Biotic dissolution of autunite under anaerobic conditions: effect of bicarbonates and Shewanella oneidensis MR1 microbial activity.

Abstract

Uranium is a contaminant of major concern across the US Department of Energy complex that served a leading role in nuclear weapon fabrication for half a century. In an effort to decrease the concentration of soluble uranium, tripolyphosphate injections were identified as a feasible remediation strategy for sequestering uranium in situ in contaminated groundwater at the Hanford Site. The introduction of sodium tripolyphosphate into uranium-bearing porous media results in the formation of uranyl phosphate minerals (autunite) of general formula {X1-2[(UO2)(PO4)]2-1·nH2O}, where X is a monovalent or divalent cation. The stability of the uranyl phosphate minerals is a critical factor that determines the long-term effectiveness of this remediation strategy that can be affected by biogeochemical factors such as the presence of bicarbonates and bacterial activity. The objective of this research was to investigate the effect of bicarbonate ions present in the aqueous phase on Ca-autunite dissolution under anaerobic conditions, as well as the role of metal-reducing facultative bacterium Shewanella oneidensis MR1. The concentration of total uranium determined in the aqueous phase was in direct correlation to the concentration of bicarbonate present in the solution, and the release of Ca, U and P into the aqueous phase was non-stoichiometric. Experiments revealed the absence of an extensive biofilm on autunite surface, while thermodynamic modeling predicted the presence of secondary minerals, which were identified through microscopy. In conclusion, the dissolution of autunite under the conditions studied is susceptible to bicarbonate concentration, as well as microbial presence.