We have examined the effects of aqueous complexation on rates of dissimilatory reductive precipitation of uranium by Shewanella putrefaciens. Uranium(VI) was supplied as sole terminal electron acceptor to Shewanella putrefaciens (strain 200R) in defined laboratory media under strictly anaerobic conditions. Media were amended with different multidentate organic acids, and experiments were performed at different U(VI) and ligand concentrations. Organic acids used as complexing agents were oxalic, malonic, succinic, glutaric, adipic, pimelic, maleic, citric, and nitrilotriacetic acids, tiron, EDTA, and Aldrich humic acid. Reductive precipitation of U(VI), resulting in removal of insoluble amorphous UO2 from solution, was measured as a function of time by determination of total dissolved U. Reductive precipitation was measured, rather than net U(VI) reduction to U(IV), to assess overall U removal rates from solution, which may be used to gauge the influence of chelation on microbial U mineralization. Initial linear rates of U reductive precipitation were found to correlate with stability constants of 1:1 aqueous U(VI):ligand and U(IV):ligand complexes. In the presence of strongly complexing ligands (e.g., NTA, Tiron, EDTA), UO2 precipitation did not occur. Our results are consistent with ligand-retarded precipitation of UO2, which is analogous to ligand-assisted solid phase dissolution but in reverse: ligand exchange with the U4+ aquo cation acts as a rate-limiting reaction moderating coordination of water molecules with U4+, which is a necessary step in UO2 precipitation. Ligand exchange kinetics governing dissociation rates of ligands from U(VI)-organic complexes may also influence overall UO2 production rates, although the magnitude of this effect is unclear relative to the effects of U(IV)-organic complexation. Our results indicate that natural microbial-aqueous systems containing abundant organic matter can inhibit the formation of biogenic amorphous UO2.
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