Electrochemical Applications in Metal Bioleaching

  • Christoph Kurt TanneEmail author
  • Axel Schippers
Part of the Advances in Biochemical Engineering/Biotechnology book series (ABE, volume 167)



Biohydrometallurgy comprises the recovery of metals by biologically catalyzed metal dissolution from solids in an aqueous solution. The application of this kind of bioprocessing is described as “biomining,” referring to either bioleaching or biooxidation of sulfide metal ores. Acidophilic iron- and sulfur-oxidizing microorganisms are the key to successful biomining. However, minerals such as primary copper sulfides are recalcitrant to dissolution, which is probably due to their semiconductivity or passivation effects, resulting in low reaction rates. Thus, further improvements of the bioleaching process are recommendable. Mineral sulfide dissolution is based on redox reactions and can be accomplished by electrochemical technologies. The impact of electrochemistry on biohydrometallurgy affects processing as well as analytics. Electroanalysis is still the most widely used electrochemical application in mineralogical research.

Electrochemical processing can contribute to bioleaching in two ways. The first approach is the coupling of a mineral sulfide to a galvanic partner or electrocatalyst (spontaneous electron transfer). This approach requires only low energy consumption and takes place without technical installations by the addition of higher redox potential minerals (mostly pyrite), carbonic material, or electrocatalytic ions (mostly silver ions). Consequently, the processed mineral (often chalcopyrite) is preferentially dissolved. The second approach is the application of electrolytic bioreactors (controlled electron transfer). The electrochemical regulation of electrolyte properties by such reactors has found most consideration. It implies the regulation of ferrous and ferric ion ratios, which further results in optimized solution redox potential, less passivation effects, and promotion of microbial activity.

However, many questions remain open and it is recommended that reactor and electrode designs are improved, with the aim of finding options for simplified biohydrometallurgical processing. This chapter focuses on metal sulfide dissolution via bioleaching and does not include other biohydrometallurgical processes such as microbial metal recovery from solution.

Graphical Abstract


Acidophilic bacteria Bioleaching Biomining Electrochemical processing Mineral sulfides Passivation 



Silver/silver chloride








Corrosion potential


Corrosion current


Molybdenum disulfide




Tungsten disulfide





Alternating current


Atomic force microscope


Direct current


Energy dispersive X-ray spectroscopy


Extracellular electron transfer


Electrochemical impedance spectroscopy


Metallic cation (divalent)


Metal sulfide


Open circuit potential


Oxidation reduction potential (solution redox potential)


