XAFS Investigation of the Interactions of UVI with Secondary Mineralization Products from the Bioreduction of FeIII Oxides

Abstract

Biogenic Fe(II) phases (magnetite, green rust, siderite, vivianite, etc.) provide a reservoir of reducing capacity in many subsurface environments that may contribute to the reduction of contaminants such as U(VI). We have examined the uptake and reduction of U(VI) in the presence of biogenic green rust (BioGR), magnetite (BioMAG), and siderite (BioSID) formed during the reduction of Fe(III) oxides by Shewanella putrefaciens CN32. Within 48 h, total solution-phase U(VI) concentrations decreased from 500 microM to 1.5 microM, 392 microM, and 472 microM in the U-BioGR, U-BioMAG, and U-BioSID systems, respectively. Analysis of the samples by U L(III) extended X-ray absorption fine structure spectroscopy (EXAFS) indicated that despite a stoichiometric excess of Fe(II), no more than 6% of U(VI) was reduced to U(IV) in the U-BioSID system, and no more than 22% of U(VI) was reduced in the U-BioMAG system. For comparison, in the U-BioGR system, >99% of U(VI) was reduced to U(IV). Uptake of U(VI) by BioGR and BioMAG was accompanied by formation of nanoparticulate uraninite. The U EXAFS data for the U-BioSID system were consistent with partial U(VI)/U(IV) substitution for Fe(II) in the surface layer of siderite particles and adsorption of U(IV).