completion. The several scientific and engineering advances have emphasize the goal of process intensification including continuous processing instead of batch operations, using high-intensity mixing in reactors or separators , combining chemical transfor mation or using micro reactors (Stankiewicz. A and Moulijin). The application of green engineering principles in the design of process intensification is an example of vapour-liquid separation based on distillation reactive di stillation coupled with catalytic distillation for methyl acetate (Malone M, Huss R and Doherty M ). Reactive and catalytic distillation is hybrid combinations of separation and reaction for chemical synthesis that offers improved efficiencies (e.g., reduced energy requirements, lower solvent use, reduced equipment investment and greater selectivity). Methyl acetate production for acetic acid and methanol invented and practiced by Eastman Chemical Company adopt reactive-distillation, which shift the proces s from conventional technology based on 11 major units to a single hybrid unit. The reactive distillation lowered the investment and energy demand by 80% compared to conventional technology (Principle No.4). In addition, two solvent were eliminated from the production process by adopting reactive distillation (Principle No.2 and 9). The reactive distillation systems are a challenge to design and control and the resulting process equipment may not be possible to reuse for another purpose if and when the original process is no longer viable.

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6. USE OF GREEN ENGINEERING IN SYSTEM DESIGN A system can be designed by considering the integration of products and processes at the beginning, which integrate all the stages of life cycle simultaneously from the start to its recovery. On focusing of the entire system, the design will have a broad perspective that considers material and energy flows from one product to another and one process to another (Principles No.2, 10 and 11) to maximize mass, energy, space and time effectively (Principle No.4). A System design is to be considered that interacts with the other constituents of the system, a set of elements that interact in a process or product. This implies that system being used for larger number of intera ctions as an issue rather than smaller issues. This concept is very helpful and useful in cases where system is dynamically complex. A case study, highlighting the system design in accordance with the principles of green engineering in explained in the manufacture of carpet tiles by M/s. Ecoworx T iles of shaw Industries of USA ( Segars J, Bradfield S, Wright J and Realff M ). The Ecoworx system design considers production use and recovery as a single system designed to optimize the environmental and econom ic benefits. In this carpet tile system design, the ability to recycle both the carpet face and backing components in the next generation and for future generations are developed (Principles No.2, 6, 7, 8, and 10). For instance, the in -process scrape is designed to be recovered immediately through the same process. This facilitate that each Ecoworx tile is back printed with a toll -free number to contact for disposition of the material for recycling. A value recovery system is incor porated to handle the end-of-life materials based on the projected return rates and this strategy result in environmental and economic benefits, which complies with green engineering principle that is need to develop the design for conservation of materials and energy in production of materials (Principle 1).

7. DISCUSSION The green engineering principles, provide a framework for the development of systems in which product design, process design and system design are incorporated in evolving manufacture of product that facilitate to the possible extent the principles are adhered in mitigating the pollution, waste and conserving the energy and raw materials. Application of these principles requires a mechanism to optimize the holistic environmental benefits of the integration of products and processes across the life cycle. Development of new system requires the design of inner connections and relationships in addition to the individual components and the framework by the concepts and principles of green engineering in the manufacture of green products. The world is facing resources crunch due to exponential growth of population and as the human needs are enhancing in various forms of products, materials, food, water, shelter, etc., which have an impact on environment, ecolog y, climate change and biosphere. More consumption and production of economic goods generate pollution due to conventional manufacturing methods, optimization of design, process and production of products in order to minimize the pollution , wastage of materials, by adapting the concepts of re -use, recycle and re-manufacture. All the industries and manufactures shall develop strategies in following the green engineering concepts such that worlds sustainability is a possible and viable proposition in maintai ning the green world ideology to make the Planet Earth is safe, less hazardous, ecosafe in the conservation of resources such that safeguards of future world could be ensured by adhering to green engineering principles in all the spheres of life for world’s endurance and sustainability.


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8. CONCLUSIONS 8.1 It is essential that the awareness of green engineering concepts and principles should be propagated and practiced in all the stages / phases of product design, process and manufacture such that optimization of resources can be achieved for sustainability of the world. 8.2 It is vital to stabilize the world’s population in checking its exponential growth that cause grave concern for world’s safety and sustainability as all the needs and requirement of human ge nerates pollution, climate change, depletion of resources, huge energy consumption, causing environmental degradation and ecological disturbance that result in unsafe future of world order for safer living and harmony. 8.3 For achieving the sustainability, al l the twelve principles of green engineering should be put -into practice and implementation by all the concerned for ensuring safe future and maintaining green world. 8.4 The case studies regarding adhering to green engineering principles are in the right dir ection for sustainability and optimizing all the resources in any product manufacture, consumption, utilization and its safe disposal. 8.5 Adhering to green engineering concepts would yield many indirect benefit s through cost of products and its processes may push-up the costs of finished products. This aspect should be taken in a right sense in contemplating the long term safe guards of the world, human race and also ensuring materials optimal use. 8.6 Education of green engineering concepts and principles shou ld imparted among all the learning community, peoples, industries, governing bodies, authorities, policy makers, agencies of government and private, NGOs, SHGs, and others to bring the awareness about safeguarding the sustainable, safe, pollution less, les s hazardous life and living environment and conditions. 8.7 Green engineering along with ‘green chemistry’ applied through science and technology would ensure enhanced quality of life, help economic development and advancing global sustainability.

REFERENCES [1] Julie Beth Zimmerman, “Sustainable Develo pment through the Principles of Green Engineering”, report of US Environmental Protection Agency. [2] Report of National Instruments on “Green Engineering – Improving the Environment and the Bottom Line”, 2006, Document version 8, www.ni.com, pp.1-15. [3] Paul T. Anastas and Julie B. Zimmerman,” Through the 12 Principles Green Engineering”, Environmental Science & Technology, March 1, 2003, American Chemical Society, pp.95 -101. [4] Julie B. Zimmerman and Paul T. Anastas”, Case Studies Illustrating The Twelve Principles of Green Engineering”. [5] Stankiewicz A and Moulijin, “Industrial Engineering Chem ical Research”, No.41, 2001, pp 192025. [6] Malone M, Huss R and Doherty M, “Environmental Science and Technology”, Vol.37, No.23, 2003, p.5325. [7] Segars J, Bradfield S, Wright J and Realff M, “Environmental Science and Technology”, Vol.37, No.23, p.5269.

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Appendix: Table 1. Green Engineering Concepts / Principles in Major Engineering Domains S. No

1

Engineering Domains Principle-Concept Engineering Designs shall ensure that all the inputs and outputs are non-hazardous

4

5

6

7

8

MECHANICAL

Green building design to facilitate the natural and energy efficient measures.

MEMS, NEMS and other modern concepts of automation CAD, CAE, CAM, etc. Increasing the efficiency operation, out-put of machines, plant & equipments

Waste Prevention rather than its Treatment

Optimization of construction materials; recycle & reuse of materials

Separation and Purification should be a component of the design Framework

Treatment materials, and other inputs for outputs

System components should be designed to maximize mass, energy, and temporal efficiency System Concepts should be output obtained rather than input interns of energy and materials

Empirical methods are to be reviewed

Design preferences should aim at recycle, reuse or beneficial outcome

Recycling and reusing of construction materials from debris & demolitions

Projected durability should be the Design Goal

Adhering to strict specification practices

Oversized capacity / Capability should be discouraged

Minimizing the size by using high strength materials

2

3

CIVIL

Green design concepts making use of natural resources

ELECTRICAL & ELECTRONICS Designs to minimize the losses, moving parts, etc.

Enhancing the efficiency of electrical methods, generators & electronics devices Minerals, ores Design based on processing for minimizing the losses manufacturing of & maintaining good metals conduction Conventional Innovative techniques methods / techniques are to be practiced / are to be modernized implemented Non-conventional Power generation by energy resources or natural resources viz., hydrogen as fuel water, wind, solar, etc. Re-machining of Rewinding, reusing tools, fittings, fixtures of materials in generation & distribution Quality assurance and Ensuring quality maintenance norms measures Reduction in weight Light-weight by going for alloys & components, parts nanobased materials and plastics

ICT (Information Communication Technology)

CHEMICAL SCIENCES

Ensuring optimal execution of programs, security, etc.

Prevention of harmful and hazardous processes.

Efficiency in power consumption, speed and miniaturization

Recycling of process wastes and safe disposed

High performance, more serviceability is aimed

Enhancing the possibility of by products

Emerging methods are to be adapted

New inventions could pave way for safety Green chemistry

Green electronics, green computing concepts Reusing would affect performance

Strengthening software security and hardware life Adopting new innovative materials with high performance

Recycling, Reusing & Regenerating is a possibility Extending Shelf-life Generation of new chemicals compositions


9

10

11

12

Material Unification should adapted to discourage multi-component based products Processes and Systems Design should include integration, inter connectivity with available energy and materials flow Performance metrics include designs for service after commercial life Design should be based on renewable and readily available inputs throughout the life-cycle

Mass proto-type building units

Reducing the assembly

New design concepts are to be evolved based real functions

CAD,CAM, etc., are adopted

Using high performance materials/structures

Optimal operation efficiency of machines Remanufacturing of input materials

Designs should be facilitate the re-use of materials for construction

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Optimizing the moving and operating parts Design can accommodate the possible

Opting for modular arrangement

Process optimization

Autonomic functioning is a feasibility

Process optimization

Minimizing losses and enhancing efficiency Recycling and Reusing of components, parts and accessories

Autonomous computing concept

Recycling & Reusing

Performance being the criterion re-using and remanufacturing is not feasible

Recovery of possible out lets for re-use

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UTILIZATION OF SUGARCANE BAGASSE AS BED MATERIAL IN SOLID STATE PRODUCTION OF LACTIC ACID THROUGH PURE CULTURES AND COCULTURE OF LACTOBACILLI M.K.GHOSH1, U.K.GHOSH2 1,2 DEPARTMENT OF PAPER TECHNOLOGY, IIT, ROORKEE, SAHARANPUR CAMPUS, SAHARANPUR, U.P. , (INDIA) AUTHOR FOR CORRESPONDENCE: M.K.GHOSH1,

EMAIL mkengg2004@ rediff.com ABSTRACT Lactic acid possesses numerous applications in food , dairy, chemical, textile, pharmaceutical and other industries. Conventionally, fungi such as Rhizopus Oryzae have been applied for solid state production of lactic acid , but the present experimental investigation brings about a comparative study of lactic acid production by pure strains of Lactobacilli (1)L. delbreuckii(NCIM2025) (2) L. pentosus (NCIM 2912) (3)Lactobacillus sp.(NCIM 2734(4) Lactobacillus sp. (NCIM2084) and coculture of first two strains in solid bed of powdered sugarcane bagasse, under the influence of different nitrogen sources such as bakers yeast, meat extract and proteose peptone, utilizing 8g powdered sugarcane bagasse , 2g/l cell dry weight (inoculum), with glucose based liquid production media at 37 0C , initial pH 6.5 for eight days incubation period under anaerobic conditions . The lowest pH values (hence highest acid formation)attained (during treatment with above mentioned nitrogen sources) has been observed with, strain (3)-pH3.68(at 1.5g/100ml bakers yeast), coculture pH3.62 (at 2.33g/100ml bakers yeast),strain(3)pH3.24(at 1.5g/100ml meat extract), strain(3) pH3.58 (1.5g/100ml proteose peptone).Set of lowest pH values is closely followed by the coculture which gives the next higher acid production values in majority of the nitrogen treatments. Maximum acid formation was witnessed with strain(3) having the meat extract containing media. The present experiments highlight the potential, industrial utility of the solid state bacterial fermentation in production of lactic acid from sugarcane agrowaste , ultimately resulting in an ecofriendly biochemical production technology. Keywords Bagasse, biodegradable, ecofriendly, lactobacilli INTRODUCTION Lactic acid(2-hydroxypropanoic acid) is a speciality chemical used as acidulant and flavouring agent and probiotics in food, bacteriocins and in production of ecofriendly biodegradable polymer (PLA) having biomedical uses[1,2 ]. The major portion (90%) of the lactic acid production is through solid state or liquid state fermentation [3] .Solid state fermentation technology utilizes the solid agro-wastes as bed materials in production of value added products , resulting into enhanced impetus to solid state fermentation technology strategies. It has been reported that the cost of yeast extract or the pure nitrogen source approximately amount to 38% of the cost of fermentative production of lactic acid , hence the use of cheaper nitrogen sources such as dried bakers yeast has been suggested [4]. The objective of the present experiments , is to investigate (1)the feasibility of solid state bacterial fermentation through various Lactobacillus strains and coculture utilizing a bed of finely powdered sugarcane bagasse , prewetted with glucose based synthetic media, under anaerobic conditions. (2) the effect of different nitrogen sources(specially the cheaper one- bakers yeast) at different doses, on lactic acid


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production by Lactobacillus strains and coculture. (3) performance of the coculture in terms of lactic acid production in comparison to its constituent strains of Lactobacilli. BACKGROUND INFORMATION Sugarcane bagasse is the major fibrous byproduct agro-industrial residue liberated from the sugar mills and juice extraction units. The abundance of the sugarcane bagasse is evident from the fact that India is among one of the largest sugarcane producing countries with yields over 250 million tones per year, engaging about 4.36 million hectares of total cropped area [5]. The frontier countries in the field of sugarcane production, such as Brazil produce more than 60,000, 000 tons of sugarcane bagasse annually [6]. The annual global production of bagasse is about328Tkg, in which Asia shares 44% portion[7 ] . Such a huge quantity of solid waste due to sugarcane bagasse can exert some deleterious effects such as chronic lung condition (pulmonary fibrosis) and bagasse disease of lungs(Chest Journal-American college of chest physicians). Hence Such large amount of bagasse has been put to beneficial uses such as production of power , chemicals, biochemicals and paper. Sugarcane bagasse has been applied in fermentative production of various biochemicals such as xylitol, organic acids, amino-acids and enzymes [ 8, 9 ]. MATERIALS AND METHODS The chemicals used in these experiments were of Merck and High media make. Pure cultures of Lactobacilli (1)L. delbreuckii(NCIM2025) (2) L. pentosus (NCIM 2912) (3)Lactobacillus sp.(NCIM 2734) (4) Lactobacillus sp. (NCIM2084) had been acquired from National Chemical Laboratory(NCL) Pune, in form of stab cultures in agar , were cultured monthly as directed. The inoculum for the lactobacilli strains were prepared in MRS(de Mann Rogosa Sharpe) media at 350 C, 180 rpm for fourteen hours .Composition of one litre MRS medium is : 10g proteose peptone, 5g yeast extract, 10g beef extract, 20g dextrose, 1g tween 80, 2g ammonium citrate, 5g sodium acetate, 0.1g MgSO4.7H2O, 0.05 g MnSO4, 2g K2HPO4 in distilled water as solvent. One litre of glucose based synthetic media consists of : 60g glucose, various levels of nitrogen sources (15,16.66,20 and 23.33) g/l ,1g sodium acetate, 0.03g MnSO4.H2O, 0.10g MgSO4.7H2O, 0.25g KH2PO4, 0.25g K2HPO4 and 0.03g FeSO4.An inoculum dose corresponding to 2g/l cell dry weight was added to sterilized and prewetted 8g of finely powdered sugarcane bagasse bed, by 40ml glucose based production media(pH6.5) containing 2% NaOH as neutralizer in 250ml Earlenmayer flasks. These were kept at37o C for six days incubation under anaerobic conditions.Aftertheincubation, the flasks were added with 50 ml distilled water , shaken and then the product is extracted ou by passing through a muslin cloth. The pH drops (hence acid formation) of the extracts were determined with the help of, a digital pH meter. RESULTS AND DISCUSSION The results in table1 revealed that best acid formation was achieved by all the Lactobacillus strains including the co-culture at15g/l dose of meat extract.Similar trend was also observed for 15g/l proteose peptone, for all the strains and co culture except Lactobacillus sp.(NCIM2084) , which attains lowest pH 3.50 at 20g/l proteose peptone concentration. The coculture showed higher acid production (lower pH) than its constituent strains (1) and(2) at 15g/l dose of meat extract and proteose peptone. The results in table2, for the first three lactobacilli strains including the coculture show a

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Table 1. pH drops (acid formation) caused by the different strains of Lactobacilli corresponding to various doses of nitrogen sources during solid state fermentation utilizing sugarcane bagasse as bed material. Bacterial strains

1 2 3 4

L.delbrueckii(NCIM2025) L.pentosus(NCIM2912) Coculture of first two Lactobacillus sp.(NCIM2734) 5 Lactobacillus sp.(NCIM2084)

Meat extract Proteose peptone 15g/l (pH) 15g/l (pH)

Meat extract Proteose peptone 20g/l (pH) 20g/l (pH)

3.92 3.84 3.70 3.24

3.64 3.93 3.76 3.58

5.80 5.68 4.20 5.11

5.92 6.12 4.96 6.15

3.75

3.79

3.92

3.50

Table 2. pH drops (acid formation) caused by the different strains of Lactobacilli corresponding to various doses of nitrogen sources during solid state fermentation utilizing sugarcane bagasse as bed material. Bacterial strains

1 2 3 4

L.delbrueckii(NCIM2025) L.pentosus(NCIM2912) Coculture of first two Lactobacillus sp.(NCIM2734) 5 Lactobacillus sp.(NCIM2084)

Bakers yeast Bakers yeast Bakers yeast Bakers yeast 15g/l (pH) 16.6g/l (pH) 20g/l (pH) 23.33g/l (pH) 6.12 6.15 5.04 3.68

5.94 4.70 4.62 4.88

5.85 4.81 4.03 5.16

3.78 4.73 3.69 5.58

4.46

3.92

3.70

4.24

decrease in pH values (enhancement in acid production) with the increasing doses of bakers yeast where minimum pH value (maximum acid formation) occurs at 23.33g/l. The coculture again exhibited higher acid formation (lower pH) than its constituent strains.Its evident from table 2 that the minimum dose of bakers yeast 15g/l gives the highest acidity (lowest pH) 3.68 for Lactobacillus sp(NCIM2734). While higher doses reduced acid formation, possibly due to increase in cell biomass . In table2 ,Lactobacillus sp(NCIM2084) , indicates increase in acid production with increasing doses of bakers yeast till minimum pH 3.70 is attained at 20g/l but a further increase in dose to 23.33g/l reduced the acid production.


