Reaction of U-VI with titanium-substituted magnetite: Influence of Ti on U-IV speciation
Reduction of hexavalent uranium (UVI) to less soluble tetravalent uranium (UIV) through enzymatic or abiotic redox reactions has the potential to alter U mobility in subsurface environments. As a ubiquitous natural mineral, magnetite (Fe3O4) is of interest because of its ability to act as a rechargeable reductant for UVI. Natural magnetites are often impure with titanium, and structural Fe3+ replacement by TiIV yields a proportional increase in the relative Fe2+ content in the metal sublattice to maintain bulk charge neutrality. In the absence of oxidation, the Ti content sets the initial bulk Fe2+/Fe3+ ratio (R). Here, we demonstrate that Ti-doped magnetites (Fe3 xTixO4) reduce UVI to UIV. The UVI-Fe2+ redox reactivity was found to be controlled directly by R, but was otherwise independent of Ti content (xTi). However, in contrast to previous studies with pure magnetite where UVI was reduced to nanocrystalline uraninite (UO2), the presence of structural Ti (xTi = 0.25 0.53) results in the formation of UIV species that lack the bidentate U-O2-U bridges of uraninite. Extended x-ray absorption fine structure spectroscopic analysis indicated that the titanomagnetite-bound UIV phase has a novel UIV-Ti binding geometry, different from the coordination of UIV in the mineral brannerite (UIVTi2O6). The observed UIV-Ti coordination at a distance of 3.43 Å suggests a binuclear corner-sharing adsorption/incorporation UIV complex with the solid phase. Furthermore, we explored the effect of oxidation (decreasing R) and solids-to-solution ratio on the reduced UIV phase. The formation of the non-uraninite UIV-Ti phase appears to be controlled by availability of surface Ti sites, rather than R. Our work highlights a previously unrecognized role of Ti in the environmental chemistry of UIV and suggests that further work to characterize the long-term stability of UIV phases formed in the presence of Ti is warranted.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1087262
- Report Number(s):
- PNNL-SA-93479; 46203; KP1702030
- Journal Information:
- Environmental Science & Technology, 47(9):4121-4130, Journal Name: Environmental Science & Technology, 47(9):4121-4130
- Country of Publication:
- United States
- Language:
- English
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