Evaluating hexavalent chromium reduction and electricity production in microbial fuel cells with alkaline cathodes

  • N. Xafenias
  • Y. Zhang
  • C. J. Banks
Original Paper


The work investigated the efficiency of microbial fuel cells (MFCs) for the treatment of alkaline hexavalent chromium containing wastewater. When lactate was used as the metal chelator in alkaline (pH 8) abiotic cathodes, hexavalent chromium concentration dropped from 10 mg l−1 to undetectable levels within the first 45 h of operation. Power density produced in the pH 8 abiotic cathodes was up to 21.4 mW m−2, and in the pH 9 cathodes up to 2.4 mW m−2; these values were well comparable with other values found in the literature for biologically catalysed cathodes, even at lower pH values. When Shewanella oneidensis MR-1 was present in a hexavalent chromium reducing cathode at pH 8, current production contributed by 26 % to the total hexavalent chromium reduced during the 36 days of operation. On the other hand, when hexavalent chromium (10 mg l−1) was controllably added in the anode where S. oneidensis MR-1 was present, up to 73 % of current decreased immediately after every hexavalent chromium addition; this toxic effect remained even after hexavalent chromium was depleted in the anode and strongly indicates that the presence of hexavalent chromium in the anodes of MFCs must be avoided. Overall, our results indicate that alkaline hexavalent chromium wastewater can be effectively remediated in the cathodes of MFCs, provided that a metal chelator is present in the cathodes and that hexavalent chromium is not present in the anodes.


Bioelectrochemical systems Hexavalent chromium remediation Shewanella oneidensis MR-1 Lactate High pH Hexavalent chromium toxicity 



Funding in support of this work was provided by the Faculty of Engineering and the Environment, University of Southampton, UK.