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REFERENCES [1]. Narayanan, N., Roychoudhary, P.K. and Srivastava, A., L(+) lactic acid fermentation and its product polymerization, Electronic Journal of Biotechnology, (2004), 7(2) [2]. Faris, A., Adnan, M. and Tan, K.P., 2007. Isolation of lactic acid bacteria from Malaysian foods and assessment of the isolates for industrial potential, Bioresource Technology , 98 :1380-1385. [3].Adsul, M.G., Varma, A.J. and Gokhale, D.V., 2007. Lactic acid production from waste sugarcane bagasse derived cellulose, Green Chemistry, 9: 58-62. [4].Altaf, M.D., Naveena,B.J., and Reddy, G., Use of inexpensive nitrogen sources and starch for

L(+) lactic acid production in anaerobic submerged fermentation,

Bioresource Technology,(2007) , 98, 498-503. [5]. Commercial crops : Sugarcane and sugarbeet, In Handbook Of Agriculture, 10001017, second reprint of fifth edition, Sept. (2008), Published by Dr. T.P. Trivedi, Project Directorate of Information and Publication of Agriculture, Indian Council of Agricultural Research, Pusa, New Delhi. [6]. Pessoa ,A., Jr., Mancilcha, I.M., and Sato, S., Acid hydrolysis of hemicellulose from sugarcane bagasse, Brazilian Journal of Chemical Engineering, (1997), 14, (3). [7].Kim,S. and Dale, B.E., Global potential of bioethanol production from wasted crops and crop residues, Biomass and Bioenergy, (2004),26, 361-375. [8].Rao, R.S., Jyothi, P.C., Sharma, P.N. and Rao, LV., Xylitol production from cornfiber and sugarcane bagasse hydrolyzates by Candida tropicalis, Bioresource Technology, (2006),97,(15), 1974-1978. [9]. Pandey, A., Soccol, C.R., Nigam, P. and Soccol, V.T., Biotechnological potential of agroindustrial residues 1: sugarcane bagasse Bioresource Technology, (2000), 74,(1),69-80.

Alternative Energy Biofuels


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PERFORMANCE AND EMISSION CHARECTERISTICS OF C I ENGINE FUELLED WITH JATROPHA METHYL ESTER/DIESEL BLENDS Dr.G.Lakshmi Narayana Rao1, Venkata Ramesh Mamilla2, M.V.Mallikarjun3 1 Professor, 2,3Associate Professor DEPARTMENT OF MECHANICAL ENGINEERING QIS COLLEGE OF ENGINEERING &TECHNOLOGY ONGOLE,ANDHRA PRADESH ,INDIA Email: [email protected],[email protected]. phone No: 9491316149,9885029816

ABSTRACT This paper deals with the study of the potential substitution of jatropha methyl ester blends for diesel as fuel for automobiles and other industrial purposes. The objective of this study is the analysis of the performance and emission characteristics of the jatropha methyl esters and comparing with petroleum diesel. The tests were carried out on a 3.7 KW, single cylinder, direct injection, watercooled diesel engine. The fuels used were neat jatropha methyl ester, diesel and different blends of the methyl ester with diesel. The experimental result shows that 20% of blend shows better performance with reduced pollution. This analysis shows that jatropha methyl ester and its blends are a potential substitute for diesel. Key words : jatropha methyl ester, water-cooled diesel engine, performance, emission characteristics

1.0 INTRODUCTION Unlike soybeans, pongamia, canola and many other agricultural sources of biodiesel, Jatropha can be cultivated on arid and semi arid non-agricultural land. This means growing Jatropha never has to compete with growing food. Also, on a per acre basis, Jatropha can yield up to 10 times the amount of oil as other sources of biodiesel. Finally, Jatropha is a perennial, lasting up to 50 years without replanting. In fact the “cake” (portion of the seed left over after extraction of the seed’s oil) is full of nitrogen compounds making it an excellent organic fertilizer. After 4 or 5 years of treatment with this “cake” the soil of this originally non-agricultural land will be suitable for planting food crops or trees for reforestation. Jatropha curcas grows almost anywhere, even on gravelly, sandy and saline soils. It can thrive on the poorest stony soil. It can grow even in the crevices of rocks. The leaves shed during the winter months form mulch around the base of the plant. The organic matter from shed leaves enhance earthworm activity in the soil around the root-zone of the plants, which improves the fertility of the soil. Regarding climate, Jatropha curcas is found in the tropics and subtropics and likes heat, although it does well even in lower temperatures and can withstand a light frost. Its water requirement is extremely low and it can stand long periods of drought by shedding most of its leaves to reduce transpiration loss. Jatropha is also suitable for preventing soil erosion and shifting of sand dunes.

1.1 Features of Jatropha Low cost seeds High oil content Small gestation period Growth on good and degraded soil Growth in low and high rainfall areas Seeds can be harvested in non rainy season Plant size is making collection of seeds more convenient

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1.2 Properties of Jatropha Specific gravity : 0.87 to 0.9 Kinematic viscosity at room temperature(m2/sec) : 0.14*10-4 Dynamic viscosity (N-sec/m2) : 12.5*10-3 Cetane number : 46 to 70 Flash point °C : 150 Fire point °C : 158 Calorific value (kj/kg) : 40105 Pour point °C : -15 to 13

2.0 EXPERIMENTAL PROCEDURE SPECIFICATIONS OF CI ENGINE MAX. BP : 3.7kW (5 H.P) SPEED : 1500 RPM BORE : 80mm STROKE : 110mm ORIFICE DIA : 20mm COMPRESSION RATIO : 16.5:1

2.1 Description The engine is four stroke vertical single cylinder diesel engine. The Mechanical brake drum is fined to the engine flywheel and are mounted on a frame and futures mounted on anti-vibrations. The panel board is provided with 3 way cock, digital temperature indicator with selector switch, digital RPM indicator and U-tube manometer.

2.2 Procedure 1.

The fuel level and lubrications oil levels are checked and three way cock is opened so that the fuel flows to the engine. 2. The cooling water is supplied to the engine cooling water jacket and to the brake drum. 3. The electrical power is supplied to the panel instrumentation. 4. The engine is de-compressed by decompression lever provided on the top of the engine head. 5. The engine is unloaded by removing the weights from the hanger. 6. The engine is started by cranking. The readings are noted are: Spring balance reading in kg-f (S). Time taken for 10cc fuel consumption in seconds (t). Manometer reading (hw). 7. The experiment is repeated for different loads 8. The above steps 7 & 8 are repeated for different blends of fuels

2.3 Experimental Results Comparisons of bio diesel with diesel ¾ BTE slightly decreases ¾ SFC slightly increases ¾ HC reduces ¾ CO reduces ¾ NOx increases ¾ CO2 increases


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3. PERFORMANCE ANALYSIS Results of the experiments in the form of brake power, brake thermal efficiency, specific fuel consumption for different load conditions for various blends of jatropha methyl esters compare with the petroleum diesel in the form of graphs

3.1 Specific Fuel Consumption BP Vs SFC

SFC(kg/kW-hr)

0.6 0.5

diesel 20%JTME 40%JTME 60%JTME 80%JTME JTME

0.4 0.3 0.2 0.1 0 -0.3

0.7

1.7

2.7

3.7

BP in KW

Fig 1 The comparison of variation of specific fuel consumption with brake power for diesel, with different blends of jatropha methyl esters are shown in Fig.1 From the fig1, it is observed that the methyl esters shows higher SFC compare to diesel as calorific value is less. It was observed that 20% blend is having comparable closer values with diesel. However SFC is higher for all the other blends. The SFC decreases with the increasing loads. It is inversly praportional to the thermal efficiency of the engine.

3.2 Brake Thermal Efficiency

BTE in %

BP Vs BTE 40 35 30 25 20 15 10 5 0 -0.3

diesel 20%JTME 40%JTME 60%JTME 80%JTME JTME 0.7

1.7

2.7

3.7

BP in kW

Fig 2 The BTE variations with load for various blends of methyl esters were shown in fig.2. From the fig.2, it is observed that the BTE is slightly lower than the diesel for jatropha methyl ester and its blends. The BTE is less for jatropha methyl ester because of less calorific value. From the fig.2, it is observed that brake thermal efficiency is low at low values of BP and is increasing with increase of BP for all blends of fuel. For a blend of 20% the brake thermal efficiency is high at low BP values when compared with other blends of fuel and is very close to diesel at high values of BP. Hence at the blend of 20% of methyl ester the performance of the engine is good .

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4.0 EMISSION ANALYSIS Results of the experiments in the form of carbon monoxide (CO), Nitrogen oxides (NOx), Hydrocarbons (HC) for different load conditions for various blends of jatropha methyl esters compare with the petroleum diesel in the form of graphs.

4.1 CO Emission BP Vs CO 0.12 0.1


COin %

0.08 0.06 0.04 0.02 0 -0.3

0.7

1.7

2.7

3.7

BP in KW

Fig.3 The comparison of variation of carbon monoxide(CO) emissions with break power for diesel, with different blends of jatropha methyl esters are shown in Fig. 3 From fig.3, it is observed that CO decreases with increasing load for all the blends of Jatropha methyl esters. If percentage of blends of Jatropha methyl esters increases, CO reduces. The concentration of CO decreases with the increase in percentage of JTME in the fuel. This may be attributed to the presence of O2 in JTME, which provides sufficient oxygen for the conversion of carbon monoxide (CO) to carbon dioxide (CO2). It can be observed that blending 20% JTME with diesel results in a slight reduction in CO emissions when compared to that of diesel.

4.2 HC Emission (in PPM) BP Vs HC 50 45


HCin PPM

40 35 30 25 20 15 10 5 0 -0.3

0.7

1.7

2.7

3.7

Bp in kW

Fig.4 The comparison of hydrocarbons (HC) emissions for diesel, neat JTME and blends of them are presented in Fig. 4


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From fig.4 it is observed that hydro carbon (HC) increases with increasing load for all the blends of Jatropha methyl esters. If percentage of blends of Jatropha methyl esters increases, HC reduces. The hydrocarbon emissions are inversely proportional to the percentage of JTME in the fuel blend. A significant difference between JTME and diesel operation can be inferred. The diesel oil operation showed the highest concentrations of HC in the exhaust at all loads. Since JTME is an oxygenated fuel, it improves the combustion efficiency and hence reduces the concentration of hydrocarbon emissions (HC) in the engine exhaust. Blending 20% JTME with diesel greatly reduces HC emissions especially at rated load condition.

4.3 NOx Emission BP vs NOx 1000 900

NOx in PPM

800 700 600

diesel

500

40%JTME

400

80%JTME

20%JTME 60%JTME JTME

300 200 100

0 -0.3

0.7

1.7

2.7

3.7

BP in kw

Fig. 5 The comparison of NOx emissions for diesel, neat JTME and blends are shown in Fig. 5 From fig.5, it is observed that NOx increases with increasing load for all the blends of jatropha methyl esters. If percentage of blends of jatropha methyl esters increases, NOx increases. It can be seen that NOx emissions increase with increase in percentage of JTME in the diesel-JTME fuel blend. The NOx increase for JTME may be associated with the oxygen content of the JTME, since the fuel oxygen may augment in supplying additional oxygen for NOx formation. Moreover, the higher value of peak cylinder temperature for JTME when compared to diesel may be another reason that might explain the increase in NOX formation.

5.0 CONCLUSION From the experiments conducted, it is concluded that biodiesel and its blends as a fuel for diesel engine have better emission characteristics compared with diesel. It is clear that, at 20% blending of biodiesel the engine performance is found to be very appreciable. At this blending trial particularly at full load and half load conditions the specific fuel consumption and indicated thermal efficiency are very closer to the values obtained without blending. The NOx emissions are high due to presence of oxygen content in the fuel. The HC and CO emissions are less compared with diesel.

6.0 REFERENCES 1. “Performance and Emission Characteristics of a diesel engine using preheated vegetable oil” by Ramesh A,Nazar J, Naglingam B 2.”Effect of certain additives on the Performance and Combustion of Jatropha oil fueled Compression Ignition Engine” by Senthil Kumar.M, Ramesh.A and Nagalingam.B 3. “Performance and Emission Characteristics of a naturally aspirated diesel engine with vegetable oil fuels ” by N.J.Barsic and A.C.Humke. 4. “Performance and Emission Characteristics of a diesel engine fueled with coconut oil-diesel fuel blend ”,Biomass and Boienergy, by Herchel T.C.Machancon,Seirchishiga,Takao Karaswa AND Hisao Nakamura. 5.”Long term CI engine test of sunflower oil”, Renewable Energy by F.Karaosmanoglu,G.Kurt and T.Qzaktas

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BIO FUELS: MAJOR ISSUES AND CHALLENGES M. Kamil and N. Sardar Department of Petroleum Studies A.M.U., Aligarh – 202 002 (U.P.), India Email: [email protected]

ABSTRACT The present article highlights the process of biofuel production with a special focus on bioethanol and biodiesel. The problems of biofuels - the first generation biofuels (in regards to their competition to feed and food production) and the second generation biofuels (in regards to the required more complex process technology) - the different steps in the process from natural resources towards the final product are presented and the underlying biotechnological challenges discussed: the pretreatment of the natural resources followed by the biotechnological processes of hydrolysis and fermentation. Optimizing the production of biofuel to be competitive with petrochemical fuels is the main challenge for the underlying process development.

HISTORY OF BIOFUELS Biofuels in the solid form has been in use ever since man discovered fire. Wood was the first form of biofuel that was used even by the ancient people for cooking and heating. With the discovery of electricity, man discovered another way of utilizing the biofuel. Biofuel had been used since a very long time for the production of electricity. This form of fuel was discovered even before the discovery of the fossil fuels, but with the exploration of the fossil fuel like gas, coal, and oil the production and use of biofuel suffered a severe impact. With the advantages placed by the fossil fuels they gained a lot of popularity especially in the developed countries. Liquid biofuel have been used in the automotive industry since its inception. One of the first inventors to convince the people of the use of ethanol was a German named Nikolaus August Otto. Rudolf Diesel is the German inventor of the diesel engine. He designed his diesel engine to run in peanut oil and later Henry Ford designed the Model T car which was produced from 1903 to 1926. This car was completely designed to use hemp derived biofuel as fuel. However, with the exploration of huge supplies of crude oil some of the parts of Texas and Pennsylvania petroleum became very cheap and thus lead to the reduction of the use of biofuels. Most of the vehicles like trucks and cars began using this form of fuel which was much cheaper and efficient. In the period of World War II, the high demand of biofuels was due to the increased use as an alternative for imported fuel. In this period, Germany was one of the countries that underwent a serious shortage of fuel. It was during this period that various other inventions took place like the use of gasoline along with alcohol that was derived from potatoes. Britain was the second country which came up with the concept of grain alcohol mixed with petrol. The wars frames were the periods when the various major technological changes took place but, during the period of peace, cheap oil from the gulf countries as well as the Middle East again eased off the pressure. With the increased supply the geopolitical and economic interest in biofuel faded away. A serious fuel crisis again hit the various countries during the period of 1973 and 1979, because of the geopolitical conflict. Thus (OPEC), organization of the petroleum Exporting countries made a heavy cut in exports especially to the non OPEC nations. The constant shortage of fuel attracted the attention of the various academics and governments to the issues of energy crisis and the use of biofuels. The twentieth century came with the attention of the people towards the use of biofuels. Some of the main reasons for the people shifting their interest to biofuels were the rising prices of oil, emission of the greenhouse gases and interest like rural development.


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Conventional fuels include: fossil fuels (petroleum oil , coal, propane and natural gas) , and nuclear materials such as uranium .Some well known alternative fuels include biodiesel , bioalcohol (ethanol , butanol), chemically stored electricity (batteries and fuel cells) , hydrogen , non-fossil methane , non-fossil natural gas , vegetable oil and other than biomass sources. The increasing demand for energy and stringent pollution regulations as a result of the population growth and technological development in the world promote research on Bio fuels. The investigations have concentrated on decreasing fuel consumption and on lowering the concentration of toxic components in combustion product by using non-petroleum, renewable, sustainable and non polluting fuels. The main purpose of fuel is to store energy in a form that is stable and can be easily transported from the place of production to the end user which helps in many ways such as transportation. Almost all fuels are Chemical fuels , that store chemical potential energy. The end user is than able to consume the fuel at will, and release energy, usually in the form of heat for a variety of applications, such as powering an engine or heating a building. The idea of using biofuels from renewable sources is attractive as biofuels could help reduce greenhouse gas emissions and our dependency on fossil fuels. However, a new study, which looked at the full life cycle of biofuels, shows that, depending on the type and source of biofuel, the benefits and environmental impacts can vary considerably. The results highlight differences that could help inform policymakers considering tax-breaks for renewable fuels.Today, biofuels provide about 1% of global transport fuel. Already, they are causing serious harm to the climate, to communities, food sovereignty and food security and to biodiversity. Most biofuels are agrofuels – made from crops and trees grown specifically for that purpose, such as sugar cane, palm oil, soya, jatropha or maize. Agrofuel expansion means more intensive agriculture and thus more agro-chemicals (including synthetic fertilizers). It also means more destruction of natural ecosystems, which play a vital role in regulating the climate, and the displacement of millions of small farmers, pastoralists and indigenous peoples.Across the world biofuels/Agro fuels are being promoted as an alternative to fossil fuels and an answer to climate change. They have however started to generate intense controversy by leading to land conflicts and rise in food prices. India plans to cultivate Jatropha in 11 million hectares. In a land starved country this diversion of land has serious consequences for rural livelihoods and rural eco systems. The Companies involved in the gold rush of Jatropha in India are D1 Oil, Godrej Agrovet Ltd, Tata Motors, Indian Oil Corporation, Kochi Refineries Ltd, Biohealthcare Pvt, The southern online Biotechnologies Ltd, Jain irrigation System Ltd, Natural Bioenergy Ltd and Reliance Energy Ltd. There are various major issues with biofuel production and use, which are presently being discussed in the popular media and scientific journals. These include: the effect of moderating oil prices, the " food versus fuel" debate, carbon emissions levels, sustainable biofuel production, deforestation and soil erosion, impact on water resources, human rights issues, poverty reduction potential, biofuel prices, energy balance and efficiency, and centralised versus decentralised production models.One of the greatest technical challenges is to develop ways to convert biomass energy specifically to liquid fuels for transportation.Now that the reality of climate change has been accepted even by its strongest sceptics, there is a rush to find answers. The latest buzz is to substitute the use of greenhouse gasemitting fossil fuels with biofuels—fuel processed from plants. Unfortunately, the way we are going about implementing this “good” idea could mean we are headed from the frying pan to the fire.There are two kinds of biofuel: ethanol, processed from sugarcane or corn, and biodiesel, made from biomass. Firstly, let us be clear that biofuels cannot substitute fossil fuels; but they can make a difference if we begin to limit the consumption of the latter. If this is the case, governments should not provide subsidies to grow crops for biofuel, as is being done in the US and Europe, but spend to limit their fuel consumption by reducing the sheer numbers of vehicles on their roads. If this is done, biofuels, which are renewable and emit less greenhouse gases, will make a difference. Otherwise, we are only fooling ourselves.Secondly, the question is where will the biofuels be used? Let us be clear that the opportunity for a massive biofuel revolution is not in the rich world’s cities, to run vehicles—but in the grid-unconnected world of Indian or African villages. It is here that there is a scarcity of energy— electricity to power homes, fuel to cook, to run generator sets to pump water and to run vehicles. It is

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also here that the use of fossil fuels will grow because there is no alternative. Instead of bringing fossil fuel long distances to feed this market, this part of the world can leapfrog to a new energy future— from no fuel to the most advanced fuel. The biofuel can come from non-edible tree crops—jatropha in India, for example—grown on wasteland, which will also employ people.This fuel market will demand a different business model. It cannot be conducted on the basis of the so-called free market model, which is based on economies of scale and, therefore, demands consolidation and leads to uncompetitive practices. In today’s model, a company will grow the crops, extract the oil, transport it first to refineries and then back to consumers.The new generation biofuel business needs a model of distributed growth in which we have millions of growers and millions of distributors and millions of users. The various details about biofuels are given elsewhere [1-24].

