Recent Advances in Environmental Management

Recent Advances in Environmental Management


Edited by

Ram Naresh Bharagava

CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2019 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed on acid-free paper International Standard Book Number-13: 978-0-8153-8314-7 (Hardback) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com

Contents Preface.......................................................................................................................ix Editor.........................................................................................................................xi Contributors............................................................................................................ xiii Chapter 1 Industrial Wastewaters: The Major Sources of Dye Contamination in the Environment, Ecotoxicological Effects, and Bioremediation Approaches...........................................................1 Roop Kishor, Ram Naresh Bharagava, and Gaurav Saxena Chapter 2 Groundwater Pollution by Emerging Industrial Pollutants and Its Remediation Techniques................................................................ 27 Pankaj Kumar Gupta, Shashi Ranjan, and Deepak Kumar Chapter 3 Textile Industry Wastewater: Environmental and Health Hazards and Treatment Approaches................................................... 47 Sujata Mani and Ram Naresh Bharagava Chapter 4 Environmental Pollution from Acid Mine Drainage and Its Mitigation Approaches........................................................................ 71 Bably Prasad Chapter 5 Nanotechnology: An Emerging Technology for Bioremediation of Environmental Pollutants.............................................................. 109 Fauzi Abdillah, Fitriana, Daniel Pramudita, Antonius Indarto, and Lienda Aliwarga Handojo Chapter 6 Applications of Nanomaterials in Subsurface Remediation Techniques: Challenges and Future Prospects.................................. 145 Shashi Ranjan and Pankaj Kumar Gupta Chapter 7 Microalgae: An Ecofriendly Tool for the Treatment of Industrial Wastewaters and Biofuel Production................................................. 167 Amit Kumar Singh and Abhay K. Pandey

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Chapter 8 Phycoremediation of Distillery Wastewater: Nutrient Uptake by Microalgae......................................................................................... 197 Sankaran Krishnamoorthy and Manickam Premalatha Chapter 9 Fungal Cell Immobilization for Treatment of Industrial Wastewaters: Application and Perspectives...................................... 215 Deepika Rajwar and JPN Rai Chapter 10 Mycoremediation: The Role of Fungi in Bioremediation of Environmental Pollutants.................................................................. 233 Amjad Ali, Fazli Wahid, Di Guo, and Zengqiang Zhang Chapter 11 Consequences of Heavy Metals Pollution in the Environment and Their Bioremediation Practices.................................................. 253 Abhishek Kumar and Bechan Sharma Chapter 12 Chromium Contamination in the Environment, Health Hazards, and Bioremediation Approaches....................................................... 281 Sandhya Mishra and Ram Naresh Bharagava Chapter 13 Plant–Microbe Symbiosis: A Synergistic Approach for HeavyMetal Bioremediation........................................................................ 299 Sanjeev Kumar, Mahesh Kumar, Ritu Singh, Dhananjay Kumar, Ravindra Prasad, Ankit, Anita Rani, and Narendra Kumar Chapter 14 Constructed Wetlands: An Emerging Phytotechnology for Treatment of Industrial Wastewaters................................................. 317 Aysenur Ugurlu, Ece Kendir, and Emine Cagla Cilingir Chapter 15 Petroleum Hydrocarbons: Environmental Contamination, Toxicity, and Bioremediation Approaches........................................ 351 Nilanjana Das, Sanjeeb Kumar Mandal, and A. Selvi Chapter 16 Bioremediation of Chlorinated and Aromatic Petrochemical Pollutants in Multiphase Media and Oily Sludge.............................. 373 Evans M. N. Chirwa, Stanford S. Makgato, Phumza V. Tikilili, and Tshilidzi B. Lutsinge

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Chapter 17 Microbes: Ecofriendly Tools for Bioremediation of PesticideContaminated Environments............................................................. 391 Arun S. Kharat, Satish G. Parte, and Nandkishor S. More Chapter 18 Biodegradation of Polycyclic Aromatic Hydrocarbons Using Fungi: New Prospects toward Cytochrome P450 Engineering......... 417 Ulises Conejo-Saucedo, Darío Rafael Olicón-Hernández, Haley Paula Stein, Jesús González-López, and Elisabet Aranda Chapter 19 Environmental Pollution and Threats from Improper Solid Waste Management........................................................................... 447 Digambar Chavan, Hiya Dhar, and Sunil Kumar Chapter 20 Biomedical Waste: Environmental Threats and Its Management.....465 Pushp Lata Sankhwar, Vineet Kumar Maurya, Devyani Mishra, S. N. Sankhwar, and Nandkishor S. More Chapter 21 Applications of Metagenomics Approaches in Bioremediation of Environmental Pollutants.............................................................. 483 Niti B. Jadeja, Shailendra Yadav, and Atya Kapley Chapter 22 Application of Hairy-Root Culture Technology in Phytoremediation for Environmental Cleanup: Past, Present, and Future Outlook........................................................................... 511 Reetika Singh and Bechan Sharma Index....................................................................................................................... 527

Preface Environmental pollution has become one of today’s most serious problems worldwide. Environmental safety and sustainability with rapid industrialization is also a major challenge. Environmental pollutants are organic and inorganic in nature and released into the environment through natural and anthropogenic activities. Organic pollutants mainly include dyes, pesticides, phenolics, chlorophenols, petroleum hydrocarbons, polychlorinated biphenyls (PCBs), polyaromatic hydrocarbons (PAHs), organometalic compounds, persistent organic pollutants (POPs), etc., whereas inorganic pollutants include a variety of toxic and non-biodegradable heavy metals such as chromium (Cr), cadmium (Cd), lead (Pb), arsenic (As), mercury (Hg), etc. Of the various sources, industrial discharges are considered as the major causes of environmental pollution. The untreated/partially treated wastewaters discharged from various industrial facilities contain potentially toxic and hazardous organic and inorganic pollutants, which cause the pollution of soil and aquatic resources, including groundwater, and have severe toxic effects in humans, animals, and plants. Governments around the globe are strictly advocating for the mitigation of environmental pollution. Hence, the removal/elimination of pollutants from the contaminated environment is of utmost importance for environmental safety and to promote the sustainable development of our society with low environmental impacts. Various approaches are being applied for the removal of toxic and hazardous pollutants from contaminated environments. Physico-chemical approaches are commonly used for the treatment and management of contaminated environments, but these approaches are environmentally destructive in nature due to generation of secondary pollutants, which is also a serious concern. An ecofriendly approach, such as bioremediation, can be a sustainable solution for the management of environments contaminated by a wide range of organic and inorganic pollutants. Bioremediation is an environmentally friendly and cost-effective technique that uses microbes such as bacteria, fungi, algae, etc. or green plants or their enzymes to degrade or detoxify environmental pollutants from contaminated environments. The ecofriendly removal of pollutants requires increasing our understanding of degradation pathways and regulatory networks to carbon flux for their degradation and detoxification, which is of utmost importance to environmental safety. Therefore, this book provides comprehensive and up-to-date knowledge on the recent advances in the management of contaminated environments using a range of new techniques including remediation of pollutants through nanoparticles (nano-remediation), microalgae (phycoremediation), fungi (mycoremediation), plant–microbe interaction, constructed wetlands, metagenomics approaches, and hairy-root culture technology. For this book, experts from colleges, universities, and research laboratories have contributed their valuable knowledge on the relevant topics from the perspective of their respective disciplines. All the chapters compiled in this book cover the different aspects of environmental problems and their remedies with up-to-date advancements in the field of biodegradation and bioremediation of pollutants including the use of nanoparticles, microalgae, fungi, various group of microbes, plant–microbe ix

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Preface

interaction, terrestrial/aquatic plants, constructed wetlands, metagenomics approaches, and hairy-root culture technology for environmental management. Therefore, this book will be of great value to researchers, environmentalists and scientists, microbiologists and biotechnologists, eco-toxicologists, waste-treatment engineers and managers, environmental-science managers, administrators and policy makers, industry persons and students at bachelor’s, master’s, and doctoral levels in relevant fields. I hope that the readers will not only find the updated information to be useful but also find the future direction for research in the field of environmental management. Ram Naresh Bharagava Babasaheb Bhimrao Ambedkar Central University Lucknow, Uttar Pradesh, India

