• Botcharnikov, Roman
• Mysen, Bjorn
• Lanzirotti, Antonio
• Kelley, Katherine A.
• Birner, Suzanne
• Cottrell, Elizabeth
• Newville, Matthew

Abstract

<p>Oxygen fugacity (fo₂) exerts first-order control on the geochemical evolution of planetary interiors, and the Fe³⁺/ΣFe ratios of silicate glasses provide a useful proxy for fO₂. Fe K-edge micro-X-ray absorption near-edge structure (XANES) spectroscopy allows researchers to micro-analytically determine the Fe³⁺/ΣFe ratios of silicate glasses with high precision. In this study we characterize hydrous and anhydrous basalt glass standards with Mössbauer and XANES spectroscopy and show that synchrotron radiation causes progressive changes to the XANES spectra of hydrous glasses as a function of radiation dose (here defined as total photons delivered per square micrometer), water concentration, and initial Fe3+/ΣFe ratio. We report experiments from eight different radiation dose conditions and show that Fe in hydrous silicate glasses can undergo rapid oxidation upon exposure to radiation. The rate and degree of oxidation correlates with radiation dose and the product of water concentration and ferrous/ferric iron oxide ratio on a molar basis (Φ = X_{HO_0.5}·X_FeO/X_{FeO_1.5}). For example, a basalt glass with 4.9 wt% dissolved H₂O and Fe³⁺/ΣFe = 0.19 from its Mössbauer spectrum may appear to have Fe³⁺/ΣFe ≥ 0.35 when analyzed over several minutes at a nominal flux density of ~2 × 10⁹ photons/s/μm². This radiation-induced increase in Fe³⁺/ΣFe ratio would lead to overestimation of fO₂ by about two orders of magnitude, with dramatic consequences for the interpretation of geological processes. The sample area exposed to radiation shows measureable hydrogen loss, consistent with radiation-induced breaking of O-H bonds, associated H migration and loss, and oxidation of Fe²⁺. This mechanism is consistent with the observation that anhydrous glasses show no damage under any beam conditions. Cryogenic cooling does not mitigate, but rather accelerates, iron oxidation. The effects of beam damage appear to persist indefinitely. We detect beam damage at the lowest photon flux densities tested (3 × 10⁶ photons/s/ μm²); however, at flux densities ≤6 × 10⁷ photons/s/μm², the hydrous glass calibration curve defined by the centroid (derived from XANES spectra) and Fe³⁺/SFe ratios (derived from Mössbauer spectra) is indistinguishable from the anhydrous calibration curve within the accuracy achievable with Mössbauer spectroscopy. Thus, published Fe³⁺/ΣFe ratios from hydrous glasses measured at low photon flux densities are likely to be accurate within measurement uncertainty with respect to what would have been measured by Mössbauer spectroscopy. These new results demonstrate that to obtain accurate Fe³⁺/ΣFe ratios from hydrous, mafic, silicate glasses, it is first necessary to carefully monitor changes in the XANES spectra as a function of incident dose (e.g., fixed-energy scan). Defocusing and attenuating the beam may prevent significant oxidation of Fe in mafic water-bearing glasses.</p>

Topics

• density
• impedance spectroscopy
• experiment
• Oxygen
• glass
• glass
• Hydrogen
• iron
• Mössbauer spectroscopy
• supercritical fluid extraction