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Uranium (U) poses a significant contamination hazard to soils, sediments, and groundwater due to its extensive use for energy production. Despite advances in modeling the risks of this toxic and radioactive element, lack of information about the mechanisms controlling U transport hinders further improvements, particularly in reducing environments where UIV predominates. Here we establish that mineral surfaces can stabilize the majority of U as adsorbed UIV species following reduction of UVI. Using X-ray absorption spectroscopy and electron imaging analysis, we find that at low surface loading, UIV forms inner-sphere complexes with two metal oxides, TiO2 (rutile) and Fe3O4 (magnetite) (at <1.3 U nm–2 and <0.037 U nm–2, respectively). The uraninite (UO2) form of UIV predominates only at higher surface loading. UIV–TiO2 complexes remain stable for at least 12 months, and UIV–Fe3O4 complexes remain stable for at least 4 months, under anoxic conditions. Adsorbed UIV results from UVI reduction by FeII or by the reduced electron shuttle AH2QDS, suggesting that both abiotic and biotic reduction pathways can produce stable UIV–mineral complexes in the subsurface. The observed control of high-affinity mineral surface sites on UIV speciation helps explain the presence of nonuraninite UIV in sediments and has important implications for U transport modeling.

Microbial reduction of ferric iron [Fe(III)] is an important biogeochemical process

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