Metaschoepite Dissolution in Sediment Column Systems - Implications for Uranium Speciation and Transport

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 (UO₃·nH₂O) 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 UO₂ 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 UO₂-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 UO₂, with UO₂ 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.