Oxidative Uranium Release from Anoxic Sediments under Diffusion-Limited Conditions

Uranium (U) contamination occurs as a result of mining and ore processing; often in alluvial aquifers that contain organic-rich, reduced sediments that accumulate tetravalent U, U­(IV). Uranium­(IV) is sparingly soluble, but may be mobilized upon exposure to nitrate (NO₃^–) and oxygen (O₂), which become elevated in groundwater due to seasonal fluctuations in the water table. The extent to which oxidative U mobilization can occur depends upon the transport properties of the sediments, the rate of U­(IV) oxidation, and the availability of inorganic reductants and organic electron donors that consume oxidants. We investigated the processes governing U release upon exposure of reduced sediments to artificial groundwater containing O₂ or NO₃^– under diffusion-limited conditions. Little U was mobilized during the 85-day reaction, despite rapid diffusion of groundwater within the sediments and the presence of nonuraninite U­(IV) species. The production of ferrous iron and sulfide in conjunction with rapid oxidant consumption suggested that the sediments harbored large concentrations of bioavailable organic carbon that fueled anaerobic microbial respiration and stabilized U­(IV). Our results suggest that seasonal influxes of O₂ and NO₃^– may cause only localized mobilization of U without leading to export of U from the reducing sediments when ample organic carbon is present.