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 = XHO0.5·XFeO/XFeO1.5). 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.
Bibliographical noteFunding Information:
With admiration, we thank Catherine McCammon, who graciously provided her raw Mössbauer spectra and laboratory notes to E.C. We thank Tim Gooding for laboratory support at Smithsonian. E.C. gratefully acknowledges support from NSF EAR 1347248, NSF EAR 1426717, and NSF OCE 1433212. S.K.B. was further supported by OCE-1434199/OCE-1620276. K.K. gratefully acknowledges support from NSF EAR 1347330 and NSF OCE 1433182. We are grateful for support from Smithson-ian’s Scholarly Studies program. F.D. also acknowledges support from a National Museum of Natural History Peter Buck Fellowship. We are grateful for support for X26Afrom Department of Energy (DOE) GeoSciences DE-FG02-92ER14244. The DOE Office of Science supported use of the NSLS under contract no. DE-AC02-98CH10886. We acknowledge the support of GeoSoilEnviroCARS (Sector 13), which is supported by the National Science Foundation—Earth Sciences (EAR-1128799), and the Department of Energy, Geosciences (DE-FG02-94ER14466). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. We thank editorial handling by Sasa Bajt and Keith Putirka as well as two anonymous reviewers for constructive comments that improved the submission.
© 2018 Walter de Gruyter GmbH, Berlin/Boston 2018.
- Invited Centennial Article
- hydrous basalt
- oxidation state
- oxygen fugacity
- synchrotron radiation