Dissimilatory metal-reducing bacteria (DMRB) can utilize Fe(III) associated with aqueous complexes or solid phases, such as oxide and oxyhydroxide minerals, as a terminal electron acceptor coupled to the oxidation of H 2 or organic substrates. These bacteria are also capable of reducing other metal ions including Mn(IV), Cr(VI), and U(VI), a process that has a pronounced effect on their solubility and overall geochemical behavior. In spite of considerable study on an individual basis, the biogeochemical behavior of multiple metals subject to microbial reduction is poorly understood. To probe these complex processes, the reduction of U(VI) by the subsurface bacterium, Shewanella putrefaciens CN32, was investigated in the presence of goethite under conditions where the aqueous composition was controlled to vary U speciation and solubility. Uranium(VI), as the carbonate complexes UO 2 (CO 3) 3(aq) 4Ϫ and UO 2 (CO 3) 2(aq) 2Ϫ , was reduced by the bacteria to U(IV) with or without goethite [␣-FeOOH (s) ] present. Uranium(VI) in 1,4-piperazinediethhanesulfonic acid (PIPES) buffer that was estimated to be present predominantly as the U(VI) mineral metaschoepite [UO 3 ⅐ 2H 2 O (s) ], was also reduced by the bacteria with or without goethite. In contrast, only ϳ30% of the U(VI) associated with a synthetic metaschoepite was reduced by the organism in the presence of goethite with 1 mM lactate as the electron donor. This may have been due to the formation of a layer of UO 2(s) or Fe(OH) 3(s) on the surface of the metaschoepite that physically obstructed further bioreduction. Increasing the lactate to a non-limiting concentration (10 mM) increased the reduction of U(VI) from metaschoepite to greater than 80% indicating that the hypothesized surface-veneering effect was electron donor dependent. Uranium(VI) was also reduced by bacterially reduced anthraquinone-2,6-disulfonate (AQDS) in the absence of cells, and by Fe(II) sorbed to goethite in abiotic control experiments. In the absence of goethite, uraninite was a major product of direct microbial reduction and reduction by AH 2 DS. These results indicate that DMRB, via a combination of direct enzymatic or indirect mechanisms, can reduce U(VI) to insoluble U(IV) in the presence of solid Fe oxides.

ABSTRACT-In oxidizing environments, the toxic and radioactive element uranium (U) is most soluble and mobile in the hexavalent oxidation state. Sorption of U(VI) on Fe-oxides minerals [such as hematite (α-Fe 2 O 3 ) and goethite (α-FeOOH)] and occlusion of U(VI) by Feoxide coatings are processes that can retard U transport in environments. In aged Ucontaminated geologic materials, the transport and the biological availability of U toward reduction may be limited by co-precipitation with Fe-oxide minerals. These processes also affect the biological availability of U(VI) species toward reduction and precipitation as the less soluble U(IV) species by metal-reducing bacteria.To examine the dynamics of interactions between U(VI) and Fe oxides during crystallization, indicated that almost all of the Fe in these solids was crystalline and that most of the U was associated with these crystalline Fe oxides. X-ray diffraction and Fourier-transform infrared (FT-IR) spectroscopic studies indicate that hematite formation is preferred over that of goethite when the amount of U in the Fe-oxides exceeds 1 mol % U (~4 wt % U). FT-IR and room temperature continuous wave luminescence spectroscopic studies with unleached U/Fe solids indicate a relationship between the mol % U in the Fe oxide and the intensity or existence of the spectra features that can be assigned to UO 2 2+ species (such as the IR asymmetric υ 3 stretch for O=U=O for uranyl). These spectral features were undetectable in carbonate-or oxalate-leached Molecular modeling studies reveal that U 6+ species could bond with O atoms from distorted Fe octahedra in the hematite structure with an environment that is consistent with the results of the XAFS. The results provide compelling evidence of U incorporation within the hematite structure.

Elevated concentrations of U are found in agricultural drainage waters from the San Joaquin Valley, CA, which are often disposed of in evaporation basins that are frequented by waterfowl. To determine the factors that affect aqueous U concentrations in the basins, sorption experiments with U(VI) were performed at various CO2 partial pressures, dissolved Ca, Mg, and P concentrations, and carbonate alkalinities. Synthetic waters, comparable in inorganic constituents to irrigation and drainage waters, were prepared, spiked with 0.1 (soil) and 2 mg U(VI) L−1 (synthetic goethite), and analyzed for U, P (when applicable), and major ions. Total chemical analyses were input into the computer program FITEQL to determine U(VI) speciation and generate U(VI) adsorption constants with the diffuse layer model (also referred to as the two‐layer model). Maximum adsorption occurred in solutions with low carbonate alkalinities (≤3 mmol L−1), ionic strengths (≤0.03 M), Ca concentrations (≤4 mmol L−1), and P concentrations (<0.005 mmol L−1 for soil). Lesser and negligible adsorption was attributed to the predicted formation of highly soluble, negatively charged U(VI) carbonates [UO2(CO3)2−2 and UO2(CO3)4−3] that did not strongly adsorb to soil surfaces. Calcium and, to some degree, Mg competition with positively charged U(VI) species for surface sites was observed at low carbonate alkalinities (<3 mmol L−1 for goethite; <14 mmol L−1 for soil). At high carbonate alkalinities, carbonates competed with anionic U(VI) species for adsorption sites. Study results suggest that elevated U concentrations in the drainage waters are due to the speciation of dissolved U(VI) into negatively charged carbonate complexes.

Influence of Mn oxides on the reduction of uranium(VI) by the Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium