, Volume 23, Issue 4, pp 525–534 | Cite as

A biogeochemical framework for bioremediation of plutonium(V) in the subsurface environment

  • Randhir P. DeoEmail author
  • Bruce E. Rittmann
Original Paper


Accidental release of plutonium (Pu) from storage facilities in the subsurface environment is a concern for the safety of human beings and the environment. Given the complexity of the subsurface environment and multivalent state of Pu, we developed a quantitative biogeochemical framework for bioremediation of Pu(V)O2 + in the subsurface environment. We implemented the framework in the biogeochemical model CCBATCH by expanding its chemical equilibrium for aqueous complexation of Pu and its biological sub-models for including Pu’s toxicity and reduction reactions. The quantified framework reveals that most of the Pu(V) is speciated as free Pu(V)O2 + (aq), which is a problem if the concentration of free Pu(V)O2 + is ≥28 μM (the half-maximum toxicity value for bacteria able to reduce Pu(V) to Pu(III)PO4(am)) or ≥250 μM (the full-toxicity value that takes the bioreduction rate to zero). The framework includes bioreduction of Fe3+ to Fe2+, which abiotically reduces Pu(V)O2 + to Pu(IV) and then to Pu(III). Biotic (enzymatic) reduction of Pu(V)O2 + directly to Pu(III) by Shewanella alga (S. alga) is also included in the framework. Modeling results also reveal that for formation of Pu(III)PO4(am), the desired immobile product, the concentration of coexisting model strong ligand—nitrilotriacetic acid (NTA)—should be less than or equal to the concentration of total Pu(III).


Plutonium Shewanella alga (S. algaModeling Biogeochemical framework Bioreduction Bioremediation 



The research was supported, in part, by Environmental Remediation Sciences Program (ERSP) of the United States Department of Energy.


