August 2011, Volume 2, No.4 International Journal of Chemical and Environmental Engineering
Adsorptive removal of chromium ions from synthetic effluents by Mentha arvensis biomass: kinetic and equilibrium modeling Haq Nawaz Bhattia,b Rabia Hafiza Muhammad Asif Hanifa a
Environmental Chemistry Laboratory, Department of Chemistry and Biochemistry, University o f Agriculture, Faisalabad-38040, Pakistan b Corresponding author Email:
[email protected] Abstract In this study the binding capacity of Mentha arvensis biomass for the chromium ions from aqueous synthetic effluents was investigated as a function of pH, biosorbent dose, biosorbent size, temperature, contact time and initial metal concentration in a batch mode. Effect of pretreatments with NaOH, HCl, acetic acid, Trition X-100 and acetone was also studied. The adsorption capacity of biomass was found to be significantly increased by pretreatments. Trition X-100 pretreated biomass showed remarkable increase in sorption capacity. Maximum adsorption of Cr(III) and Cr(VI) was observed at pH 4 and 2 respectively. The adsorption of Cr(III) and Cr(VI) onto Mentha arvensis waste biomass decreased with increase in temperature and biosorbent dose while the adsorption of Cr(III) and Cr(VI) increased with increase in contact time. Equilibrium data was better described by Langmuir isotherm model as compared to Freundlich isotherm. The overall adsorption process was best described by pseudo-second-order kinetics. Desorption study was also carried out to recover the chromium ions from the biomass using different concentration of HCl.. The results indicated that Mentha arvensis biomass could be used for removal of toxic metal ions from industrial effluents. Keywords: Chromium; adsorption; kinetics, thermodynamics; recovery
1. Introduction The contamination of water streams by the environmental pollutants is a worldwide problem especially in the developing countries where high – cost remediation technology is not affordable [1]. Although water covers more than 70 % of the earth’s surface, only 1 % of the earth’s water is available as a source of drinking water. Unfortunately our limited supplies of water are often polluted with contaminants. Heavy metals ions are one of the important pollutants affecting our ecosystems. These metals ions are widely used in industrial activities such as metal finishing, electroplating, painting, dying, photography, surface treatment, printed circuit board manufacture etc. [2]. Water from different industries enters into the water bodies which affect the aquatic life. Self purification system of water fails due to high concentration of pollutants. Chromium is commonly used in metal alloys and pigments for paints, cement, paper, rubber, and other materials. Among the several oxidation states trivalent chromium and hexavalent skin and cause ulceration. Long-term exposure can cause damage to liver, kidney and nerve tissue. Chromium often accumulates in aquatic
life, adding to the danger of eating fish that may have been exposed to high levels of chromium [3-5]. According to Environmental Protection Agency (EPA), the permissible limits for chromium ions in drinking water is 0.1 mg/L Oxidation/reduction, mechanical filtration, precipitation, ion exchange, membrane separation and adsorption are commonly used methods for the removal of environmental pollutants from industrial effluents [6]. Chemical precipitation is most commonly used for remediation of chromium-containing effluents. However, the major drawbacks of this treatment technology are high cost and the production of significant amount of sludge [7]. Therefore, removal of toxic heavy metals to an environmentally safe level in a cost effective and environment friendly manner assumes great importance [8]. In recent years the search for new technologies is recommended. In this contest, biosorption has been recognized as an effective tool for the treatment of industrial effluents [9, 10]. The major advantages of biosorption over conventional treatment methods include, low cost, high efficiency, minimization of chemical and/or biological sludge, no additional nutrient requirement, regeneration of biosorbent and possibility of metal recovery.
Adsorptive removal of chromium ions from synthetic effluents by Mentha arvensis biomass: kinetic and equilibrium modeling
Mentha arvensis is cultivated world wide for its essential oil contents. Mentha arvensis distillation waste left after essential oil extraction is a waste material of no commercial importance. Keeping in view the hazardous affects of chromium ions, the present study is undertaken by utilization of immobilized Mentha arvensis (mint) waste biomass for chromium (III) and chromium (VI) uptake from aqueous solution.
2. Materials and Methods 2.1. Biomass collection Mentha arvensis biomass was collected from Agricultural fields of the University of Agriculture, Faisalabad, Pakistan. Biomass was extensively washed with distilled water to remove particulate material from their surface, and oven dried at 60 °C for 72 h. Dried biomass was cut, ground using food processor (Moulinex, France) and then sieved through Octagon siever (OCT-DIGITAL) 4527-01) to obtain adsorbent with homogenous known particle size. The fraction with < 0.250-1.00 mm was selected for use in the adsorption studies.