  1. Alam M, Hossain A, Yonge DR, Peyton BM, Petersen JN (2006) Bioreduction of hexavalent chromium in flow-through quartz sand columns. J Environ Eng 132(3):358–366CrossRefGoogle Scholar
  2. APHA (2005) Standard methods for the examination of water and wastewater. Standard Methods for the Examination of Water and Wastewater, 21st-Centennial edn. American Public Health Association (APHA), American Water Works Association (AWWA), Water Environment Federation (WEF), Washington DCGoogle Scholar
  3. Bencheikh-Latmani R, Obraztsova A, Mackey MR, Ellisman MH, Tebo BM (2007) Toxicity of Cr(III) to Shewanella sp. strain MR-4 during Cr(VI) reduction. Environ Sci Technol 41(1):214–220. doi: 10.1021/es0622655 CrossRefGoogle Scholar
  4. Bowmer CT, Hooftman RN, Hanstveit AO, Venderbosch PWM, van der Hoeven N (1998) The ecotoxicity and the biodegradability of lactic acid, alkyl lactate esters and lactate salts. Chemosphere 37(7):1317–1333. doi: 10.1016/s0045-6535(98)00116-7 CrossRefGoogle Scholar
  5. Brandhuber P, Frey M, McGuire MJ, Chao P, Seidel C, Amy G, Yoon J, McNeill L, Banerjee K (2004) Low-level hexavalent chromium treatment options: bench-scale evaluation. American water works association Research FoundationGoogle Scholar
  6. Brodie EL, Joyner DC, Faybishenko B, Conrad ME, Rios-Velazquez C, Malave J, Martinez R, Mork B, Willett A, Koenigsberg S, Herman DJ, Firestone MK, Hazen TC (2011) Microbial community response to addition of polylactate compounds to stimulate hexavalent chromium reduction in groundwater. Chemosphere 85(4):660–665. doi: 10.1016/j.chemosphere.2011.07.021 CrossRefGoogle Scholar
  7. Chaudhuri SK, Lovley DR (2003) Electricity generation by direct oxidation of glucose in mediatorless microbial fuel cells. Nat Biotechnol 21(10):1229–1232CrossRefGoogle Scholar
  8. Clark WJ, McCreery RL (2002) Inhibition of corrosion-related reduction processes via chromium monolayer formation. J Electrochem Soc 149(9):B379–B386CrossRefGoogle Scholar
  9. Deng B, Stone AT (1996) Surface-catalyzed chromium(VI) reduction: reactivity comparisons of different organic reductants and different oxide surfaces. Environ Sci Technol 30(8):2484–2494. doi: 10.1021/es950780p CrossRefGoogle Scholar
  10. Farmer JC, Bahowick SM, Harrar JE, Fix DV, Martinelli RE, Vu AK, Carroll KL (1997) Electrosorption of chromium ions on carbon aerogel electrodes as a means of remediating ground water. Energy Fuels 11(2):337–347. doi: 10.1021/ef9601374 CrossRefGoogle Scholar
  11. Hamada YZ, Carlson B, Dangberg J (2005) Interaction of malate and lactate with chromium(III) and iron(III) in aqueous solutions. Synth React Inorg Met-Organ Nan-Met Chem 35(7):515–522. doi: 10.1080/15533170500198887 CrossRefGoogle Scholar
  12. Hsu L, Masuda SA, Nealson KH, Pirbazari M (2012) Evaluation of microbial fuel cell Shewanella biocathodes for treatment of chromate contamination. RSC Adv 2(13):5844–5855CrossRefGoogle Scholar
  13. Huang L, Chen J, Quan X, Yang F (2010) Enhancement of hexavalent chromium reduction and electricity production from a biocathode microbial fuel cell. Bioprocess Biosyst Eng 33(8):937–945CrossRefGoogle Scholar
  14. Huang L, Chai X, Chen G, Logan BE (2011a) Effect of set potential on hexavalent chromium reduction and electricity generation from biocathode microbial fuel cells. Environ Sci Technol 45(11):5025–5031. doi: 10.1021/es103875d CrossRefGoogle Scholar
  15. Huang L, Chai X, Cheng S, Chen G (2011b) Evaluation of carbon-based materials in tubular biocathode microbial fuel cells in terms of hexavalent chromium reduction and electricity generation. Chem Eng J 166(2):652–661. doi: 10.1016/j.cej.2010.11.042 CrossRefGoogle Scholar
  16. Hurley BL, McCreery RL (2003) Raman spectroscopy of monolayers formed from chromate corrosion inhibitor on copper surfaces. J Electrochem Soc 150(8):B367–B373CrossRefGoogle Scholar
  17. Kim JR, Cheng S, Oh S-E, Logan BE (2007) Power generation using different cation, anion, and ultrafiltration membranes in microbial fuel cells. Environ Sci Technol 41(3):1004–1009. doi: 10.1021/es062202m CrossRefGoogle Scholar
  18. Li ZJ, Zhang XW, Lei LC (2008) Electricity production during the treatment of real electroplating wastewater containing Cr6+ using microbial fuel cell. Process Biochem 43(12):1352–1358. doi: 10.1016/j.procbio.2008.08.005 CrossRefGoogle Scholar