CLASSIFICATION OF BIOFUELS Biofuels are the best way of reducing the emission of the greenhouse gases. They can also be looked upon as a way of energy security which stands as an alternative of fossil fuels that are limited in availability. Today, the use of biofuels has expanded throughout the globe. Some of the major producers and users of biogases are Asia, Europe and America. Theoretically, biofuel can be easily produced through any carbon source; making the photosynthetic plants the most commonly used material for production. Almost all types of materials derived from the plants are used for manufacturing biogas. One of the greatest problems that is being faced by the researchers in the field is how to covert the biomass energy into the liquid fuel. There are two methods currently brought into use to solve the above problem. In the first one, sugar crops or starch are grown and through the process of fermentation, ethanol is produced. In the second method, plants are grown that naturally produce oil like jatropha and algae. These oils are heated to reduce their viscosity after which they are directly used as fuel for diesel engines. This oil can be further treated to produce biodiesel which can be used for various purposes. Most of the biofuels are derived from biomass or bio waste. Biomass can be termed as material which is derived from recently living organism. Most of the biomass is obtained from plants and animals and also include their by products. The most important feature of biomass is that they are renewable sources of energy unlike other natural resources like coal, petroleum and even nuclear fuel. Some of the agricultural products that are specially grown for the production of biofuels are switchgrass, soybeans and corn in United States. Brazil produces sugar cane, Europe produces sugar beet and wheat while, China produces cassava and sorghum, south-east Asia produces miscanthus and palm oil while India produces jatropha. The first generation biofuels refer to the fuels that have been derived from sources like starch, sugar, animal fats and vegetable oil. The oil is obtained using the conventional techniques of production. Some of the most popular types of first generation biofuels are: Biodiesel: This is the most common type of biofuel commonly used in the European countries. This type of biofuel is mainly produced using a process called transesterification. This fuel if very similar to the mineral diesel and is chemically known as fatty acid methyl. This oil is produced after mixing the biomass with methanol and sodium hydroxide. The chemical reaction thereof produces biodiesel. Biodiesel is very commonly used for the various diesel engines after mixing up with mineral diesel. Now in many countries the manufacturers of the diesel engine ensure that the engine works well even with the biodiesel. Vegetable oil: These kinds of oil can be either used for cooking purpose or even as fuel. The main fact that determines the usage of this oil is the quality. The oil with good quality is generally used for cooking purpose. Vegetable oil can even be used in most of the old diesel engines, but only in warm atmosphere. In most of the countries, vegetable oil is mainly used for the production of biodiesel. Biogas: Biogas is mainly produced after the anaerobic digestion of the organic materials. Biogas can also be produced with the biodegradation of waste materials which are fed into anaerobic digesters which yields biogas. The residue or the by product can be easily used as manure or fertilizers for agricultural use. The biogas produced is very rich in methane which can be easily recovered through the use of mechanical biological treatment systems. A less clean form of biogas is the landfill gas which is produced by the use of naturally occurring anaerobic digesters, but the main threat is that these gases can be a severe threat if escapes into the atmosphere.


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Bioalcohols: These are alcohols produced by the use if enzymes and micro organisms through the process of fermentation of starches and sugar. Ethanol is the most common type of bioalcohol whereas butanol and propanol are some of the lesser known ones. Biobutanol is sometimes also referred to as a direct replacement of gasoline because it can be directly used in the various gasoline engines. Butanol is produced using the process of ABE fermentation, and some of the experiments have also proved that butanol is a more energy efficient fuel and can be directly used in the various gasoline engines. Syngas: This is a gas that is produce after the combined process of gasification, combustion and pyrolysis. Biofuel used in this process is converted into carbon monoxide and then into energy by pyrolysis. During the process, very little oxygen is supplied to keep combustion under control. In the last step known as gasification the organic materials are converted into gases like carbon monoxide and hydrogen. The resulting gas Syngas can be used for various purposes. . The most important advantage of using liquid as fuel is that they can be easily pumped and can also be handled easily. This is the main reason why almost all the vehicles use liquid form of fuels for combustion purpose. For other forms of non transportation applications there are other alternative solid biomass fuel like wood. These non transportation applications can bring into use these solid biomass fuels as they can easily bear the low power density of external combustion. Wood has been brought into use since a very long period and is one of the major contributors of global warming. Biofuels are the best way of reducing the emission of the greenhouse gases. They can also be looked upon as a way of energy security which stands as an alternative of fossil fuels that are limited in availability. Today, the use of biofuels has expanded throughout the globe. Some of the major producers and users of biogases are Asia, Europe and America. Theoretically, biofuel can be easily produced through any carbon source; making the photosynthetic plants the most commonly used material for production. Almost all types of materials derived from the plants are used for manufacturing biogas. One of the greatest problems that is being faced by the researchers in the field is how to covert the biomass energy into the liquid fuel. There are two methods currently brought into use to solve the above problem. In the first one, sugar crops or starch are grown and through the process of fermentation, ethanol is produced. In the second method, plants are grown that naturally produce oil like jatropha and algae. These oils are heated to reduce their viscosity after which they are directly used as fuel for diesel engines. This oil can be further treated to produce biodiesel which can be used for various purposes. Most of the biofuels are derived from biomass or bio waste. Biomass can be termed as material which is derived from recently living organism. Most of the biomass is obtained from plants and animals and also include their by products. The most important feature of biomass is that they are renewable sources of energy unlike other natural resources like coal, petroleum and even nuclear fuel. Some of the agricultural products that are specially grown for the production of biofuels are switchgrass, soybeans and corn in United States. Brazil produces sugar cane, Europe produces sugar beet and wheat while, China produces cassava and sorghum, south-east Asia produces miscanthus and palm oil while India produces jatropha.

Biodiesel Advantages •

Miscible with any Diesel Fuel and in any proportion

•

Fuel quality Improvements – High Cetane No – Low Sulfur content. – High Flash point – Better Lubricity HFRR

~ 65 0-200 ppm >1000c 325 micron (460 micron)

•

Exhaust Emissions

PM

•

Bio degradable, ideal for use in fragile areas e.g. nature reserves, bodies of water etc.

25-50%

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Biofuels- Indian Perspective Bio-fuels – Rationale • Biofuels are renewable energy source • Environmentally safer • Very high potential to rejuevenate local/rural economy and employment generation • Provide Energy security & alternate to fossil fuels • Easy to develop and use National Mission on Bio-diesel: To produce bio-diesel in the country for blending in HSD – Jatropha plantation required. Bio diesel technology has been indigenously developed & licensed.

SUSTAINABLE BIOFUELS: PROSPECTS AND CHALLENGES Unless biofuel development is supported by appropriate policies and economic instruments then there is a risk that we may become locked into inefficient biofuel supply chains that potentially create harmful environmental and social impacts. New technologies need to be accelerated that can help address these issues, aided by policies that provide direct incentives to invest in the most efficient biofuels. Brazil, the world’s largest exporter of ethanol, a fuel produced from sugarcane, is also struggling with infrastructure difficulties. These are not only putting pressure on supplies available for export, but also lowering prices - because exporters are forced to sell due to a lack of port facilities. Brazil’s state-owned petroleum company, Petrobras, and local industry are exploring the development of several intra-state ethanol pipelines to avoid transporting fuel via the country’s poor highway network. The food versus fuel debate is an especially important one in Africa, where harsh climatic conditions, civil disturbance and poor land use patterns cause millions to go without their daily food requirements. When moving forward with biofuel projects, it is vital to ensure the food supply isn’t in jeopardy in the region where the project is being developed. Meeting future energy needs while tackling climate change is of the utmost importance but the debate on how to achieve this often considers single technologies in isolation. This document is the report of a two-day discussion meeting Towards a low carbon future that was held at the Royal Society on 17 - 18 November 2008. The meeting reviewed the current and potential technological options and considers how they can contribute to an integrated energy strategy for the future.The key conclusion arising from the meeting was that there is no single best solution in moving towards a low carbon future: an integrated approach making best use of all available technologies is required. A number of areas were suggested that require considerable research to be undertaken now if we are to be able to make full future use of technologies such as renewables, bio-energy and fusion. Nontechnological developments were also seen as essential in realising the potential technological developments.

BIOFUELS OPPORTUNITIES Requirement of large agricultural areas in order to grow the sufficient amount of raw materials for biofuel production. This leads to less availability of land for conventional farming for crops and cattle and a balance needs to be found between fuel-food productions. For the usage of higher percentages of biofuels, the entire fuel infrastructure needs to be altered in order to be suitable for biofuel combustion. Not only the refineries of fuels are required, but also the transportations infrastructure. The performance is slightly lower in comparison to conventional fuels.

CONCLUSIONS A sustainable energy system includes energy efficiency, energy reliability, energy flexibility, fuel poverty, and environmental impacts. A sustainable biofuel has two favorable properties, which are availability from renewable raw material and its lower negative environmental impact than that of


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fossil fuels. Biomass could play an important role in the future energy supply in its form of energy resource. Due to its environmental merits, the share of biofuel in the automotive fuel market will grow fast in the next decade. In the future, the competitiveness of future large-scale conversion facilities depends on the evolvement of an international biomass market, with large quantities of biomass against low costs. Modern biomass options includes various benefits e.g. employment creation in rural areas, reduction of a country’s dependency on imported energy carriers, related improvement of the balance of trade, better waste control, and potentially benign effects with regard to biodiversity, desertification, recreational value. As a result, biomass can significantly contribute to sustainable development both in developed and developing countries. Biomass has a vital role to play in climate stabilization. Another major reason why the use of biomass for energy will increase is the growth in energy demand in developing countries, where affordable alternatives are often unavailable.

REFERENCES 1. Boogert, A.C., W.J.G. van der Vliet (2008) “Biofuels- Current technological status” Energy Conversion Technologies. 2. Business Insights (2005), Biofuels for Transportation: Market analysis, country profiles and growth forecasts to 2010. 3. Barnwal, B. K., Sharma, M. P. 2005. Prospects of Biodiesel production from vegetable oils in India. Renewable and sustainable energy reviews, 9, 363 – 398. 4. Chiaramonti, D., Bonini, M., Fratini, E., Tondi, G., Gartner, K., Bridgwater, A.V., Grimm,H.P., Soldaini, I., Webster, A., Baglioni, P.(2003) Development of Emulsion from biomasspyrolysis liquid and diesel and their use in engine – Part 2: tests in diesel engines. 5. Davies, Mathew P., (1998) “Non-Conventional Energy Development in India”. 6. Gonsalves, Joseph B., (2006) “An Assessment of the Biofuels Industry in India”. 7. Gubitz, G. M., Mittelbach, M., Trabi, M. 1999. Exploitation of the tropical oil seed plant, Jatropha Curcas L. Bioresource Technology, 67, 73 – 82. 8. Janulis, P. 2004. Reduction of energy consumption in biodiesel fuel life cycle. Renewable energy, 29, 861 – 871. 9. Kumar, L., Mohan, M.P. Ram. (2005) Biofuels: The Key to India’s Sustainable Energy Needs, Energy and Resources Institute (TERI), New Delhi, India. 10. Kumar, P. 1998. Food Demand and Supply Projections for India Agricultural Economics Policy Paper 98-01. IARI, New Delhi. 11. Biodiesel fuel at Ohio University: waste grease to algae, Russ College of Engg. & Tech, Ohio University 12. Basics of Algae and Algae fuel, http://www.oilgae.com 13. http://en.wikipedia.org 14. Biodiesel Conclave; Indian Habitat centre Lodhi Road N Delhi ;Nov 05,2005 15. Tian, Y., Zhao, L., Meng, H., Sun, L., Yan, J., Estimation of un-used land potential for biofuels development in China, Applied Energy 86 (SUPPL. 1), pp. S77-S85, 2009. 16. Petrou, E.C., Pappis, C.P., Biofuels: a survey on pros and cons, Energy and Fuels 23 (2), pp. 1055-1066, 2009. 17. Reijnders, L., Microalgal and terrestrial transport biofuels to displace fossil fuels, Energies 2 (1), pp. 48-56, 2009. 18. Demain, A.L., Biosolutions to the energy problem, Journal of Industrial Microbiology and Biotechnology 36 (3), pp. 319-332, 2009. 19. Robles-Medina, A., González-Moreno, P.A., Esteban-Cerdán, L., Molina-Grima, E., Biocatalysis: Towards ever greener biodiesel production, Biotechnology Advances 27 (4), pp. 398-408, 2009. 20. Pienkos, P.T., Darzins, A., Perspective: The promise and challenges of microalgal-derived biofuels, Biofuels, Bioproducts and Biorefining 3 (4), pp. 431-440, 2009. 21. M. B. Celik, Experimental determination of suitable ethanol-gasoline blend rate at high compression ratio for gasoline engine, Applied Thermal Engineering, 28 (2008), 396-404.

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22. T. Topgul, H.S. Yucesu, C. Cinar, A. Koca, The effects of ethanol-unleaded gasoline blends and ignition timing on engine performance and exhaust emissions, Renewable Energy, 31(2006),2534-2542. 23. M Kafeel, M Kamil, M Yusuf Ansari and A Mateen, Experimental Study on Low Ethanol Blended Gasoline, Proceeding of National Conference on Advances in Petroleum Refining & Petrochemicals Technologies, Aligarh, March 2009, P-14. 24. A. Ashfaq, S. Badar, I.H. Farooqui, Biofuels: status, applications and problems associated, Proceeding of National Conference on Advances in Petroleum Refining & Petrochemicals Technologies, Aligarh, March 2009, P-13


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Comparative Study of Vehicle Pollution Load with Conventional and Clean Fuel in Delhi S.L.Bhandarkar 1*Mohammed Sharif2 1 Department of Automobile Engineering, Pusa Polytechnic, New Delhi 2

Department of Civil Engineering, Jamia Millia Islamia, New Delhi, India. * Corresponding author Email:[email protected]

Abstract: The present paper describes the causes of air pollution in Delhi and suggests various measures to curb the menace. At present about 55 lakhs vehicles in Delhi pollute the atmosphere with noxious emissions. Delhi is ranked fourth among the 41 cities of the world monitored for air pollution. Delhi is responsible for largest amount of lead emissions by automobiles, as compared to other metros. The Supreme Court had directed the union government to determine the feasibility of using an ecofriendly fuel in the vehicle as in many developed countries. The various policies have been declared and legislation has been passed to curb the air pollution in Delhi. In this study, a traffic survey has been conducted on NH- 2 Delhi - Mathura Road for a 2 kms stretch between Okhla More and Ashram chowk. This road has been selected because it is observed that almost all category of vehicles ply on this road, and this has made pollution load calculations more reliable. The traffic survey was conducted in the morning peak hours that is from 8am to 9am and 9am to 10am, evening peak hours from 5pm to 6pm and 6pm to 7pm, and also in the lean hours from 12 noon to 1.0pm. Based on the data collected the pollution load has been calculated and compared with the expected pollution load if clean fuel were to be used in these vehicles. The reduction in pollution level obtained by the use of CNG in place of conventional Diesel and Petrol Vehicles has been estimated. Key Words: Air pollution, Delhi, Clean fuel, CNG. Introduction At present about 51lakh vehicles pollute the atmosphere of Delhi with noxious emissions. In a bid to curb vehicular pollution, the Supreme Court had directed that the entire diesel – run commercial vehicles should be made to run on Delhi roads with eco friendly Compressed Natural Gas (CNG). The Centre for Science & Environment [C.S.E] has reported that diesel fumes are more carcinogenic. It is believed that the cancer potency level of the exhaust from diesel vehicles in India is double that of petrol run vehicles. The risk from diesel fumes is enhanced by their ability to trigger a wide range of non–cancerous effect, including allergy, asthma and other respiratory problems. The unleaded petrol introduced earlier in Delhi for all vehicles to curb air pollution led to a controversy as it was apprehended that unleaded petrol used in vehicles without catalytic converters will emit more poisonous gases like benzene. The Supreme Court then directed that petrol in Delhi should be made available with 0.05% sulphur and 1% benzene. Earlier the petrol used to contain 0.1% sulphur. Delhi is ranked fourth among the 41 cities of the world monitored for air pollution. Delhi is responsible for largest amount of lead emissions by automobiles, as compared to other metros. The two stroke, two & three wheelers consume 60 percent of the total gasoline produced in India. The Supreme Court had directed the union government to determine the feasibility of using propane as an eco-friendly fuel in the vehicle as in many developed countries. A majority of autos have not turned to propane because the conversion kit is expensive. Lead from automobile exhaust and Industry accumulates in the form of dust. City road dust has been found to contain two grams of lead per kilograms of dust. For this reason, leaded petrol has been banned in some developed countries. Controlling urban air pollution is turning out to be an enormous challenge not only because of the rising numbers of total vehicles but also due to the increased toxic risk from the growing numbers of diesel cars. In 1999 CSE had advocated the ban on diesel Vehicles. We need cleaner alternatives. Serious efforts are needed to create awareness among the consumers to make their vehicles eco– friendly to reduce emissions. There is also a need to exploit propane and other cleaner fuels such as bio–diesel. CNG is considered as an alternative fuel because of its many advantages and are as given below.


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Benefits of CNG - No visible tail pipe emissions. - Eliminates sulphur and lead from the exhaust emissions. - Reduction in CO, NOx and Particulate emissions. - Significant reduction in benzene and other toxic emissions. - Higher octane value of CNG reduces knocking problems of a vehicle. - Reduces noise from running vehicles. - CNG cannot be adulterated. - Reduce noise in operation. Now, two wheelers are not recommended for alternative fuels because of not much difference in emissions.

