Feb 25, 2007 - Informa Ltd Registered in England and Wales Registered Number: 1072954 ... simulated effluents of the copper industry, Hindustan Copper Limited, Ghatshila, India, ... dried at 60°C, ground into small particles and used as biosorbent. .... K. Christian, "Biosorption of zinc by mycelial wastes" Appl. Microbiol.
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Decontamination of metals from metallurgical effluent utilizing rhizopus arrhizus biomass a
E. Subudhi & R. N. Kar
a
a
Regional Research Laboratory (CSIR) , Bhubaneswar, 751 013, India Published online: 25 Feb 2007.
To cite this article: E. Subudhi & R. N. Kar (1996) Decontamination of metals from metallurgical effluent utilizing rhizopus arrhizus biomass, International Journal of Environmental Studies, 50:2, 111-116, DOI: 10.1080/00207239608711046 To link to this article: http://dx.doi.org/10.1080/00207239608711046
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Intern. J. Environmental Studies, 1996, Vol. 50, pp. 111-116 Reprints available directly from the publisher Photocopying permitted by license only
© 1996 OPA (Overseas Publishers Association) Amsterdam B.V. Published in The Netherlands under license by Gordon and Breach Science Publishers SA Printed in Malaysia
DECONTAMINATION OF METALS FROM METALLURGICAL EFFLUENT UTILISING RHIZOPUS ARRHIZUS BIOMASS E. SUBUDHI and R. N. KAR* Downloaded by [University of Bristol] at 07:46 27 February 2015
Regional Research Laboratory (CSIR), Bhubaneswar India (Received in Final Form: July 10, 1994) Rhizopus arrhizus biomass adsorbed copper at a faster rate than nickel and the kinetics of copper adsorption remained unaffected in presence of nickel. Change in pH of mixed solution from 4.5 to 6.0 had very little but favourable effect on adsorption rates of both metals. The rate of biosorption increased with the increase of contact time from 30 to 60 minutes at lower biomass concentration (< 0.30 gms.). At optimum pH (5.5) and contact time (60 mins), increase in biomass concentration from 0.1 to 1.0 gm showed a marked increase in uptake rates of both copper and nickel. About 99% of total metal could be removed from solution by taking 1.0 gm of biomass. KEYWORDS: Biosorption, wastewater, rhizopus arrhizus, biomass, copper, nickel.
INTRODUCTION Discharge of untreated and incompletely treated effluents of metallurgical industries, is the major source of heavy metal pollution in aquatic ecosystems, in addition to other important sources such as indiscriminate use of pesticides and acid mine drainage. 1 Metallurgical effluents usually contain more than one metal and this requires the search for efficient treatment techniques before disposal into water bodies. The waste biomass of different fungal species of Aspergillus, Rhizopus and Penicillium etc from antibiotics and alcohol industries have been know for their metal decontamination ability from synthetic and waste solutions.2'9 However, their potential to trap metals from the metallurgical effluents containing more than one metal is yet to be thoroughly investigated. In the present paper, the results of investigation on the usability of dead Rhizopus arrhizus biomass to remove copper and nickel from synthetic solutions as well as from simulated effluents of the copper industry, Hindustan Copper Limited, Ghatshila, India, containing copper and nickel, is reported. Effects of different parameters on metal sorbing capacity were studied and optimised.
*To whom correspondence should be addressed: R. N. Kar, Regional Research Laboratory, Bhubaneswar 751 013, India 111
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E. SUBUDHI AND R. N. KAR
EXPERIMENTAL Biosorbent The filamentous fungus Rhizopus arrhizus (NCIM 878), grown for four days in Martin's Rose bengal broth containing (g/L) Glucose 10, peptone 5, MgSO4 • 7H2O 0.5, Rose bengal 0.033 at pH 7.0, was autoclaved at 120°C for 15 mins. The killed biomass was dried at 60°C, ground into small particles and used as biosorbent.
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Adsorbate Weighed quantities of copper and nickel sulphate salts of AnalaR grade were used separately for the preparation of 30 mg/L solution. These salts were also taken together to prepare a mixed synthetic solution containing 30 mg/L copper and nickel each. Initial pH of the solution was adjusted to 4.5 and 6.0 from the original pH of 5.5 by using 0.1 N HCLandO.lNNaOH. Adsorption experiment Weighed biomass was taken in a glass reactor containing 100 ml of solution bearing copper and nickel individually and in combination and stirred at 200 rpm. Samples were drawn at intervals of 30, 60 and 90 minutes. The collected samples were filtered and necessary dilutions were made to analyse copper and nickel concentration by AAS. All exeperiments were done at 32°C. Different sets of experiments were carried out to study the effect of several parameters, such as presence of other metal, pH, contact time and biomass concentration on the metal accumulating capacity of the biosorbent.
RESULTS AND DISCUSSION Copper adsorption by Rhizopus arrhizus biomass follows more rapid kinetics than nickel from their respective solutions with an initial concentration of 30 mgfl. 96.66% of copper and 74.99% of nickel were found to be adsorbed at pH 5.5, contact time of 60 minutes and biomass concentration 0.3 gms. Adsorption of copper and nickel at different contact times were shown in Figure 1. Coionic effect The rate of copper biosorption was remained unaffected in presence of nickel, whereas the rate of nickel bioadsorption was found to be reduced to 61.9% from 74.99%, which might be due to the presence of copper in solution. The results are shown in the Figure 1. This indicates that there is no much synergistic or antagonistic effect of nickel on copper adsorption but copper has a little antagonistic effect on nickel adsorption. In other words the sites for copper adsorption might not be affected by the presence of nickel whereas copper ions in the solution seems to compete for sites of nickel adsorption.
