Improved chromium reduction and removal from wastewater in continuous flow bioelectrochemical systems

  • Shashikanth Gajaraj
  • Xining Sun
  • Chiqian ZhangEmail author
  • Zhiqiang HuEmail author
Research Article


Bioelectrochemical systems (BESs) including microbial electrolysis cells (MECs) and microbial fuel cells (MFCs) are promising for hexavalent chromium [Cr(VI)] reduction and total chromium (Cr) removal from wastewater. This study assessed the performance of simple, inexpensive, and continuous flow BESs with neither cathode catalyst nor proton exchange membrane for Cr(VI) reduction and total Cr removal. The effect of bioreactor configuration and wastewater feed mode on the performance of the BESs was investigated. Biological Cr(VI) reduction in the MEC followed a first-order kinetics with a rate constant of 0.103 d−1, significantly higher than that of the control (0.033 d−1). For comparison, the first-order reduction rate constants in the MFCs with the Cr(VI) fed to the anodic and the cathodic zones were 0.072 and 0.064 d−1, respectively. The BESs improved total Cr removal through coprecipitating Cr(III) and phosphors as evidenced from the scanning electron microscopy energy-dispersive X-ray spectroscopy analysis. The total Cr removal efficiencies in the control, MFCs, and MEC were 26.1%, 56.7%, and 66.2%, respectively. Only 25.1% to 26.7% of total Cr was present intracellularly in the BESs (both MFCs and MEC), whereas 31.8% ± 1.4% and 38.0% ± 0.9% of total Cr in the anodic and cathodic zones of the control were present intracellularly. Overall, the BESs demonstrated a great potential to reduce Cr(VI) and remove total Cr with the MEC having the fastest Cr(VI) reduction and most efficient total Cr removal. Furthermore, the BESs significantly reduced the intracellular total Cr content.


Microbial fuel cell Microbial electrolysis cell Bioelectrochemical systems Hexavalent chromium Coprecipitation Wastewater 