Emissions from Diesel Vehicles Due to low volatility, evaporative emissions are non-significant. Though the concentration of CO and unburnt HC in the diesel exhaust are rather low, they are compensated by high concentration of NOx. There are smoke particles and oxygenated HC, including aldehydes and odour-producing compounds. Fueled vehicles are CO, HC, NOx and Pb while pollutants from diesel-fueled vehicles are particulate matter (including smoke), NOX, SO2, PAH. Residence time and turbulence in the combustion chamber, flame temperature and excess O2 affect CO formation. NOX includes nitric oxide (NO), nitrous oxide (N2O), nitrogen dioxide (NO2), dinitrogen trioxide (N2O3) and nitrogen pentoxide (N2O5). NO and NO2 collectively represented as NOX, are the main nitrogen oxides emitted by vehicles. About 90% of these emissions are in the form of NO. NO is produced in the vehicle engine by combustion of nitrogen at high temperatures. NO2 formed by oxidation of NO, has a reddish brown colour and pungent odour. In developing countries, the transport sector accounts for 49% of NOX emissions and the power sector, 25%; the industrial sector, 11%; the residential and commercial sectors, 10% and other sources 5%. Another important gas emitted is carbon-di-oxide which is a green house gas associated with global warming resulting mainly from increased combustion of fossil fuels including motor vehicle fuels.

Motivation for present study Delhi, the heart of the country is plagued today by environmental degradation. Mainly due to Air pollution is particularly alarming because of its harmful effects on human health. Today Delhi has approximately three times more vehicles than Mumbai. Delhi is the metropolitan city where commuters are primarily dependent on the road transport system. This has led to an enormous increase in the number of vehicles with the associated problems of traffic-congestion and an alarming increase in air pollution. Therefore, there is an urgent need for vehicles in Delhi to switch over to various alternative fuels such as CNG., Auto-LPG, and LNG. to minimize air pollution in Delhi. The major pollutants emitted by motor vehicles include CO, NOx, sulphur oxides, (SO), HC, lead (Pb) and suspended particulate matter (SPM). These pollutants have damaging effects on both human health and ecology. The human health effects of air pollution vary in the degree of severity, covering a range of minor effects to serious illness, as well as premature death in certain cases. Most of the conventional air pollutants are believed to directly affect the respiratory and cardio-vascular systems. In particular, high levels of SO2and SPM are associated with increased mortality, morbidity and impaired pulmonary function, Lead prevents hemoglobin synthesis in red blood cells in bone marrow, impairs liver and kidney function and causes neurological disorders. Therefore, it is important to reduce pollution from vehicular emissions Euro III diesel cars emit 7.5 times more toxic particulate matter (PM) than comparable petrol cars. This means, one diesel car is equivalent to adding 7.5 petrol cars to the car fleet in terms of the particulate matter. Diesel Vehicles are legally allowed to emit nearly three times more NOx as Bharat Stage III (Euro III equivalent) norms. Investigations carried out by Centre for Science and Environment (CSE), based on actual emissions data available from the Pune-based Automotive Research Association of India; expose enormous differences in the actual emission levels of Euro III

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(Bharat Stage III) diesel and petrol cars that are currently sold in Delhi and other major Indian cities. Euro III diesel cars emit 7.5 times more toxic particulate matter (PM) than comparable petrol cars. This means, one diesel car is equal to adding 7.5 petrol cars to the car fleet in terms of PM emissions and 3 petrol cars in terms of NOx emissions. This clearly reflects the flawed emission standards that allow diesel cars to emit more NOx and Particulate Matter compared to petrol cars.

Objectives of Study The principal objective of the present research is to suggest strategies for minimizing vehicular pollution in Delhi. The specific objectives are 1. To carry out relevant literature review 2. Collection of data related to various alternative fuels 3. Collection of data pertaining to emission factors 4. Collection of traffic data, classification of vehicles data and emission factors for various categories of vehicles and fuels. 5. Comparison of emission level for various classes of vehicles with the combination of alternative fuels. 6. To suggest pollution reduction measures in Delhi.

CNG Given the availability and the infrastructure, CNG qualifies to be one of the most prominent alternative fuels. It stands substantially better than conventional fuels both in life cycle emissions and vehicle exhaust emissions. Table:1: gives the comparative emissions from CNG and conventional diesel. Table 1: Comparative Emissions from Diesel and CNG for Buses Fuel Pollution Parameter CO NOx PM Diesel 2.4 g/km 21 g/km 0.38 g/km CNG 0.4 g/km 8.9 g/km 0.012 g/km % Reduction 84 58 97 Source: Frailey et al. (2000) as referred in World Bank (2001b: 2).

Disadvantages of CNG CNG is now established as a very successful alternative fuel for automobiles throughout the world. The disadvantage of this fuel, if any, is easily overruled by the advantages associated with this fuel. Nevertheless, infrastructure, on-board storage and issues on safety need proper attention for this fuel. Natural gas is neither corrosive nor toxic. It’s ignition temperature is high and it is lighter than air. It has a narrow flammability range, making it an inherently safe fuel compared to other fuel sources. Natural gas cannot contaminate soil or water. It will always rise to the atmosphere out of doors, unlike other fuels, which are heavier than air and can pool, either as a liquid or a vapour, upon the ground. Natural gas contains a distinctive odorant (mercaptan), which allows natural gas to be detected at 0.5% concentration in air, well below levels that can cause drowsiness due to inhalation and well below the weakest concentration that can support combustion. Due to high ignition temperature of natural gas (540 degree C), simple exposure to a hot surface (such as exhaust manifold) is unlikely to lead a fire.


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METHODOLOGY The following methodology has been adopted for conducting the present study. 1. The details of different categories of vehicles have been collected by conducting survey at Mathura Road-Okhla More of New Delhi. 3. The emission levels of various class vehicles have been collected from Central Pollution Control Board, New Delhi and from other reliable sources. 4. Available data has been analyzed with the objective of minimizing vehicular pollution with alternative fuels/categories of vehicles A traffic survey has been conducted at Mathura Road (Okhla More) on 15-02-2008. This point has been selected because vehicles plying on this road run for almost 2 kms from Aashram fly over to Modi Mill fly over. This makes the pollution loads calculations easier and more reliable. The traffic survey was conducted to categorize the vehicles properly for this study. The results are as given below. Table 2: Vehicle Distribution on the day of survey. Type of Vehicle Petrol Cars Diesel Cars CNG Taxi CNG Three Wheelers Two Wheelers CNG Buses Diesel Buses Diesel Trucks Total

Number of Vehicles 13494 3584 277 5596 13328 842 285 353 37759

From Table 2, it can seen that the two wheelers and Petrol Cars are more than any other class of Vehicles, CNG three wheelers and Diesel Cars follow them in numbers. Figure1 shows the distribution of total number of Vehicles surveyed on 15-02-2008 at Okhla More (Traffic Junction) on Mathura Road.

Calculation of pollution loads This section describes the procedure for calculations of pollution loads. With the help of available data firstly the Pollution Load of CNG Buses and Diesel Bus / Trucks can be calculated for the vehicles running on Mathura Road, at Okhla More (Traffic Intersection). The total Diesel Buses and trucks counted on 15/02/2008 were about 638. Table 3: Emission Benefits of Replacing Conventional Diesel with CNG in Buses/Trucks Pollution Parameter Fuel

CO gm/km

NOx gm/km

Diesel 2.4 21 CNG 0.4 8.9 % Reduction 84 58 Source: Frailey et al. (2000) as referred in World Bank (2001b: 2).

PM gm/km 0.38 0.012 97

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Table 4: Total Number of Diesel Bus and Trucks at the time of Traffic Survey Diesel Buses Diesel Trucks Total

285 353 638

Figure 1: Distribution of vehicles By using data from Table 3 and Table 4, the pollution Load can be calculated at Mathura Road by the Diesel Busses and Trucks as shown in Table 5. Table 5: Pollution Load of Diesel Buses and Trucks Pollution CO in gm/km Parameter Fuel

NOx in gm/km

PM in gm/km

Diesel

21*638=13398

0.38*638=243

2.4*638=1531

If CNG is used in place of Diesel Fuel then the Pollution load can be reduced at Mathura road as below


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Table 6: Pollution Load of CNG Buses Pollution Parameter Fuel CNG

CO in gm/km

NOx in gm/km

PM in gm/km

0.4*638=255.2

8.9*638=5678.2

0.012*638=7.656

In this way the Pollutants can be reduced as shown in Table 6, CO can be reduced to 255.2 gm/km and NOx to 5678.2 gm/km and PM to 7.566 gm/km. The percentage reduction in CO is 78%> For NOx and PM it is about 58% and 97% respectively. Table 7: Reduction in Pollution load in gm/km by the use of CNG Reduction in gm

CO

NOx

PM

Per Km

1276

7719.8

234.78

2 Km stretch

2552

154349.6

469.56

Figure 2: Percentage of Reduction in Pollutants by the use of CNG

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Now using the total number of Petrol cars that is 13494, as per the survey conducted at Mathura Road - Okhla More, the total Pollution load of 13494 Petrol Cars can be calculated, and if CNG is used for all these cars, then the reduction in Pollutants in gm/km and Percentage of reduction in Pollutants are as shown in Table 8. And it shows the pollution loads for a stretch of 2km at Mathura Road– Okhla More for petrol and CNG Cars. Table 8: Pollution load in gms for two km stretch for petrol and CNG cars Fuel/Pollutants Petrol CNG Reduction

PM10 2699 1349 1349

PM2.5 809.64 539.76 269.88

SO2 1889.16 0.00 1889.16

NOx 5397.6 539.76 4857.84

CO 134940 26988 107952

CO2 5397600 2698800 2698800

HC 26988 2698.8 24289

Figure 3 Percentage reductions in pollutants by the use of CNG in place of Petrol cars

And now by using data given below in the Table 9 and using the total Number of Diesel Cars i.e., 3584, as per the survey conducted at Mathura Road - Okhla More, then calculate the total Pollution load of 3584 Diesel Cars, and if CNG is used for all these Cars, then the reduction in Pollutants in gm/km and Percentage of reduction in Pollutants are as shown in Table 10Table . By referring Table 9 and Table.10 given below, it can be concluded that if CNG is used in place of Diesel Cars then pollutants can be reduced as PM10=95%, PM2.5=96%, SO2=100%, NOx=84%, CO=50%, CO2=60%, and HC=95% at Mathura Road – Okhla More


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Table 9: Comparative pollutants load of Diesel and CNG cars. Pollutants

Diesel

CNG

PM10

1.00

0.05

PM2.5

0.60

0.02

SO2

0.40

0.00

NOx

1.25

0.20

CO

2.00

1.00

CO2

250

100

HC

0.40

0.02

in gm/km

(Source: Dr. Sarath Guttikunda, New Delhi,

July 2008, Four Simple Equations for Vehicular Emissions

Inventory, Simple Interactive Models for Better Air Quality, www.sim-air.org) Table 10: Reduction of pollutants by the use of CNG in place of Diesel cars in gm/km Pollutants

Diesel

CNG

Reduction

% Reduction

PM10

3584.00

179.20

3404.8

95

PM2.5

2150.40

71.68

2078.72

96

SO2

1433.60

0.00

1433.60

100

NOx

4480.00

716.80

3763.20

84

CO

7168.00

3584.00

3584

50

CO2

896000

358400

537600

60

HC

1433.60

71.68

1361.92

95

Conclusion A traffic survey has been conducted on NH- 2 Delhi - Mathura Road for a 2 kms stretch between Okhla More and Ashram chowk. This road has been selected because it is observed that almost all category vehicles are plying on this road, and this has made pollution load calculations more reliable. The traffic survey was conducted in the morning peak hours that is from 8am to 9am and 9am to 10am, evening peak hours from 5pm to 6pm and 6pm to 7pm, and also in the lean hours from 12 noon to 1.0pm. Based on the data collected the pollution load has been calculated and compared with the expected pollution load if clean fuel will be used in these vehicles. The reduction in pollution level obtained by the use of CNG in place of conventional Diesel and Petrol Vehicles has been estimated. It can be concluded that considerable reduction in pollution load can be obtained if petrol and diesel vehicles are replaced by CNG cars.

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ALTERNATIVE SOURCE OF BIOFUELS: MICRO DIESEL Dr. Sabiha Imran Sr. Lecturer, Deptt. of Biotechnology, CITM, Manav Rachna International University, Faridabad, Haryana, India [email protected]

ABSTRACT Demand for energy - transport fuels as well as stationary energy (electricity) - has grown dramatically throughout the world during the 21st century. Oil prices have risen considerably since 2002 and as the climate is changing-the greenhouse gas emissions must be reduced in order to protect the environment. Biofuels have been put forward as one of a range of alternatives with lower emissions and a higher degree of fuel security. There are different types of bio fuels in which Bio diesel is famous. Biodiesel is an alternative energy source and a substitute for petroleum-based diesel fuel. It is produced from renewable biomass by transesterification of triacylglycerols from plant oils, yielding monoalkyl esters of long-chain fatty acids with short-chain alcohols such as fatty acid methyl esters and fatty acid ethyl esters (FAEEs). Despite numerous environmental benefits, a broader use of biodiesel is hampered by the extensive acreage required for sufficient production of oilseed crops. Therefore, processes are urgently needed to enable biodiesel production from more readily available bulk plant materials like sugars or cellulose. Toward this goal, the study is established for the biosynthesis of biodiesel-adequate FAEEs, referred to as Microdiesel, in metabolically engineered Escherichia coli. This is achieved by heterologous expression in E. coli of the Zymomonas mobilis pyruvate decarboxylase and alcohol dehydrogenase and the unspecific acyltransferase from Acinetobacter baylyi strain ADP1. By this approach, ethanol formation will be combined with subsequent esterification of the ethanol with the acyl moieties of coenzyme A thioesters of fatty acids is formed if the cells are cultivated under aerobic conditions in the presence of glucose and oleic acid. Ethyl oleate will be the major constituent of these FAEEs, with minor amounts of ethyl palmitate and ethyl palmitoleate. This novel approach might pave the way for industrial production of biodiesel equivalents from renewable resources by employing engineered micro-organisms, enabling a broader use of biodiesel-like fuels in the future.

Key Words : FAEE, fatty acid ethyl ester; FAME, fatty acid methylester; TAG, triacylglycerol, WS/DGAT, wax ester synthase/acylcoenzymeA : diacylglycerol acyltransferase. 1. INTRODUCTION Global energy and environmental problems have stimulated increasing efforts toward the development of alternatives to fossil fuels. Oil is running out. Our yearly usage of oil, coal, and natural gas are the products of around 1 million years worth of organic matter converting sunlight to chemical energy, and unfortunately for us, much of our way of life depends upon the plentiful supply of petrochemicals.


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Bio fuels are one of the few technologies currently available that have the potential to displace oil and provide benefit to the transport system (Oliver and King, 2009). First generation biofuels are made from sugar, vegetable oil, or animal fats using conventional technology as lower quality vegetable oil, biodiesel, bioalcohals, bioethers, biogas, syngas and solid biofuels. The second generation biofuels are more viable solution is to increase industrial support from non food crops. These include waste biomass, stalks of wheat, corn, wood and special – energy-or-biomass crops. Many second generation biofuels are under development such as biohydrogen, biomethanol. Third generation biofuels include algae fuel. Algae are low input; high yield feeds stocks to produce biofuels. Biodiesel, as currently produced on a technical scale, has also numerous drawbacks and limitations (Alterthumand Ingram, 1989). Production is dependent on the availability of sufficient vegetable oil feedstocks, mainly rapeseed in Continental Europe, soybean in North America and palm oil in South East Asia. Therefore, industrial-scale biodiesel production will remain geographically and seasonally restricted to oilseed-producing areas (Alvarez and Steinbuchel, 2002). Vegetable oils predominantly consisting of TAGs cannot be used directly as diesel fuel substitute, mainly because of viscosity problems. Additional problems are the reliability of product quality in bulk quantities and filter plugging at low temperatures due to crystallization. Therefore, plant oils must be transesterified with short-chain alcohols like methanol or ethanol to yield the FAME and FAEE constituents of biodiesel. This transesterification process and the subsequent purification steps are cost intensive and energy consuming, thereby reducing the possible energy yield and increasing the price (Bockey and Schenck, 2005). FAMEs and FAEEs have comparable chemical and physical fuel properties and engine performances (Peterson et al ,1995) scale) but for economic reasons, only FAMEs are currently produced on an industrial due to the much lower price of methanol compared to ethanol. Methanol, however, is currently mainly produced from natural gas. Thus, FAME-based biodiesel is not a truly renewable product since the alcohol component is of fossil origin. Furthermore, methanol is highly toxic and hazardous, and its use requires special precautions. Use of bioethanol for production of FAEE-based biodiesel could result in a fully sustainable fuel, but only at the expense of much higher production costs. (Dien et al,2003). The major limitation impeding a more widespread use of biodiesel is the extensive acreage needed for production of oilseed crops. The yield of biodiesel from rapeseed is only 1300 l ha–1, since only the seed oil is used for biodiesel production, whereas the other, major part of the plant biomass is not used for this purpose. Furthermore, oilseed crops like rapeseed and soybean are not self-compatible; therefore, their cultivation requires a frequent crop-rotation regime. In consequence, biodiesel based on oilseed crops will probably not be able to substitute more than 5–15 % of petroleum-based diesel in the future. A recent study assessing the use of bioethanol for fuel came to the conclusion that large-scale use will require a cellulose-based technology (Farrell et al.,2006). A substantial increase of biodiesel production and a more significant substitution of petroleum-based diesel fuel in the future will probably only be feasible when processes are developed enabling biodiesel synthesis from bulk plant materials such as sugars and starch, and in particular cellulose and hemicellulose. Intracytoplasmic storage lipid accumulation in the Gram-negative bacterium Acinetobacter baylyi strain ADP1 (Vaneechoutte et al.,2006) is mediated by the wax ester synthase/acylcoenzyme A: diacylglycerol acyltransferase (WS/DGAT; the atfA gene product). This unspecific acyltransferase simultaneously synthesizes wax esters and TAGs by utilizing longchain fatty alcohols or diacylglycerols and fatty acid coenzyme. A thioesters (acyl-CoA) is used as substrates. Biochemical characterization of WS/DGAT revealed that this acyltransferase exhibits an extremely low acyl acceptor molecule specificity in vitro. The remarkably broad substrate range of WS/DGAT comprises short chain-length up to very long

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chain-length linear primary alkyl alcohols; cyclic, phenolic and secondary alkyl alcohols; diols and dithiols; mono- and diacylglycerols as well as sterols (Stoveken et al., 2005, Uthoff et al., 2005). By expression of WS/DGAT in different recombinant hosts, this substrate promiscuity has already been exploited to synthesize various fatty acid ester molecules in vivo. Use of Bacteria to produce biodiesel (microdiesel) is a quite novel approach .The objective of this study is the development of a microbial process for the production of FAEEs for use as biodiesel from simple and renewable carbon sources particularly from cellulose and lignin, which are major plant polymers. The work is therefore in a process to establish a FAEE biosynthesis in recombinant E. coli by coexpression of the ethanol production genes from the ethanol-producing fermentative bacterium Zymomonas mobilis in combination with the WS/DGAT gene from A. baylyi strain ADP1 and for energy purpose the source will be available from food wastage consisted of cellulose and lignin.

