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Title: Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure: Silicate Glasses at High Pressure

Abstract

The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe2+-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption thatmore » coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2]
  1. Division of Geological and Planetary Sciences, Caltech, Pasadena California USA
  2. IMPMC-Muséum National d'Histoire Naturelle-CNRS, Paris France
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCESNSFDOE-NNSAFOREIGNOTHER
OSTI Identifier:
1397300
Resource Type:
Journal Article
Journal Name:
Journal of Geophysical Research. Solid Earth
Additional Journal Information:
Journal Volume: 122; Journal Issue: 8; Journal ID: ISSN 2169-9313
Publisher:
American Geophysical Union
Country of Publication:
United States
Language:
ENGLISH
Subject:
58 GEOSCIENCES

Citation Formats

Solomatova, Natalia V., Jackson, Jennifer M., Sturhahn, Wolfgang, Rossman, George R., and Roskosz, Mathieu. Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure: Silicate Glasses at High Pressure. United States: N. p., 2017. Web. doi:10.1002/2017JB014363.
Solomatova, Natalia V., Jackson, Jennifer M., Sturhahn, Wolfgang, Rossman, George R., & Roskosz, Mathieu. Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure: Silicate Glasses at High Pressure. United States. doi:10.1002/2017JB014363.
Solomatova, Natalia V., Jackson, Jennifer M., Sturhahn, Wolfgang, Rossman, George R., and Roskosz, Mathieu. Tue . "Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure: Silicate Glasses at High Pressure". United States. doi:10.1002/2017JB014363.
@article{osti_1397300,
title = {Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure: Silicate Glasses at High Pressure},
author = {Solomatova, Natalia V. and Jackson, Jennifer M. and Sturhahn, Wolfgang and Rossman, George R. and Roskosz, Mathieu},
abstractNote = {The physical properties of silicate melts within Earth's mantle affect the chemical and thermal evolution of its interior. Chemistry and coordination environments affect such properties. We have measured the hyperfine parameters of iron-bearing rhyolitic and basaltic glasses up to ~120 GPa and ~100 GPa, respectively, in a neon pressure medium using time domain synchrotron Mössbauer spectroscopy. The spectra for rhyolitic and basaltic glasses are well explained by three high-spin Fe2+-like sites with distinct quadrupole splittings. Absence of detectable ferric iron was confirmed with optical absorption spectroscopy. The sites with relatively high and intermediate quadrupole splittings are likely a result of fivefold and sixfold coordination environments of ferrous iron that transition to higher coordination with increasing pressure. The ferrous site with a relatively low quadrupole splitting and isomer shift at low pressures may be related to a fourfold or a second fivefold ferrous iron site, which transitions to higher coordination in basaltic glass, but likely remains in low coordination in rhyolitic glass. These results indicate that iron experiences changes in its coordination environment with increasing pressure without undergoing a high-spin to low-spin transition. We compare our results to the hyperfine parameters of silicate glasses of different compositions. With the assumption that coordination environments in silicate glasses may serve as a good indicator for those in a melt, this study suggests that ferrous iron in chemically complex silicate melts likely exists in a high-spin state throughout most of Earth's mantle.},
doi = {10.1002/2017JB014363},
journal = {Journal of Geophysical Research. Solid Earth},
issn = {2169-9313},
number = 8,
volume = 122,
place = {United States},
year = {2017},
month = {8}
}

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