A multimodal X-ray spectroscopy investigation of uranium speciation in ThTiO compounds with the brannerite structure.

ThTiO derived compounds with the brannerite structure were designed, synthesised, and characterised with the aim of stabilising incorporation of U or U, at dilute concentration. Appropriate charge compensation was targeted by co-substitution of Gd, Ca, Al, or Cr, on the Th or Ti site. U L edge X-ray Absorption Near Edge Spectroscopy (XANES) and High Energy Resolution Fluorescence Detected U M edge XANES evidenced U as the major oxidation state in all compounds, with a minor fraction of U (2-13%). The balance of X-ray and Raman spectroscopy data support uranate, rather than uranyl, as the dominant U speciation in the reported brannerites. It is considered that the U concentration was limited by unfavourable electrostatic repulsion arising from substitution in the octahedral Th or Ti sites, which share two or three edges, respectively, with neighbouring polyhedra in the brannerite structure.