2.

METHODS

2.1 Bacterial Strains, Culture Conditions and Vectors E. coli was cultured in Luria broth (LB) at 37 'C. Phage was propagated in E. coli grown on NZY medium. Media were supplemented with 100, ug/ml of ampicillin and 2, ug/ml of 5bromo-4-chloro-3-indolyl-/J-D-galactopyranoside to select for E coli transformants and recombinants, respectively. To identify recombinant E. coli strains that expressed cellulase activity, bacterial colonies, grown on LB-agar supplemented with medium-viscosity CMC, were stained with 1 % Congo red for5 min and destained with 1 M NaCl. Cellulase-expressing E. coli colonies were surrounded by clear haloes against a red background (Teather and Wood,1982). The phage and plasmids employed in this work wereAZAPII, pBluescriptSK- (Stratagene) For harbouring the Zymomonas mobilis genes plasmid pLOI297 and for pyruvate decarboxylase (pdc) and alcohol dehydrogenase (adhB) cloned in pUC18 collinear to the lacZ promoter (12), and pKS : : atfA and pBBR1MCS-2 : : atfA harbouring the WS/DGAT gene from A. baylyi strain ADP1 collinear to the lacZ promoter in pBluescript KS. Recombinant strains of E. coli were cultivated in LB medium (0.5 %, w/v, yeast extract, 1 %, w/v, tryptone and 1 %, w/v, NaCl) containing 1 mM IPTG and 2 % (w/v) glucose at 37 °C in the presence of ampicillin (75 mg l–1) and kanamycin (50 mg l–1) for selection of pLOI297, pKS : : atfA and pMicrodiesel or pBBR1MCS-2 : : atfA, respectively. Where indicated, sodium oleate was added from a 10 % (w/v) stock solution in H2O to a final concentration of 0.1 or 0.2 % (w/v). Cells were grown aerobically in 300 ml baffled Erlenmeyer flasks containing 50 ml medium on an orbital shaker (130 r.p.m.).

2.2 Bioreactor Cultivation Fermentation experiments were done in a 2 litre stirred bioreactor (B. Braun Biotech International) with an initial volume of 1.5 l LB medium containing 0.2 % (w/v) sodium oleate, 2 % (w/v) glucose, 1 mM IPTG and appropriate antibiotics for plasmid selection (see above). Cultivations were done at 37 °C and at a stirring rate of 200 r.p.m. If not stated otherwise, the pH was controlled at 7.0 by automated addition of 4 M HCl or NaOH. Cells were cultivated either aerobically (aeration rate 3 vvm), under restricted oxygen conditions


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(aeration rate 0.75 vvm), or anaerobically. Inoculum was 5 % (v/v) of saturated overnight cultures.

2.3 Thin-layer chromatography TLC analysis of lipid extracts from whole cells was done using the solvent system hexane/diethyl ether/acetic acid (90 : 7.5 : 1, by vol.). Lipids were visualized by spraying with 40 % (v/v) sulfuric acid and charring. Ethyl oleate was used as reference substance for FAEEs. Increased ethanol production has been achieved in E. coli upon heterologous expression of pyruvate decarboxylase (the pdc gene product) and alcohol dehydrogenase (the adhB gene product) from the strictly anaerobic ethanologenic Gram-negative bacterium Zymomonas mobilis. Using this system, efficient ethanol biosynthesis was achieved from glucose via the glycolysis product pyruvate even under aerobic conditions (Ingram et al.,1987,Alterthum and Ingram,1989).

3. RESULTS In this study, the FAEE biosynthesis in a recombinant E. coli by combining expression of the Z. mobilis genes pdc and adhB and of the atfA gene from A. baylyi strain ADP (Figure. 1)

Figure 1. Pathway of FAEE biosynthesis in recombinant E. coli.

FAEE formation was achieved by coexpression of the ethanolic enzymes pyruvate decarboxylase (Pdc) and alcohol dehydrogenase (AdhB) from Z. mobilis and the unspecific acyltransferase WS/DGAT from A. baylyi strain ADP1.

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Using plasmids pLOI297 (pdc and adhB) and pBBR1MCS-2 : : atfA. Recombinant strains carrying either plasmid alone did not exhibit FAEE levels detectable by TLC (Figure 2a, lanes 1 and 2). However, coexpression of all three relevant genes in a strain carrying both plasmids resulted in significant FAEE formation (Fig. 2a, lane 3). FAEE biosynthesis was strictly dependent on the presence of sodium oleate in the medium .Growth of strains harbouring plasmid pLOI297 was very poor in LB medium without glucose addition, and FAEE synthesis was not observable in E. coli harbouring both plasmids under these conditions.The FAEEs formed were accumulated intracellularly, and no significant extracellular lipids were found in cell-free culture supernatants .

Figure 2: Chemical analysis of FAEEs produced by recombinant E. coli

(a) TLC analysis of intracellular lipids accumulated by recombinant E. coli TOP10. Cells were cultivated aerobically in shake flasks for 24 h at 37 °C in LB medium containing 2 % (w/v) glucose, 0.1 % (w/v) sodium oleate, 1 mM IPTG and appropriate antibiotics . A,oleic acid; B, ethyl oleate; C, oleyl oleate; 1, E. coli (pLOI297); 2, E. coli (pBBR1MCS-2 : : atfA); 3, E. coli (pBBR1MCS-2 : : atfA+pLOI297). Total lipid extracts each obtained from 1.5 mg lyophilized cells were applied in lanes 1–3. (b) Total ion profile of GC/MS analysis of FAEEs isolated from E. coli (pBBR1MCS-2 : : atfA+pLOI297). Cells were cultivated as described above. FAEEs were purified by preparative TLC.

3.1 Construction of Plasmid pmicrodiesel To simplify the process by reducing the number of antibiotics required for plasmid stabilization and to potentially increase FAEE yield by providing all three relevant genes on a high-copy-number vector, plasmid pMicrodiesel was constructed. For this, a 3.2 kbp DNA


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fragment was amplified from plasmid pLOI297 by tailored PCR using the oligonucleotides 5'AAAGGATCCGCGCAACGTAATTAATGTGAGTT-3' (forward primer) and 5'TTTGGATCCCCAAATGGCAAATTATT-3' (reverse primer) introducing BamHI restriction sites (underlined). This 3.2 kbp BamHI fragment, which comprised the Z. mobilis genes pdc and adhB and the upstream lacZ promoter region, was cloned into BamHI-linearized pKS : : atfA, a derivative of the high-copy-number plasmid pBluescript KS–, yielding pMicrodiesel (Figure 3). The orientation of atfA, pdc and adhB was determined by EcoRI restriction and DNA sequence analysis. Plasmid pMicrodiesel carried all three genes relevant for FAEE synthesis in a collinear orientation, with atfA driven by a lacZ promoter and with pdc and adhB controlled by a second lacZ promoter, thereby ensuring effective transcription of all three genes.

Figure 3: Map of plasmid pMicrodiesel.

Relevant characteristics: rep, origin of replication; AmpR, ampicillin-resistance gene; PlacZ, lacZ promoter; pdc, pyruvate decarboxylase gene from Z.mobilis; adhB, alcohol dehydrogenase gene from Z. mobilis; atfA, WS/DGAT gene from A. baylyi strain ADP1.

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3.2 Fed-batch Fermentation of E. coli (pMicrodiesel) for FAEE Production Shake-flask experiments with E. coli harbouring either pMicrodiesel alone or pLOI297 plus pBBR1MCS-2 : : atfA revealed a more than twofold higher FAEE production using the newly constructed plasmid pMicrodiesel (0.64 g l–1 compared to 0.26 g l–1) whereas ethanol concentrations were similar. This indicated the positive influence of provision of all three relevant genes on a high copy-number vector and, as consequence, potentially higher expression rates on FAEE yield.

Figure 5: FAEE production during fed-batch fermentation of E. coli (pMicrodiesel). Cultivation was done in a 2 litre stirred bioreactor initially filled with 1.5 l LB medium containing 0.2 % (w/v) sodium oleate, 2 % (w/v) glucose, 1 mM IPTG and 75 mg ampicillin l–1 under aerobic conditions (aeration rate 3 vvm) The pH was kept between 6.0 and 8.5 by automated addition of 4 M HCl or NaOH. To prevent carbon limitation, 1 g glucose l–1 was fed several times during cultivation (indicated by arrows). Sodium oleate causes turbidity of the medium, explaining the high initial optical density. , OD600; , ethanol concentration; , FAEE concentration.

4. Discussion Biodiesel is an interesting alternative energy source and is already being used as substitute for petroleum-based diesel. Offering numerous environmental benefits, it has attracted broad public interest and is being produced in increasing amounts. However, a broader use of biodiesel and a more significant substitution of petroleum-based fuels in the future will only be possible if production processes are developed that are not solely based on oilseed crops but on more bulk plant materials like cellulose. Toward this goal, the present study proposes using a novel approach to establish biotechnological production of biodiesel using metabolically engineered micro-organisms, whuch could be referred as Microdiesel. The early optimization studies described here revealed FAEE yields of up to 26 % of the bacterial dry biomass. Even though these yields are still far below the needs for an industrial process, the present study might open new avenues potentially enabling microbial production of fuel equivalents from cheap and readily available renewable bulk plant materials like sugars, starch, cellulose or hemicellulose in the future.


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Microbial FAEE biosynthesis for Microdiesel production is based on the exploitation of the extraordinarily low substrate specificity of the acyltransferase (WS/DGAT) of A. baylyi strain ADP1, which in its natural host mediates wax ester and TAG biosynthesis from acyl-CoA thioesters plus long chain-length fatty alcohols or diacylglycerols E. coli does not produce such substances by its natural metabolism; however, recombinant strains enabled to produce large amounts of ethanol and simultaneously expressing WS/DGAT provided an unusual, alternative substrate for this acyltranferase. This resulted in production of substantial amounts of FAEEs utilizing WS/DGAT's substrate promiscuity. E. coli forms ethanol, among other fermentation products, during mixed acid fermentation under anaerobic conditions from acetyl-CoA via two sequential NADH-dependent reductions catalysed by a multifunctional alcohol dehydrogenase (the adhE gene product) (Goodlove et al., 1989, Kessler et al., 1992). However, ethanol levels naturally occurring in E. coli under anaerobic conditions are probably not sufficient to support formation of significant amounts of FAEE. In addition, several other fermentation products besides ethanol occur in substantial amounts. By using a recombinant system employing Z. mobilis pyruvate decarboxylase and alcohol dehydrogenase, this limitation was circumvented, resulting in substantial amounts of ethanol under aerobic conditions(In fed-batch fermentations conducted under controlled aeration rates, the highest FAEE levels were observed in recombinant E. coli under aerobic conditions (approximately six times higher compared to anaerobic conditions) although ethanol levels were similar. This indicates that uptake of exogenous fatty acids from the medium and their activation to the corresponding acyl-CoA thioesters is probably another factor limiting Microdiesel production in E. coli under anaerobic conditions. Although an impressive FAEE content as high as 26 % of the cellular dry weight was finally obtained. Future optimization of biotechnological Microdiesel production will also benefit from the progress made in recent years in lignocellulose utilization as feedstock for bioethanol production by recombinant micro-organisms (Dien et al.,2003, Zaldiver et al.,2001). Optimized Microdiesel production by engineered micro-organisms could finally offer some major advantages over established conventional production processes. Biotechnological Microdiesel production could be significantly less expensive than conventional biodiesel production if plant products like starch or lignocellulose are used for its production. These plant polymers are not only much cheaper than plant oils, but are also much more abundant, and Microdiesel production will not be restricted to oilseed-producing regions of the world. In contrast to conventional FAME-based biodiesel, Microdiesel is a fully sustainable biofuel completely derived from renewable materials, also avoiding the use of highly toxic methanol.

5. Conclusion In conclusion, this study provides a basis to achieve more competitive production costs by utilizing cellulose and ligin containing materials, and therefore a more substantial substitution of petroleum-derived fuels by biofuels in the future

References Alterthum, F. & Ingram, L. O. (1989). Efficient ethanol production from glucose, lactose, and xylose by recombinant Escherichia coli. Appl Environ Microbiol 55, 1943–1948.

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Alvarez, H. M. & Steinbu¨ chel, A. (2002). Triacylglycerols in prokaryotic microorganisms. Appl Microbiol Biotechnol 60, 367–376 Dien, B. S., Cotta, M. A. & Jeffries, T. W. (2003). Bacteria engineered for fuel ethanol production: current status. Appl Microbiol Biotechnol, 63, 258–266 Farrell, A. E., Plevin, R. J., Turner, B. T., Jones, A. D., O’Hare, M. &Kammen, D. M. (2006). Ethanol can contribute to energy and environmental goals. Science 113, 506–508 Goodlove, P. E., Cunningham, P. R., Parker, J. & Clark, D. P. (1989).Cloning and sequence analysis of the fermentative alcoholdehydrogenase-encoding gene of Escherichia coli. Gene 85,209–214 Ingram, L. O., Conway, T., Clark, D. P., Sewell, G. W. & Preston, J. F.(1987). Genetic engineering of ethanol production in Escherichia coli.. Appl Environ Microbiol 53, 2420– 2425. Kalscheuer, R. & Steinbu¨ chel, A. (2005). Thio wax ester biosynthesis utilizing the unspecific bifunctional wax ester synthase/acyl-CoA : diacylglycerol acyltransferase of Acinetobacter sp. Strain ADP1. Appl Environ Microbiol 71, 790–796.

Oliver R.Inderwildi,David A.King (2009).”Quo Vadis Biofuels”. Energy and Environmental Sciences 2: 343 Sto¨ veken, T., Kalscheuer, R., Malkus, U., Reichelt, R. & Steinbu¨ chel, A. (2005). The wax ester synthase/acyl coenzyme A : diacylglycerol acyltransferase from Acinetobacter sp. strain ADP1:characterization of a novel type of acyltransferase. J Bacteriol 187, 1369–1376 Teather, R. M. and Wood, P. J. (1982), Use of Congo red-polysaccharide interactions in enumeration and characterization of cellulolytic bacteria from the bovine rumen. Appl. Environ. Microbiol. 43, 777-780 Uthoff, S., Sto¨ veken, T., Weber, N., Vosmann, K., Klein, E., Kessler, D., Herth, W. & Knappe, J. (1992). Ultrastructure and pyruvateformate-lyase radical quenching property of the multienzymic AdhE protein of Escherichia coli. J Biol Chem 267, 18073–18079 Vaneechoutte, M., Young, D. M., Ornston, L. N., De Baere, T., Nemec, A., van der Reijden, T., Carr, E., Tjernberg, I. & Dijkshoorn, L.(2006). Naturally transformable Acinetobacter sp. strain ADP1 belongsto the newly described species Acinetobacter baylyi. Appl Environ Microbiol 72, 932–936. Zldivar, J., Nielsen, J. & Olsson, L. (2001). Fuel ethanol production from lignocellulose: a challenge for metabolic engineering and process integration. Appl Microbiol Biotechnol 56, 17–34.


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ALGAE FUEL – TOWARDS A SUSTAINABLE ENVIRONMENT Prof. Amita Tayal Applied Sciences LIMAT, Faridabad

Dipti Mohan Lecturer, AEI Deptt MRCE, Faridabad

I. INTRODUCTION Energy , being the lifeline of global economy, and its ever increasing demand has led to the depletion of petroleum sourced fuels. Their continuous use and combustion has lead to increased energy related emissions of green house gases (GHG) i.e. CO2, SO2 & (NOx) Nitrogen Oxides. The future for ecological energy generation will reside in multi-faceted approach that includes nuclear, solar, hydrogen, fossil fuels and biofuels. Biofuels can be broadly classified as solid, liquid or gas fuel consisting of ,or derived from biomass. The first generation biofuels are derived from food crops such as sugarcane , sugar beet, maize, sorghum , wheat etc. Burning fuels derived from existing biomass has an environmental impact similar to combustion of fossil fuel in terms of carbon balance i.e. conversion of fixed carbon to CO2.Inefficiency and sustainability have become a major concern for these biofuels. Their large scale production consume vast swaths of farmlands, drive up food prices and results in less reduction in GHG emissions. In contrast, the second generation biofuels, are derived from non-food feedstock. They are extracted from microalgae and other microbial sources. They are extracted from microalgae and other microbial sources, rice straws and bio ethers and are seemingly a better option regarding food and energy security and environmental concerns. Microalgae may be defined as all unicellular or simple multicellular photosynthetic microorganisms be they prokaryotes(cyanobacteria) or eukaryotes. They have high growth rates and photosynthetic efficiencies due to simple structures. Infact, biomass doubling time for microalgae during exponential growth can be short as 3.5 h. Biodiesel production using microalgal farming offers the following advantages: 1. The high growth rate of microalgae makes it possible to satisfy the massive demand on biofuels using limited land resources without causing potential biomass deficit. 2. Microalgal cultivation consume less water and can also be carried out with sea water using marine microalgal species as producers. 3. The tolerance of microalgae to high CO2 content in gas stream allow high efficiency Co2 mitigation. The ability of algae to fix CO2has been proposed as a method of removing CO2from flue gases from power plants and thus reduce the emissions of GHG. 4. Nitrous Oxide release could be minimized when microalgae are used for biofuel production. 5. Microalgal farming could potentially be more cost effective than conventional farming. Limitations for production of micro algal biofuel production are: 1. Low biomass concentration in microalgal culture due to limit of light penetration along with small size of algal cells. 2. Large water content of harvested algal biomass require drying making it an energy consuming process. 3. High cost and intensive care and intensive care required by microalgal farming impedes the commercial implementation of microalgal biofuel.

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II. BIOFUELS FROM MICROALGAE The commercial development of algae fuel has been discouraged because of high production costs and limitations. Research developments in last 15 years illustrate the commercial potential of microalgae to shift from agriculture, fine chemicals and health to fuel production.

A. BIODIESEL Biodiesel is produced by a mono alcoholic trans-esterification, in which triglycerides react with mono-alcohal with the catalysis of alkali, acids or enzymes. It has the combustion properties similar to that of diesel and has been produced commercially to fuel vehicles. Significant technical advances have been achieved to optimize trans-estrification process.

