U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

Green rusts (GRs) are redox active FeII–FeIII minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce UVI, the dynamics of the transformations and the speciation and stability of the resulting UIV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of UVI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove UVI from synthetic groundwater via reduction to UIV. The initial products in the ChemGR system are solids-associated UIV–carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ∼95% to ∼10%. In contrast, solid-phase UIV atoms in the BioGR system remain relatively extractable, nonuraninite UIV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of UIV in the BioGR system. These data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.