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Microbial reduction of chlorite and uranium followed by air oxidation
US Department of Energy Publications
  • Gengxin Zhang, Chinese Academy of Sciences
  • William D. Burgos, The Pennsylvania State University
  • John M. Senko, University of Akron
  • Michael E. Bishop, Miami University
  • Hailiang Dong, Miami University
  • Maxim Boyanov, Argonne National Laboratory
  • Kenneth M. Kemner, Argonne National Laboratory
Date of this Version
1-1-2011
Citation

Chemical Geology 283 (2011) 242–250; doi:10.1016/j.chemgeo.2011.01.021

Abstract

To evaluate the stability of biogenic nanoparticulate U(IV) in the presence of an Fe(II)-rich iron-bearing phyllosilicate, we examined the reduction of structural Fe(III) in chlorite CCa-2 and uranium(VI) by Shewanella oneidensis MR-1, and the reoxidation of these minerals (after pasteurization) via the introduction of oxygen. Bioreduction experiments were conducted with combinations of chlorite, U(VI), and anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify the reduction of U(VI) by chemically-reduced chlorite-associated Fe(II), the oxidation of nanoparticulate U(IV) by unaltered structural Fe(III) in chlorite, and the sorption of U(VI) to chlorite, to elucidate interactions between U(VI)/ U(IV) and Fe(II)/Fe(III)-chlorite. Solids were characterized by X-ray diffraction, scanning electron microscopy, and X-ray absorption spectroscopy to confirm Fe and U reduction and reoxidation. U(VI) enhanced the reduction of structural Fe(III) in chlorite and nanoparticulate U(IV) was oxidized by structural Fe(III) in chlorite, demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to chlorite-Fe(III). Abiotic reduction of U(VI) by chlorite-associated Fe(II) was very slow compared to biological U(VI) reduction. The rate of nanoparticulate U(IV) oxidation by dissolved oxygen increased in the presence of chlorite-associated Fe(II), but the extent of U(IV) oxidation decreased as compared to no-chlorite controls. In identical experiments conducted with bioreduced suspensions of nanoparticulate U(IV) and nontronite (another iron-bearing phyllosilicate), the rate of U(IV) oxidation by dissolved oxygen increased in the presence of nontronite-associated Fe(II). In summary, we found that structural Fe(III) in chlorite delayed the onset of U(VI) loss from solution, while chlorite-associated Fe(II) enhanced the oxidation rate of U(IV) by dissolved oxygen, indicating that chlorite-associated Fe(II) could not protect nanoparticulate U(IV) from oxygen intrusion but instead increased the oxidation rate of U(IV).

Citation Information
Gengxin Zhang, William D. Burgos, John M. Senko, Michael E. Bishop, et al.. "Microbial reduction of chlorite and uranium followed by air oxidation" (2011)
Available at: http://works.bepress.com/john_senko/1/