Editor Dr. Ram Naresh Bharagava was born in 1977 and completed school education from government schools at Lakhimpur Kheri, Uttar Pradesh (U.P.), India. He received his BSc (1998) in zoology, botany, and chemistry from the University of Lucknow, Lucknow, U.P., India and a MSc (2004) in molecular biology and biotechnology from Govind Ballabh Pant University of Agriculture & Technology (GBPUAT), Pantnagar, Uttarakhand, India. He earned his PhD (2010) in microbiology jointly from Environmental Microbiology Division, CSIR-Indian Institute of Toxicology Research (CSIR-IITR), Lucknow, and Pt. Ravishankar Shukla University, Raipur, Chhattisgarh, India. He qualified twice (2002 & 2003) for a CSIR-Junior Research Fellowship (JRF) and Graduate Aptitude Test in Engineering (GATE) in 2003 and was a Junior and Senior Research Fellow (JRF/SRF) during his PhD. His major research work during his PhD was focused on the bacterial degradation and detoxification of recalcitrant melanoidin from distillery wastewater. He has authored one book entitled Bacterial Metabolism of Melanoidins and edited three books entitled Bioremediation of Industrial Pollutants, Environmental Pollutants and their Bioremediation Approaches, and Emerging and Ecofriendly Approaches for Waste Management. He has authored and coauthored a number of research/review papers and two book reviews in prestigious national and international journals published by Springer, Elsevier, and Taylor & Francis Group. He has also written many chapters for national and international edited books and has published many scientific articles and popular science articles in newspapers and national and international magazines. He has presented many papers relevant to his research areas in national and international conferences. He is also serving as a potential reviewer for various national and international journals in his respective areas of the research. He was awarded a postdoctoral appointment at CSIR-IITR, Lucknow, after which he joined (2011) Babasaheb Bhimrao Ambedkar (Central) University, Lucknow, UP, India, where he now works as assistant professor of microbiology and is actively engaged in teaching at the postgraduate and doctoral level. Dr. Bharagava also conducts research on various Government of India (GOI)sponsored projects in the area of environmental toxicology and bioremediation at the Laboratory for Bioremediation and Metagenomics Research (LBMR) under the Department of Environmental Microbiology (DEM). The University Grants Commission (UGC) and Department of Science and Technology (DST), India, have supported his research. He has been the advisor to forty postgraduate students and is currently the mentor of one project fellow and six doctoral students. His major areas of research are the toxicology, biodegradation, and bioremediation of environmental pollutants, metagenomics, and wastewater microbiology. He is a member of the Academy of Environmental Biology (AEB), Association of Microbiologists of India (AMI), and Biotech Research Society (BRSI), Indian Science Congress Association (ISCA), India. In his spare time, he enjoys roaming in peaceful environments and spends maximum time with his family. He lives in south Lucknow with his wife (Ranjana) and three children (Shweta, Abhay, and Shivani). He can be reached at [email protected], [email protected]. xi

Contributors Fauzi Abdillah Department of Chemical Engineering Institut Teknologi Bandung Kampus ITB Ganesha Bandung, Indonesia

Emine Cagla Cilingir Department of Environmental Engineering Hacettepe University Ankara, Turkey

Amjad Ali College of Natural Resources and Environment Northwest A & F University Yangling, Shaanxi, China

Ulises Conejo-Saucedo Department of Microbiology University of Granada Granada, Spain

Ankit Centre for Environmental Sciences Central University of Jharkhand Ranchi, Jharkhand, India Elisabet Aranda Department of Microbiology University of Granada Granada, Spain Ram Naresh Bharagava Department of Environmental Microbiology Babasaheb Bhimrao Ambedkar University Lucknow, Uttar Pradesh, India Digambar Chavan Solid and Hazardous Waste Management Division CSIR-National Environmental Engineering Research Institute Nehru Marg, Nagpur, India Evans M. N. Chirwa Department of Chemical Engineering University of Pretoria South Africa

Nilanjana Das School of Biosciences and Technology VIT University Vellore, Tamilnadu, India Hiya Dhar Solid and Hazardous Waste Management Division CSIR-National Environmental Engineering Research Institute Nehru Marg, Nagpur, India Fitriana Department of Engineering Physics Institut Teknologi Bandung Kampus ITB Ganesha Bandung, Indonesia Jesús González-López Department of Microbiology University of Granada Granada, Spain Di Guo College of Natural Resources and Environment Northwest A&F University Yangling, Shaanxi, China

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Pankaj Kumar Gupta Department of Hydrology Indian Institute of Technology Uttarakhand, India Lienda Aliwarga Handojo Department of Chemical Engineering Institut Teknologi Bandung Kampus ITB Ganesha Bandung, Indonesia Antonius Indarto Department of Chemical Engineering Institut Teknologi Bandung Kampus ITB Ganesha Bandung, Indonesia Niti B. Jadeja Environmental Biotechnology and Genomics Division CSIR-National Environmental Engineering Research Institute Nehru Marg, Nagpur, India Atya Kapley Environmental Biotechnology and Genomics Division CSIR-National Environmental Engineering Research Institute Nehru Marg, Nagpur, India Ece Kendir Department of Environmental Engineering Hacettepe University Ankara, Turkey Arun S. Kharat Department of Biotechnology Dr. Babasaheb Ambedkar Marathwada University Maharashtra, India Roop Kishor Department of Environmental Microbiology Babasaheb Bhimrao Ambedkar University Lucknow, Uttar Pradesh, India

Contributors

Sankaran Krishnamoorthy Algae Biotechnology Laboratory Department of Energy & Environment National Institute of Technology Tiruchirappalli, Tamil Nadu, India Abhishek Kumar Department of Biochemistry University of Allahabad Allahabad, Uttar Pradesh, India Deepak Kumar Department of Soil & Water Conservation Engineering G.B. Pant University of Agriculture and Technology Uttarakhand, India Dhananjay Kumar Department of Environmental Sciences Babasaheb Bhimrao Ambedkar University Lucknow, India Mahesh Kumar Department of Environmental Sciences Babasaheb Bhimrao Ambedkar University Lucknow, India Narendra Kumar Department of Environmental Sciences Babasaheb Bhimrao Ambedkar University Lucknow, India Sanjeev Kumar Centre for Environmental Sciences Central University of Jharkhand Ranchi, Jharkhand, India Sunil Kumar Solid and Hazardous Waste Management Division CSIR-National Environmental Engineering Research Institute Nehru Marg, Nagpur, India

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Contributors

Tshilidzi B. Lutsinge Department of Chemical Engineering University of Pretoria South Africa

Dario Rafael Olicón-Hernández Department of Microbiology University of Granada Granada, Spain

Stanford S. Makgato Madupi Power Station South Africa

Abhay K. Pandey Department of Biochemistry University of Allahabad Allahabad, India

Sanjeeb Kumar Mandal School of Biosciences and Technology VIT University Vellore, Tamilnadu, India Sujata Mani Department of Environmental Microbiology Babasaheb Bhimrao Ambedkar University Lucknow, Uttar Pradesh, India Vineet Kumar Maurya Department of Obstetrics and Gynecology King George Medical University Lucknow, India Devyani Mishra Department of Obstetrics and Gynecology King George Medical University Lucknow, India Sandhya Mishra Department of Environmental Microbiology Babasaheb Bhimrao Ambedkar University Lucknow, Uttar Pradesh, India Nandkishor S. More Department of Environmental Science Babasaheb Bhimrao Ambedkar University Lucknow, Uttar Pradesh, India

Satish G. Parte Department of Biotechnology Dr. Babasaheb Ambedkar Marathwada University Maharashtra, India Daniel Pramudita Department of Chemical Engineering Institut Teknologi Bandung Kampus ITB Ganesha Bandung, Indonesia, India Bably Prasad Natural Resources and Environment Management CSIR-Central Institute of Mining and Fuel Research Dhanbad, Jharkhand, India Ravindra Prasad Department of Environmental Science University of Delhi New Delhi, India Manickam Premalatha Algae Biotechnology Laboratory Department of Energy & Environment National Institute of Technology Tiruchirappalli, Tamil Nadu, India JPN Rai Department of Environmental Science Govind Ballabh Pant University of Agriculture & Technology Uttarakhand, India

