Using flow through reactors to study the non-reductive biomineralization of uranium phosphate minerals

Uranium contaminations of the subsurface in the vicinity of nuclear materials processing sites pose a health risk as the uranyl ion in its oxidized state, U(VI), is highly mobile in aquifers. Current remediation strategies such as pump and treat or excavation are invasive and expensive to implement on a large scale. In situ bioremediation represents an alternative strategy that uses the ability of local microbial communities to immobilize contaminants and is actively studied for uranium remediation. The immobilization of U(VI) in groundwater is achieved either by bioreduction to solid uraninite (U(IV)), adsorption to the soil matrix, or non-reductive precipitation of uranium phosphate minerals through the activity of bacterial phosphatases. Bioreduction has been widely studied for remediation of the saturated zone, as anaerobic conditions typically prevail in these environments. This process is only efficient at circumneutral pH, however, and the end product uraninite is unstable under aerobic conditions or in the presence of manganese oxides, nitrite, or even freshly formed iron oxides. Although non-reductive biomineralization of uranium catalyzed by bacterial phosphatase activity successfully removes uranium from the vadose zone, further studies are needed to assess the ability of microbial communities to hydrolyze organophosphate compounds in the saturated zone where oxygen is often depleted and uranium bioreduction may be significant. To investigate this process under anaerobic conditions, low pH soil samples from a uranium contaminated site at the Oak Ridge Field Research Center were incubated anaerobically in flow through reactors in the presence of exogenic organophosphate compounds to stimulate the natural microbial communities in the original soil matrix. Aqueous uranium was injected continuously in the reactors to determine the fraction of uranium removed during these incubations. The reactors amended with organophosphate produced inorganic phosphate in the effluent, suggesting that bacterial phosphatase activity can be stimulated even in anaerobic environments at low pH. Removal of U(VI) in a control amended with organophosphate over a short time period was similar compared to reactors amended with organophosphate for long times suggesting that adsorption may also play a role in U(VI) immobilization. A sequential extraction technique was optimized to differentiate the fraction of uranium loosely adsorbed and the fraction of uranium precipitated as phosphate minerals and batch adsorption experiments were performed to obtain thermodynamic parameters that could be used to predict the fraction of U(VI) adsorbed onto the soil matrix. Results indicated that 100% uranium adsorption was favorable from pH 5 to 10 (without the presence of phosphate), and that most of the solid phase uranium was extracted in the step defined for the strongly adsorbed/uranium phosphate mineral in both long and short-term amended reactors. Overall, these results demonstrate that the biomineralization of uranium phosphate minerals is a viable bioremediation strategy in both the vadose and saturated zones of aquifers at both low and high pH, provided an organophosphate source is available.MSCommittee Chair: Taillefert, Martial; Committee Member: DiChristina, Thomas; Committee Member: Van Cappellen, Philipp