X-ray absorption spectroscopic studies of Fe environments in borosilicate waste glasses synthesized under a variety of redox conditions

Abstract

Fe K-edge X-ray absorption spectroscopy (XAS) was performed on two borosilicate waste glass series to determine Fe valence and coordination changes over a wide range of redox synthesis conditions. Data were also collected on eight Fe-silicate standards, including the rare phase, pellyite, that was used as a tetrahedral Fe2+O4 standard. X-ray absorption near-edge structure (XANES) linear combination fits of the Fe2+O4, Fe2+O5, and Fe3+O4 standards data to the glass spectra determined Fe2+/Fetotal ratios from 0.07 to 0.90 that are within 10 % of Mössbauer findings. As the glasses become reduced, XANES indicates Fe3+O4 tetrahedra are being replaced by Fe2+O4 tetrahedra, and possibly, Fe2+O5 sites, while extended X-ray absorption fine structure analyses show average Fe-O distances increase from 1.88 to 1.96 Å. The XANES-determined three Fe-site population distributions in the glasses are similar to findings reported in a recent molecular dynamics study of Fe redox effects in waste glass.