Saturated calomel electrode


X-ray photoelectron spectroscopy


X-ray fluorescence


  1. 1.
    Schippers A, Hedrich S, Vasters J, Drobe M, Sand W, Willscher S (2014) Biomining: metal recovery from ores with microorganisms. Adv Biochem Eng Biotechnol 141:1–47PubMedGoogle Scholar
  2. 2.
    Crundwell FK (2003) How do bacteria interact with minerals? Hydrometallurgy 71(1–2):75–81CrossRefGoogle Scholar
  3. 3.
    Tributsch H (2001) Direct versus indirect bioleaching. Hydrometallurgy 59(2–3):177–185CrossRefGoogle Scholar
  4. 4.
    Vera M, Schippers A, Sand W (2013) Progress in bioleaching: fundamentals and mechanisms of bacterial metal sulfide oxidation—part A. Appl Microbiol Biotechnol 97(17):7529–7541PubMedCrossRefGoogle Scholar
  5. 5.
    Gralnick JA, Newman DK (2007) Extracellular respiration. Mol Microbiol 65(1):1–11PubMedPubMedCentralCrossRefGoogle Scholar
  6. 6.
    Hernandez ME, Newman DK (2001) Extracellular electron transfer. Cell Mol Life Sci 58(11):1562–1571PubMedCrossRefGoogle Scholar
  7. 7.
    Kato S (2015) Biotechnological aspects of microbial extracellular electron transfer. Microbes Environ 30(2):133–139PubMedPubMedCentralCrossRefGoogle Scholar
  8. 8.
    Shi L, Dong H, Reguera G, Beyenal H, Lu A, Liu J et al (2016) Extracellular electron transfer mechanisms between microorganisms and minerals. Nat Rev Microbiol 14(10):651–662PubMedCrossRefGoogle Scholar
  9. 9.
    Weber KA, Achenbach LA, Coates JD (2006) Microorganisms pumping iron. Anaerobic microbial iron oxidation and reduction. Nat Rev Microbiol 4(10):752–764PubMedCrossRefGoogle Scholar
  10. 10.
    Newman DK (2010) Microbiology. Feasting on minerals. Science (New York, NY) 327(5967):793–794CrossRefGoogle Scholar
  11. 11.
    Simonte F, Sturm G, Gescher J, Sturm-Richter K (2017) Extracellular electron transfer and biosensors. Adv Biochem Eng Biotechnol. Google Scholar
  12. 12.
    Johnson DB (2014) Biomining-biotechnologies for extracting and recovering metals from ores and waste materials. Curr Opin Biotechnol 30:24–31PubMedCrossRefGoogle Scholar
  13. 13.
    Watling HR (2015) Review of biohydrometallurgical metals extraction from polymetallic mineral resources. Fortschr Mineral 5(1):1–60Google Scholar
  14. 14.
    Brierley CL (2016) Biological processing of sulfidic ores and concentrates—integrating innovations. In: Lakshmanan VI, Roy R, Ramachandran V (eds) Innovative process development in metallurgical industry. Springer International, Cham, pp 109–135CrossRefGoogle Scholar
  15. 15.
    Johnson DB (2015) Biomining goes underground. Nature Geosci 8(3):165–166CrossRefGoogle Scholar
  16. 16.
    Quatrini R, Johnson DB (2016) Acidophiles: life in extremely acidic environments. Caister Academic, NorfolkGoogle Scholar
  17. 17.
    Brierley CL, Brierley JA (2013) Progress in bioleaching: part B: applications of microbial processes by the minerals industries. Appl Microbiol Biotechnol 97(17):7543–7552PubMedCrossRefGoogle Scholar
  18. 18.
    Hedrich S, Rübberdt K, Glombitza F, Sand W, Schippers A, Véliz MV, Willscher S (2017) 22nd Biohydrometallurgy Symposium. Solid State Phenomena, vol 262. Trans Tech Publications, ZurichGoogle Scholar
  19. 19.
    Schippers A, Sand W (1999) Bacterial leaching of metal sulfides by two indirect mechanisms via thiosulfate or via polysulfides and sulfur. Appl Environ Microbiol 65(1):319–321Google Scholar
  20. 20.
    Sander M, Hofstetter TB, Gorski CA (2015) Electrochemical analyses of redox-active iron minerals. A review of nonmediated and mediated approaches. Environ Sci Technol 49(10):5862–5878PubMedCrossRefGoogle Scholar
  21. 21.
    Vaughan DJ (2006) Sulfide mineralogy and geochemistry. Introduction and overview. Rev Mineral Geochem 61(1):1–5CrossRefGoogle Scholar
  22. 22.
    Córdoba EM, Muñoz JA, Blázquez ML, González F, Ballester A (2008) Leaching of chalcopyrite with ferric ion. Part I. General aspects. Hydrometallurgy 93(3–4):81–87CrossRefGoogle Scholar
  23. 23.
    Khoshkhoo M, Dopson M, Shchukarev A, Sandström Å (2014) Chalcopyrite leaching and bioleaching. An X-ray photoelectron spectroscopic (XPS) investigation on the nature of hindered dissolution. Hydrometallurgy 149:220–227CrossRefGoogle Scholar
