Uranium incorporation into aluminum-substituted ferrihydrite during iron(ii)-induced transformation

Abstract

Uranium retention processes (adsorption, precipitation, and incorporation into host minerals) exert strong controls on U mobility in the environment, and understanding U retention is therefore crucial for predicting the migration of U within surface and groundwater. Uranium can be incorporated into Fe (hydr)oxides during Fe(II)-induced transformation of ferrihydrite to goethite. However, ferrihydrite seldom exists as a pure phase within soils or sediments, and structural impurities such as Al alter its reactivity. The presence of Al in ferrihydrite, for example, decreases the rate of transformation to goethite, and thus may impact the retention pathway, or extent of retention, of U. Here, we investigate the extent and pathways of U(VI) retention on Al-ferrihydrite during Fe(II)-induced transformation. Ferrihydrite containing 0%, 1%, 5%, 10%, and 20% Al was reacted with 10 μM U and 300 μM Fe(II) in the presence of 0 mM and 4 mM Ca²⁺ and 3.8 mM carbonate at pH 7.0. Solid reaction products were characterized using U L₃-edge EXAFS spectroscopy to differentiate between adsorbed U and U incorporated into the goethite lattice. Uranium incorporation into Al-ferrihydrite declined from ∼70% of solid-phase U at 0% and 1% Al to ∼30% of solid phase U at 20% Al content. The decrease in U incorporation with increasing Al concentration was due to two main factors: (1) decreased transformation of ferrihydrite to goethite; and, (2) a decrease of the goethite lattice with increasing Al, making the lattice less compatible with large U atoms. However, uranium incorporation can occur even with an Al-substituted ferrihydrite precursor in the presence or absence of Ca²⁺. The process of U incorporation into Al-goethite may therefore be a potential long-term sink of U in subsurface environments where Al-substituted iron oxides are common, albeit at lower levels of incorporation with increasing Al content.