Funding information

This work was financially supported by the MIZZOU Advantage Program at the University of Missouri (Columbia, MO).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Al-Shannag M, Al-Qodah Z, Bani-Melhem K, Qtaishat MR, Alkasrawi M (2015) Heavy metal ions removal from metal plating wastewater using electrocoagulation: kinetic study and process performance. Chem Eng J 260:749–756Google Scholar
  2. APHA (2012) Standard Methods for the Examination of Water and Wastewater, American Public Health Association (APHA), American Water Works Association (AWWA), and Water Environment Federation (WEF), 22nd edn, Washington, DC, USAGoogle Scholar
  3. Arias YM, Tebo BM (2003) Cr(VI) reduction by sulfidogenic and nonsulfidogenic microbial consortia. Appl Environ Microbiol 69(3):1847–1853Google Scholar
  4. Bozzola JJ, Russell LD (1999) Electron Microscopy: Principles and Techniques for Biologists, 2nd edn. Jones and Bartlett Publishers, Inc, Boston, USAGoogle Scholar
  5. Buerge IJ, Hug SJ (1997) Kinetics and pH dependence of chromium(VI) reduction by iron(II). Environ Sci Technol 31(5):1426–1432Google Scholar
  6. Cheballah K, Sahmoune A, Messaoudi K, Drouiche N, Lounici H (2015) Simultaneous removal of hexavalent chromium and COD from industrial wastewater by bipolar electrocoagulation. Chem Eng Process 96:94–99Google Scholar
  7. Chen JM, Hao OJ (1998) Microbial chromium (VI) reduction. Crit Rev Environ Sci Technol 28(3):219–251Google Scholar
  8. Cheng S, Liu H, Logan BE (2006) Increased power generation in a continuous flow MFC with advective flow through the porous anode and reduced electrode spacing. Environ Sci Technol 40(7):2426–2432Google Scholar
  9. Clauwaert P, Rabaey K, Aelterman P, De Schamphelaire L, Pham TH, Boeckx P, Boon N, Verstraete W (2007) Biological denitrification in microbial fuel cells. Environ Sci Technol 41(9):3354–3360Google Scholar
  10. Eary LE, Rai D (1987) Kinetics of chromium(III) oxidation to chromium(VI) by reaction with manganese dioxide. Environ Sci Technol 21(12):1187–1193Google Scholar
  11. Gajaraj S, Hu Z (2014) Integration of microbial fuel cell techniques into activated sludge wastewater treatment processes to improve nitrogen removal and reduce sludge production. Chemosphere 117:151–157Google Scholar
  12. Gregory KB, Lovley DR (2005) Remediation and recovery of uranium from contaminated subsurface environments with electrodes. Environ Sci Technol 39(22):8943–8947Google Scholar
  13. Gupta S, Yadav A, Verma N (2017) Simultaneous Cr(VI) reduction and bioelectricity generation using microbial fuel cell based on alumina-nickel nanoparticles-dispersed carbon nanofiber electrode. Chem Eng J 307:729–738Google Scholar
  14. Habibul N, Hu Y, Wang YK, Chen W, Yu HQ, Sheng GP (2016) Bioelectrochemical chromium(VI) removal in plant-microbial fuel cells. Environ Sci Technol 50(7):3882–3889Google Scholar
  15. Han R, Li F, Liu T, Li X, Wu Y, Wang Y, Chen D (2016) Effects of incubation conditions on Cr(VI) reduction by c-type cytochromes in intact Shewanella oneidensis MR-1 cells. Front Microbiol 7:746Google Scholar
  16. Hosseini MS, Belador F (2009) Cr(III)/Cr(VI) speciation determination of chromium in water samples by luminescence quenching of quercetin. J Hazard Mater 165(1-3):1062–1067Google Scholar
  17. Hu Z, Chandran K, Grasso D, Smets BF (2002) Effect of nickel and cadmium speciation on nitrification inhibition. Environ Sci Technol 36(14):3074–3078Google Scholar
  18. 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):937–945Google Scholar
  19. 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):5025–5031Google Scholar
  20. Huang L, Cheng S, Chen G (2011b) Bioelectrochemical systems for efficient recalcitrant wastes treatment. J Chem Technol Biotechnol 86(4):481–491Google Scholar
  21. Huang L, Wang Q, Jiang L, Zhou P, Quan X, Logan BE (2015) Adaptively evolving bacterial communities for complete and selective reduction of Cr(VI), Cu(II), and Cd(II) in biocathode bioelectrochemical systems. Environ Sci Technol 49(16):9914–9924Google Scholar
  22. Ishibashi Y, Cervantes C, Silver S (1990) Chromium reduction in Pseudomonas putid. Appl Environ Microbiol 56(7):2268–2270Google Scholar
  23. Jin W, Du H, Zheng S, Zhang Y (2016) Electrochemical processes for the environmental remediation of toxic Cr(VI): a review. Electrochim Acta 191:1044–1055Google Scholar
  24. Li Z, Zhang X, Lei L (2008) Electricity production during the treatment of real electroplating wastewater containing Cr6+ using microbial fuel cell. Process Biochem 43(12):1352–1358Google Scholar
  25. Li M, Zhou S, Xu Y, Liu Z, Ma F, Zhi L, Zhou X (2018) Simultaneous Cr(VI) reduction and bioelectricity generation in a dual chamber microbial fuel cell. Chem Eng J 334:1621–1629Google Scholar
  26. Liang Z, Hu Z (2012) Start-up performance evaluation of submerged membrane bioreactors using conventional activated sludge process and modified Luzack-Ettinger process. J Environ Eng 138(9):932–939Google Scholar
  27. Liu C, Gorby YA, Zachara JM, Fredrickson JK, Brown CF (2002) Reduction kinetics of Fe(III), Co(III), U(VI), Cr(VI), and Tc(VII) in cultures of dissimilatory metal-reducing bacteria. Biotechnol Bioeng 80(6):637–649Google Scholar
  28. Liu L, Yuan Y, Li F, Feng C (2011) In-situ Cr(VI) reduction with electrogenerated hydrogen peroxide driven by iron-reducing bacteria. Bioresour Technol 102(3):2468–2473Google Scholar
  29. Liu W, Ni J, Yin X (2014) Synergy of photocatalysis and adsorption for simultaneous removal of Cr (VI) and Cr (III) with TiO2 and titanate nanotubes. Water Res 53:12–25Google Scholar
  30. Logan BE, Hamelers B, Rozendal R, Schröder U, Keller J, Freguia S, Aelterman P, Verstraete W, Rabaey K (2006) Microbial fuel cells: methodology and technology. Environ Sci Technol 40(17):5181–5192Google Scholar
