Influence of Sediment Bioreduction and Reoxidation on Uranium Sorption

The influence of sediment bioreduction and reoxidation on U(VI) sorption was studied using Fe(III) oxide-containing saprolite from the U.S. Department of Energy (DOE) Oak Ridge site. Bioreduced sediments were generated by anoxic incubation with a metal reducing bacterium, Shewanella putrefaciens strain CN32, supplied with an electron donor. The reduced sediments were subsequently reoxidized by air contact. U(VI) sorption was studied in Na-NO3-HCO3 electrolytes that were both closed and open to atmosphere, and where pH, U(VI) and carbonate concentration was varied. Moessbauer spectroscopy and chemical analyses showed that 50% of the Fe(III)-oxides were reduced to Fe(II) that was sorbed to the sediment during incubation with CN32. However, this reduction and subsequent reoxidation of the sorbed Fe(II) had negligible influence on the rate and extent of U sorption, or the extractability of sorbed U by 0.2 mol/L NaHCO3. Various results indicated that U(VI) surface complexation was the primary process responsible for uranyl sorption by the bioreduced and reoxidized sediments. A two-site, non-electrostatic surface complexation model best described U(VI) adsorption under variable pH, carbonate and U(VI) conditions. A ferrihydrite-based diffuse double layer model provided a better estimation of U(VI) adsorption without parameter adjustment than did a goethite-based model, even though a majority of the Fe(III)-oxides in the sediments were goethite