  19. Li Y, Lu AH, Ding HR, Jin S, Yan YH, Wang CQ, Zen CP, Wang X (2009) Cr(VI) reduction at rutile-catalyzed cathode in microbial fuel cells. Electrochem Commun 11(7):1496–1499. doi: 10.1016/j.elecom.2009.05.039 CrossRefGoogle Scholar
  20. Liu L, Yuan Y, Li F-b, Feng C-h (2011) In-situ Cr(VI) reduction with electrogenerated hydrogen peroxide driven by iron-reducing bacteria. Bioresour Technol 102(3):2468–2473. doi: 10.1016/j.biortech.2010.11.013 CrossRefGoogle Scholar
  21. Palmer CD, Puls RW (1994) Natural attenuation of hexavalent chromium in groundwater and soils. EPA Ground Water Issue. U.S. Environmental Protection AgencyGoogle Scholar
  22. Pandit S, Sengupta A, Kale S, Das D (2011) Performance of electron acceptors in catholyte of a two-chambered microbial fuel cell using anion exchange membrane. Bioresour Technol 102(3):2736–2744. doi: 10.1016/j.biortech.2010.11.038 CrossRefGoogle Scholar
  23. Pinchuk GE, Geydebrekht OV, Hill EA, Reed JL, Konopka AE, Beliaev AS, Fredrickson JK (2011) Pyruvate and lactate metabolism by Shewanella oneidensis MR-1 under fermentative, oxygen-limited and fumarate-respiring conditions. Appl Environ Microbiol:AEM.05382-05311. doi: 10.1128/aem.05382-11
  24. Puzon GJ, Roberts AG, Kramer DM, Xun L (2005) Formation of soluble organo-chromium(III) complexes after chromate reduction in the presence of cellular organics. Environ Sci Technol 39(8):2811–2817. doi: 10.1021/es048967g CrossRefGoogle Scholar
  25. Rabaey K, Ossieur W, Verhaege M, Verstraete W (2005) Continuous microbial fuel cells convert carbohydrates to electricity. Water Sci Technol 52(1):515–523Google Scholar
  26. Rosenbaum M, Cotta MA, Angenent LT (2010) Aerated Shewanella oneidensis in continuously fed bioelectrochemical systems for power and hydrogen production. Biotechnol Bioeng 105(5):880–888Google Scholar
  27. Silva A, Kong X, Hider R (2009) Determination of the pKa value of the hydroxyl group in the α-hydroxycarboxylates citrate, malate and lactate by 13C NMR: implications for metal coordination in biological systems. Biometals 22(5):771–778. doi: 10.1007/s10534-009-9224-5 CrossRefGoogle Scholar
  28. Stewart DI, Burke IT, Mortimer RJG (2007) Stimulation of microbially mediated chromate reduction in alkaline soil-water systems. Geomicrobiol J 24(7):655–669CrossRefGoogle Scholar
  29. Sun X-F, Ma Y, Liu X-W, Wang S-G, Gao B-Y, Li X-M (2010) Sorption and detoxification of chromium(VI) by aerobic granules functionalized with polyethylenimine. Water Res 44(8):2517–2524CrossRefGoogle Scholar
  30. Tandukar M, Huber SJ, Onodera T, Pavlostathis SG (2009) Biological chromium(VI) reduction in the cathode of a microbial fuel cell. Environ Sci Technol 43(21):8159–8165. doi: 10.1021/es9014184 CrossRefGoogle Scholar
  31. U.S.E.P.A. (2000) In situ treatment of soil and groundwater contaminated with chromium-technical resource guide. U.S. Environmental Protection Agency, Office of Research and Development, Washington DCGoogle Scholar
  32. Vollbrecht D, Nawawy MA, Schlegel HG (1978) Excretion of metabolites by hydrogen bacteria I. Autotrophic and heterotrophic fermentations. Eur J Appl Microbiol Biotechnol 6(2):145–155. doi: 10.1007/bf00504426 CrossRefGoogle Scholar
  33. Wang G, Huang LP, Zhang YF (2008) Cathodic reduction of hexavalent chromium [Cr(VI)] coupled with electricity generation in microbial fuel cells. Biotechnol Lett 30(11):1959–1966. doi: 10.1007/s10529-008-9792-4 CrossRefGoogle Scholar
  34. Xafenias N, Zhang Y, Banks C (2013) Enhanced performance of hexavalent chromium reducing cathodes in the presence of Shewanella oneidensis MR-1 and lactate. Environ Sci Technol 47(9):4512–4520. doi: 10.1021/es304606u CrossRefGoogle Scholar
  35. Zhang B, Feng C, Ni J, Zhang J, Huang W (2012) Simultaneous reduction of vanadium (V) and chromium (VI) with enhanced energy recovery based on microbial fuel cell technology. J Power Sour. doi: 10.1016/j.jpowsour.2012.01.013

Copyright information

© Islamic Azad University (IAU) 2014

Authors and Affiliations

  1. 1.Industrial Biotechnology Group, Department of Chemical and Biological EngineeringChalmers University of TechnologyGothenburgSweden
  2. 2.Bioenergy and Organic Resources Research Group, Faculty of Engineering and the EnvironmentUniversity of SouthamptonHighfield, SouthamptonUK

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