XANES calibrations for the oxidation state of iron in a silicate glass

Fe K-edge X-ray absorption near edge structure (XANES) spectra were recorded for a series of anorthite-diopside eutectic glasses containing I Wt% (Fe2O3)-Fe-57 quenched from melts equilibrated over a range of oxygen fugacities at 1409 degreesC. The Fe3+/SigmaFe ratios were determined previously by Fe-57 Mossbauer spectroscopy and vary between 0 (fully reduced) and I (fully oxidized). Using the Mossbauer results as a reference, various methods for extracting Fe3+/SigmaFe ratios from XANES spectra were investigated. The energy of the Is --> 3d pre-edge transition centroid was found to correlate linearly with the oxidation state. Correlations also exist with the energy of the K absorption edge and the area of peaks in the derivative spectrum associated with the Is --> 4s and crest (Is --> 4p) transitions. The Fe3+/SigmaFe ratios determined from linear combinations of end-member spectra (Fe3+/SigmaFe similar to0 and similar to1) were found to deviate significantly from the Mossbauer values. This may indicate the susceptibility of this method either to errors arising from the treatment of the background or to changes in Fe2+ or Fe3+ coordination with the Fe3+/SigmaFe ratio. The general applicability of any XANES calibration for determining oxidation states is limited by variations in the Fe coordination environment, which affects both the intensity and energy of spectral features. Thus previous calibrations based on mineral spectra are not applicable to silicate glasses. Nevertheless, systematic trends in spectral features suggest that Fe3+/SigmaFe values may be obtained from XANES spectra, with an accuracy comparable to Mossbauer spectroscopy, by reference to empirical calibration curves derived from compositionally similar standards.