Iron oxidation state in the Fe-rich layer and silica matrix of Libyan Desert Glass: a high-resolution XANES study

Libyan Desert Glass (LDG) is an enigmatic type of glass that occurs in western Egypt in the Libyan Desert. Fairly convincing evidence exists to show that it formed by impact, although the source crater is currently unknown. Some rare samples present dark-colored streaks with variable amounts of Fe, and they are supposed to contain a meteoritic component. We have studied the iron local environment in an LDG sample by means of Fe K-edge high-resolution X-ray absorption near edge structure (XANES) spectroscopy to obtain quantitative data on the Fe oxidation state and coordination number in both the Fe-poor matrix and Fe-rich layers. The pre-edge peak of the high-resolution XANES spectra of the sample studied displays small but reproducible variations between Fe-poor matrix and Fe-rich layers, which is indicative of significant changes in the Fe oxidation state and coordination number. Comparison with previously obtained data for a very low-Fe sample shows that, while iron is virtually all trivalent and in tetrahedral coordination ([4]Fe3+) in the low-Fe sample, the sample containing the Fe-rich layers display a mixture of tetra-coordinated trivalent iron ([4]Fe3+) and penta-coordinated divalent iron ([5]Fe2+), with the Fe in the Fe-rich layer being more reduced than the matrix. From these data, we conclude the following: a) the significant differences in the Fe oxidation state between LDG and tektites, together with the wide intra-sample variations in the Fe-oxidation state, confirm that LDG is an impact glass and not a tektite-like glass; b) the higher Fe content, coupled with the more reduced state of the Fe, in the Fe-rich layers suggests that some or most of the Fe in these layers may be directly derived from the meteoritic projectile and that it is not of terrestrial origin.