B. BIO-OIL AND BIO_SYNGAS When the biomass is processed under high temperature in the absence of oxygen, products are produced in 3 phases: the vapor phase, liquid phase and the solid phase. The liquid phase is a complex mixture called biofuel. The composition of bio-oil vary significantly with the types of feedstock and processing conditions. Several technologies such as entrained flow reactor, circulating fluid bed gasifier and vaccum pyrolysis are there for biomass conversion. These technologies are classified into 2 categories: 1. Pyrolysis , the primary product of which is pyrolytic liquids(bio-oils) 2. Gasification with ‘syngas’ as primary product. Recent studies have shown that microalgae bio-oils are of high quality than bio-oil from wood.

C. BIO HYDROGEN Hydrogen is an important fuel with wide application in fuel cells, liquefaction of coal and upgradation of heavy oils(e.g. bitumen).Hydrogen can be produced biologically by a variety of means including photolysis of water catalyzed by special microalgal species.

III. INTEGRATED APPROACH TO BIOFUEL PRODUCTION USING MICROALGAE AS WELL AS POLLUTION CONTROL A. MICROALGAL FARMING AND CO2 MITIGATION One of the major advantages of microalgae lies in the capability of microalgal species to tolerate high CO2 content in feeding airstreams, allowing efficient capturing of CO2 from high CO2 streams such as flue gases and flaring gases(CO2 content 5 -15 %). In comparison to terrestrial plants, which typically absorb CO2 from atmosphere containing 0.03-0.06% CO2, benefit of microalgae is evident in terms of CO2 mitigation. It was reported that using a outdoor cultivation of Chlorella species in a 55m2 culture area photobioreactor ,flue gas containing 6-8% by volume of CO2 , 10-50% CO2 mitigation(flue gas decarbonization)was achievable and the residual NO2 and NO in the flue gas was not found to affect the algal growth. Depending on the microalgal species and condition used in the facilities, algal biomass could further be processed for biodiesel, bio-oil and bio-syngas production.


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B. MICROALGAL FARMING USING WASTEWATER Using waste water for algal growth would certainly allow conservation of freshwater, a precious resource specially for dry or populous countries. The major concern is contamination which can be managed by using appropriate pretreatment technologies to remove sediment and sterilize the waste water. Extensive work s have been carried out for waste water treatment using microalgal ie removal of nitrogen and phosphorous from effluents. This is done by allowing the consumption of nitrogen and phosphorus by microalgae in controlled manner rather than deteriorating the environment. Levels of several contaminant such as heavy metals have also been reduced by the cultivation of microalgae.

C. MICROALGAL FARMING USING MARINE MICROALGAE Freshwater is another resource that can be used for biofuel production. Marine microalgae can be employed for CO2 mitigation and biofuel production. Several cultivation techniques have been developed by researchers for commercial microalgal production of biofuels. Microalgae arte most commonly grown in open ponds and photobioreactors.the open pond cultures are economically more favourable but raise the issue of land use cost, water availability and appropriate climatic conditions. Moreover, there is a problem of contamination by fungi, bacteria and protozoa & competition by other microalgae Photobioreactors offers a closed culture environment, controlled temperature with enhanced CO2 fixation that is bubbled through cultured medium and is relatively safe from invading microorganisms. Because of infrastructure costs, this technology is relatively expensive. Many different designs of photobioreactors have been developed but a tubular photobioreactor seems to be most satisfactory for producing algal biomass on scale needed for biofuel production.

D. SELECTION OF COST EFFECTIVE TECHNIQUES FOR BIOMASS HARVESTING AND DRYING Due to low biomass concentration obtained in microalgal cultivation systems due to limit of light penetration (typical in range 1-5 g/L) and small size of microalgal cells(range 2-20 µm in diameter), costs and energy consumption for biomass harvesting are causing significant concern. Different technologies including chemical flocculation, biological flocculation , filtration and ultrasonic aggregation are being used for microalgal biomass harvesting. Chemical and biological flocculation require low operating costs but have long processing time and have the risk of bioreactive product decomposition. On the other hand, filtration, centrifuge and ultrasonic flocculation are more efficient but costly. The selection of appropriate harvesting technology depends upon the value of target products, biomass concentration and the size of microalgal cells. Biomass drying is also done before lipid/byproduct extraction or thermochemical processing. Sun drying is cheapest drying method employed but takes long drying time, requires large drying surface and risks the loss of some bioreactive products. Low pressure shelf drying is another low cost drying technology but of less efficiency. More efficient but costly technologies that can be used are drum drying, spray drying, fluidized bed drying, freeze drying and refractance window dehydration technology. To maximize the net output of the fuels, balance between drying efficiency and cost effectiveness has to be maintained.

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E. DIRECT LIQUEFACTION OF ALGAE FOR BIODIESEL PRODUCTION Relatively high water content and inferior heat content makes microalgal biomass difficult to be used for heat and power generation. Thus, necessitating pretreatments to reduce water content and increase the energy density, resulting in increase in energy costs. Direct hydrothermal liquefaction in sub-critical water conditions can be used to convert wet biomass material to liquid fuel. This technology recreates natural geographic processes thought to be involved in the formation of fossil fuel but in time scale of hours or even minutes. It essentially utilizes the high activity of water in sub-critical conditions in order to decompose the biomass material to shorter and smaller molecular materials with high energy density or more valuable chemicals. In addition, integrated utilization of high temperature and pressure conditions in the process of hydrothermal liquefaction of wet biomass would improve significantly improve the overall thermal efficiency of the process. Suitable systems for recreation of such system are an internal heat exchanger, or combined heat and power (CHP) plant. Different conversion techniques have been compared i.e. supercritical CO2 , organic solvent extraction, pyrolysis and hydrothermal technology for production of microalgal biodiesel. The hydrothermal liquefaction technique has found to be more effective for extraction of microalgal biodiesel than using supercritical carbon dioxide. Due to limited information level in hydrothermal liquefaction of algae, more research is needed in this area.

IV.

CONCLUSION

Biofuels produced from renewable energy biomass are sustainable energy resource with greatest potential for CO2 neutral production. The first generation biofuels produced from corn, sugarcane, soya etc perform poorly with respect to environmental context. Second generation biofuels can overcome energy and environmental needs by integrating technologies. A sustainable and profitable biodiesel production from microalgae is possible. Microalgae are a diverse group of photosynthetic micro organisms that can rapidly due to their simple structure which can be utilized for the production of biodiesel, bio oil, bio-syngas and biohydrogen. To overcome energy and environmental concerns, intergrated approach has to be adopted. Microalgal farming at thermal power stations can sequester CO2 ,waste water treatment and emission control, integration of an internal heat exchanger network and utilization of high temperature and pressure for power generation. It can be carried out with seawater as medium, provided marine microalgal species are adopted. Combining microalgal farming along and production of biofuels is expected to enhance the overall effectiveness of biofuel from microalgal approach. Direct hydrothermal liquefication of wet algal biomass is energy efficient technique for producing biodiesel from microalgae.However, more research is needed in this area. Technological advances, including photobioreactor design, microalgal biomass harvesting and drying etc may enhance the cost effectiveness and therefore , making commercial implementation cost-effective.

V. 1.

REFERENCES

Li Yanqun, Horsman Mark , Dubois-Calero Nathalie. Biofuels from Microalgae. Biotechnology Prog 2008,24, 815-820. 2. Patil Vishwanath, Tran Khanh-Quang, Ragnar Hans. Towards Sustainable Production of Biofuels from Microalgae. Published online 2008 July 9. doi: 10.3390/ijms9071188.


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3. Richmond A. Microalgal biotechnology at the turn of the millennium: a personal view. J Appl Phycol. 2000;12:441–451. 4 Huntley ME, Redalje DG. CO2 mitigation and renewable oil from photosynthetic microbes: a new appraisal. Mitigation Adapt Strat GlobalChange. 2007;12:573–608. 5 Crutzen PJ, Mosier AR, Smith KA, Winiwarter W. N2O release from agro-biofuel production negates global warming reduction by replacing fossil fuels. Atmos Chem Phys Discuss. 2007;7:11191–11205. 6 Nakamura DN. Journally speaking: the mass appeal of biomass. Oil GasJ. 2006;104:15. 7. Demirbas A. Oily products from mosses and algae via pyrolysis. Energy Sources A . 2006;28:933–940. 8. Barkley WCW, Lewin RA, Cheng L. In: Sadler T, editor. Development of Microalgal Systems for the Production of Liquid Fuels. Villeneuve d’Ascq, France, Elsevier Applied Science, 1987. 9. De la Noue J, De Pauw N. The potential of microalgal biotechnology: a review of production and uses of microalgae. Biotechnol Adv. 1988;6:725–770. 10 Chisti Y. Biodiesel from microalgae. Biotechnol Adv. 2007;25:294–306. 11 Ji-lu Z. Bio-oil from fast pyrolysis of rice husk: yields and related properties and improvement of the pyrolysis system. J Anal Appl Pyrolysis. 2007;80:30–35. 12 Meier D, Faix O. State of the art of applied fast pyrolysis of lignocellulosic materials-A review. Bioresour Technol. 1999;68:71–77. 13. Pakdel H, Roy C. Hydrocarbon content of liquid products and tar from pyrolysis and gasification of wood. Energy Fuels. 1991;5:427–436. 14. Demirbas A. Biomass resource facilities and biomass conversion processing for fuels and chemicals. Energy Convers Manage. 2001;42:1357–1378. 15. Patil V, Reitan KI, Knudsen G, Mortensen L, Kallqvist T, Olsen E, Vogt G, Gislerød HR. Microalgae as Source of Polyunsaturated Fatty Acids for Aquaculture. Curr Topics Plant Biol. 2005;6:57–65. 16. Matthijs HCP, Balke H, Van Hes UM, Kroon BMA, Mur LR, Binot RA. Application of Light- emitting Diodes in Bioreactors: Flashing Light Effects and Energy Economy in Algal Culture (Chlorella pyrenoidosa). Biotechnol Bioeng. 1996;50:98–107. [PubMed] 17 Tredici M. In: Encyclopedia of Bioprocess Technology Fermentation Biocatalysis and Bioseparation. Flickinger MC, Drew SW, editors. Volume 1. Wiley; New York, USA: 1999. p. 395 18. Bohlmann JT, Lorth CM, Drews A, Buchholz R. Microwave High Pressure Thermochemical Conversion of Sewage Sludge as an Alternative to Incineration. Chem Eng Technol. 1999;22:404–409. 19. Feng W, van der Kooi HJ, de Swaan Arons J. Biomass Conversions in Subcritical and Supercritical Water: Driving Force, Phase Equilibria, and Thermodynamic Analysis. Chem Eng Process. 2004;43:1459–1467. 20. inowa T, Yokoyama S-Y, Kishimoto M, Okakura T. Oil Production from Algal Cells of Dunaliella tertiolecta by Direct Thermochemical Liquefaction. Fuel. 1995;74:1735–1738. 21. Aresta M, Dibenedetto A, Barberio G. Utilization of macro-algae for enhanced CO2 fixationand biofuels production: Development of a computing software for an LCA study. Fuel Process Technol. 2005a;86:1679–1693. 22. Aresta M, Dibenedetto A, Carone M, Colonna T, Fragale C. Production of Biodiesel from Macroalgae by Supercritical CO2 Extraction and Thermochemical Liquefaction. Environ Chemistry Lett. 2005b;3:136–139. 23. Scharlemann JPW, Laurance WF. How Green Are Biofuels? Science. 2008;319:43–44. 24. Zah R, Böni H, Gauch M, Hischier R, Lehmann M, Wäger P. Life Cycle Assessment of Energy Products: Environmental Assessment of Biofuels. Empa; St. Gallen, Switzerland: 2007.

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RENEWABLE ENERGY AND ENERGY CONSERVATION TECHNOLOGIES AUTHORS: i)Ms. Huma Anwar Asstt. Director IPM, Ghaziabad Mobile: 09818230520 E-Mail: [email protected] ii) Ms Monica Bansal Lecturer IPM, Ghaziabad Mobile: 09968067492 E-Mail: [email protected] ABSTRACT: Renewable energy is energy generated from natural resources—such as sunlight, wind, rain, tides and geothermal heat—which are renewable (naturally replenished). In 2006, about 18% of global final energy consumption came from renewables, with 13% coming from traditional biomass, such as wood-burning. Hydroelectricity was the next largest renewable source, providing 3% of global energy consumption and 15% of global electricity generation. Wind power is growing at the rate of 30 percent annually, with a worldwide installed capacity of 121,000 megawatts (MW) in 2008, and is widely used in European countries and the United States. The annual manufacturing output of the photovoltaic industry reached 6,900 MW in 2008, and photovoltaic (PV) power stations are popular in Germany and Spain. Solar thermal power stations operate in the USA and Spain, and the largest of these is the 354 MW SEGS power plant in the Mojave Desert. The world's largest geothermal power installation is The Geysers in California, with a rated capacity of 750 MW. Brazil has one of the largest renewable energy programs in the world, involving production of ethanol fuel from sugar cane, and ethanol now provides 18 percent of the country's automotive fuel. Ethanol fuel is also widely available in the USA. While most renewable energy projects and production is large-scale, renewable technologies are also suited to small off-grid applications, sometimes in rural and remote areas, where energy is often crucial in human development. Kenya has the world's highest household solar ownership rate with roughly 30,000 small (20–100 watt) solar power systems sold per year. Some renewable energy technologies are criticized for being intermittent or unsightly, yet the renewable energy market continues to grow. Climate change concerns coupled with high oil prices, peak oil and


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increasing government support are driving increasing renewable energy legislation, incentives and commercialization. New government spending, regulation, and policies should help the industry weather the 2009 economic crisis better than many other sectors. Keywords: Renewable Energy, Wind Power, Solar Thermal Power, Hydropower.

Introduction: Because of the limited amount of nonrenewable energy sources on Earth, it is important to conserve our current supply or to use renewable sources so that our natural resources will be available for future generations. Energy conservation is also important because consumption of nonrenewable sources impacts the environment. Specifically, our use of fossil fuels contributes to air and water pollution. For example, carbon dioxide is produced when oil, coal, and gas combust in power stations, heating systems, and car engines. Carbon dioxide in the atmosphere acts as a transparent blanket that contributes to the global warming of the earth, or "greenhouse effect." It is possible that this warming trend could significantly alter our weather. Possible impacts include a threat to human health, environmental impacts such as rising sea levels that can damage coastal areas, and major changes in vegetation growth patterns that could cause some plant and animal species to become extinct. Sulfur dioxide is also emitted into the air when coal is burned. The sulfur dioxide reacts with water and oxygen in the clouds to form precipitation known as "acid rain." Acid rain can kill fish and trees and damage limestone buildings and statues. We can help solve these global problems. Main Forms/Sources of Renewable Energy Renewable energy effectively utilizes natural resources such as sunlight, wind, tides and geothermal heat, which are naturally replenished. Renewable energy technologies range from solar power, wind power, and hydroelectricity to biomass and biofuels for transportation. A non-renewable resource is a natural resource that cannot be re-made, re-grown or regenerated on a scale comparative to its consumption. It exists in a fixed amount that is being renewed or is used up faster than it can be made by nature. Fossil fuels (such as coal, petroleum and natural gas) and nuclear power are non-renewable resources, as they do not naturally re-form at a rate that makes the way we use them sustainable and consumer materials to produce electricity.

The majority of renewable energy technologies are powered by the sun. The Earth-Atmosphere system is in equilibrium such that heat radiation into space is equal to incoming solar radiation, the resulting level of energy within the Earth-Atmosphere system can roughly be described as the Earth's "climate." The hydrosphere (water) absorbs a major fraction of the incoming radiation. Most radiation is absorbed at low latitudes around the equator, but this energy is dissipated around the globe in the form of winds and ocean currents. Wave motion may play a role in the process of transferring mechanical energy between the atmosphere and the ocean through wind

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stress. Solar energy is also responsible for the distribution of precipitation which is tapped by hydroelectric projects, and for the growth of plants used to create biofuels. Each of these sources has unique characteristics which influence how and where they are used. 1.Wind Power Airflows can be used to run wind turbines. Modern wind turbines range from around 600 kW to 5 MW of rated power, although turbines with rated output of 1.5–3 MW have become the most common for commercial use; the power output of a turbine is a function of the cube of the wind speed, so as wind speed increases, power output increases dramatically. Areas where winds are stronger and more constant, such as offshore and high altitude sites, are preferred locations for wind farms. Since wind speed is not constant, a wind farm's annual energy production is never as much as the sum of the generator nameplate ratings multiplied by the total hours in a year. The ratio of actual productivity in a year to this theoretical maximum is called the capacity factor. Typical capacity factors are 20-40%, with values at the upper end of the range in particularly favorable sites. For example, a 1 MW turbine with a capacity factor of 35% will only produce an average of 0.35 MW. Over a year, output would be .35x24x365 = 3,066 MWh instead of 24x365 = 8,760 MWh. Online data is available for some locations and the capacity factor can be calculated from the yearly output. Globally, the long-term technical potential of wind energy is believed to be five times total current global energy production, or 40 times current electricity demand. This could require large amounts of land to be used for wind turbines, particularly in areas of higher wind resources. Offshore resources experience mean wind speeds of ~90% greater than that of land, so offshore resources could contribute substantially more energy. This number could also increase with higher altitude ground-based or airborne wind turbines. Wind power is renewable and produces no greenhouse gases during operation, such as carbon dioxide and methane. 2.Water Power Energy in water (in the form of kinetic energy, temperature differences or salinity gradients) can be harnessed and used. Since water is about 800 times denser than air, even a slow flowing stream of water, or moderate sea swell, can yield considerable amounts of energy.

There are many forms of water energy:


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a. Hydroelectric energy is a term usually reserved for large-scale hydroelectric dams. Examples are the Grand Coulee Dam in Washington State and the Akosombo Dam in Ghana. b. Micro hydro systems are hydroelectric power installations that typically produce up to 100 kW of power. They are often used in water rich areas as a Remote Area Power Supply (RAPS). There are many of these installations around the world, including several delivering around 50 kW in the Solomon Islands. c. Damless hydro systems derive kinetic energy from rivers and oceans without using a dam. d. Ocean energy describes all the technologies to harness energy from the ocean and the sea: e. Marine current power. Similar to tidal stream power, uses the kinetic energy of marine currents f.