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Deepika Rajwar Department of Environmental Science Govind Ballabh Pant University of Agriculture & Technology Uttarakhand, India Anita Rani University of Delhi New Delhi, India Shashi Ranjan Department of Hydrology Indian Institute of Technology Uttarakhand, India Pushp Lata Sankhwar Department of Obstetrics and Gynecology King George Medical University Lucknow, India S. N. Sankhwar Department of Urology King George Medical University Lucknow, India Gaurav Saxena Department of Environmental Microbiology Babasaheb Bhimrao Ambedkar University Lucknow, Uttar Pradesh, India A. Selvi Environmental Molecular Microbiology Research (EMMR) Lab Department of Biotechnology Thiruvalluvar University Serkadu, Vellore, Tamilnadu, India Bechan Sharma Department of Biochemistry University of Allahabad Allahabad, Uttar Pradesh, India Amit Kumar Singh Department of Biochemistry University of Allahabad Allahabad, India

Contributors

Reetika Singh Department of Biochemistry University of Allahabad Allahabad, Uttar Pradesh, India Ritu Singh Department of Environmental Sciences Central University of Rajasthan Ajmer, Rajasthan, India Haley Paula Stein Department of Microbiology University of Granada Granada, Spain Phumza V. Tikilili Department of Chemical Engineering University of Pretoria South Africa Aysenur Ugurlu Department of Environmental Engineering Hacettepe University Ankara, Turkey Fazli Wahid Department of Agriculture University of Swabi Swabi, Pakistan Shailendra Yadav Environmental Biotechnology and Genomics Division CSIR-National Environmental Engineering Research Institute Nehru Marg, Nagpur, India Zengqiang Zhang College of Natural Resources and Environment Northwest A & F University Yangling, Shaanxi, China

1 The Major Sources of

Industrial Wastewaters Dye Contamination in the Environment, Ecotoxicological Effects, and Bioremediation Approaches Roop Kishor, Ram Naresh Bharagava, and Gaurav Saxena

CONTENTS 1.1 Introduction.......................................................................................................2 1.2 Dyes...................................................................................................................4 1.2.1 Nature and Characteristics....................................................................4 1.2.2 Structure and Classification...................................................................5 1.2.2.1 Acid Dye................................................................................. 6 1.2.2.2 Basic Dye................................................................................6 1.2.2.3 Direct Dye............................................................................... 6 1.2.2.4 Disperse Dye........................................................................... 6 1.2.2.5 Reactive Dye........................................................................... 6 1.2.2.6 Vat Dye...................................................................................6 1.2.2.7 Solvent Dye.............................................................................7 1.2.2.8 Mordant Dye........................................................................... 7 1.3 Environmental Contamination and Toxicity Profile.......................................... 7 1.4 Bioremediation Approaches for Decolorization of Dyes...................................8 1.4.1 Decolorization by Microbes.................................................................. 8 1.4.1.1 Decolorization by Bacteria.....................................................9 1.4.1.2 Decolorization by Fungi....................................................... 10 1.4.1.3 Decolorization by Yeast........................................................ 11 1.4.1.4 Decolorization by Algae....................................................... 11 1.4.2 Enzymatic Decolorization of Dyes...................................................... 12 1.4.3 Decolorization by Plant (Phytoremediation)....................................... 14 1.4.4 Other Methods..................................................................................... 14 1.5 Mechanism of Dye Degradation and Decolorization...................................... 15 1.6 Prospects and Challenges................................................................................ 16 1

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1.7 Conclusion and Recommendations.................................................................. 17 Acknowledgment...................................................................................................... 17 References................................................................................................................. 18

1.1 INTRODUCTION Rapid increase in industrialization and population has led to the release of several unwanted toxic substances in the environment, which are liable to create pollution of our natural environment and toxicity in living beings (Gautam et al. 2017; Goutam et al. 2018). Industries are the key players in the economy of many nations but are also the major polluters worldwide due to their potentially toxic wastewater, which contains a variety of organic and inorganic pollutants and which thus causes serious environmental pollution and toxicity in living beings upon exposure (Bharagava et al. 2018; Saxena and Bharagava 2015, 2016, 2017). Industries use large quantities of different synthetic chemicals (mainly dye) for various purposes, including as a dyeing and finishing agent. A number of synthetic dyes are used heavily in different industries and include azo, triphenylmethane, anthraquinone, phthalein, nitro, methane, and quinoline dyes (Kabra et al. 2011a,b; Khan et al. 2013; Saxena et al. 2016) (Table 1.1).

TABLE 1.1 Industrial Wastewaters Containing Different Dyes and Their Characteristics Industrial Wastewaters

Dyes

Textile wastewater

Azo or anthraquinone

Tannery wastewater

Acid dyes, mordant dyes, direct dyes, basic dyes, and pre-metal, methyl orange Vat dyes, basic dyes, sulfur dyes and cationic direct dyes

Paper industry wastewater

Pharmaceutical wastewater

Synthetic dyes brilliant blue, allura red, tartrazine and erythrosine

Wastewater Characteristics Major pollutants in textile wastewater COD, BOD, solids, phenols, sulfur, and the intense color caused by different dyes and several toxic heavy metals like Cd, Cr, Cu, Fe, Pb, Mn, Ni and minerals like K, P. Tannery wastewater contains high BOD, COD, TDS, TSS, phenols, chlorophenols, tannins, azo dyes, toxic metals such as Cr, Cd, Pb. Paper industry wastewater contains dark brown color, very high level of BOD, COD, TDS due to presence of lignin and its derivatives from the raw cellulosic materials, chlorinated compounds, suspended solids (mainly fibers), fatty acids, tannins, resin acids, sulfur and sulfur compounds, etc. Pharmaceutical wastewater contains intense color, conductivity, salinity, turbidity and contains very high chloride, COD, BOD, TSS, TDS, nitrates, phosphates, sulfates, alkalinity, and several toxic metals like Cd, Co, Fe, Mn, Ni, Pb, and Zn.

Abbreviations: COD: Chemical oxygen demand; BOD: Biochemical oxygen demand; TDS: Total dissolved solids; TSS: Total suspended solids.

Industrial Wastewaters

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As a result, these highly toxic dyes are discharged along with different industrial wastewaters into the natural ecosystem, which includes rivers, ponds, lakes, and soil, and thus create serious environmental pollution. The wastewater-containing organic and inorganic pollutants also support the growth of a variety of pathogenic bacteria, which also create serious health hazards in living beings upon exposure (Mani and Bharagava 2016a,b; Saxena et al. 2015). W. H. Perkin discovered the first synthetic organic dye, mauve (or aniline), in 1956. It is estimated that up to 10,000 tons of different synthetic dyes and pigments are used in the textile industry and over 70,000 tons of synthetic dyes are produced every year worldwide (Aftab et al. 2011; Daneshvar et al. 2007; Parshetti et al. 2006). Moreover, it is estimated that approximately 200,000 tons of wastewater are generated every year during washing, dyeing, bleaching, and finishing operations in the textile industry. The wastewater causes adverse impacts on water quality and chemistry, including impacting color, pH, biological oxygen demand (BOD), total organic carbon (TOC), chemical oxygen demand (COD), total suspended solid (TSS), total nitrogen (TN), total solid (TS), and a variety of organic and inorganic pollutants (Mani and Bharagava 2016a; Senthilkumaar et al. 2006; Shengfang 2010). Several industries are also generating a huge amount of dye-containing wastewater, such as the textile, paper, leather, and pharmaceutical industries (Table 1.1) (Arulazhagan 2016; Saratale et al. 2006). The textile industry discharges hazardous wastewater with some highly toxic substances including different heavy metals such as As, Cr, Zn, Cd, Cu, Mn, and Co, which have mutagenic and carcinogenic effects (Ambrosio et al. 2012; Kabra et al. 2011b; Mani and Bharagava 2016b). The dye-containing wastewater discharged from textile industries into the aquatic resources causes reduction of sunlight penetration into water bodies and thus decreases the dissolved oxygen content and ultimately affects the aquatic life through creating a negative impact on zooplankton, phytoplankton, and other aquatic living organisms (Garg and Tripathi 2013). Dyes are of both natural and synthetic origin and are widely employed in the textile, paper, food, cosmetic, leather, and pharmaceutical industries because of their capability to provide ease of production, stability, and various colors compared with the other naturalistic dyes. In other words, dyes are the organic compound which are applied as coloring agents because of their capability to permanently color the silk/fibers and because they are highly resistant to light, water, soap, oxidizing agents, acids, alkaline agents, and microbial action (Saratale et al. 2011; Shah et al. 2013a,b). Further, according to an annual report by Union Ministry of Environment and Forests (MoEF), 13,011 industrial units have produced about 4.4 million tons of harmful wastes spread over 373 districts of the country (Pointing 2001). Industries discharge approximately one ton of wastewater in daily life through dyeing processes. According to an estimate, through the end of the nineteenth century, approximately 10,000 synthetic dyes have been discovered and employed in industry for various purposes. Textile industries consume a large volume of potable water for different dye application and, therefore, discharge a huge quantity of dye-containing wastewater into the environment, which create serious environmental pollution and health threats to living beings. Therefore, it is essential to adequately treat the wastewater to protect the environment and public health. Physico-chemical approaches are currently