2.2. Pretreatments of biomass In order to test the effects of chemical pretreatments on the chromium uptake capacity, the biomass of Mentha arvensis was pretreated with 0.1N NaOH, 0.1N HCI,, 0.1N acetone, 0.1 N acetic acid and 0.1N Triton-X100 (5 g of biomass/ 50 mL of each chemical solution) in orbital shaking incubator (PA 250/25.H) at 150 rpm and 30 °C for 30 min. These pretreatments were done to check enhancement or decrease in adsorption capacity of biomass [3, 6]. Then these pretreated biomasses were filtered through (Whatman No. 40, ashless) and washed extensively with DDW up to neutral pH, followed by drying and grinding. The pretreated biomass was sieved through Octagon siever (OCT-DIGITAL 4527-01) to obtain adsorbent with homogenous known particle size ( acetone (52.39) >HCl (51.35) > NaOH (50.23) > native (48.77). Similarly for Cr(VI), the decreasing order was : Triton-X-100 (59.09)> acetic acid (54.57)> acetone (53.25) >HCl (53.13) > NaOH (51.35) > native (48.77) (Fig. 9). Surfactants and acids can enhance uptake capacity of biomass by increasing the surface area and porosity of original sample [6]. Similarly organic solvents remove the lipids of biomass and hence more adsorptions sites are available for the adsorbents. Removal of impurities from surface and rupturing of cellmembrane is reason behind the increase in metal uptake capacity of biomass after basis pretreatment [24].
4. Conclusions In this study Mentha arvensis biomass was used to adsorb chromium ions from aqueous solutions. The experimental results revealed that the adsorption capacity of biomass was significantly increased by pretreatments and maximum adsorption capacity was obtained with Trition X-100 pretreated biomass. Maximum removal of Cr(III) and Cr(VI) was observed at pH 4 and 2 respectively. The adsorption capacity of Mentha arvensis waste biomass decreased with increase in temperature and biosorbent dose. Equilibrium data was better described by Langmuir isotherm model as compared to Freundlich isotherm, indicating that adsorption of chromium on biomass was as a monolayer. The results showed that Mentha arvensis biomass has potential to remove the toxic metal ions from industrial effluents. ACKNOWLEDGEMENTS The authors are thankful to Higher Education Commission of Pakistan for financial assistance.
70 Cr (III) Cr (VI )
60
REFERENCES
q(mg/g)
50
40
30
[1]
B. Volesky, “Sorption and Biosorption” BV-Sorbex Inc., St. Lambert, Quebec, Canada, 2003, pp. 316.
[2]
S.K. Papageorgiou, F.K. Katsaros, E.P. Kouvelos, J.W. Nolan, H.L. Deit, N.K. Kanellopoulos, “Heavy metal sorption by calcium alginate beads from Laminaria digitata,” J. Hazard. Mater. Vol. 137, pp. 1765– 1772, 2006.
[3]
G. Yan, T. Viraraghavan, “Effect of pretreatment on the bioadsorption of heavy metals on Mucor rouxii,” Water SA, Vol. 26, pp.119–124, 2000.
[4]
H. Barrera, F.U. Nunez, B. Bilyeu, C.B. Diaz, “Removal of chromium and toxic ions presents in mine drainage by Ectodermis of Opuntia,” J. Hazard. Mater. Vol. 136, pp. 846853, 2006.
[5]
A.R. Iftikhar, H.N. Bhatti, M.A. Hanif, R. Nadeem, “Kinetic and thermodynamic aspects of Cu(II) and Cr(III) removal from aqueous solutions using rose waste biomass,” J. Hazard. Mater. Vol.161, pp. 941–947, 2009.
[6]
H.N. Bhatti, B. Mumtaz, M.A. Hanif, R. Nadeem, “Removal of Zn (II) ions fro aqueous solution using Moringa oleifera Lam. (Horseradish tree) biomass,” Process Biochem. Vol, 42, pp. 547-553, 2007.
[7]
Y.S.Yun, D. Park, J.M. Park, B. Volesky,“ Biosorption of trivalent chromium on the brown seaweed biomass,” Environ. Sci. Technol. Vol. 35, pp. 4353-4358, 2001.
[8]
S.S. Ahluwalia, D. Goyal, “Microbial and plant derived biomass for removal of heavy metals from wastewater,” Bioresour. Technol. Vol. 8, pp. 2243- 2257, 2006.
[9]
M.A. Hanif, R. Nadeem, H.N. Bhatti, N.R. Ahmed, T.M. Ansari, “Ni(II) biosorption by Cassia fistula (Golden Shower) biomass,” J. Hazard. Mater, Vol.139, pp.345-355, 2007.
[10]
H.N. Bhatti, R. Khalid, M.A. Hanif, “Dynamic biosorption of Zn(II), Cu(II) using pretreated Rosa gruss an teplitz (red rose) distillation sludge,” Chem. Eng. J. 148, pp. 434– 443, 2009.Vol.