Ocean thermal energy conversion (OTEC) uses the temperature difference between the warmer surface of the ocean and the colder lower recesses. To this end, it employs a cyclic heat engine. OTEC has not been field-tested on a large scale.

g. Tidal power captures energy from the tides. Two different principles for generating energy from the tides are used at the moment: h. Tidal motion in the vertical direction — Tides come in, raise water levels in a basin, and tides roll out. Around low tide, the water in the basin is discharged through a turbine, exploiting the stored potential energy. i.

Tidal motion in the horizontal direction — Or tidal stream power. Using tidal stream generators, like wind turbines but then in a tidal stream. Due to the high density of water, about eight-hundred times the density of air, tidal currents can have a lot of kinetic energy. Several commercial prototypes have been built, and more are in development.

j.

Wave power uses the energy in waves. Wave power machines usually take the form of floating or neutrally buoyant structures which move relative to one another or to a fixed point. Wave power has now reached commercialization.

k. Osmotic power or salinity gradient power, is the energy retrieved from the difference in the salt concentration between seawater and river water. Reverse electrodialysis (PRO) is in the research and testing phase. l.

Vortex power is generated by placing obstacles in rivers in order to cause the formation of vortices which can then be tapped for energy.

m. Deep lake water cooling, although not technically an energy generation method, can save a lot of energy in summer. It uses submerged pipes as a heat sink for climate control systems. Lakebottom water is a year-round local constant of about 4 °C. 3.Solar Energy In this context, "solar energy" refers to energy that is collected from sunlight. Solar energy can be applied in many ways, including to: a. Generate electricity using photovoltaic solar cells.

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b. c. d. e. f. g. h. i.


Generate electricity using concentrated solar power. Generate electricity by heating trapped air which rotates turbines in a Solar updraft tower. Generate hydrogen using photoelectrochemical cells. Heat and cool air through use of solar chimneys. Heat buildings, directly, through passive solar building design. Heat foodstuffs, through solar ovens. Heat water or air for domestic hot water and space heating needs using solar-thermal panels. Solar air conditioning

4.Wastewater Power can also be obtained from sewage water. The technique used herefore are Microbial fuel cells. Also using the same microbial fuel cells, instead of from wastewater, energy may also be obtained directly from (certain) aquatic plants. These include reed sweetgrass, cordgrass, rice, tomatoes, lupines, algae 5.Biofuel Plants use photosynthesis to grow and produce biomass. Also known as biomatter, biomass can be used directly as fuel or to produce biofuels. Agriculturally produced biomass fuels, such as biodiesel, ethanol and bagasse (often a by-product of sugar cane cultivation) can be burned in internal combustion engines or boilers. Typically biofuel is burned to release its stored chemical energy. Research into more efficient methods of converting biofuels and other fuels into electricity utilizing fuel cells is an area of very active work. 6.Liquid Biofuel Liquid biofuel is usually either a bioalcohol such as ethanol fuel or an oil such as biodiesel or straight vegetable oil. Biodiesel can be used in modern diesel vehicles with little or no modification to the engine. It can be made from waste and virgin vegetable and animal oils and fats (lipids). Virgin vegetable oils can be used in modified diesel engines. In fact the diesel engine was originally designed to run on vegetable oil rather than fossil fuel. A major benefit of biodiesel use is the reduction in net CO2 emissions, since all the carbon emitted was recently captured during the growing phase of the biomass. The use of biodiesel also reduces emission of carbon monoxide and other pollutants by 20 to 40%. In some areas corn, cornstalks, sugarbeets, sugar cane, and switchgrasses are grown specifically to produce ethanol (also known as grain alcohol) a liquid which can be used in internal combustion engines and fuel cells. Ethanol is being phased into the current energy infrastructure. E85 is a fuel composed of 85% ethanol and 15% gasoline that is sold to consumers. Biobutanol is being developed as an alternative to bioethanol. There is growing international criticism of the production of biofuel crops in association


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with food crops with respect to issues such as food security, environmental impacts (deforestation) and energy balance. Another source of biofuel is sweet sorghum. It produces both food and fuel from the same crop. Some studies have shown that the crop is net energy positive i.e. it produces more energy than is consumed in its production and utilization. Sugar cane residue can be used as a biofuel 7.Solid Biomass Solid biomass is most commonly used directly as a combustible fuel, producing 10-20 MJ/kg of heat. Biomass can also be used to feed bacteria, which can transform it in another form of energy such as hydrogen, using a process called Fermentative hydrogen production. Its forms and sources include wood fuel, the biogenic portion of municipal solid waste, or the unused portion of field crops. Field crops may or may not be grown intentionally as an energy crop, and the remaining plant byproduct used as a fuel. Most types of biomass contain energy. Even cow manure still contains two-thirds of the original energy consumed by the cow. Energy harvesting via a bioreactor is a cost-effective solution to the waste disposal issues faced by the dairy farmer, and can produce enough biogas to run a farm. With current technology, it is not ideally suited for use as a transportation fuel. Most transportation vehicles require power sources with high power density, such as that provided by internal combustion engines. These engines generally require clean burning fuels, which are generally in liquid form, and to a lesser extent, compressed gaseous phase. Liquids are more portable because they can have a high energy density, and they can be pumped, which makes handling easier. Non-transportation applications can usually tolerate the low power-density of external combustion engines, that can run directly on less-expensive solid biomass fuel, for combined heat and power. One type of biomass is wood, which has been used for millennia. Two billion people currently cook every day, and heat their homes in the winter by burning biomass, which is a major contributor to man-made climate change global warming. The black soot that is being carried from Asia to polar ice caps is causing them to melt faster in the summer. In the 19th century, wood-fired steam engines were common, contributing significantly to industrial revolution unhealthy air pollution. Coal is a form of biomass that has been compressed over millennia to produce a non-renewable, highly-polluting fossil fuel. Wood and its byproducts can now be converted through processes such as gasification into biofuels such as woodgas, biogas, methanol or ethanol fuel; although further development may be required to make these methods affordable and practical. Sugar cane residue, wheat chaff, corn cobs and other plant matter can be, and are, burned quite successfully. The net carbon dioxide emissions that are added to the

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atmosphere by this process are only from the fossil fuel that was consumed to plant, fertilize, harvest and transport the biomass. Processes to harvest biomass from short-rotation trees like poplars and willows and perennial grasses such as switchgrass, phalaris, and miscanthus, require less frequent cultivation and less nitrogen than do typical annual crops. Pelletizing miscanthus and burning it to generate electricity is being studied and may be economically viable. 8.Biogas Biogas can easily be produced from current waste streams, such as paper production, sugar production, sewage, animal waste and so forth. These various waste streams have to be slurried together and allowed to naturally ferment, producing methane gas. This can be done by converting current sewage plants into biogas plants. When a biogas plant has extracted all the methane it can, the remains are sometimes more suitable as fertilizer than the original biomass. Alternatively biogas can be produced via advanced waste processing systems such as mechanical biological treatment. These systems recover the recyclable elements of household waste and process the biodegradable fraction in anaerobic digesters. Renewable natural gas is a biogas which has been upgraded to a quality similar to natural gas. By upgrading the quality to that of natural gas, it becomes possible to distribute the gas to the mass market via the existing gas grid. 9.Geothermal Energy Geothermal energy is energy obtained by tapping the heat of the earth itself, both from kilometers deep into the Earth's crust in some places of the globe or from some meters in geothermal heat pump in all the places of the planet . It is expensive to build a power station but operating costs are low resulting in low energy costs for suitable sites. Ultimately, this energy derives from heat in the Earth's core. Three types of power plants are used to generate power from geothermal energy: dry steam, flash, and binary. Dry steam plants take steam out of fractures in the ground and use it to directly drive a turbine that spins a generator. Flash plants take hot water, usually at temperatures over 200 °C, out of the ground, and allows it to boil as it rises to the surface then separates the steam phase in steam/water separators and then runs the steam through a turbine. In binary plants, the hot water flows through heat exchangers, boiling an organic fluid that spins the turbine. The condensed steam and remaining geothermal fluid from all three types of plants are injected back into the hot rock to pick up more heat.


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The geothermal energy from the core of the Earth is closer to the surface in some areas than in others. Where hot underground steam or water can be tapped and brought to the surface it may be used to generate electricity. Such geothermal power sources exist in certain geologically unstable parts of the world such as Chile, Iceland, New Zealand, United States, the Philippines and Italy. The two most prominent areas for this in the United States are in the Yellowstone basin and in northern California. Iceland produced 170 MW geothermal power and heated 86% of all houses in the year 2000 through geothermal energy. Some 8000 MW of capacity is operational in total. There is also the potential to generate geothermal energy from hot dry rocks. Holes at least 3 km deep are drilled into the earth. Some of these holes pump water into the earth, while other holes pump hot water out. The heat resource consists of hot underground radiogenic granite rocks, which heat up when there is enough sediment between the rock and the earths surface. Several companies in Australia are exploring this technology. Renewable Energy Commercialization Wind power is growing at the rate of 30 percent annually, with a worldwide installed capacity of over 100 GW, and is widely used in several European countries and the United States. The manufacturing output of the photovoltaics industry reached more than 2,000 MW in 2006, and photovoltaic (PV) power stations are particularly popular in Germany and Spain. Solar thermal power stations operate in the USA and Spain, and the largest of these is the 354 MW SEGS power plant in the Mojave Desert.. The world's largest geothermal power installation is The Geysers in California, with a rated capacity of 750 MW. Brazil has one of the largest renewable energy programs in the world, involving production of ethanol fuel from sugar cane, and ethanol now provides 18 percent of the country's automotive fuel. Ethanol fuel is also widely available in the USA. Growth of Renewable: From the end of 2004 to the end of 2008, solar photovoltaic (PV) capacity increased sixfold to more than 16 gigawatts (GW), wind power capacity increased 250 percent to 121 GW, and total power capacity from new renewables increased 75 percent to 280 GW. During the same period, solar heating capacity doubled to 145 gigawatts-thermal (GWth), while biodiesel production increased sixfold to 12 billion liters per year and ethanol production doubled to 67 billion liters per year.

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Selected renewable energy indicators

Source:Integrated Energy Policy ,Planning Commission ,2006 Developing Country Markets


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Renewable energy can be particularly suitable for developing countries. In rural and remote areas, transmission and distribution of energy generated from fossil fuels can be difficult and expensive. Producing renewable energy locally can offer a viable alternative. Renewable energy projects in many developing countries have demonstrated that renewable energy can directly contribute to poverty alleviation by providing the energy needed for creating businesses and employment. Renewable energy technologies can also make indirect contributions to alleviating poverty by providing energy for cooking, space heating, and lighting. Renewable energy can also contribute to education, by providing electricity to schools. Kenya is the world leader in the number of solar power systems installed per capita (but not the number of watts added). More than 30,000 very small solar panels, each producing 12 to 30 watts, are sold in Kenya annually. For an investment of as little as $100 for the panel and wiring, the PV system can be used to charge a car battery, which can then provide power to run a fluorescent lamp or a small television for a few hours a day. More Kenyans adopt solar power every year than make connections to the country’s electric grid. Potential Future Utilization Sustainable development and global warming groups propose a 100% Renewable Energy Source Supply, without fossil fuels and nuclear power. Scientists from the University of Kassel have suggested that Germany can power itself entirely by renewable energy. Constraints and Opportunities Critics suggest that some renewable energy applications may create pollution, be dangerous, take up large amounts of land, or be incapable of generating a large net amount of energy. Proponents advocate the use of "appropriate renewables", also known as soft energy technologies, as these have many advantages. Availability and Reliability There is no shortage of solar-derived energy on Earth. Indeed the storages and flows of energy on the planet are very large relative to human needs. • Annual photosynthesis by the vegetation in the United States is 50 billion GJ, equivalent to nearly 60% of the nation’s annual fossil fuel use. • The amount of solar energy intercepted by the Earth every minute is greater than the amount of energy the world uses in fossil fuels each year. • The energy in the winds that blow across the United States each year could produce more than 16 billion GJ of electricity—more than one and one-half times the electricity consumed in the United States in 2000. • Tropical oceans absorb 560 trillion gigajoules (GJ) of solar energy each year, equivalent to 1,600 times the world’s annual energy use. A criticism of some renewable sources is their variable nature. But renewable power sources can actually be integrated into the grid system quite well, as Amory Lovins explains:

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Variable but forecastable renewables (wind and solar cells) are very reliable when integrated with each other, existing supplies and demand. For example, three German states were more than 30 percent windpowered in 2007—and more than 100 percent in some months. Mostly renewable power generally needs less backup than utilities already bought to combat big coal and nuclear plants' intermittence. The challenge of variable power supply may be readily alleviated by grid energy storage. Available storage options include pumped-storage hydro systems, batteries, hydrogen fuel cells, thermal mass and compressed air. Initial investments in such energy storage systems may be high, although the costs can be recovered over the life of the system. Of all U.S. nuclear plants built, 21 percent were abandoned and 27 percent have failed at least once. Successful reactors must close for refueling every 17 months for 39 days. And when shut in response to grid failure, they can't quickly restart. This is simply not the case for wind farms, for example. Wave energy and some other renewables are continuously available. A wave energy scheme installed in Australia generates electricity with an 80% availability factor. How Long We Can Have Them? Though a source of renewable energy may last for billions of years, renewable energy infrastructure, like hydroelectric dams, will not last forever, and must be removed and replaced at some point. Events like the shifting of riverbeds, or changing weather patterns could potentially alter or even halt the function of hydroelectric dams; lowering the amount of time they are available to generate electricity. Some have claimed that geothermal being a renewable energy source depends on the rate of extraction being slow enough such that depletion does not occur. If depletion does occur, the temperature can regenerate if given a long period of non-use. The government of Iceland states: "It should be stressed that the geothermal resource is not strictly renewable in the same sense as the hydro resource." It estimates that Iceland's geothermal energy could provide 1700 MW for over 100 years, compared to the current production of 140 MW. Radioactive elements in the Earth's crust continuously decay, replenishing the heat. The International Energy Agency classifies geothermal power as renewable. India’s Energy Scenario: • • •

• •

Population: 1.1Billion 5th in primary energy consumption – 438 mtoe: commercial; 139 mtoe: traditional sources in 2001 72% rural population – Largely depending on traditional fuels – Likely to shift to commercial fuels with improved access & better lifestyles Low per capita commercial energy use ~35% Below Poverty Line ($1/day, 2000 PPP)

India’s Developmental Goals: a. Reduction of Poverty Ratio by 15% by 2012 b. Providing gainful and high quality employment at least to addition to the labour force over the five year plan period.


c. d. e. f. g. h. i.

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Reduction in gender gaps in literacy and wage rates by at least 50% by 2009 Reduction in the decadal rate of population growth between 2001 and 2011 to 16% Increase in literacy rates to 75% Reduction of IMR (Infant Mortality Rate)to 28 per 1000 live births by 2012 Reduction of MMR (Mother Mortality Rate)to 1 per 1000 live births by 2012. Increase in forest and tree cover to 33% by 2012 All villages to have sustained access to potable drinking water within the Plan Period

Thus India needs more energy for its target goals. Conclusion: No matter where on Earth you live--whether the crowded streets of Delhi or New York City--your lifestyle has an impact on the global environment. Decisions, such as where you reside and how you get around, have repercussions on the planet well beyond your neighborhood. So its high time that Renewable resources should come into picture not only in specific areas but our way of living should be changed to incorporate such sources incessantly. References: 1.

Renewables Global Status Report 2009

2.

Global Status Report 2007 .

3.

Renewables Global Status Report: 2009 .

4.

Excerpts from MDP on “Green Business” at BIMTech,Greater Noida

5.

Energy Report of TERI,India

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IMPORTANCE OF P-SERIES FUELS FOR THE FAST DEVELOPING ECONOMIES Sadaf Zaidi Department of Chemical Engineering, Aligarh Muslim University, Aligarh-202002 (U.P.) India. e-mail: [email protected] M. A. Khan Department of Post harvest Engineering and Technology, Aligarh Muslim University, Aligarh202002 (U.P.) India. e-mail: [email protected]

ABSTRACT Fast developing countries like India and China have to think in right earnest about employing sustainable alternative fuels on a large scale for their ever expanding fleet of transportation vehicles, given the finite quantity of petroleum remaining in the earth. A number of alternative fuels are being assessed as possible replacements for gasoline and diesel the world over. Among these, the P- Series fuels seem to be an attractive and sustainable option to replace gasoline in IC engines. They can be generated from inexpensive municipal and agricultural wastes. They spew lesser emissions of hydrocarbons and carbon dioxide and also have a lower ozone forming potential than gasoline. However, the efforts to adopt this type of fuel in the developing countries are very feeble. The aim of this paper is to bring into focus the importance of this fuel and its relevance for developing economies.

INTRODUCTION The discovery of crude oil and other fossil fuels provided man with cheap fuel source that meaningfully helped to industrialize the world and improved the standards of living. Now, with the dwindling petroleum reserves and the near stagnation in petroleum production at about 85 million barrels per day combined with increased demand from emerging economies, and heightened environmental and political concerns about the use of fossil fuels, it has become imperative not only to develop economical and energy efficient processes for the sustainable production of existing fuels but also to diversify the energy portfolio by including a broad collection of fuels from renewable sources, recycling of waste streams and development of creative new technologies. Attention needs to be paid to alternative fuels which, unlike gasoline are sustainable products. Most of these can be created domestically with local raw materials and resources, thereby generating employment and reducing or altogether stopping costly petroleum imports. Fast developing economies like India and China have to take the right steps to employ alternative fuels for replacement of petroleum derived gasoline as engine fuels for flexible fuel vehicles (FFVs). One such alternative fuel is the P-series fuels. The P-series fuels have somehow been ignored, inspite of the fact that they have a high percentage of renewable components, possess good fuel properties and have substantial environmental benefits. This study makes an attempt to present the P-series fuels as a viable alternative or as a complement to gasoline for use in FFVs. Due to an acute scarcity of data on these fuels, this paper has had to rely to a fair degree on the Federal Register [1] to make a case for P-series fuels. While defining these fuels, their attractive attributes are discussed and it is shown that why they can be suitable for fast developing economies.