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being applied for the treatment of wastewater by industries. These are effective, but environmentally destructive as these utilize a huge amount of toxic chemicals and salts, which then end up in the environment and impart a negative impact on the environment as well as generating a huge amount of sludge as a secondary pollutant (Pandey et al. 2007; Zhang et al. 2004). However, bioremediation or biological approaches are promising ecofriendly approaches that utilize a variety of microbes for environmental cleanup and thus are viewed as a low-cost strategy for the treatment and management of industrial effluents (Forgacs et al. 2004; Mani and Bharagava 2016a; Saratale et al. 2006; Shah et al. 2013a,b). Therefore, this chapter mainly focuses on the toxicity profile of dyes and bioremediation approaches for dye-containing wastewater for environmental safety.

1.2 DYES Dyes are the synthetic aromatic compounds that are extremely employed as coloring agents and sometimes used to develop color or change the color of substances. The dyes are widely used in the various industrial sectors for different purposes, which include coloring of fiber and cloth coloring, biological and biochemical stains, foods and cosmetics, color photography, electronics and lasers, solar cells, display panels, pigments in modern paints, printer inks, and leather products. Mostly, dyes are constituted of an abundant class of organic compounds with covalently attached unsaturated or saturated functional groups including chromophore and auxochrome groups. These unsaturated groups (N=N, C=C or C≡C) are accountable for absorbing light in the visible zone, approximately (350–750 nm), where they only show color. The chromophore group is called an electron acceptor, which is also responsible for the dye’s color, while the auxochrome group (–SH, –OH, or NH2) represents the electron donor that is liable for dyeing capacity as well as enhancing the color of the dye. Dyes must be soluble in the solvent or naturally occurring and synthetic in nature. Not all colored compounds can be considered as dyes. Some dyes are also applied as adhesives and used in art supplies, beverages, and construction, glass, wax, biomedicine, soap, and plastics products. Dyes are also the fundamental component of microbiological experiments; crystal violet (C-8650) and safranin (S-0700) are the most commonly used dyes in the Gram’s stain technique. Gram’s stain is used to differentiate bacteria into two different categories: Gram-positive and Gram-negative bacteria. A good dye has good shine power, suitable color, and weathering ability and must be resistant to the action of light, water, soap, detergents, sweat, and other chemical substances during the washing or dry cleaning process.

1.2.1 Nature and Characteristics Dyes are broadly classified into two different categories on the basis of origin: natural dyes and synthetic dyes. Natural dyes are extracted from naturally occurring substances, mainly different parts of plants, and do not need any chemicals for their extraction. Natural dyes are mostly used for the dyeing of all types of natural fibers to improve nonharmful properties. These dyes are also used in the coloring of textiles, food, cosmetics, pharmaceuticals, handicraft items, and toys and in the leathering

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processing. Dyes are produced from renewable resources that are ecofriendly and have biodegradable features. They yield soft color that is pleasant to the eye and that is consistent with nature. Certain natural dyes show mutagenic effects, such as elderberry color and safflower yellow, as well as carmine that causes asthma by continuous inhalation. Natural dyes better than synthetic dyes because they are less toxic and less allergenic. Some examples include marigold, turmeric, safflower, weld, onion, myrobolan, morinda, quercetin, and turmeric dyes. Synthetic dyes are the organic dyes that are fundamentally obtained from petroleum, coal tar derivatives, and sometimes, a combination of mineral components extracted from benzene and its derivatives. The first human synthesized dye, mauveine, was discovered by W. H. Perkin in 1956. Natural dyes are extremely useful for dyeing and printing at large scale in industry. Synthetic dyes can be applied anywhere but should be used very carefully because these are highly toxic in nature. Currently, the use of synthetic dyes is increasing because of their low cost and a more excellent quality compared with natural dye substances. Some examples of synthetic dyes include diphenylmethane derivatives, triphenylmethane, oxazine compounds xanthine compounds, and azo dyes.

1.2.2 Structure and Classification Dyes are complex structures and used for various applications in industrial units (Figure 1.1). The description of some important dyes is provided. O O2N

H N

N H NO2 Nitro dye

Xanthine dye OH

CI– +

N

Triphenyl methane dye N

O+ OH

U

N

N H

HO

O O S O–Na+

O

HN O

O–Na+

H N

OH

HO O

HO OH

OH O Weld dye

Methine dye

O2N –O

O O Br Br India dye

CI

CI Eosin dye

FIGURE 1.1 Chemical structure of different dyes.

N

Azo dye

CI CI CI OH

COO– NO2

NH2 N

OH

Myrobolan dye

Indigo dye

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1.2.2.1 Acid Dye Acid dyes are extremely soluble in water due to the presence of sulfonic acid groups and can be applied in both acidic and neutral conditions. Acid dyes are called anionic (negative charge) dyes and are widely used in the coloring of silk, wool, and nylon; these cannot be used to dye cotton. Acid dyes are highly complex in structure, having large aromatic molecules and sulfonyl and amino groups to enhance solubility. Some examples of acid dyes include nigrosine, eosin, India ink, and picric acid. 1.2.2.2 Basic Dye Basic dyes are a cationic (positively charge) colorant compound and are insoluble in water but soluble in alcohol and methylated spirit. These dyes consist of basic groups such as (–NH2) or (–NR2) groups, which are responsible for the positive charge. Basic dyes can be only applied in acidic conditions, constantly react with negative sites present on the fabrics and are attached to them. These are synthetic in nature and mostly employed for jute dyeing and jute printing but also for wool and acrylic fibers. Some examples include malachite green and crystal violet. 1.2.2.3 Direct Dye Direct dyes are anionic in nature and soluble in water and can be applied in both neutral and alkaline aqueous solutions. The direct dyes dispose shiny color but show lousy wash fastness. Direct dyes are used for coloring of cotton, paper, leather, wool, silk, wool, rayon, and nylon. These are also used as pH indicators and as biological stains. 1.2.2.4 Disperse Dye Disperse dyes are organic synthetic dyes and are less soluble in water. They are organic coloring substances that are suitable for dyeing hydrophobic fibers. Disperse dyes are nonionic in nature and free from ionizing groups. Disperse dyes are used for the coloring of nylon, polyester, and polyacrylonitrile. 1.2.2.5 Reactive Dye Reactive dyes are a unique dyes that form covalent bonds between dyes molecules and end sites (–NH2, –OH, –SH and –Cl) of substrates like fiber. These dyes are anionic in nature and can be applied in both alkaline and neutral conditions. These dyes are soluble in water and available in different forms such as powder, liquid, and print paste. They are the relatively inexpensive as well as having excellent wash and light fastness. Reactive dyes are extensively used in the coloring of cotton, rayon, flax, cellulose, polyamide, and wool fibers. 1.2.2.6 Vat Dye Vat dyes are the natural coloring substances obtained from natural matter like that vegetables and animals. These dyes cannot be used directly because of their insolubility in water. They give great color stability to fiber matters when employed in alkaline condition. Vat dyes have excellent fastness, but not good robbing characteristics. These are not good because they are costly, usually finite, and cause side effects such as skin diseases. Vat dyes are used for coloring cellulosic fiber, especially cotton fiber.


