title: Real-time X-ray absorption spectroscopy of uranium, iron, and manganese in contaminated sediments during bioreduction.
abstract: The oxidation status of uranium in sediments is important because the solubility of this toxic and radioactive element is much greater for U(VI) than for U(IV) species. Thus, redox manipulation to promote precipitation of UO2 is receiving interest as a method to remediate U-contaminated sediments. Presence of Fe and Mn oxides in sediments at much higher concentrations than U requires an understanding of their redox status as well. This study was conducted to determine changes in oxidation states of U, Fe, and Mn in U-contaminated sediments from Oak Ridge National Laboratory. Oxidation states of these elements were measured in real-time and nondestructively using X-ray absorption spectroscopy on sediment columns supplied with synthetic groundwater containing organic carbon (OC, 0, 3, 10, 30, and 100 mM OC as lactate) for over 400 days. In sediments supplied with OC > or = 30 mM, 80% of the U was reduced to U(IV), with transient reoxidation at about 150 days. Mn(III,IV) oxides were completely reduced to Mn(II) in sediments infused with OC > or = 3 mM. However, Fe remained largely unreduced in all sediment columns, showing that Fe(III) can persist as an electron acceptor in reducing sediments over long times. This result in combination with the complete reduction of all other potential electron acceptors supports the hypothesis that the reactive Fe(III) fraction was responsible for reoxidizing U(IV).
authors.affiliation: Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA. tktokunaga@lbl.gov
authors.forename: Tetsu K
authors.initials: TK
authors.lastname: Tokunag
authors.forename: Jiamin
authors.initials: J
authors.lastname: Wan
authors.forename: Yongman
authors.initials: Y
authors.lastname: Kim
authors.forename: Steve R
authors.initials: SR
authors.lastname: Sutton
authors.forename: Matthew
authors.initials: M
authors.lastname: Newville
authors.forename: Antonio
authors.initials: A
authors.lastname: Lanzirotti
authors.forename: William
authors.initials: W
authors.lastname: Rao
mesh_terms: D019015:Geologic Sediments; D007501:Iron / Q000737:chemistry*; D008345:Manganese / Q000737:chemistry*; D010084:Oxidation-Reduction; D013057:Spectrum Analysis / Q000379:methods; D014501:Uranium / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000737:chemistry*; D014875:Water Pollutants, Radioactive / Q000737:chemistry*; D014965:X-Rays
chemical_list: D014874:Water Pollutants, Chemical; D014875:Water Pollutants, Radioactive; D008345:Manganese; D014501:Uranium; D007501:Iron