WHAT ARE P-SERIES FUELS? P-Series are a member of a family of renewable, non-petroleum, liquid fuels that can be substituted for gasoline. They were developed by Dr. Stephen Paul of Princeton University. P-series fuels were awarded Patent number 5,697,987 by the US Patent and Trademark Office on Dec 16, 1997 [1]. Pure Energy Corporation holds the exclusive world wide license to manufacture and distribute the P-series fuels. P-Series fuels were officially designated as an alternative fuel by the U.S. Department of Energy (DOE) in 1999 on a petition filed by Pure Energy Corporation to include them in the list of alternate fuels. P-series are inexpensive fuels generated from municipal and agricultural wastes. They are blends of ethanol, methyltetrahydrofuran (MeTHF), and pentanes plus, with butane added for blends that would be


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used in severe cold-weather conditions to meet cold-start requirements [1]. The percent volume composition of three grades of these fuels is given in Table.1. Table – 1 The percent-volume composition of three grades of P-series fuels Constituent Regular Premium Cold Weather Pentanes plus

32.5

27.5

16.0

MeTHF

32.5

17.5

26.0

Ethanol

35.0

55.0

47.0

n-Butane

0.0

0.0

11.0

Source: Ref [1]

WHY P-SERIES FUELS? P-series fuels join the list of alternatives to gasoline that includes ethanol E85 (85% ethanol/15% gasoline), methanol M85 (85 methanol/15% gasoline), natural gas, propane and electricity. P-series are designed to be used alone or freely mixed with gasoline in any proportion inside the gas tank of an FFV. A flexible fuel vehicle has one tank and is designed to operate on gasoline, alcohol (methanol or ethanol) or a mixture of gasoline and alcohol. Now, the basic capability for utilizing P-series fuels in FFVs has been incorporated. Evaluation of the full fuel cycle greenhouse emissions of P-series fuels by the Department of Energy (DOE) of the United States, confirmed the fact that over their entire production, distribution and end-use cycle, the P-series fuels will result in greenhouse gas emissions 45 to 50 percent below those of reformulated gasoline (RFG) provided both the ethanol and MeTHF are made from biomass. P-series fuels address the following problems: the need for non-petroleum energy sources, solid waste management, affordability and energy security. Using feedstock with a negative cost-that means waste that municipalities would otherwise pay to have hauled away-allows the fuel’s selling price to be about the same as mid-grade gasoline. It also gives urban areas control over a large portion of the generated trash stream without relying on burning, burying, or bequeathing it to other states. The feedstock is not incinerated, but chemically digested, so there is no combustion with the accompanying toxic air emissions. Use of the fuel will also create fewer greenhouse gases, lower tail pipe emissions, and reduce the environmental pollution from automobiles and dependence on foreign oil. In addition, P-series fuels could reduce fossil energy use by 49% to 57% and petroleum use by 80% relative to RFG. P-series fuels require no refining and contain essentially very small quantities of olefins, sulfur or aromatics, such as benzene. Pure Energy Corporation notes that each gallon of the P-series fuel directly displaces 0.88 gallons of RFG in vehicle use and also states that the energy required to produce a one gallon equivalent of the fuel is roughly 13,800 Btu less than that required to produce one gallon of RFG. P-series fuels are clear, colorless, 89-93% octane, liquid blends that can be formulated specifically for winter or summer for use in flexible FFVs. Refueling with P-series is as quick and familiar as with gasoline. However, they cannot be used straightaway in an exclusive gasoline engine. As with gasoline, low vapor pressure formulations are produced to prevent excessive evaporation during summer and high vapor pressure formulations are used for easy starting in the winter, as given in Tables I and 2. The Pseries fuels are particularly attractive for developing economies on account of their attractive fuel properties, substantially non-petroleum/renewable composition and environmental benefits [1].

Attractive Fuel Properties Table 2 gives a description of the relevant properties of P-series fuels and compares them with other gasoline type fuels. It can be seen that P-series fuels have high Anti-Knock Index values compared with UTG-96, RFG II and also COMS. Their calorific value is better than that of E-85 fuel. They have adequate RVP for ease of starting. Sulfur and benzene, the two sources of major concern, are in very small amounts. They have a high percentage of oxygen, which reduces the formation of carbon monoxide. The disadvantage of a low percentage of aromatics from calorific point of view is offset by other attributes of the fuel. What is most encouraging is the fact that the percentage of renewable components in P-series

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fuels is high. This means that countries like India and China with vast reservoirs of biomass resource stand to gain by adopting P-series to power their ever expanding fleet of transport vehicles. Table – 2 Comparison of the properties of P-series fuels with the other gasoline type fuels Fuel property (units) UTG-96 RFG II COMS E-85 P-series Anti-Knock Index(R+M/2) 91.6 91.7 89.6 96.0 90.2-93.8 Energy (Btu/gal) 114,500 111,800 115,200 83,500 ~104,000 RVP (psi) 9.2 8.4 7.4 6.9 7.2-7.8 Sulfur (ppm) 100 290 330 8 corn grain> lignocellulose. The feedstock costs are 53 and 28 % of ethanol production costs from sugarcane and lignocellulose. Lignocellulose has the lowest feedstock cost and research is underway to reduce the cost of cellulosic ethanol [6].

RELEVANCE OF P-SERIES FUELS FOR DEVELOPING ECONOMIES India and China are endowed with vast reservoirs of biomass resource, waiting to be tapped. Large amounts of non plantation biomass resources are available for modern energy applications in the Asian countries. The estimated sustainable non-plantation bioenergy potential in 2010 in China, India, Philippines, Sri Lanka and Thailand is about 8.90, 8.77, 0.97, 0.14 and 0.82 EJ, respectively. The potential is estimated to be about 17, 45, 34, 33, and 14% of the projected total energy consumption in 2010 respectively in these countries. Primary and secondary residues are the major non-plantation biomass


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energy sources accounting about 60, 75, 45, 46, and 75% of the total non plantation biomass energy sources in China, India, Philippines, Sri Lanka, and Thailand in 2010, respectively [13 ] The requirement for motor spirit in India is projected to be from a little over 7 million metric tonnes (MMT) in 2001-02 to 12.848 MMT in 2011-12 [3 ]. India produced roughly 880 thousand bbl/d of total oil in 2008, of which approximately 650 thousand bbl/d was crude oil, with the rest of production resulting from other liquids and refinery gain. India has over 3,600 operating oil wells. Although oil production in India has slightly trended upwards in recent years, it has failed to keep pace with demand and is expected by the Energy Information Administration, USA (EIA)[14] to decline slightly in 2009.India’s oil consumption has continued to be robust in recent years. In 2007, India consumed approximately 2.8million bbl/d, making it the fifth largest consumer of oil in the world. Demand grew to nearly 3million bbl/d in 2008.EIA anticipates consumption growth rates flattening in 2009 largely due to slowing economic growth rates and the recent global financial crisis. The combination of rising oil consumption and relatively flat production has left India increasingly dependent on imports to meet its petroleum demand. In 2006, India was the seventh largest net importer of oil in the world. With 2007 net imports of 1.8 million bbl/d, India is currently dependent on imports for 68 percent of its oil consumption. The EIA expects India to become the fourth largest net importer of oil in the world by 2025, behind the United States, China, and Japan [14]. China consumed an estimated 7.8 million barrels per day (bbl/d) of oil in 2008, making it the second-largest oil consumer in the world behind the United States. During that same year, China produced an estimated 4.0 million bbl/d of total oil liquids, of which 96 percent was crude oil. China’s net oil imports were approximately 3.9 million bbl/d in 2008, making it the third-largest net oil importer in the world behind the United States and Japan. EIA forecasts that China’s oil consumption will continue to grow during 2009 and 2010, with oil demand reaching 8.2 million bbl/d in 2010. This anticipated growth of over 390,000 bbl/d between 2008 and 2010 represents 31 percent of projected world oil demand growth in the non-OECD countries for the 2-year period according to the July 2009 Short-Term Energy Outlook. By contrast, China’s oil production is forecast to remain relatively flat at 4 million bbl/d in 2009. China had 16 billion barrels of proven oil reserves as of January 2009 [14]. If one looks at the position of the automobile industry in India and China, it becomes clear that this industry is growing rapidly and is little affected by the current recession. The number of vehicles produced and the number of owners is increasing at a very fast rate. Automobile sales in China may accelerate 28 percent from a year ago to reach 12 million vehicles this year and overtake the number of autos sold in the United States, according to a regulatory official. With more than 176.5 million motor vehicles in the country, a whopping 14 percent of Chinese nationals have obtained a driving licence, the Chinese Ministry of Public Security has revealed [15]. US-based consultancy Keystone-a subsidiary of LaSalle Consulting Associates-has forecast that India will become the world's third largest automobile market by 2030, behind just China and the US. An ageing population and increasing costs of ownership will see auto market shrinking in Japan, Korea and Europe while increasing per capita income will fuel the two Asian giants' growth, it says. Over the next quarter century, emerging markets will replace the mature markets of America, Europe and Japan as the primary driver of sales growth and will account for 69% of industry sales and 87% of vehicle registrations. Over the next 25 years, more motor vehicles will be sold than in the entire history of the industry, the report says. The projected size for China is 62 million and for US 23 million. The size of the Indian vehicle market is forecast to cross 20 million (assuming a consistent GDP growth rate of 6%) from the one million plus vehicles sold in 2004. This amounts to a compounded annual growth rate (CAGR) of over 12%. The next two countries in the pecking order would be Brazil and Japan, whose sales are projected to be in single digit millions. Currently, the top five motor vehicle markets are the US, Japan, China, Germany and the UK. In 2017, China is projected to become the world largest market for motor vehicle sales, surpassing the United States. Around the same time, India's auto market, too, is projected to surpass Japan. In terms of vehicle ownership per thousand population, developed countries would have vehicle ownership propensity of well over 600 vehicles per thousand. India and China, which are at believed to be at 8 and 14 respectively, will see substantial increases in their

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ownership rates. Within the next quarter century, China is projected to reach an ownership rate of close to 380 and India around 140 per thousand [16] This trend is going to result in an increase in the demand for fuels and with the limited production of petroleum based fuels it will become very necessary to explore some other alternative sources. It is here that P-series fuels with their high renewable content can act as an able complement or even replacement for non-renewable petroleum based fuels.

CONCLUSION The P-series fuels have a high renewable content; they can be used independently of gasoline and have substantial environmental benefits vis-à-vis gasoline. P-series fuels could reduce fossil energy use by 49% to 57% and petroleum use by 80% relative to RFG. They produce less carbon monoxide emissions, less hydrocarbon emissions, less carbon dioxide emissions and have a considerably less ozone forming potential than RFG. The feedstocks for the production of renewable components are cheaply available in abundance in countries like India and China. The processes for the production of ethanol and MeTHF can be easily built up in these countries on a large scale; thereby generating employment and a sustainable source of fuels. The fast depleting reserves of petroleum in the world, the high economic growth rate and the ever increasing fleet of automobiles in these countries, are all positive signs for the adoption and development of P-series fuels for use in FFVs.

REFERENCES 1. Federal Register, 1999. Alternative fuel transportation program; p-series fuels, Federal Register, Rules and Regulations Vol. 64, 94:26829. 2. Irshad, A. 2001. Engineered fuels for a cleaner environment: E-diesel and P-series alternative fuels. Paper presented at the 7th National Clean Cities Conference & Expo, Philadelphia, Pennsylvania, May 13-16, 2001. 3. Report of the Committee on Development of Biofuels. 2003. Planning Commission, Government of India, New Delhi. 4. Hoffman, J. 1998. Pure energy plans new fuel based on chemicals and NGLs. Chem. Market Rep., 253(3):13-18. 5. Science Daily. 1998. Chemical process provides new source for alternate fuels. [http://www.sciencedaily.com/release/1998/108103008400.htm]. 6. Huber, G.W., Iborra and Corma, A. 2006. Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering. Chem. Rev. 106: 4044-4098. 7. Alternative Fuel Data Center, 2000. P-series general information. Alternative fuels. [http://w.w.w.afdc.doe-gov/pse-general.html]. 8. OTI, 2000. Commercialization of the biofine technology for levulinic acid production from paper sludge. OTI (Office of Industrial Technologies), US Department of Energy. Forest Products, Product Fact Sheet, [http://w.w.w.oit..doe..gov./forest/biofine.htm]. 9. Fitzpatrick, S. W. 1990. Manufacture of furfural and levulinic acid by acid degradation of lignocellulosic. World Patent 8910362 to Biofine Incorporated. 10. Fitzpatrick, S. W. 1997. Production of levulinic acid by the hydrolysis of carbohydrate-containing materials. World Patent 9640609 to Biofine Incorporated. 11. Bozell, J. J., Moens, L., Elliott, D. C., Wang, Y., Neuenscwander, G. G., Fitzpatrick, S. W., Bilski, R. J., and Jamefeld, J. L. 2000. Production of levulinic acid and use as a platform chemical for derived products. Resources, Conservation and Recycling 28:227-239. 12. Wyman, C. 2004. In Encyclopedia of Energy, Vol.2; Cleveland, C. J., Ed; Elsevier, London. 13. Bhattacharya, S .C., Attalage, R. A., Leon, M.A., Amur, G.Q., Salam, A. P., Thanawat, C. 1999. Potential of biomass fuel conservation in selected Asian countries. Energy conservation & Management; 40:1141–62. 14. Short Term Energy Outlook, 2009. http://www.eia.doe.gov 15. China has 176.5 million motor vehicles, 188.8 million drivers as of July 2009. http://blog.taragana.com/n/china.


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16. The Financial Express.2005. India to be world's 3rd largest car market: A Study. http://www.expressindia.com/news/fullstory. Posted online: Thursday, December 01, 2005 at 1327 hours IST.

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BIOBUTANOL- A GREEN ALTERNATIVE TO BIOETHANOL Moina Athar* and M. Kamil Department of Petroleum Studies Z H College of Engg. & Technology AMU, Aligarh-202002. * [email protected]

ABSTRACT The present study deals with the experimental determination of various properties of gasoline and gasoline blended butanol. The percentages of butanol used in the gasoline were 2, 5, 7 and 10 respectively. For each blend different tests were carried out to give an idea about its suitability .It has been found that low blends of biobutanol with gasoline can be used without any engine modification.

INTRODUCTION Energy is the life blood of our modern society. The world’s energy system is still largely based on fossil fuels. Fossil fuels are depleting at a rapid rate and are harder to retrieve. The energy prices are sky rocketing and will not be available for many individuals or countries in future. Fossil fuels are also harmful for environment. Burning of fossil fuel leads to a increase of Co2 in the atmosphere. The above problems can be solved by renewable bio-energy source. World production of biofuels has experienced a phenomenal growth. The majority of the growth in bio-fuel has been in the production of bioethanol. Presently in India we are adding 5% ethanol in gasoline. Ethanol however has serious draw backs and limitations that can be addressed by ‘biobutanol’. The production of biobutanol is nearly identical to bioethanol. They both are produced by fermentation process. A number of studies [1-10] are reported in the literature on different aspects of production and uses of biofuels namely biobutanol.

WHY BIOBUTANOL? Biobutanol, an advanced bio fuel, offers a number of advantages and can help accelerate biofuel adoption in countries around the world. It provides greater option for sustainable renewable transportation fuels, reduces dependence on imported oil, lowers green house gas emissions, and expand markets for agricultural products world wide. Can be blended into standard grade gasoline or gasoline containing ethanol, is compatible with existing vehicle technology and has the potential to be incorporated into the existing fuel supply infrastructure. Can be easily added to conventional gasoline due to its low vapour pressure. Has an energy content and octane number closer to that of gasoline than ethanol so consumers face less of compromise on fuel economy-this is particularly important as the amount of biofuel in the fuel blend increases. Can be blended at higher concentrations than bioethanol for use in standard vehicle engines. Does not require automakers to compromise on performance to meet stringent environmental regulations. Is less susceptible to separation in the presence of water than ethanol/gasoline blends, and therefore allows it to use the industry’s existing distribution infrastructure without requiring modifications in blending facilities, storage tanks or retail station pumps. Is expected to be potentially suitable for transport in pipelines, unlike existing biofuels; as a result, biobutanol has the potential to be introduced into gasoline quickly and avoid the need for additional large scale supply infrastructure.


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Biobutanol is produced from the same agricultural feedstocks as ethanol (i.e. corn, wheat, sugar beet, cassava, sugarcane, biomass etc). Existing ethanol capacity can be cost-effectively retrofitted to biobutanol production (minor changes in fermentation and distillation). There is a vapour pressure co-blend synergy with biobutanol and gasoline containing ethanol, which facilitates ethanol blending. Will have process compatible with future biofuel feedstock such as lignocelluloses from fast-growing energy crops (e.g. grasses) or agricultural byproducts (e.g. corn stalks). Biobutanol’s low vapour pressure (lower than gasoline), means that vapour pressure specifications do not need to be compromised leading to higher VOC emissions (i.e. no requirement for a vapour pressure relaxation). Like other alcohols biobutanol is ultimately quite biodegrable, which limits its environmental impact in the event of a spill or leak. Biobutanol is good for farmers globally as it provides another marketing opportunity for key agricultural products, thus enhancing value to farmers. By facilitating / smoothing the introduction of biofuels into gasoline, either directly as biobutanol or indirectly through biobutanol’s synergy with ethanol, biobutanol will help expand the biofuels market as well as the markets for related agricultural products, enhancing value for farmer. Table-1 Comparison of Properties of Gasoline and Alcohol Fuels Properties Energy Density MJ/L Air-Fuel Ratio Specific Energy MJ/Kg air Heat of Vaporization MJ/Kg RON MON RVP psi @ 100 F Oxygen Wt% Specific Gravity @ 60 F Water Solubility % @ 25 C

Gasoline 32 12-15 2.9

Butanol 29.2 11.2 3.2

Ethanol 19.6 9 3

.36

.43

.92

91-99 81-89 4.5

96 78 .33

129 102 2

< 2.7

21.6

34.7

.720-.775 < .01

.814 9.1

.794 100

PRODUCTION OF BIOBUTANOL Production of industrial butanol and acetone via ABE (Acetone, Butanol, Ethanol) fermentation started in 1916 during the First World War. The Acetone, Butanol & Ethanol (ABE) fermentation is one of the oldest known industrial fermentations. It was ranked second only to ethanol fermentation by yeast in its scale of production, and is one of the largest biotechnological processes ever known. Since the 1950’s ABE fermentation declined continuously and almost all butanol is now produced via petrochemical routes. The production of butanol by fermentation declined mainly because the price of petrochemicals dropped below that of starch and sugar substrates such as corn and molasses. The labor intensive batch fermentation system’s overhead combined with the low yields of 1.3 gallons butanol and 0.75 for acetone per bushel corn and a low concentration of only 1 to 1.5 percent butanol before the microbes died was also a reason.

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In a typical ABE fermentation, butyric, propionic, lactic and acetic acids are first produced by C. acetobutylicum the culture pH drops and then undergoes a metabolic shift and butanol, acetone, isopropanol and ethanol are formed. Increasing butyric acid concentration to >2 g/L and decreasing the pH to > l, whereas one needs to include the flow mode associated with the inner scale for lower heights. For the inner scale mode, it is possible likewise to obtain analytical solution to the flow perturbations taking into account the correct similarity profile of the turbulent diffusivity K = u * k z. As the inner scale l satisfies l