  24. 24.
    Tshilombo AF (2004) Mechanism and kinetics of chalcopyrite passivation and depassivation during ferric and microbial leaching. Ph.D. thesis, University of British ColumbiaGoogle Scholar
  25. 25.
    Crundwell FK (1988) Effect of iron impurity in zinc sulfide concentrates on the rate of dissolution. AICHE J 34(7):1128–1134CrossRefGoogle Scholar
  26. 26.
    Crundwell FK (2015) The semiconductor mechanism of dissolution and the pseudo-passivation of chalcopyrite. Can Metall Q 54(3):279–288CrossRefGoogle Scholar
  27. 27.
    Osseo-Asare K (1992) Semiconductor electrochemistry and hydrometallurgical dissolution processes. Hydrometallurgy 29(1–3):61–90CrossRefGoogle Scholar
  28. 28.
    Gerischer H (1990) The impact of semiconductors on the concepts of electrochemistry. Electrochim Acta 35(11–12):1677–1699CrossRefGoogle Scholar
  29. 29.
    Debernardi G, Carlesi C (2013) Chemical-electrochemical approaches to the study passivation of chalcopyrite. Miner Process Extr Metall Rev 34(1):10–41CrossRefGoogle Scholar
  30. 30.
    Tributsch H, Bennett JC (1981) Semiconductor-electrochemical aspects of bacterial leaching. I. Oxidation of metal sulphides with large energy gaps. J Chem Technol Biotechnol 31(1):565–577CrossRefGoogle Scholar
  31. 31.
    Tributsch H, Bennett JC (1981) Semiconductor-electrochemical aspects of bacterial leaching. Part 2. Survey of rate-controlling sulphide properties. J Chem Technol Biotechnol 31(1):627–635CrossRefGoogle Scholar
  32. 32.
    Mustin C, Berthelin J, Marion P, Donato P d (1992) Corrosion and electrochemical oxidation of a pyrite by Thiobacillus ferrooxidans. Appl Environ Microbiol 58(4):1175–1182PubMedPubMedCentralGoogle Scholar
  33. 33.
    Ballester A, Blázquez ML, González F, Muñoz JA (2007) Catalytic role of silver and other ions on the mechanism of chemical and biological leaching. In: Donati ER, Sand W (eds) Microbial processing of metal sulfides. Springer, Dordrecht, pp 77–101CrossRefGoogle Scholar
  34. 34.
    Lara RH, Garcia-Meza JV, González I, Cruz R (2013) Influence of the surface speciation on biofilm attachment to chalcopyrite by Acidithiobacillus thiooxidans. Appl Microbiol Biotechnol 97(6):2711–2724PubMedCrossRefGoogle Scholar
  35. 35.
    Gu G-H, Sun X-j, Hu K-T, Li J-H, Qiu G-Z (2012) Electrochemical oxidation behavior of pyrite bioleaching by Acidthiobacillus ferrooxidans. Trans Nonferrous Metals Soc China 22(5):1250–1254CrossRefGoogle Scholar
  36. 36.
    Mehta AP, Murr LE (1983) Fundamental studies of the contribution of galvanic interaction to acid-bacterial leaching of mixed metal sulfides. Hydrometallurgy 9(3):235–256CrossRefGoogle Scholar
  37. 37.
    Zhao H, Wang J, Hu M, Qin W, Zhang Y, Qiu G (2013) Synergistic bioleaching of chalcopyrite and bornite in the presence of Acidithiobacillus ferrooxidans. Bioresour Technol 149:71–76PubMedCrossRefGoogle Scholar
  38. 38.
    Misra M, Bukka K, Chen S (1996) The effect of growth medium of Thiobacillus ferrooxidans on pyrite flotation. Miner Eng 9(2):157–168CrossRefGoogle Scholar
  39. 39.
    Arena FA, Suegama PH, Bevilaqua D, dos Santos ALA, Fugivara CS, Benedetti AV (2016) Simulating the main stages of chalcopyrite leaching and bioleaching in ferrous ions solution. An electrochemical impedance study with a modified carbon paste electrode. Miner Eng 92:229–241CrossRefGoogle Scholar
  40. 40.
    Hiroyoshi N, Kitagawa H, Tsunekawa M (2008) Effect of solution composition on the optimum redox potential for chalcopyrite leaching in sulfuric acid solutions. Hydrometallurgy 91(1–4):144–149CrossRefGoogle Scholar
  41. 41.
    Bevilaqua D, Acciari HA, Benedetti AV, Garcia Jr O (2007) Electrochemical techniques used to study bacterial-metal sulfides interactions in acidic environments. In: Donati ER, Sand W (eds) Microbial processing of metal sulfides. Springer, Dordrecht, pp 59–76CrossRefGoogle Scholar
  42. 42.
    Bevilaqua D, Suegama PH, Garcia Jr O, Benedetti AV (2011) Electrochemical studies of sulphide minerals in the presence and absence of A. ferrooxidans. In: Sobral LGS, de Oliveira DM, de Souza CEG (eds) Biohydro-metallurgical processes: a practical approach. Centro de Tecnologia Mineral, Ministry of Science, Education and Innovation, Rio de Janeiro, pp 141–167Google Scholar
