Removal of uranium(VI) from the aqueous phase by iron(II) minerals in presence of bicarbonate

Uranium(VI) mobility in groundwater is strongly affected by sorption of mobile U(VI) species (e.g. uranyl, UO22+) to mineral surfaces, precipitation of U(VI) compounds, such as schoepite (UO2)4O(OH)6·6H2O), and by reduction to U(IV), forming sparingly soluble phases (uraninite; UO2). The latter pathway, in particular, would be very efficient for long-term immobilization of U. In nature, Fe(II) is an important reducing agent for U(VI) because it frequently occurs either dissolved in natural waters, sorbed to matrix minerals, or structurally bound in many minerals. Redox reactions between U(VI) and Fe(II) depend not only on the availability of Fe(II) in the environment, but also on the chemical conditions in the aqueous solution. Under natural groundwater condition U(VI) forms complexes with many anionic ligands, which strongly affect its speciation. Carbonate, in particular, is known to form stable complexes with U, raising the question, if U(VI), when complexed by carbonate, can be reduced to UO2. The goal of this study was to find out if Fe(II) when structurally bound in a mineral (as magnetite, Fe3O4) or sorbed to a mineral surface (as corundum, Al2O3) can reduce U(VI) to U(IV) in the presence of HCO3-. Batch experiments were conducted under anaerobic conditions to observe U removal from the aqueous phase by the two minerals depending on HCO3- addition (1 mM), U concentration (0.01–30 μM) and pH value (6–10). Immediately after the experiments, the mineral surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) to obtain information on the redox state of U bound to the solid surfaces. XPS results gave evidence that U(VI) can be reduced both by magnetite and by corundum amended with Fe(II). In the presence of HCO3- the amount of reduced U on the mineral surfaces increased compared to carbonate-free solutions. This can be explained by the formation of Fe(II) carbonates on the mineral surfaces which represent an easily available Fe(II) pool for the U(VI) reduction. A facilitated U(VI) reduction is also considered possible when U is present as a carbonate complex compared to non-complexed U (e.g. uranyl).