Thermodynamic constraints on the oxidation of biogenic UO2 by Fe(III) (Hydr)oxides.
Uranium mobility in the environment is partially controlled by its oxidation state, where it exists as either U(VI) or U(IV). In aerobic environments, uranium is generally found in the hexavalent form, is quite soluble, and readily forms complexes with carbonate and calcium. Under anaerobic conditions, common metal respiring bacteria can reduce soluble U(VI) species to sparingly soluble UO2 (uraninite); stimulation of these bacteria, in fact, is being explored as an in situ uranium remediation technique. However, the stability of biologically precipitated uraninite within soils and sediments is not well characterized. Here we demonstrate that uraninite oxidation by Fe(III) (hydr)oxides is thermodynamically favorable under limited geochemical conditions. Our analysis reveals that goethite and hematite have a limited capacity to oxidize UO2(biogenic) while ferrihydrite can lead to UO2(biogenic) oxidation. The extent of UO2(biogenic) oxidation by ferrihydrite increases with increasing bicarbonate and calcium concentration, but decreases with elevated Fe(II)(aq) and U(VI)(aq) concentrations. Thus, our results demonstrate that the oxidation of UO2(biogenic) by Fe(III) (hydr)oxides may transpire under mildly reducing conditions when ferrihydrite is present.
Ginder-Vogel
Matthew
M
Department of Geological and Environmental Sciences, Stanford University, Stanford, California 94305, USA.
Criddle
Craig S
CS
Fendorf
Scott
S
D001419:Bacteria / Q000378:metabolism; D002254:Carbonates / Q000737:chemistry; D005290:Ferric Compounds / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D058085:Iron Compounds / Q000737:chemistry; D008903:Minerals; D010084:Oxidation-Reduction; D013816:Thermodynamics; D017974:Uranium Compounds / Q000737:chemistry* / Q000378:metabolism
D002254:Carbonates; D005290:Ferric Compounds; D058085:Iron Compounds; D008903:Minerals; D017974:Uranium Compounds; C094886:goethite; C000499:ferric oxide; C092844:ferric oxyhydroxide; C012597:uranium dioxide