Polymorphic transformations of titanium oxides contribute to economic uranium mineralization in sandstone

Abstract

Sandstone-hosted uranium (U) deposits provide a significant U resource for nuclear energy worldwide. Driven by redox reactions, tetravalent uranium-bearing minerals are commonly associated with reductants (e.g., pyrite and organic matter). However, numerous observations have revealed that tetravalent uranium-bearing minerals can spatially coexist with chemically stabilized titanium oxides in sandstone-hosted U deposits, requiring a complementary mechanism to interpret these findings. We present a new model based on in situ texture, trace-element content, and titanium isotopic ratio, as well as polymorph type and related transformation for titanium oxides from the Yaojia Formation of the southwestern Songliao Basin in northeast China. Specifically, in our model, abundant nanopores were generated during the spontaneous transformation of anatase to rutile, producing a porous material for hexavalent U adsorption. Facilitated by a U-rich source rock, adsorbed U in porous titanium oxide from the lower Yaojia Formation was up to several thousand parts per million. In order to minimize surface energy, a subsequent decrease in surface area by merging small pores is inevitable. When the evolved surface area was small enough, hexavalent U would be desorbed and subsequently transformed to tetravalent U by local reductants, forming uraninite nanoparticles on the surface of U-rich rutile with relatively large pores. Our newly proposed mechanism not only contributes to a better understanding of economic U mineralization in sandstone, but also suggests that U occurred as uranium oxide instead of brannerite in sandstone-hosted U deposits, providing a nano-mineralogical perspective required for industrial processing.