Multimodal X-ray microanalysis of a UFeO4: evidence for the environmental stability of ternary U(v) oxides from depleted uranium munitions testing†
An environmentally aged radioactive particle of UFeO4 recovered from soil contaminated with munitions depleted uranium (DU) was characterised by microbeam synchrotron X-ray analysis. Imaging of uranium speciation by spatially resolved X-ray diffraction (μ-XRD) and X-ray absorption spectroscopy (μ-XAS) was used to localise UFeO4 in the particle, which was coincident with a distribution of U(V). The U oxidation state was confirmed using X-ray Absorption Near Edge Structure (μ-XANES) spectroscopy as +4.9 ± 0.15. Le-Bail fitting of the particle powder XRD pattern confirmed the presence of UFeO4 and a minor alteration product identified as chernikovite (H3O)(UO2)(PO4)·3H2O. Refined unit cell parameters for UFeO4 were in good agreement with previously published values. Uranium–oxygen interatomic distances in the first co-ordination sphere were determined by fitting of Extended X-ray Absorption Fine Structure (μ-EXAFS) spectroscopy. The average first shell U–O distance was 2.148 ± 0.012 Å, corresponding to a U valence of +4.96 ± 0.13 using bond valence sum analysis. Using bond distances from the published structure of UFeO4, U and Fe bond valence sums were calculated as +5.00 and +2.83 respectively, supporting the spectroscopic analysis and confirming the presence of a U(V)/Fe(III) pair. Overall this investigation provides important evidence for the stability of U(V) ternary oxides, in oxic, variably moist surface environment conditions for at least 25 years.