7

1.2.2.7 Solvent Dye Solvent dyes are soluble in the inorganic solvent but insoluble in water and applicable for textile coloring processes. These dyes have excellent solubility in non-polar organic solvents. These dyes are also applied to color lubricants in the automotive and industrial cutting industries. Industrial plastics body and solvent-related dyes are used to color a variety of solid materials, such as acetates, nylon, polyester, acrylics, PVC, PMMA, PETP, polystyrene, and styrene monomers, as well as identify various cell structure components in medical diagnostics and scientific research. 1.2.2.8 Mordant Dye Mordant dyes may be of natural and synthetic nature, with the ability to bind with metals to form insoluble color lakes. Mordant dyes are most commonly applied as inorganic chromium and are thus sometimes called chrome dyes. These dyes are mostly soluble in cold water and have an excellent color durability character. Mordant dyes are mostly used in protein fibers, nylon, and modacrylic fibers.

1.3 ENVIRONMENTAL CONTAMINATION AND TOXICITY PROFILE Textile industries are the major source of environmental pollution. Over 10,000 tons of different synthetic dyes are generated every year worldwide from different industrial units (Chen et al. 2004). Several synthetic dyes are employed in different industries, such as textile, food, cosmetic, paper, printing, color photography, leather, and pharmaceutical industries, for various applications such as dyeing, scouring, bleaching, and finishing. But, textile industries are consuming the highest amount of total dyes (Saratale et al. 2013). Dyes are also applied for coloring purposes such as coloring fibers and cloth; biological and biochemical stains; color photography; pigments in modern paints, printer inks, leather, nylon, polyester, polystyrene, cotton, rayon, flax, cellulosic, and polyamide and lubricants in the automotive and industrial cutting industries, and thus, they end up in the wastewaters (Ajao et al. 2011; Cunningham and Siago 2001; Saratale et al. 2006). Dye effluents are highly colored, contain various toxic chemicals such as chlorine, formaldehyde, solvent, organic and inorganic compounds, aromatic amines, xenobiotic, pigments, alkali salts, and toxic heavy metals (lead, chromium, and mercury) (Bharagava and Mishra 2018; Chowdhary et al. 2017; Mishra and Bharagava 2016; Yadav et al. 2017). The solid wastes are discharged by several industries into water bodies such as ponds, lakes, rivers, streams, etc., where they have harmful effects on water and soil ecology and lead to water and soil pollution and ecotoxicity in the environment (Kagalkar et al. 2010; Mani and Bharagava 2017). Dye effluent is highly carcinogenic and mutagenic in nature because of the presence of recalcitrant organic and inorganic pollutants, and if not adequately treated, it gets discharged into natural ecosystems and causes serious problems of environmental contamination and health hazards (Aftab et al. 2011; Mani and Bharagava 2016a). Dye effluents affect the chemical and biological properties of water or soil and thus create environmental pollution (Parshetti et al. 2011). This has a negative effect on fishes as well as damages the phytoplankton and zooplankton species and thus ultimately affects the aquatic ecosystem (Aftab

8


et al. 2011; Hashimoto et al. 2013). Dye effluents are also responsible for disturbed biogeochemical (nutrient) cycling, which occurs in soil niches, and thus create soil pollution. It has been reported that approximately 15% of the total azo dye effluent discharged every year comes from textile industries (Chen 2007; Stolz 2001). Dye effluent contains the highest amount of recalcitrant coloring pollutants, suspended solids, or other toxic metals, which cause a negative impact on water chemistry such as color, BOD and COD levels. Dyes have chromophoric groups that are able to strongly absorb sunlight, thus adversely affecting the photosynthesis process of phytoplankton or algae species (Kagalkar et al. 2010). Azo dyes are generally soluble in water and hence highly assimilate, even through skin touch and inhalation, which causes cancer, splenic sarcomas, hepatocarcinomas, allergic reactions, and nuclear anomalies in experimental animals and chromosomal aberrations in mammalian cells (Bayoumi et al. 2010; Puvaneswari et al. 2006). Dye effluents have some specific toxic chemicals that cause mutagenic, carcinogenic, and teratogenic effects in several organisms (Mani and Bharagava 2016a,b; Mathur and Bhatnagar 2007; Novotny et al. 2006; Parshetti et al. 2011).

1.4 BIOREMEDIATION APPROACHES FOR DECOLORIZATION OF DYES The term “bioremediation” is mainly composed of two words, that is, “bio” means biological materials and “remediation” means to clean up problems. Bioremediation is a waste management technique and recognized as an ecofriendly approach for the degradation and detoxification of environmental pollutants in contaminated environments (Bharagava et al. 2017a; Mani and Bharagava 2016b; Parshetti et al. 2011). It utilizes an array of microbes such as bacteria, fungi, and algae and plants (phytoremediation) for environmental cleanup. It is inexpensive in nature, environmentally safe, and does not disturb the remediating environment. It can be classified as microbial bioremediation (application of microorganisms to degrade/ detoxify highly pollutants into nontoxic form, e.g., bacteria), phytoremediation (application of green plants to bind, extract, and to solve environmental problems such as pesticides, petroleum hydrocarbons, metals, and chlorinated solvents), mycoremediation (application of fungi to break down contamination such as pesticides, hydrocarbons, and heavy metals by the secretion of enzymes, acids, and toxins), and phytoremediation (application of algae or microalgae for the removal of heavy metals from industrial wastewaters) (Aftab et al. 2011; Jadhav et al. 2011).

1.4.1 Decolorization by Microbes The decolorization of dyes has been a primary target of a wide variety of dye effluents treatment processes. A huge amount of dye effluents discharged from various industrial units into the natural aquatic systems contains suspended solids, toxic chemicals with intense dark color (Sudha et al. 2014). As a result, this ultimately inhibits the photosynthesis of aquatic plants and algae and affects other living organisms. The discharged dye-containing effluents also contain a variety of organic

9


and inorganic pollutants such as toxic metals, which causes serious environmental pollution (soil/water) and toxicity in living beings (Aftab et al. 2011; Asad et al. 2007). Biological methods for the decolorization of dye effluents is an excellent approach as compared with other physico-chemical treatment approaches because of their ease of application, environmentally friendly and inexpensive nature, and generation of nontoxic sludge with complete mineralization (Arulazhagan 2016; Levin et al. 2010; Saratale et al. 2009). Biological approaches employ a variety of microbes such as bacteria, fungi, yeasts, actinomycetes, algae, and plants for the treatment of various dye effluents for environmental safety. 1.4.1.1 Decolorization by Bacteria A number of bacterial strains are capable of the treatment of various kinds of dye effluents (Table 1.2). Bacteria secrete various primary and secondary metabolites such as organic acid, enzymes, antibiotics, toxins, and some other components, which are directly responsible for the conversion of various toxic effluents into less toxic or nontoxic products. Many researchers report that azo dye contains some specific saturated (–SH, –OH, –NH2) or unsaturated (N=N, C=C) functional groups, which are directly and indirectly responsible for some specific functions, such as absorbing light, showing color, producing color, acting as an electron acceptor or electron donor, and enhancing color capacity. The biodegradation of various dyes can take place under both aerobic and anaerobic conditions, performed by different groups of bacteria, since some bacterial species TABLE 1.2 Decolorization of Various Dyes by Pure and Mixed Bacterial Cultures Name of Strains

Dyes Decolorization (%) Duration

Bacillus lentus BI377 Alcaligenes sp. AA09

Reactive red 141 (99.11) Reactive red BL (100)

6 h 1 day

B. subtilis ETL-2211 Sphingomonas paucimobilis Agrobacterium radiobacter Bacillus spp. Sphingomonas paucimobilis Agrobacterium radiobacter Pseudomonas sp. Enterobacter EC3 Aeromonas hydrophila Bacillus sp. Consortium SKB-II (B. vallismortis and B. Megaterium) Consortium of halophilic and halotolerant bacteria Consortium of Enterobacter sp., Serratia sp., Yersinia sp.