[11]
B. Volesky, Z.R. Holan, “Biosorption of heavy metals – review,” Biotechnol. Prog., Vol. 11, pp. 235-250, 1995.
20
10
0 Nat ive
NaOH
Aceto ne
Acet ic acid
Trit on X-100
HCl
Fig. 9: Effect of pretreatments on the sorption of Cr (III) and Cr (VI) from aqueous solution by Mentha arvensis biomass.
3.10. Desorption study: Desorption study is usually conducted to explore the possibility of recovery of adsorbent and adsorbate, which in turn as expected to make the adsorption process economical [25]. After the adsorbent was saturated with metal ions, it was regenerated with different concentration of HCl (Fig. 10). The quantitative recovery of metal ions is possible. Maximum desorption (84 %) of chromium ions occurred at 0.5 and 0.6 HCl solution. This confirms that ions exchange is the phenomenon of the desorption process. Cr ( III) Cr ( IV)
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%Recovered
84 82 80 78 76 74 72 0.1
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HCl (M)
Fig. 10: Effect of desorption on Cr (III) and Cr (VI) from aqueous solution by Mentha arvensis biomass.
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Adsorptive removal of chromium ions from synthetic effluents by Mentha arvensis biomass: kinetic and equilibrium modeling
[12] N.R. Bishnoi, A. Pant, Garima, “ Biosorption of copper from aqueous solution using algal biomass,” J. Sci. Ind. Res. Vol. 63, pp. 813-816, 2004. [13]
N. Tewari, P. Vasudevan, B.K. Guha, “Study of biosorption of Cr(VI) by Mucor hiemalis. Biochem. Eng. J. Vol. 23, pp.185192, 2005.
[20] F. Shafqat, H.N. Bhatti, M.A. Hanif, A. Zubair, “Kinetic and equilibrium studies of Cr(III) and Cr(VI) sorption from aqueous solution using Rosa gruss an teplitz (red rose) waste biomass,” J. Chil. Chem. Soc. Vol. 54, pp.1-6, 2008. [21]
B.R. Sudha, T.E. Abraham. “Biosorption of Cr(VI) from aqueous solution by Rizopus nigricans. Bioresour. Technol. Vol. 79, 73-81, 2001.
[22]
Z. Aksu, T.A. Kutsal, “A bioseqaration process for removing Pb(II) ions form wastewater by using C. vulgaris,” J. Chem. Technol. Biotechnol., Vol. 52, pp. 108-118, 1991.
R. Saravanane, T. Sundararajan, S. Sivamurthyreddy, “Efficiency of chemically modified low cost adsorbents for the removal of eavy metals from wastewater,” Ind. J. Environ. Health Vol. 44, pp.78-81, 2002.
[23]
[16] A. Ozer, D. Ozer, “Comparative study of the biosorption of Pb (II), Ni (II) and Cr (VI) ions onto S.cerevisiae: determination of biosorption heats,” J. Hazard. Mater. Vol. 100, pp.219-229, 2003.
S. Tunali, I. Kiran, T. Akar, “Chromium (VI) biosorption Characteristics of Neurospora crassa fungal biomass,” Mineral Eng. Vol. 18, pp. 681-689, 2005.
[24]
S.F. Nomanbhay, Palanisamy, “Removal of heavy metal from Industrial waste water using chitosan coated oil palm shell chaorcoal,” Elec. J. Biotechnol. Vol. 8, pp. 44-53, 2005.
M. Loace, R. Olier, J. Guezennec, “Uptake of lead, cadmium and zinc by a novel bacterial expolysaccharide,” Water Res. Vol. 31, pp. 1171-1179, 1997.
[25]
M. Arami,N.Y. limaee, N.M. Mahmoodi, N.S. Tabrizi, “Removal of dyes from colored textile waste water by orange peel adsorbent equilibrium and kinetic studies,” J. Coll. Sci. Vol. 288, pp.371-376, 2005.
[14]
[15]
[17]
Y. Sahin, A. Ozturk, “Biosorption of chromium(VI) ions from aqueous solution by the bacterium Bacillus thuringiensis,” Process Biochem. Vol. 40, pp.1895–1901, 2005.
[18]
B. Cordero, P. Loderio, R. Herrero, M.E.S. de-Vicente, “Biosorption of cadmium by Fucus spiralis,” Environ. Chem. Vol.1, pp.180-187, 2004.
[19]
Zubair, A. H.N. Bhatti, M.A. Hanif, F. Shafqat, “Kinetic and equilibrium modeling for Cr (III) and Cr (VI) removal from aqueous solutions by Citrus reticulata waste biomass,” Water, Air & Soil Pollut. Vol. 191, pp. 305-318, 2008.
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