Geochemical coupling of uranium and phosphorous in soils overlying an unmined uranium deposit: Coles Hill, Virginia

Abstract: The mineralogy and geochemistry of soils developed over the unmined Coles Hill uranium deposit (Virginia) were studied to determine how phosphorous influences the speciation of uranium in oxidizing soil/saprolite systems typical of the eastern US. Results from this study have implications for both uranium remediation (e.g. in situ stabilization) and uranium resource exploration (e.g. near-surface geochemical sampling). The primary uranium ore (coffinite and uraninite hosted in quartzo-feldspathic gneiss) weathers to saprolites containing the same uranium concentration as the underlying ore (approximately 1000 mg U/kg saprolites). In these water saturated (below water table) saprolites the uranium is retained as uranyl phosphates of the meta-autunite group (mainly meta-uranocircite). Above the water table the soils overlying the deposit contain approximately 200 mg uranium per kg soil (20 times higher than uranium concentrations in similar soils formed from unmineralized rocks adjacent to the deposit). In these unsaturated zone soils uranium is retained by two processes: (1) incorporation into barium–strontium–calcium aluminum phosphate minerals of the crandallite group (mainly gorceixite), and (2) sorption of uranium with phosphorous onto iron oxides that coat the surfaces of other soil minerals. Thermodynamic calculations suggest that the meta-autunite group minerals present in the saprolites below the water table are not stable in the unsaturated zone soils overlying the deposit due to the drop in soil pH from ∼6.0 down to ∼4.5. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group minerals react to form U(VI)-bearing aluminum phosphates and U(VI) surface complexes or nano-precipitates associated with ferric oxides. These results therefore indicate that models predicting U(VI) speciation in phosphate amended soils must simultaneously account for variations in pH, ion activities (aluminum appears to be particularly important) and surface complexation with iron oxide mineral surfaces. [Copyright &y& Elsevier]