Crystal violet (90) Crystal violet (91) Crystal violet (91)

– – 3 days

Crystal violet (100) Reactive blue 13 (83.2) Reactive black 5 (92.56) Various azo dyes (70) Congo red (100) Brodeaux, ranocid fast blue (85) Azo dyes (100)

– 3 days 1.5 days

Reactive red 195 (90)

References Oturkar et al. (2013) Pandey and Dubey (2012) Shah et al. (2013a,b) Cheriaa et al. (2012) Cheriaa et al. (2012)

2 days 5 days

Parshetti et al. (2011) Lin et al. (2010) Wang et al. (2009) Hsueh et al. (2009) Kannappan et al. (2009) Tony et al. (2009)

5 days

Asad et al. (2007)

2 days

Jirasripongpun et al. (2007)

10


rapidly grow aerobically (in the presence of oxygen) or an aerobically (in the absence of oxygen). Biodegradation of azo dye was first described in 1937. The main goal of the bacterial decolorization of azo dye is to cleave the azo bond (N=N) under anaerobic conditions with the help of azo reductase enzyme into aromatic amines, which show no color as well as potentially being toxic in nature (Coughlin et al. 2003; Kalyani et al. 2008; Nakanishi et al. 2001). A number of bacterial species, such as Bacillus, Pseudomonas, Aeromonas, Proteus, Micrococcus, and purple non-sulfur photosynthetic bacteria, have been reported in the anaerobic degradation of a number of dyes (Arulazhagan 2016; Chang et al. 2001; Khandare et al. 2011b; Saratale et al. 2009). 1.4.1.2 Decolorization by Fungi A diverse group of fungi can degrade/decolorize a number of complex dye substances into nontoxic metabolites (Fu and Viraraghavan 2001) (Table 1.3). Most of the fungal species are capable of secreting extracellular ligninolytic enzymes such as laccase, manganese peroxidase, and lignin peroxidase (Gomi et al. 2011). These enzymes are responsible for degradation of many dye effluents. Pleurotus ostreatus, Pichia species, Penicillium species, and Candida tropicalis are capable of the decolorization of different dyes (Ali et al. 2009; Zhuo et al. 2011). Currently, white-rot fungi is a unique group of fungal organism, which has a strong capacity for the degradation/ decolorization of lignin in the broad scale and has extracellular or nonspecific enzymes that are implicated in the degradation of various persistent compounds and lignin (Abedin 2008; Weisburger 2002; Yang et al. 2009). Several groups of whiterot fungi such as Phanerochaete chrysosporium, Trametes versicolor, Pleurotus

TABLE 1.3 Degradation and Decolorization of Various Dyes by Fungal Species Name of Strains

Dyes and Decolorization (%)

Duration

References

Irpex lacteus Aspergillus foetidus Ganoderma sp. Rhizopus arrhizus Aspergillus flavus Alternaria solani Fusarium solani Trametes sp. SQ01

Remazol brilliant blue R (100) Remazole (98) Malachite green (91) Viny selphone (37) Malachite green (97.43) Malachite green (96.91) Crystal voilet (97.6) Bromophenol blue and Everzol turquoise blue-G (100) Trypan blue (70)

6 days 2 days – – 6 days 6 days 2 days 7 days

Novótny et al. (2004) Sumathi and Phatak (1999) Zhuo et al. (2011) Aksu and Tezer (2000) Ali et al. (2009) Ali et al. (2009) Abedin (2008) Yang et al. (2009)

2 days

Annuar et al. (2009)

Reactive blue 4 (70) Malachite green (98) Poly R-478 (97)

3 days 5 days

Nilsson et al. (2006) Yogita et al. (2011) Pazarlioglu et al. (2005)

Remazol brilliant (100) (80)

6 days 20 days

Kasinath et al. (2003) Kapdan and Kargi (2002)

Pycnoporus sanguineus Tinea versicolor Pleurotus spp. Phanerochaete chrysosporium Irpex lacteus Coriolus versicolor

11


ostreatus, Pycnoporus sanguineus, Irpex flavus, and Phellinus gilvus can degrade a number of textile dyes such as azo, indigoid, and triphenylmethane dyes, as well as heterocyclic dyes (Khan et al. 2012; Pajot et al. 2010). A new white-rot fungi strain Ganoderma sp. En3, which was isolated from the forest of Tzu-chin Mountain in China has potential for the degradation of huge quantities of textile dye such as methyl orange, malachite green, bromophenol blue, crystal violet, and textile dye effluents (Asgher et al. 2008; Liu et al. 2011; Parshetti et al. 2011). 1.4.1.3 Decolorization by Yeast Yeast is widely distributed in nature with a wide variety of habitats such as soil, vegetation, and aquatic ecosystems. Yeast represents attractive features compared with bacteria and algae. Yeasts are an inexpensive, easily available source of biomass and can grow faster than most filamentous fungi. They also have the ability to tolerate adverse environmental conditions such as pH, temperature, and nutrient availability, as well as high pollutant concentrations. Different classes of yeast species are involved in the decolorization of a wide range of dyes effluents, including Galactomyces geotrichum, Saccharomyces cerevisiae, and Trichosporon beigelii, etc. (Jadhav et al. 2008a,b) (Table 1.4). Recently, Candida palmioleophila JKS4 isolated from activated sludge have been reported for decolorization of several azo dyes under aerobic condition (Khan et al. 2013; Waghmode et al. 2011). Kluyveromyces marxianus IMB3 was also reported to have role in the decolorization of remazol black-B into a less toxic form (Meehan et al. 2000). 1.4.1.4 Decolorization by Algae Algae are a diverse group of photosynthetic organisms, which are mostly inhabiting both marine and freshwater algae and are found almost everywhere on earth. Activate algae can decolorize the textile industry dye effluent. A wide variety of algae have been reported for the decolorization a wide range of dyes such as Spirogyra species (Gupta et al. 2006), Chlorella vulgaris, C. sorokiniana, Lemna minuscula (Khandare et al. 2011a), Scenedesmus obliquus, C. pyrenoidosa, and Closterium lunula (Yan and Pan 2004) (Table 1.5). A number of species of Chlorella and Oscillitoria are capable of the TABLE 1.4 Decolorization of Various Dyes by Yeast Name of Strains Trichosporon akiyoshidainum Galactomyces geotrichum Galactomyces geotrichum Candida rugopelliculosa Pichia fermentans Trichosporon beigelii Candida albicans Candida krusei Pseudozyma rugulosa

Dyes Decolorization (%)

Duration

References

Reactive black 5 (100)

1 day

Pajot et al. (2011)

Methyl red (100) Brilliant blue (88) Reactive blue 13 (90) Basic violet 3 (70) Navy blue HER (100) Direct violet 51 (73.2) Reactive brilliant red K-2BP (98) Reactive brilliant red K-2BP (99)

1 h 1 day 2 days 6 days 2 days 3 days 2 days 2 days

Khan et al. (2013) Waghmode et al. (2011) Liu et al. (2011) Das et al. (2010) Saratale et al. (2009) Vitor and Corso (2008) Yu and Wen (2005) Yu and Wen (2005)

12


TABLE 1.5 Degradation and Detoxification of Various Dyes by Algal Species Name of Strains Nostoc linckia Spirogyra rhizopus Cosmarium sp. Synechocystis sp. Cystoseira barbatala Pithophora sp.