  43. 43.
    Horta DG, Bevilaqua D, Acciari HA, Garcia Jr O, Benedetti AV (2009) Optimization of the use of carbon paste electrodes (CPE) for electrochemical study of the chalcopyrite. Quím Nova 32(7):1734–1738CrossRefGoogle Scholar
  44. 44.
    Olvera OG, Rebolledo M, Asselin E (2016) Atmospheric ferric sulfate leaching of chalcopyrite. Thermodynamics, kinetics and electrochemistry. Hydrometallurgy 165:148–158CrossRefGoogle Scholar
  45. 45.
    Viramontes-Gamboa G, Rivera-Vasquez BF, Dixon DG (2006) The active-to-passive transition of chalcopyrite. In: 209th ECS Meeting. Denver, Colorado, May 7–May 12, pp 165–175Google Scholar
  46. 46.
    Viramontes-Gamboa G, Rivera-Vasquez BF, Dixon DG (2007) The active-passive behavior of chalcopyrite. J Electrochem Soc 154(6):C299–C311CrossRefGoogle Scholar
  47. 47.
    Renock D, Shuller-Nickles LC (2015) Predicting geologic corrosion with electrodes. Elements 11(5):331–336CrossRefGoogle Scholar
  48. 48.
    Warren GW, Wadsworth ME, El-Raghy SM (1982) Passive and transpassive anodic behavior of chalcopyrite in acid solutions. Metall Trans B 13(4):571–579CrossRefGoogle Scholar
  49. 49.
    Holmes PR, Crundwell FK (1995) Kinetic aspects of galvanic interactions between minerals during dissolution. Hydrometallurgy 39(1–3):353–375CrossRefGoogle Scholar
  50. 50.
    Majima H (2013) How oxidation affects selective flotation of complex sulphide ores. Can Metall Q 8(3):269–273CrossRefGoogle Scholar
  51. 51.
    Attia YA, El-Zeky M (1990) Effects of galvanic interactions of sulfides on extraction of precious metals from refractory complex sulfides by bioleaching. Int J Miner Process 30(1–2):99–111CrossRefGoogle Scholar
  52. 52.
    Wan RY, Miller JD, Simkovich G (1984) Enhanced ferric sulphate leaching of copper from CuFeS2 and C particulate aggregates. In: Proceedings of MINTEK 50: an International Conference on Recent Advances in Mineral Science and Technology, Johannesburg, South Africa (2), pp 575–588Google Scholar
  53. 53.
    Liu W, Yang H-Y, Song Y, Tong L-L (2015) Catalytic effects of activated carbon and surfactants on bioleaching of cobalt ore. Hydrometallurgy 152:69–75CrossRefGoogle Scholar
  54. 54.
    Mehrabani JV, Shafaei SZ, Noaparast M, Mousavi SM (2016) Bioleaching of different pyrites and sphalerite in the presence of graphite. Geomicrobiol J:1–12Google Scholar
  55. 55.
    Córdoba EM, Muñoz JA, Blázquez ML, González F, Ballester A (2008) Leaching of chalcopyrite with ferric ion. Part III. Effect of redox potential on the silver-catalyzed process. Hydrometallurgy 93(3–4):97–105CrossRefGoogle Scholar
  56. 56.
    Ghahremaninezhad A, Radzinski R, Gheorghiu T, Dixon DG, Asselin E (2015) A model for silver ion catalysis of chalcopyrite (CuFeS2) dissolution. Hydrometallurgy 155:95–104CrossRefGoogle Scholar
  57. 57.
    Muñoz JA, Gómez C, Ballester A, Blázquez ML, González F, Figueroa M (1997) Electrochemical behaviour of chalcopyrite in the presence of silver and Sulfolobus bacteria. J Appl Electrochem 28(1):49–56CrossRefGoogle Scholar
  58. 58.
    Biegler T (1977) Reduction kinetics of a chalcopyrite electrode surface. J Electroanal Chem Interfacial Electrochem 85(1):101–106CrossRefGoogle Scholar
  59. 59.
    Felker DL (1984) The electrochemical dissolution of copper sulfides using a fluidized bed electrochemical reactor. PhD thesis of Iowa State University, Ames, Retrospective Theses and Dissertations, 8162Google Scholar
  60. 60.
    Yunker SB, Radovich JM (1986) Enhancement of growth and ferrous iron oxidation rates of T. ferrooxidans by electrochemical reduction of ferric iron. Biotechnol Bioeng 28(12):1867–1875PubMedCrossRefGoogle Scholar
  61. 61.
    Natarajan KA (1992) Effect of applied potentials on the activity and growth of Thiobacillus ferrooxidans. Biotechnol Bioeng 39(9):907–913PubMedCrossRefGoogle Scholar
  62. 62.
    Natarajan KA (1992) Bioleaching of sulphides under applied potentials. Hydrometallurgy 29(1–3):161–172CrossRefGoogle Scholar
  63. 63.
    Natarajan KA (1992) Electrobioleaching of base metal sulfides. Metall Trans B 23(1):5–11CrossRefGoogle Scholar
