Reduction of uranium(VI) under sulfate-reducing conditions in the presence of Fe(III)-(hydr)oxides

Hexavalent uranium [U(VI)] dissolved in a modified lactate-C medium was treated under anoxic conditions with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz. The mass of Fe(Ill)-(hydr)oxide mineral was varied to give equivalent Fe(Ill)-mineral surface areas. After equilibration, the U(VI)-mineral suspensions were inoculated with sulfate-reducing bacteria, Desulfovibrio desulfuricans G20. Inoculation of the suspensions containing sulfate-limited medium yielded significant G20 Growth, alone, with concomitant reduction of sulfate and U(VI) from solution. With lactate-limited medium, however, some of the uranium that had been removed from solution was resolubilized in the hematite treatments and. to a lesser extent, in the goethite treatments, once the lactate was depleted. No resolubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of 4 months. Uranium resolubilization was attributed to reoxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Analysis by U L-3-edge XANES spectroscopy of mineral specimens sampled at the end of the experiments yielded spectra similar to that of uraninite, but having distinct features, notably a much more intense and slightly broader white line consistent with precipitation of nanometer-sized particles. The XANES spectra thus provided strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, our results suggest that SRB mediate reduction of soluble U(VI) to an insoluble U(IV) oxide, so long as a suitable electron donor is available. Depletion of the electron donor may result in partial reoxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III)(hydr)oxides are incompletely reduced. Copyright (C) 2004 Elsevier Ltd.