Duration

References

CV (72) Acid Red 247 Malachite Green (87.2) Reactive Red (55) Methylene Blue (90) Malachite Green (89)

– – 1 day 26 days 23 days 24 days

Sharma et al. (2011) Ozer et al. (2006) Daneshvar et al. (2007) Karacakaya et al. (2009) Caparkaya and Cavas (2008) Kumar et al. (2005)

decolorization of azo dyes by breaking the azo linkage into the aromatic amines, which are highly toxic or colorless intermediates and can be further degraded into the simpler nontoxic compounds CO2 or H2O (Karacakaya et al. 2009; Kumar et al. 2005). Moreover, the decolorization of dyes depends on the type of dyes and species of algae used. Hence, in the stabilization of ponds, algae can play a direct role in the degradation of azo dyes, rather than only providing oxygen for bacterial growth (Khandare et al. 2011a; Sharma et al. 2009). Further, cyanobacteria and diatoms are also reported in the decolorization of various dyes such as monoazo and diazo dyes. The cyanobacterium Phormidium can decolorize the indigo dye extensively (91%) but is not able to decolorize the sulfur black and Remazol Brilliant Blue R (RBBR) dyes (Caparkaya and Cavas 2008). Microalgae are also reported in the decolorization of textile dye effluent (Mostafa et al. 2009).

1.4.2 Enzymatic Decolorization of Dyes Enzymatic treatment is very effective in decolorization of textile dyes, including azo, triarylmethane, anthraquinone, and indigoid dyes, which are decolorized with enzyme as a bioremediation tool (Table 1.6). Microorganisms are found almost everywhere in the environment, including soil, water, air, and many other locations. They normally survive in an optimum environmental condition, which includes the appropriate temperature, pH, light, nutrient, salinity, water and aerobic/anaerobic environment. Any alteration in the environmental conditions may lead to the shift in the microbial diversity and number of microbial species capable of producing a diverse group of enzymes such as azo reductase, laccase, lignin, and peroxidase. These enzymes are directly and indirectly involved in the degradation and decolorization of several dyestuffs from various industrial wastewaters. Azo reductase enzyme has been reported to be involved in the decolorization of textile dyes (Gopinath et al. 2009; Oturkar et al. 2013). The main goal of the decolorization of azo dye is to break down the azo linkage (N=N) under aerobic conditions with the help of azo reductase enzyme, resulting in the formation of aromatic amines, which are colorless but are potential carcinogenic in nature (Pandey et al. 2007). These aromatic amines have a recalcitrant nature and they further break down into the intermediate metabolites under anaerobic conditions with release of organic compounds H2O and CO2. Azo reductase enzyme has potential application in designing of bio-treatment methods for wastewaters containing azo dyes (Bafana et al. 2009; Tian et al. 2014).

13


TABLE 1.6 Decolorization of Various Dyes by Azo Reductase and Laccase EnzymeProducing Bacterial and Fungal Cultures Strains


Duration

References

Azo Reductase-Producing Culture Mutant Bacillus sp. ACT2 Bacillus lentus BI377 Alcaligenes sp. AA09 Pseudomonas aeruginosa NBARI Bacillus megaterium Pluteus luteuls Enterococcus gallinarum Bacillus strain SF

Phanerochaete chrysosporium Comamonas spp., UVS Coprinopsis cinerea Armillaria sp. F022 Ganoderma sp. Lentinus polychrous Pycnoporus sanguineus

Congo red (20) Reactive red 141 (70) Reactive red BL (100) Reactive blue 172 (83)

2 days 2 days 2 days 1 day

Gopinath et al. (2009) Oturkar et al. (2013) Pandey and Dubey (2012) Bhatt et al. (2005)

Red 2G (64.89) Reactive red 22 (98) Direct black 38 (100) Reactive black 5 (86)

NA 5 days 1 day 6 h

Khan et al. (2013) Hu (1994) Bafana et al. (2009) Maier et al. (2004)

Laccase-Producing Fungal Culture Poly R-478 (80) 1 day

Mielgo et al. (2003)

Direct 5B (100) Methyl orange (47.7) Reactive black 5 (86) Methyl orange (90) Congo red (75) Trypan blue (70)

Jadhav et al. (2008a,b) Tian et al. (2014) Hadibarata et al. (2012) Zhuo et al. (2011) Suwannawong et al. (2010) Annuar et al. (2009)

1 day 4h 4 days 3 days 3 h 1 day

Moreover, many researchers have reported a few catalytic proteins from various microbes which can decolorize textile dyes, such as Pigmentiphaga kullae K24, Enterococcus faecalis, and Staphylococcus aureus (Blumel et al. 2002; Blumel and Stolz 2003; Chen et al. 2004, 2005; Tian et al. 2014; Yan et al. 2004). Laccases (EC 1.10.3.2) are copper-containing oxidase enzymes that decolorize azo dyes through a highly nonspecific free radical mechanism forming phenolic compounds, thereby avoiding the formation of toxic aromatic amines (Bafana et al. 2009; Tian et al. 2014). These enzymes are generally found in higher plants and fungi but recently were found in some bacteria such as S. lavendulae, S. cyaneus, and Marinomonas mediterranea (Naik and Singh 2012; Suwannawong et al. 2010). Laccase play an important role in the paper and pulp industry, the textile industry, cosmetics, and bioremediation and biodegradation approaches (Tian et al. 2014). Laccase is produced by a great number of white-rot fungi, such as Trametes versicolor, Phlebia radiata, Polyporus pinisitus, and Penicillium chrysogenum, and over 60 fungal strains from various classes (Naik and Singh 2012; Tian et al. 2014). Various textile dyes have been decolorized by Trametes hirsuta laccase to an extent of 80% and showed no general rule in detoxification tendencies (Naik and Singh 2012; Suwannawong et al. 2010). The presence of lignin peroxidase and/or manganese peroxidase in addition to laccase increases decolorization by up to 25% (Annuar et al. 2009; Hadibarata et al. 2012). Several microorganisms have been

14


reported to produce soluble cytosolic enzymes like azo reductases with low substrate specificity, which reductively cleaves the azo bond at the expense of a reducing agent, typically NADPH, serving as an electron donor for the reaction (Jadhav et al. 2008a,b; Tian et al. 2014) and resulting in the production of colorless aromatic amines which may be toxic, mutagenic, and possibly carcinogenic to animals.

1.4.3 Decolorization by Plant (Phytoremediation) Phytoremediation is the most important technique for transformation and detoxification of textile-dye wastewater. It is the direct use of green plants to remove, degrade, and immobilize environmental pollutants or to prevent pollution, thus restoring the original natural surroundings and preventing further pollution (Chandra et al. 2015). Phytoremediation of textile dyes has been reported using some wetland, as well as terrestrial, plants. For instance, Typha angustifolia has been used in the treatment of synthetic reactive dye-containing wastewater (Nilratnisakorn et al. 2007). Wild plants, tissue cultures, and suspension cultures of Blumea malcolmii have been shown to efficiently decolorize and degrade textile dyes like malachite green, reactive red 2, and direct red 5B (Kagalkar et al. 2009, 2011). Tagetes patula hairy roots have been used to degrade reactive red 198 (Patil et al. 2009). Wild plants of Aster amellus can degrade remazol red dye (Khandare et al. 2011a). Wild plants and tissue cultures of Portulaca grandiflora and Zinnia angustifolia show the degradation of navy blue HE2R and remazol black-B, respectively (Khandare et al. 2011a). Glandularia pulchella is efficient in the degradation of green HE4B and remazol orange 3R (Kabra et al. 2011a,b). Recently, Sesuvium portulacastrum, a halophytic plant, has been shown to decolorize green HE4B (Patil et al. 2011). Further, the use of common garden plants for the phytoremediation purposes appears to be a novel and practical approach with sincere efforts.

1.4.4 Other Methods The other emerging method for the biological treatment of dye-containing wastewater is the use of constructed wetlands (CWs). CWs are considered to be the promising technology for wastewater treatment (Bharagava et al. 2017b). There are many studies available on the treatment of dye-containing textile wastewater using CWs (Davies et al. 2006; Ong et al. 2009; Saeed and Sun 2013; Sivakumar et al. 2013; Shehzadi et al. 2014); these have reported average removal efficiencies of 72%–77%, 68%–73%, and 53%–59% for color, COD, and sulfate, respectively, from textile wastewater in a pilot-scale engineered wetland system planted with Typha species and Colocasia species in Dares Salaam city, Tanzania. Saeed and Sun (2013) have reported simultaneous removal of BOD5 up to 74%–79% and ammonia up to 59%–66% from textile wastewater in the lab-scale hybrid wetland systems consisting of a vertical flow (VF) and a horizontal flow (HF) wetland planted with Phragmites australis, Dracaena sanderiana, and Asplenium platyneuron, and the wetland systems were operated under high hydraulic loading (HL) (566–5660 mm/d) and inorganic nitrogen (254–508 g N/m2⋅d) and organics loadings (9840–19,680 g COD/m2⋅d and 2154–4307 g BOD5/m2⋅d).


