Influence of Uranyl Speciation and Iron Oxides on Uranium Biogeochemical Redox Reactions

Abstract

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates its partitioning between the aqueous- and solid-phases, and thus controls its dissolved concentration and, coupled with groundwater flow, its migration within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO₂ ²⁺ and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO₂. However, various factors within soils and sediments may limit biological reduction of U(VI), inclusive of alterations in U(VI) speciation and competitive electron acceptors. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction with specific emphasis on speciation changes induced by dissolved Ca, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite and hematite) varying in free energies of formation on U reduction. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% with no Ca or ferrihydrite present but only 24% (with ferrihydrite) and 14% (no ferrihydrite) were removed for systems with 0.8 mM Ca. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Dissimilatory reduction of Fe(III) and U(VI) can proceed through different enzyme pathways, even within a single organism, thus providing a potential second means by which Fe(III) bearing minerals may impact U(VI) reduction. We quantify rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concentration (0 to 0.8 mM), and using a mathematical construct implemented with the reactive transport code MIN3P, we reveal the predominant influence of uranyl speciation, specifically the formation of uranyl-calcium-carbonato complexes, and ferrihydrite on the rate and extent of uranium reduction in complex geochemical systems.

Keywords:

• uranium
• redox
• biogeochemistry
• uraninite
• microbial

ACKNOWLEDGMENTS

We would like to thank Shawn Benner for his constructive input on this manuscript, Jim Neiss for experimental assistance, and Guangchao Li for assisting with experimental measurements. This work was funded by the Environmental Remediation Science Program, Office of Biological and Environmental Science, U.S. Department of Energy (grant number ER63609-1021814), by the Stanford NSF Environmental Molecular Sciences Institute (NSF-CHE-0431425), and in part by the U.S. Department of Energy, Office of Science, Office of Biological and Environmental Resources as part of the Subsurface Science Scientific Focus Area under Award Number DE-AC02-05CH11231.