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An overview is given on the current state of X-ray absorption measurements on silicate melts and glasses. The challenges, limitations, and achievements of analyzing X-ray absorption spectra measured in liquids to determine structural properties of major and minor elements in magmas are described, with particular focus on describing non-Gaussian pair distribution functions in highly disordered glasses and melts, measured at in situ conditions. This includes a discussion on the progress of combining experiments with data from molecular dynamics simulations. For the measurements at conditions of the deep Earth, various experimental approaches and necessities are discussed and two examples are described in more detail. Finally, the achievements and prospects are presented for measuring X-ray absorption spectra indirectly by X-ray Raman scattering.
In silicate glasses and melts, water acts according to two main processes. First, it can be dissolved in high temperature/high pressure melts. Second, it constitutes a weathering agent on the glass surface. A number of in-situ x- ray absorption fine structure (XAFS) studies for Fe, Ni, Zr, Th and U show that the more charged cations (Zr, Nb, Mo, Ta, Sn, Th and U) are little affected by the presence of dissolved water in the melt. In contrast, divalent iron and nickel are highly sensitive to the presence of water, which enhance nucleation processes, for example, of phyllosilicates at the angstrom-scale. Such information provides additional constraints on the role of water deep in the Earth, particularly in magmatology. By contrast, the weathering of glass surfaces by water can be studied from a durability perspective. Experimental weathering experiments Of nuclear waste glasses performed in the laboratory show a variety of surface enrichments (carbon, chlorine, alkalis, iron) after exposure to atmospheric fluids and moisture. Mn-, and Fe-surface enrichments of analogous glasses of the XIVth century are related to the formation of Mn and Fe oxy/ hydroxides on the surface. The impact on the glass darkening is considered in terms of urban pollution and mass tourism
The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt
(2005)
Experimental investigations have been performed at T = 1200 degrees C, P = 200 MPa and fH(2) corresponding to H2O-MnO-Mn3O4 and H2O-QFM redox buffers to study the effect of H2O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mossbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe3+/Sigma Fe ratio of the glass is directly related to aH(2)O in a H-2-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H2O <-> H-2 + 1/2 O-2). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO(2) and Fe3+/Fe2+ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of similar to 0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + 1/4 O-2 = FeO1.5). The mean centre shifts for Fe2+ and Fe3+ absorption doublets in Mossbauer spectra show little change with increasing Fe3+/Sigma Fe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses. Copyright (c) 2005 Elsevier Ltd
The iron speciation in hydrous haplotonalitic and haplogranitic silicate glasses was studied using XAFS spectroscopy and transmission electron microscopy (TEM). Spectral features occurring at the main crest of the XANES at the iron K-edge of hydrous glasses indicate contributions to the spectra by iron-moieties present in a more ordered structural environment than found in the dry glass. These differences are also suggested by analysis of the EXAFS. These effects are not completely suppressed even for those samples that were quenched with a higher cooling rate. Strongest differences to the dry glass are observed for a sample that was quenched slowly through the temperature of glass transformation. Crystals (60 to 1500 nm in size) of magnetite, maghemite and another unidentified phase were observed in this sample by TEM, whereas no crystals were found in samples quenched with regular or high cooling rates. In-situ XANES measurements up to 700 degrees C and 500 MPa were performed to reveal the origin (i.e., during synthesis or quench) of the structural differences for those hydrous glasses that do not display any detectable crystallization. The comparison of XANES spectra collected on Fe2+ in water-saturated haplogranitic melt at 700 degrees C and 500 MPa and on Fe2+ in dry melt at 1150 degrees C shows that the local structural environment of Fe2+ in both systems is similar. This indicates that there is no detectable and direct influence of water on the local structure around iron in this type of melt. Hence, the differences observed between hydrous and dry glasses can only be related to artefacts formed during the quench process. (c) 2006 Elsevier B.V. All rights reserved