  31. Lovley DR, Phillips EJP, Gorby YA, Landa ER (1991) Microbial reduction of uranium. Nature 350(6317):413–416Google Scholar
  32. Lu J, Wang Z, Liu Y, Tang Q (2016) Removal of Cr ions from aqueous solution using batch electrocoagulation: Cr removal mechanism and utilization rate of in situ generated metal ions. Process Saf Environ Prot 104:436–443Google Scholar
  33. Mandiwana K, Panichev N, Kataeva M, Siebert S (2007) The solubility of Cr(III) and Cr(VI) compounds in soil and their availability to plants. J Hazard Mater 147(1-2):540–545Google Scholar
  34. Mohan D, Pittman CU Jr (2006) Activated carbons and low cost adsorbents for remediation of tri- and hexavalent chromium from water. J Hazard Mater 137(2):762–811Google Scholar
  35. Nancharaiah Y, Mohan SV, Lens P (2015) Metals removal and recovery in bioelectrochemical systems: a review. Bioresour Technol 195:102–114Google Scholar
  36. 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):2736–2744Google Scholar
  37. Qin G, McGuire MJ, Blute NK, Seidel C, Fong L (2005) Hexavalent chromium removal by reduction with ferrous sulfate, coagulation, and filtration: a pilot-scale study. Environ Sci Technol 39(16):6321–6327Google Scholar
  38. Rai D, Eary L, Zachara JM (1989) Environmental chemistry of chromium. Sci Total Environ 86(1-2):15–23Google Scholar
  39. Rozendal RA, Hamelers HVM, Rabaey K, Keller J, Buisman CJN (2008) Towards practical implementation of bioelectrochemical wastewater treatment. Trends Biotechnol 26(8):450–459Google Scholar
  40. Rutigliano L, Fino D, Saracco G, Specchia V, Spinelli P (2008) Electrokinetic remediation of soils contaminated with heavy metals. J Appl Electrochem 38(7):1035–1041Google Scholar
  41. Schmieman EA, Yonge DR, Rege MA, Petersen JN, Turick CE, Johnstone DL, Apel WA (1998) Comparative kinetics of bacterial reduction of chromium. J Environ Eng 124(5):449–455Google Scholar
  42. Song T, Jin Y, Bao J, Kang D, Xie J (2016) Graphene/biofilm composites for enhancement of hexavalent chromium reduction and electricity production in a biocathode microbial fuel cell. J Hazard Mater 317:73–80Google Scholar
  43. Sukkasem C, Xu S, Park S, Boonsawang P, Liu H (2008) Effect of nitrate on the performance of single chamber air cathode microbial fuel cells. Water Res 42(19):4743–4750Google Scholar
  44. 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):8159–8165Google Scholar
  45. Tebo BM, Obraztsova AY (1998) Sulfate-reducing bacterium grows with Cr(VI), U(VI), Mn(IV), and Fe(III) as electron acceptors. FEMS Microbiol Lett 162(1):193–198Google Scholar
  46. Tovar-Sanchez A, Sañudo-Wilhelmy SA, Garcia-Vargas M, Weaver RS, Popels LC, Hutchins DA (2003) A trace metal clean reagent to remove surface-bound iron from marine phytoplankton. Mar Chem 82(1-2):91–99Google Scholar
  47. Vainshtein M, Kuschk P, Mattusch J, Vatsourina A, Wiessner A (2003) Model experiments on the microbial removal of chromium from contaminated groundwater. Water Res 37(6):1401–1405Google Scholar
  48. Vaiopoulou E, Gikas P (2012) Effects of chromium on activated sludge and on the performance of wastewater treatment plants: a review. Water Res 46(3):549–570Google Scholar
  49. Villaescusa I, Marti S, Matas C, Martine M, Ribó JM (1997) Chromium(VI) toxicity to luminescent bacteria. Environ Toxicol Chem 16(5):871–874Google Scholar
  50. Virdis B, Rabaey K, Rozendal RA, Yuan Z, Keller J (2010) Simultaneous nitrification, denitrification and carbon removal in microbial fuel cells. Water Res 44(9):2970–2980Google Scholar
  51. Wang H, Ren ZJ (2014) Bioelectrochemical metal recovery from wastewater: a review. Water Res 66:219–232Google Scholar
  52. Wang G, Huang L, Zhang Y (2008) Cathodic reduction of hexavalent chromium [Cr(VI)] coupled with electricity generation in microbial fuel cells. Biotechnol Lett 30(11):1959–1966Google Scholar
  53. Wang H, Luo H, Fallgren PH, Jin S, Ren ZJ (2015) Bioelectrochemical system platform for sustainable environmental remediation and energy generation. Biotechnol Adv 33(3):317–334Google Scholar
  54. Wang Q, Huang L, Pan Y, Quan X, Li Puma G (2017) Impact of Fe(III) as an effective electron-shuttle mediator for enhanced Cr(VI) reduction in microbial fuel cells: reduction of diffusional resistances and cathode overpotentials. J Hazard Mater 321:896–906Google Scholar
  55. Wu S, Ge Y, Wang Y, Chen X, Li F, Xuan H, Li X (2018) Adsorption of Cr(VI) on nano Uio-66-NH2 MOFs in water. Environ Technol 39(15):1937–1948Google Scholar
  56. Xu C, Yang W, Liu W, Sun H, Jiao C, Lin A (2018) Performance and mechanism of Cr(VI) removal by zero-valent iron loaded onto expanded graphite. J Environ Sci 67:14–22Google Scholar
  57. Zhang C, Liang Z, Hu Z (2014) Bacterial response to a continuous long-term exposure of silver nanoparticles at sub-ppm silver concentrations in a membrane bioreactor activated sludge system. Water Res 50:350–358Google Scholar
  58. Zhang C, Brown PJ, Miles RJ, White TA, Grant DG, Stalla D, Hu Z (2019) Inhibition of regrowth of planktonic and biofilm bacteria after peracetic acid disinfection. Water Res 149:640–649Google Scholar
  59. Zhou L, Li R, Zhang G, Wang D, Cai D, Wu Z (2018) Zero-valent iron nanoparticles supported by functionalized waste rock wool for efficient removal of hexavalent chromium. Chem Eng J 339:85–96Google Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Civil & Environmental EngineeringUniversity of MissouriColumbiaUSA
  2. 2.HDR, Inc.Kansas CityUSA
  3. 3.College of Natural Resources and EnvironmentNorthwest A&F UniversityYanglingPeople’s Republic of China
  4. 4.School of Civil and Environmental EngineeringGeorgia Institute of TechnologyAtlantaUSA

Personalised recommendations