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METALS REMOVAL FROM EFFLUENTS
Adsorption in % .
100
1-
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80
60
40
20
m HI Ba fflfk
mm
Eg ran
mm
BBBSn
m
H
1 i 1 11
1 11 11
il
n
1 60
30
NI
I 1 1 •
90
Time in mins.
NI (Nl+Cu)
Cu
Cu (Nl+Cu)
FIGURE 1 Coionic effect of Ni and Cu on adsorption rate at various contact times from mixed (Ni + Cu) and individual solutions.
Effects ofpH It is clear from the data given in Table I that increase in solution pH from 4.5 to 5.5 showed only a slight change in adsorption rate of both the metals, with an uptake of 29.83 mg/L of copper and 29.81 mg/L of nickel, respectively, and pH higher than 5.5 had no effect on the adsorption rate. However, to carry out experiments at pH > 6.0, another factor, chemical precipition was introduced Therefore, throughout the experiments pH 5.5 was considered optimum. Effect of contact time Rate of adsorption of both the metals was found to be higher at 60 minutes than at 30 minutes contact time but thereafter remained unchanged up to 90 minutes, as shown in
E. SUBUDHI AND R. N. KAR
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TABLE I Effect of pH on adsorption of copper and nickel by Rhizopus arrhizus biomass. pH of the solution
Contact time (mins.)
Nickel (mg/1)
Copper (mg/1)
4.5
0 30 60
0 27.50 28.00
0 28.00 28.50
2.
5.5
0 30 60
0 28.20 28.82
0 29.20 29.80
3.
6.5
0 30 60
0 28.25 28.90
0 29.31 29.83
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No of Exps.
Adsorption In mg
0.3
Cu (30)
0.5 0.7 Biomass in gms. I Cu (60)
CZU NI (30)
Ni (60)
FIGURE 2 Adsorption of Cu and Ni at different biomass concentrations and contact times (30 and 60 minutes). pH = 5.5 Metal concentration = 30.0 mg/L.
METALS REMOVAL FROM EFFLUENTS
115
Figure 1. However, it was of interest to note that the contact time had little effect on kinetics of adsorption when the biomass concentration was increased to more than 0.3 gm, as in Figure 2. At lower biomass concentration the ratio of binding sites to metal ions available was low. Therefore, a slower rate of adsorption resulted and binding sites remained unsaturated for a longer period of contact time, i.e. up to 60 mins sequestering about 99% of both the metals at 0.3 gm biomass concentration, as in Figure 1. But when the biomass concentration was high, the above ratio becomes high and more rapid kinetics were observed within the initial 30 mins, as shown in Figure 2.
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Effect of biomass concentration As depicted in Figure 2, the increase in biomass concentration from 0.1 to 1.0 gm. at optimum conditions showed a remarkable increase in uptake of both copper (29.83 mg) and nickel (29.82 mg), respectively, and there was a reduction in contact time to 30 mins. About 99% of both the metals could be removed from the solution using 1.0 gm of biomass. This might be due to the availability of sufficient binding sites at higher biomass concentration as compared to the metal ions. CONCLUSIONS i) ii) iii) iv)
v)
Copper follows more rapid kinetics than nickel adsorption. Copper has little antagonistic effect on nickel adsorption when both are present in the solution. pH 5.5 was chosen optimum for adsorption of copper and nickel. Either higher contact time at lower biomass concentration or lower contact time at higher biomass concentration should be maintained for efficient removal of metals. Rhizopus arrhizus biomass can serve as a suitable biosorbent to remove copper from effluent of copper industries, even when nickel is present in significant quantity.
ACKNOWLEDGEMENTS
The authors are thankful to H.O.D, Dr. R. P. Das, for his valuable suggestions and Director, RRL Bhubaneswar, for giving permission to publish this paper. The encouragement and help of Dr. G. Roychoudhury is gratefully acknowledged. The authors also acknowledge the financial support of DOE, Govt. of India, for the research work.
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3. D. W. Darnall and A. Gabel, "A new biotechnology for recovering heavy metal ions from waste waters" Proc. Third Intl. Conf. Frontier for Hazadous Water Management, Washington D.C., US Govt. Printing office, EPA/600/9-89/072. 217-225 (1989). 4. E. Fourest and J. C. Roux, "Heavy metal biosorption by fungal mycelial by-products, mechanisms and influence of pH" Appl. Microbiol. Biotechnol. 36, 399-403 (1992). 5. N. Kuyucak and B. Volesky, "Biosorbents for recovery of metals from industrial solutions" Biotechnol. Letters 10, 137-172 (1988). 6. L. de Rome and G. M. Gadd, "Copper Adsorption by Rhizopus arrhizus, Cladosporium resinae, Penicilium italium", Appl. Microbol. Biotechnol. 26, 84-90 (1987). 7. L. Shoujian, Y. Changhou, Z. Dayuan and T. Junjie, "Adsorption of lead by Rhizopus arrhizus biomass" Sichuan Daxue. Xuebao. Ziran. Kexueban. 28, 261-264 (1991). 8. L. Edith, P. Theodor and K. Christian, "Biosorption of zinc by mycelial wastes" Appl. Microbiol. Biotechnol. 34, 688-692 (1991). 9. A. Zumriye, S. Yesim and K. Tulin, "The usage of microorganisms in wastewater treatement containing copper(II) ions" (Recent Adv. Biotechnol.) NATO ASI Ser. Ser. E. 210, 545-546 (1992).