15

Davies et al. (2006) reported simultaneous removal of color up to 99% and COD up to 93% during the aerobic degradation of acid orange 7 (AO7) in a VF CW planted with Phragmites species, which was fed with 127 mg/L of AO7 at hydraulic loads of 28, 40, 53, and 108 L/m⋅day. Bulc and Ojstrsek (2008) have reported average removal efficiencies of 84%, 65%, 89%, 52%, 87%, 88%, 80%, 93%, and 90% for COD, BOD, total organic carbon, total nitrogen, nitrogen organic, NH4-N, sulfate, anionic surfactants, total suspended solids, and color, respectively, from textile wastewater in a pilot-scale hybrid CW consisting of VF and HF CW planted with Phragmites australis. Dogdu and Yalcuk (2015) have reported an average removal in color up to 97% and COD up to 62% from synthetic textile wastewater containing commercial indigo dye in a VF CW planted with C. indica and T. angustifolia. Ong et al. (2009) have reported average removal efficiencies of 86% and 96% for COD and NH4-N, respectively, in the aerated reactors, whereas the average removal efficiencies were 78%–82% and 41%–48% for COD and NH4-N, respectively, from azo dye-containing wastewater in the non-aerated reactors of laboratory-scale up-flow CWs (UFCWs) planted with Phragmites australis and Manchurian wild rice. Sivakumar et al. (2013) have reported the average removal efficiencies of 87.2%, 90.2%, 82.6%, 86.8%, 78.5%, 91.3%, and 92.8% for electrical conductivity (EC), total dissolved solids (TDSs), chloride, sulfate, phenols, BOD, and COD, respectively, from textile industry wastewater in a CW planted with Eichhornia crassipes. Shehzadi et al. (2014) have reported the average removal efficiencies of 79%, 77%, 59%, and 27% for COD, BOD, TDSs, and TSSs, respectively, from textile industry wastewater within 72 hours in a CW planted with Typha domingensis inoculated with two endophytic bacterial strains, Microbacterium arborescens TYSI04 and Bacillus pumilus PIRI30. Khan et al. (2013) and Oturkar et al. (2013) have reported the average removal efficiencies of approximately 68% ± 8%, 69% ± 8%, and 67% ± 4% for textile azodye, AO7, COD, and TOC, respectively, from AO7 dye-containing textile wastewater in a pilot-scale CW planted with Phragmites australis.

1.5 MECHANISM OF DYE DEGRADATION AND DECOLORIZATION Dyes are of highly complex nature and thus their degradation and decolorization is very challenging. Here, we focus on the mechanism of microbial degradation of azo dyes. This involves the reductive cleavage of azo bonds (–N=N–) with the help of azo reductase under anaerobic conditions and facilitates the transfer of four electrons (reducing equivalents), which proceeds through two stages at the azo linkage. In each stage, two electrons are transferred to the azo dye, which acts as a final electron acceptor, resulting in the dye decolorization and the formation of colorless solutions, and the resulting intermediates, often termed as the metabolites (e.g., aromatic amines), are further degraded, aerobically or anaerobically (Khan et al. 2012). Further, the presence of oxygen usually inhibits the azo bond reduction activity since the aerobic respiration relies on the supply of NADH, thus impeding the electron transfer from NADH to azo bonds (Chang et al. 2004) (Figure 1.2). The potential toxicity, mutagenicity, and carcinogenicity of azo dyes have been well

16

Recent Advances in Environmental Management X Redox mediatorOx Redox mediatorRed

Colorless solution containing amines NH2

X Azo bond

X

N

Azoreductase

+

N X

Colored solution containing

NADH NAD+ Oxidation Carbon products complexes Dehydrogenase (enzyme liberating e–) Cell

NH2 Oxidation NH O

FIGURE 1.2 Proposed mechanism of bacterial degradation of azo dyes. (Adapted from Pearce, C.I. et al. 2003. Dyes Pigments 58: 179–196; Khan, R. et al. 2013. Reviews in Environmental Science Biotechnology 12: 75–97.)

documented and reviewed elsewhere (Khan et al. 2013; Tian et al. 2014). A great deal of literature is in the public domain on the degradation and decolorization of azo dyes using single bacterial cultures. The species of Bacillus, Pseudomonas, Aeromonas, Proteus, Micrococcus, and purple non-sulfur photosynthetic bacteria have been found to be effective in the anaerobic degradation of a number of dyes (Khan et al. 2013; Saratale et al. 2009; Sudha et al. 2014). In contrast, under aerobic conditions, the enzymes mono- and dioxygenase catalyze the incorporation of oxygen from O2 into the aromatic ring of organic compounds prior to ring fission. However, in the presence of specific oxygencatalyzed enzymes, that is, azo reductases, some aerobic bacteria are able to degrade and decolorize the azo compounds and produce aromatic amines (Naik and Singh 2012; Pearce et al. 2003; Stolz 2001). Some examples of aerobic azo reductases were found in Pseudomonas species strains K22 and KF46 (Zimmermann et al. 1982, 1984).

1.6 PROSPECTS AND CHALLENGES Bioremediation has emerged as an inexpensive and ecofriendly technology of the degradation and decolorization of various dyes using different fungi, bacteria, yeasts and their enzymes, and plants and algae. It is becoming a promising approach for the low-cost treatment of dye-containing industrial wastewaters. The bioremediation ability of microorganisms can be enhanced by gradually exposing them to higher concentrations of dye wastewater. Adaptation of a microbial community toward toxic or recalcitrant coloring compounds has been reported to be very useful in improving the rate of the decolorization and degradation process. The adaptation of microorganisms to the higher concentrations of coloring pollutants is called acclimatization and leads


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to forced or directed evolution. Microorganisms exposed to higher levels of pollutants evolve mechanisms and pathways for degradation and decolorization of recalcitrant coloring pollutants. This happens through the expression of genes encoding for enzymes responsible for bioremediation. Alternatively, the identification, isolation, and transfer of genes encoding for bioremediation enzymes may greatly help in the designing of microbes with enhanced decolorization capabilities (engineered microbes). Further, the ecofriendly treatment of a huge amount of colored wastewater at the wastewater treatment plant is a major challenge because microbes are not greatly adapted to such highly polluted wastewater and thus need to be optimized before application on a large scale. These are the major challenges in the way of commercialization of environmental bioremediation technologies; however, continued efforts are required for improvement in existing bioremediation technologies.

1.7 CONCLUSION AND RECOMMENDATIONS Dyes are important coloring substances and are currently being applied in various industries and thus are generating a huge amount of highly colored wastewater containing a variety of recalcitrant coloring pollutants that cause serious environmental pollution and severe health hazards in living beings. From this chapter, the following conclusions and recommendations can be made:

1. Dyes are important coloring compounds, but some are highly toxic in nature and cause serious environmental pollution and health hazards, and thus their degradation and decolorization is most important for environmental protection. 2. The physico-chemical approaches are highly efficient for the degradation and decolorization of highly toxic dyes but are environmentally destructive and require high capital investment for environmental cleanup. 3. The biological approaches, especially bioremediation technologies, including bacterial treatment, mycoremediation, and phytoremediation, can be the ecofriendly approaches for the decolorization of various dyes in different kind of wastewaters for environmental safety and human health protection. 4. There is a need to search for potential microbial strains for the effective degradation and decolorization of recalcitrant coloring pollutants from various industrial effluents. 5. Further, continued efforts are required to realize the economic feasibility of bioremediation technologies, including mycoremediation and phytoremediation for field-scale applications for their commercialization in near future.

ACKNOWLEDGMENT The authors are highly thankful to the University Grant Commission (UGC) and Department of Science and Technology (DST), Government of India (GOI), New Delhi, India, for financial support for our research work.

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