  1. Banaszak JE, Reed DT, Rittmann BE (1998a) Speciation-dependent toxicity of neptunium(V) toward Chelatobacter heintzii. Environ Sci Technol 32(8):1085–1091CrossRefGoogle Scholar
  2. Banaszak JE, VanBriesen JM, Rittmann BE, Reed DT (1998b) Mathematical modelling of the effects of aerobic and anaerobic chelate biodegradation on actinide speciation. Radiochim Acta 82:445–451Google Scholar
  3. Banaszak JE, Rittmann BE, Reed DT (1999) Subsurface interactions of actinide species and microorganisms: implications for the bioremediation of actinide-organic mixtures. J Radioanal Nucl Chem 241(2):385–435CrossRefGoogle Scholar
  4. Boukhalfa H, Icopini GA, Reilly SD, Neu MP (2007) Plutonium(IV) reduction by the metal-reducing bacteria Geobacter metallireducens GS15 and Shewanella oneidensis MR1. Appl Environ Microbiol 73(18):5897–5903PubMedCrossRefGoogle Scholar
  5. Caccavo F, Blakemore RP, Lovley DR (1992) A hydrogen-oxidizing, Fe(III)-reducing microorganism from the Great Bay estuary, New Hamshire. Appl Environ Microbiol 58(10):3211–3216PubMedGoogle Scholar
  6. Caccavo F, Ramsing NB, Costerton JW (1996) Morphological and metabolic responses to starvation by the dissimilatory metal-reducing bacterium Shewanella alga BrY. Appl Environ Microbiol 62(12):4678–4682PubMedGoogle Scholar
  7. Choppin GR (2003) Actinide speciation in the environment. Radiochim Acta 91:645–649CrossRefGoogle Scholar
  8. Choppin GR, Bond AH (1996) Actinide oxidation state speciation. J Anal Chem 51(12):1129–1138Google Scholar
  9. Cleveland JM, Rees TF (1981) Characterization of plutonium in Maxey Flats radioactive trench leachates. Science 212(4502):1506–1509PubMedCrossRefGoogle Scholar
  10. Demirkanli DI, Molz FJ, Kaplan DI, Fjeld RA, Serkiz SM (2007) Modeling long-term plutonium transport in the Savannah River Site vadose zone. Vadose Zone J 6(2):344–353CrossRefGoogle Scholar
  11. Deo RP, Rittmann BE, Reed DT (2011) Bacterial Pu(V) reduction in the absence and presence of Fe(III)-NTA: modeling and experimental approach. Biodegradation 22:921–929PubMedCrossRefGoogle Scholar
  12. Francis AJ (2007) Microbial mobilization and immobilization of plutonium. J Alloys Compd 444:500–505CrossRefGoogle Scholar
  13. Francis AJ, Dodge CJ (2008) Bioreduction of uranium(VI) complexed with citric acid by Clostridia affects its structure and solubility. Environ Sci Technol 42(22):8277–8282PubMedCrossRefGoogle Scholar
  14. Francis AJ, Dodge CJ, Gillow JB (2008) Reductive dissolution of Pu(IV) by Clostridium sp. under anaerobic conditions. Environ Sci Technol 42(7):2355–2360PubMedCrossRefGoogle Scholar
  15. Gustafsson JP (2009) Visual MINTEQ: version 2.61. KTH, Department of Land and Water Resources Engineering, StockholmGoogle Scholar
  16. Hacherl EL, Kosson DS (2003) A kinetic model for bacterial Fe(III) oxide reduction in batch cultures. Water Resour Res 39: HWC 3-1Google Scholar
  17. Icopini GA, Lack JG, Hersman LE, Neu MP, Boukhalfa H (2009) Plutonium(V/VI) reduction by the metal-reducing bacteria Geobacter metallireducens GS-15 and Shewanella oneidensis MR-1. Appl Environ Microbiol 75(11):3641–3647PubMedCrossRefGoogle Scholar
  18. Liu CX, 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):637–649PubMedCrossRefGoogle Scholar
  19. Marcus AK, Torres CI, Rittmann BE (2010) Evaluating the impacts of migration in the biofilm anode using the model PCBIOFILM. Electrochim Acta 55(23):6964–6972Google Scholar
  20. Neu MP, Icopini GA, Boukhalfa H (2005) Plutonium speciation affected by environmental bacteria. Radiochim Acta 93(11):705–714CrossRefGoogle Scholar
  21. Rai D, Gorby YA, Fredrickson JK, Moore DA, Yui M (2002) Reductive dissolution of PuO2(am): the effect of Fe(II) and hydroquinone. J Solut Chem 31(6):433–453CrossRefGoogle Scholar
  22. Reed DT, Lucchini JF, Aase SB, Kropf AJ (2006) Reduction of plutonium(VI) in brine under subsurface conditions. Radiochim Acta 94(9–11):591–597CrossRefGoogle Scholar
  23. Reed DT, Pepper SE, Richmann MK, Smith G, Deo R, Rittmann BE (2007) Subsurface bio-mediated reduction of higher-valent uranium and plutonium. J Alloy Compd 444:376–382CrossRefGoogle Scholar
  24. Reed DT, Deo RP, Rittmann BE (2010) Subsurface interactions of actinide species with microorganisms. In: Morss LR, Edelstein NM, Fuger J (eds) The chemistry of the actinide and transactinide elements, vol 6. Springer, New York (In press)Google Scholar
  25. Renshaw JC, Law N, Geissler A, Livens FR, Lloyd JR (2009) Impact of the Fe(III)-reducing bacteria Geobacter sulfurreducens and Shewanella oneidensis on the speciation of plutonium. Biogeochemistry 94(2):191–196CrossRefGoogle Scholar
  26. Rittmann BE, McCarty PL (2001) Environmental biotechnology: principles and applications. The McGraw-Hill Companies Inc, New York 10020Google Scholar
  27. Rittmann BE, VanBriesen JM (1996) Microbiological processes in reactive modeling. React Transp Porous Media 34:311–334Google Scholar
  28. Rittmann BE, Banaszak JE, VanBriesen JM, Reed DT (2002a) Mathematical modeling of precipitation and dissolution reactions in microbiological systems. Biodegradation 13(4):239–250PubMedCrossRefGoogle Scholar
  29. Rittmann BE, Banaszak JE, Reed DT (2002b) Reduction of Np(V) and precipitation of Np(IV) by an anaerobic microbial consortium. Biodegradation 13(5):329–342PubMedCrossRefGoogle Scholar
  30. Rusin PA, Quintana L, Brainard JR, Strietelmeier BA, Tait CD, Ekberg SA, Palmer PD, Newton TW, Clark DL (1994) Solubilization of plutonium hydrous oxide by iron-reducing bacteria. Environ Sci Technol 28(9):1686–1690PubMedCrossRefGoogle Scholar
  31. Schwarz AO, Rittmann BE (2007a) A biogeochemical framework for metal detoxification in sulfidic systems. Biodegradation 18(6):675–692PubMedCrossRefGoogle Scholar
  32. Schwarz AO, Rittmann BE (2007b) Modeling bio-protection and the gradient-resistance mechanism. Biodegradation 18(6):693–701PubMedCrossRefGoogle Scholar
  33. Smith RM, Martell AE, Motekaitis RJ (2004) NIST critically selected stability constants of metal complexes database, Version 4.0, NIST: Standard Reference Data Program, GaithersburgGoogle Scholar
  34. Songkasiri W (2003) Biological processes in nuclear waste treatment: bio-reduction and bio-sorption of actinides. Northwestern University, EvanstonGoogle Scholar
  35. Tabak HH, Lens P, van Hullebusch ED, Dejonghe W (2005) Developments in bioremediation of soils and sediments polluted with metals and radionuclides – 1. Microbial processes and mechanisms affecting bioremediation of metal contamination and influencing metal toxicity and transport. Rev Environ Sci Biotechnol 4:115–156Google Scholar
  36. Truex MJ, Peyton BM, Valentine NB, Gorby YA (1997) Kinetics of U(VI) reduction by a dissimilatory Fe(III)-reducing bacterium under non-growth conditions. Biotechnol Bioeng 55(3):490–496PubMedCrossRefGoogle Scholar
  37. VanBriesen JM, Rittmann BE (1999) Modeling speciation effects on biodegradation in mixed metal/chelate systems. Biodegradation 10(5):315–330CrossRefGoogle Scholar
  38. VanBriesen JM, Rittmann BE (2000a) Mathematical description of microbiological reactions involving intermediates. Biotechnol Bioeng 67(1):35–52PubMedCrossRefGoogle Scholar
  39. VanBriesen JM, Rittmann BE (2000b) Modeling biogeochemical interactions in co-contaminant systems. Abstracts of Papers of the American Chemical Society 220, U338Google Scholar
  40. Willett AI, Rittmann BE (2003) Slow complexation kinetics for ferric iron and EDTA complexes make EDTA non-biodegradable. Biodegradation 14(2):105–121PubMedCrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2011

Authors and Affiliations

  1. 1.Chemistry Department, Division of Natural Sciences, College of Natural and Applied SciencesUniversity of GuamMangilaoUSA
  2. 2.Center for Environmental BiotechnologyBiodesign Institute at Arizona State UniversityTempeUSA

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