The contaminant of most concern in groundwater at the Oak Ridge Y-12 Plant's Bear Creek Valley Characterization Area is soluble uranium. The removal mechanism of soluble uranium from groundwater by zero-valent iron (ZVI, Fe0) was investigated. X-ray photoelectron spectroscopy (XPS, ESCA) was used to determine the uranium oxidation state at the Fe0 or iron oxide surface. Product speciation and relative reaction kinetics for the removal of soluble uranium under aerobic and anaerobic conditions with ZVI are presented. Under aerobic conditions, U6+ is rapidly and strongly sorbed to hydrous ferric oxide particulates (“rust”), whereas U6+ is slowly and incompletely reduced to U4+ under anaerobic conditions.

Removal of uranium from contaminated ground water using zero valent iron is currently under evaluation at several U.S. Department of Energy (DOE) facilities. Uranium removal by zero valent iron may occur via adsorption onto iron corrosion products, and by reduction to less soluble valence states by reactions with elemental iron. This research investigated the effects of water chemistry and surface precipitate buildup on the removal of soluble uranium by zero valent iron. Batch testing was performed to assess solution chemistry effects on uranium adsorption to the potential iron corrosion products, magnetite and a mixed valent amorphous iron oxide. Uranium adsorption to the simulated iron corrosion products was highly dependent on pH, and the concentration and speciation of the background electrolyte solution. Uranium removal via reduction by elemental iron closely approximated pseudo‐first‐order removal kinetics, despite the buildup of up to 40,000 monolayers of precipitated uranium on the iron surfaces. This indicates that the rate of uranium removal is not strongly dependent on the thickness of the adsorbed uranium layer. Short‐term rates of uranium reduction were similar for all solutions tested, but long‐term rates were highly dependent on water chemistry. Compared to deionized water, uranium removal rates were increased in sodium chloride containing solutions and reduced in sodium nitrate solutions. The strong influence of water chemistry on long‐term reduction rates indicates that system design will require extnded testing with the ground water of interest.

Micro-Raman spectroscopy has been utilized to examine the spectra of solid samples of α-UF5, β-UF5, UF6, three types of UO2F2, the powder residue from a static UF6 release, and γ-UO3. The spectra are presented and compared to previous literature values, with new features indicated where appropriate. With the implied constraint of proper sample handling, micro-Raman spectroscopy is a useful technique for the ready identification of uranium fluorides, oxyfluorides, and oxides.