title: Bacterial siderophores promote dissolution of UO2 under reducing conditions.
abstract: Tetravalent actinides are often considered environmentally immobile due to their strong hydrolysis and formation of sparingly soluble oxide phases. However, biogenic ligands commonly found in the soil environment may increase their solubility and mobility. We studied the adsorption and dissolution kinetics of UO2 in the presence of a microbial siderophore, desferrioxamine-B (DFO-B), under reducing conditions. Using batch and continuous flow stirred tank reactors (CFSTR),we found that DFO-B increases the solubility of UIV and accelerates UO2 dissolution rates through a ligand-promoted dissolution mechanism. DFO-B adsorption to UO2 followed a Langmuir-type isotherm. The maximum adsorbed DFO-B concentrations were 3.3 micromol m(-2) between pH 3 and 8 and declined above pH 8. DFO-B dissolved UO2 at a DFO-B surface-saturated net rate of 64 nmol h(-1) m(-2) (pH 7.5, l = 0.01 M) according to the first-order rate equation R = kL[Lads], with a rate coefficient kL of 0.019 h(-1). Even at very low siderophore concentrations (e.g. 1 microM), net dissolution rates (16 nmol h(-1) m(-2), pH 7.5, l = 0.01 M) were substantially greater than net proton-promoted dissolution rates (3 nmol h(-1) m(-2), pH 7-7.5, l = 0.01 M). Interestingly, adding dissolved FeIII had negligible effects on DFO-B-promoted UO2 dissolution rates, despite its potential as a competitor for DFO-B and as an oxidant of UIV. Our results suggest that strong organic ligands could influence the environmental mobility of tetravalent actinides and should be considered in predictions for nuclear waste storage and remediation strategies.
authors.affiliation: Institute of Terrestrial Ecology, Swiss Federal Institute of Technology Zürich, Grabenstrasse 3, Schlieren CH-8952, Switzerland.
authors.forename: Scott W
authors.initials: SW
authors.lastname: Frazier
authors.forename: Ruben
authors.initials: R
authors.lastname: Kretzschmar
authors.forename: Stephan M
authors.initials: SM
authors.lastname: Kraemer
mesh_terms: D000327:Adsorption; D003676:Deferoxamine / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008956:Models, Chemical; D010084:Oxidation-Reduction; D012990:Soil Pollutants, Radioactive; D012995:Solubility; D017974:Uranium Compounds / Q000737:chemistry*
chemical_list: D012990:Soil Pollutants, Radioactive; D017974:Uranium Compounds; D003676:Deferoxamine; C012597:uranium dioxide