Uranium is a risk-driving radionuclide in both radioactive waste disposal and contaminated land scenarios. In these environments, a range of biogeochemical processes can occur, including sulfate reduction, which can induce sulfidation of iron (oxyhydr)­oxide mineral phases. During sulfidation, labile U­(VI) is known to reduce to relatively immobile U­(IV); however, the detailed mechanisms of the changes in U speciation during these biogeochemical reactions are poorly constrained. Here, we performed highly controlled sulfidation experiments at pH 7 and pH 9.5 on U­(VI) adsorbed to ferrihydrite and investigated the system using geochemical analyses, X-ray absorption spectroscopy (XAS), and computational modeling. Analysis of the XAS data indicated the formation of a novel, transient U­(VI)–persulfide complex as an intermediate species during the sulfidation reaction, concomitant with the transient release of uranium to the solution. Extended X-ray absorption fine structure (EXAFS) modeling showed that a persulfide ligand was coordinated in the equatorial plane of the uranyl moiety, and formation of this species was supported by computational modeling. The final speciation of U was nanoparticulate U­(IV) uraninite, and this phase was evident at 2 days at pH 7 and 1 year at pH 9.5. Our identification of a new, labile U­(VI)-persulfide species under environmentally relevant conditions may have implications for U mobility in sulfidic environments pertinent to radioactive waste disposal and contaminated land scenarios.

Uranium is typically the most abundant radionuclide by mass in radioactive wastes and is a significant component of effluent streams at nuclear facilities. Actinide(IV) (An(IV)) colloids formed via various pathways, including corrosion of spent nuclear fuel, have the potential to greatly enhance the mobility of poorly soluble An(IV) forms, including uranium. This is particularly important in conditions relevant to decommissioning of nuclear facilities and the geological disposal of radioactive waste. Previous studies have suggested that silicate could stabilize U(IV) colloids. Here the formation, composition, and structure of U(IV)-silicate colloids under the alkaline conditions relevant to spent nuclear fuel storage and disposal were investigated using a range of state of the art techniques. The colloids are formed across a range of pH conditions (9-10.5) and silicate concentrations (2-4 mM) and have a primary particle size 1-10 nm, also forming suspended aggregates <220 nm. X-ray absorption spectroscopy, ultrafiltration, and scanning transmission electron microscopy confirm the particles are U(IV)-silicates. Additional evidence from X-ray diffraction and pair distribution function data suggests the primary particles are composed of a UO-rich core and a U-silicate shell. U(IV)-silicate colloids formation correlates with the formation of U(OH)(HSiO) complexes in solution indicating they are likely particle precursors. Finally, these colloids form under a range of conditions relevant to nuclear fuel storage and geological disposal of radioactive waste and represent a potential pathway for U mobility in these systems.

Metaschoepite is commonly found in U-contaminated environments and metaschoepite-bearing wastes may be managed via shallow or deep disposal. Understanding metaschoepite dissolution and tracking the fate of any liberated U is thus important. Here, discrete horizons of metaschoepite (UO 3 • nH 2 O) particles were emplaced in flowing sediment/groundwater columns representative of the UK Sellafield Ltd. site. The column systems either remained oxic or became anoxic due to electron donor additions, and the columns were sacrificed after 6-and 12-months for analysis. Solution chemistry, extractions, and bulk and micro/nano-focus X-ray spectroscopies were used to track changes in U distribution and behavior. In the oxic columns, U migration was extensive, with UO 2 2+ identified in effluents after 6-months of reaction using fluorescence spectroscopy. Unusually, in the electron-donor amended columns, during microbially mediated sulfate reduction, significant amounts of UO 2 -like colloids (>60% of the added U) were found in the effluents using TEM. XAS analysis of the U remaining associated with the reduced sediments confirmed the presence of trace U(VI), noncrystalline U(IV), and biogenic UO 2 , with UO 2 becoming more dominant with time. This study highlights the potential for U(IV) colloid production from U(VI) solids under reducing conditions and the complexity of U biogeochemistry in dynamic systems.

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The stabilization of uranyl(V) (UO2+) by Fe(II) in natural systems remains an open question in uranium chemistry. Stabilization of UVO2+ by Fe(II) against disproportionation was also demonstrated in molecular complexes....