  64. 64.
    Selvi SC, Modak JM, Natarajan KA (1998) Electrobioleaching of sphalerite flotation concentrate. Miner Eng 11(8):783–788CrossRefGoogle Scholar
  65. 65.
    Kumari A, Natarajan KA (2001) Electrobioleaching of polymetallic ocean nodules. Hydrometallurgy 62(2):125–134CrossRefGoogle Scholar
  66. 66.
    Kumari A, Natarajan KA (2002) Development of a clean bioelectrochemical process for leaching of ocean manganese nodules. Miner Eng 15(1–2):103–106CrossRefGoogle Scholar
  67. 67.
    Kumari A, Natarajan KA (2002) Electrochemical aspects of leaching of ocean nodules in the presence and absence of microorganisms. Int J Miner Process 66(1–4):29–47CrossRefGoogle Scholar
  68. 68.
    Ahmadi A, Ranjbar M, Schaffie M (2012) Catalytic effect of pyrite on the leaching of chalcopyrite concentrates in chemical, biological and electrobiochemical systems. Miner Eng 34:11–18CrossRefGoogle Scholar
  69. 69.
    Ahmadi A, Ranjbar M, Schaffie M (2013) Effect of activated carbon addition on the conventional and electrochemical bioleaching of chalcopyrite concentrates. Geomicrobiol J 30(3):237–244CrossRefGoogle Scholar
  70. 70.
    Ahmadi A, Schaffie M, Manafi Z, Ranjbar M (2010) Electrochemical bioleaching of high grade chalcopyrite flotation concentrates in a stirred bioreactor. Hydrometallurgy 104(1):99–105CrossRefGoogle Scholar
  71. 71.
    Ahmadi A, Schaffie M, Petersen J, Schippers A, Ranjbar M (2011) Conventional and electrochemical bioleaching of chalcopyrite concentrates by moderately thermophilic bacteria at high pulp density. Hydrometallurgy 106(1–2):84–92CrossRefGoogle Scholar
  72. 72.
    Third KA, Cord-Ruwisch R, Watling HR (2002) Control of the redox potential by oxygen limitation improves bacterial leaching of chalcopyrite. Biotechnol Bioeng 78(4):433–441PubMedCrossRefGoogle Scholar
  73. 73.
    Harvey PI, Crundwell FK (1996) The effect of As(III) on the growth of Thiobacillus ferrooxidans in an electrolytic cell under controlled redox potentials. Miner Eng 9(10):1059–1068CrossRefGoogle Scholar
  74. 74.
    Fowler TA, Crundwell FK (1999) Leaching of zinc sulfide by Thiobacillus ferrooxidans: bacterial oxidation of the sulfur product layer increases the rate of zinc sulfide dissolution at high concentrations of ferrous ions. Appl Environ Microbiol 65(12):5285–5292PubMedPubMedCentralGoogle Scholar
  75. 75.
    Fowler TA, Holmes PR, Crundwell FK (1999) Mechanism of pyrite dissolution in the presence of Thiobacillus ferrooxidans. Appl Environ Microbiol 65(7):2987–2993PubMedPubMedCentralGoogle Scholar
  76. 76.
    Holmes PR, Crundwell FK (2013) Polysulfides do not cause passivation. Results from the dissolution of pyrite and implications for other sulfide minerals. Hydrometallurgy 139:101–110CrossRefGoogle Scholar
  77. 77.
    Khoshkhoo M, Dopson M, Shchukarev A, Sandström Å (2014) Electrochemical simulation of redox potential development in bioleaching of a pyritic chalcopyrite concentrate. Hydrometallurgy 144–145:7–14CrossRefGoogle Scholar
  78. 78.
    Lotfalian M, Ranjbar M, Fazaelipoor MH, Schaffie M, Manafi Z (2015) The effect of redox control on the continuous bioleaching of chalcopyrite concentrate. Miner Eng 81:52–57CrossRefGoogle Scholar
  79. 79.
    Klauber C (2008) A critical review of the surface chemistry of acidic ferric sulphate dissolution of chalcopyrite with regards to hindered dissolution. Int J Miner Process 86(1–4):1–17CrossRefGoogle Scholar
  80. 80.
    Nancharaiah YV, Mohan SV, Lens PNL (2016) Biological and bioelectrochemical recovery of critical and scarce metals. Trends Biotechnol 34(2):137–155PubMedCrossRefGoogle Scholar
  81. 81.
    Ni G, Christel S, Roman P, Wong ZL, Bijmans MFM, Dopson M (2016) Electricity generation from an inorganic sulfur compound containing mining wastewater by acidophilic microorganisms. Res Microbiol 167(7):568–575PubMedPubMedCentralCrossRefGoogle Scholar

Copyright information

© Springer International Publishing AG 2017

Authors and Affiliations

  1. 1.Federal Institute for Geosciences and Natural Resources (BGR), Resource GeochemistryHannoverGermany

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