Iron Vacancies Accommodate Uranyl Incorporation into Hematite

Radiotoxic uranium contamination in natural systems and nuclear waste containment can be sequestered by incorporation into naturally abundant iron (oxyhydr)oxides such as hematite (α-Fe₂O₃) during mineral growth. The stability and properties of the resulting uranium-doped material are impacted by the local coordination environment of incorporated uranium. While measurements of uranium coordination in hematite have been attempted using extended X-ray absorption fine structure (EXAFS) analysis, traditional shell-by-shell EXAFS fitting yields ambiguous results. We used hybrid functional ab initio molecular dynamics (AIMD) simulations for various defect configurations to generate synthetic EXAFS spectra which were combined with adsorbed uranyl spectra to fit experimental U L₃-edge EXAFS for U⁶⁺-doped hematite. We discovered that the hematite crystal structure accommodates a trans-dioxo uranyl-like configuration for U⁶⁺ that substitutes for structural Fe³⁺, which requires two partially protonated Fe vacancies situated at opposing corner-sharing sites. Surprisingly, the best match to experiment included significant proportions of vacancy configurations other than the minimum-energy configuration, pointing to the importance of incorporation mechanisms and kinetics in determining the state of an impurity incorporated into a host phase under low temperature hydrothermal conditions.