title: Influences of organic carbon supply rate on uranium bioreduction in initially oxidizing, contaminated sediment.
abstract: Remediation of uranium-contaminated sediments through in situ stimulation of bioreduction to insoluble UO2 is a potential treatment strategy under active investigation. Previously, we found that newly reduced U(IV) can be reoxidized under reducing conditions sustained by a continuous supply of organic carbon (OC) because of residual reactive Fe(III) and enhanced U(VI) solubilitythrough complexation with carbonate generated through OC oxidation. That finding motivated this investigation directed at identifying a range of OC supply rates that is optimal for establishing U bioreduction and immobilization in initially oxidizing sediments. The effects of OC supply rate, from 0 to 580 mmol of OC (kg of sediment)(-1) year(-1), and OC form (lactate and acetate) on U bioreduction were tested in flow-through columns containing U-contaminated sediments. An intermediate supply rate on the order of 150 mmol of OC (kg of sediment)(-1) year(-1) was determined to be most effective at immobilizing U. At lower OC supply rates, U bioreduction was not achieved, and U(VI) solubilitywas enhanced by complexation with carbonate (from OC oxidation). At the highest OC supply rate, the resulting highly carbonate-enriched solutions also supported elevated levels of U(VI), even though strongly reducing conditions were established. Lactate and acetate were found to have very similar geochemical impacts on effluent U concentrations (and other measured chemical species), when compared at equivalent OC supply rates. While the catalysts of U(VI) reduction to U(IV) are presumably bacteria, the composition of the bacterial community,the Fe-reducing community, and the sulfate-reducing community had no direct relationship with effluent U concentrations. The OC supply rate has competing effects of driving reduction of U(VI) to low-solubility U(IV) solids, as well as causing formation of highly soluble U(VI)-carbonato complexes. These offsetting influences will require careful control of OC supply rates in order to optimize bioreduction-based U stabilization.
authors.affiliation: Lawrence Berkeley National Laboratory, Berkeley, California 94720, and University of California, Berkeley, California 94720, USA. tktokunaga@lbl.gov
authors.forename: Tetsu K
authors.initials: TK
authors.lastname: Tokunaga
authors.forename: Jiamin
authors.initials: J
authors.lastname: Wan
authors.forename: Yongman
authors.initials: Y
authors.lastname: Kim
authors.forename: Rebecca A
authors.initials: RA
authors.lastname: Daly
authors.forename: Eoin L
authors.initials: EL
authors.lastname: Brodie
authors.forename: Terry C
authors.initials: TC
authors.lastname: Hazen
authors.forename: Don
authors.initials: D
authors.lastname: Herman
authors.forename: Mary K
authors.initials: MK
authors.lastname: Firestone
mesh_terms: D000085:Acetates / Q000378:metabolism; D001419:Bacteria / Q000378:metabolism; D001673:Biodegradation, Environmental; D002244:Carbon / Q000378:metabolism*; D002245:Carbon Dioxide / Q000378:metabolism; D004566:Electrodes; D019015:Geologic Sediments / Q000737:chemistry*; D019344:Lactic Acid / Q000378:metabolism; D009930:Organic Chemicals / Q000378:metabolism*; D010084:Oxidation-Reduction; D010313:Partial Pressure; D012990:Soil Pollutants, Radioactive / Q000032:analysis / Q000302:isolation & purification*; D013997:Time Factors; D014501:Uranium / Q000032:analysis / Q000302:isolation & purification*
chemical_list: D000085:Acetates; D009930:Organic Chemicals; D012990:Soil Pollutants, Radioactive; D002245:Carbon Dioxide; D019344:Lactic Acid; D014501:Uranium; D002244:Carbon