Bioremediation of uranium contaminated sites through the formation of U(vi) phosphate (bio)minerals

Abstract

Operations at uranium (U)-mining and nuclear facilities have left a global legacy of significant radionuclide contamination in groundwaters which must be managed to minimize environmental harm. Uranium groundwater contamination is present at several sites globally, including Oak Ridge National Laboratory and Hanford, USA and Sellafield nuclear site, UK. In situ phosphate biomineralisation offers a promising method for radionuclide (including ⁹⁰Sr and U) remediation at these sites. Typically, phosphate-generating amendments are injected into the subsurface to sequester select radionuclides in groundwaters by precipitation of poorly soluble Ca-phosphate phases and subsequent adsorption and/or incorporation of radionuclides to these poorly soluble phases, a remediation route being explored for both U and ⁹⁰Sr. In this study, we investigate the mechanisms of U-phosphate precipitation in two phosphate-generating amendments (Ca-citrate/Na-phosphate and glycerol phosphate) under conditions relevant to Sellafield, UK. Using aerobic batch sediment experiments, we show both Ca-citrate/Na-phosphate and glycerol phosphate amendments are effective at enhancing removal of U(VI) from representative groundwaters (from 94% to >97%). Aqueous geochemical data coupled to speciation modelling highlighted that precipitation of U(VI) phosphate phases was the likely mechanism of U(VI) removal from groundwaters. Further X-ray absorption spectroscopy (XAS) analysis of solids confirmed U was present as a highly insoluble uranyl orthophosphate-like phase after treatment with both Ca-citrate/Na-phosphate and glycerol phosphate amendments. These data provide underpinning information on U-phosphate remediation in Sellafield relevant conditions thus expanding the range of treatment options for radionuclide contaminated groundwaters and defining the transport and fate of U during phosphate biomineralisation.