Fate of Adsorbed U(VI) during Sulfidization of Lepidocrocite and Hematite

The impact on U(VI) adsorbed to lepidocrocite (γ-FeOOH) and hematite (α-Fe₂O₃) was assessed when exposed to aqueous sulfide (S(-II)_aq) at pH 8.0. With both minerals, competition between S(-II) and U(VI) for surface sites caused instantaneous release of adsorbed U(VI). Compared to lepidocrocite, consumption of S(-II)_aq proceeded slower with hematite, but yielded maximum dissolved U concentrations that were more than 10 times higher, representing about one-third of the initially adsorbed U. Prolonged presence of S(-II)_aq in experiments with hematite in combination with a larger release of adsorbed U(VI), enhanced the reduction of U(VI): after 24 h of reaction about 60-70% of U was in the form of U(IV), much higher than the 25% detected in the lepidocrocite suspensions. X-ray absorption spectra indicated that U(IV) in both hematite and lepidocrocite suspensions was not in the form of uraninite (UO₂). Upon exposure to oxygen only part of U(IV) reoxidized, suggesting that monomeric U(IV) might have become incorporated in newly formed iron precipitates. Hence, sulfidization of Fe oxides can have diverse consequences for U mobility: in short-term, desorption of U(VI) increases U mobility, while reduction to U(IV) and its possible incorporation in Fe transformation products may lead to long-term U immobilization.