skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 Fe 2+-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 assumptionmore » 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.« less

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  2. Centre National de la Recherche Scientifique (CNRS), Paris (France)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1397300
Grant/Contract Number:  
[AC02- 06CH11357; NSF-CSEDI-EAR-1600956; NSF-EAR-1322082]
Resource Type:
Accepted Manuscript
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; silicate glass; silicate melt; Mossbauer spectroscopy; high pressure; coordination environment; ferrous iron

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. Thu . "Electronic environments of ferrous iron in rhyolitic and basaltic glasses at high pressure: Silicate Glasses at High Pressure". United States. doi:10.1002/2017JB014363. https://www.osti.gov/servlets/purl/1397300.
@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},
number = [8],
volume = [122],
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Optical absorption and Mössbauer spectra of Fe, Ti silicate glasses
journal, March 1980


Mössbauer spectroscopy of tektites
journal, June 1994

  • Aramu, F.; Brovetto, P.; Maxia, V.
  • Il Nuovo Cimento D, Vol. 16, Issue 6
  • DOI: 10.1007/BF02451660

Iron spin state in silicate glass at high pressure: Implications for melts in the Earthʼs lower mantle
journal, January 2014


An infrared reflectance study of Si–O vibrations in thermally treated alkali-saturated montmorillonites
journal, September 1999


Spectroscopic standards for four- and fivefold-coordinated Fe 2+ in oxygen-based minerals
journal, July 2001

  • Rossman, George R.; Taran, Michael N.
  • American Mineralogist, Vol. 86, Issue 7-8
  • DOI: 10.2138/am-2001-0713

Recoilless Nuclear Resonance Absorption
journal, December 1962


High-pressure radiative conductivity of dense silicate glasses with potential implications for dark magmas
journal, November 2014

  • Murakami, Motohiko; Goncharov, Alexander F.; Hirao, Naohisa
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6428

Evidence for partial melt at the core–mantle boundary north of Tonga from the strong scattering of seismic waves
journal, February 1998

  • Vidale, John E.; Hedlin, Michael A. H.
  • Nature, Vol. 391, Issue 6668
  • DOI: 10.1038/35601

Iron in Silicate Glasses a Systematic Analysis of PreEdge, XANES and EXAFS Features
journal, January 2005


Fast temperature spectrometer for samples under extreme conditions
journal, January 2015

  • Zhang, Dongzhou; Jackson, Jennifer M.; Zhao, Jiyong
  • Review of Scientific Instruments, Vol. 86, Issue 1
  • DOI: 10.1063/1.4905431

Investigation of calcium-iron-silicate glasses by the Mössbauer method
journal, September 1978

  • Iwamoto, Nobuya; Tsunawaki, Yoshiaki; Nakagawa, Hirotaka
  • Journal of Non-Crystalline Solids, Vol. 29, Issue 3
  • DOI: 10.1016/0022-3093(78)90155-2

Speciation of Fe in silicate glasses and melts by in-situ XANES spectroscopy
journal, January 2007

  • Wilke, M.; Farges, F.; Partzsch, G. M.
  • American Mineralogist, Vol. 92, Issue 1
  • DOI: 10.2138/am.2007.1976

Pressure calibration of diamond anvil Raman gauge to 310GPa
journal, August 2006

  • Akahama, Yuichi; Kawamura, Haruki
  • Journal of Applied Physics, Vol. 100, Issue 4
  • DOI: 10.1063/1.2335683

Local structure variations observed in orthoenstatite at high pressures
journal, September 2011

  • Zhang, D.; Jackson, J. M.; Sturhahn, W.
  • American Mineralogist, Vol. 96, Issue 10
  • DOI: 10.2138/am.2011.3721

Spin crossover in Fe 2 SiO 4 liquid at high pressure
journal, July 2014

  • Ramo, David Muñoz; Stixrude, Lars
  • Geophysical Research Letters, Vol. 41, Issue 13
  • DOI: 10.1002/2014GL060473

Baseline Studies of the Clay Minerals Society Source Clays: Infrared Methods
journal, January 2001


Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions
journal, January 1986

  • Mao, H. K.; Xu, J.; Bell, P. M.
  • Journal of Geophysical Research, Vol. 91, Issue B5, p. 4673-4676
  • DOI: 10.1029/JB091iB05p04673

Superplume, supercontinent, and post-perovskite: Mantle dynamics and anti-plate tectonics on the Core–Mantle Boundary
journal, January 2007


A Mössbauer effect investigation of correlated hyperfine parameters in natural glasses (tektites)
journal, January 1998


MÖSsbauer Spectroscopy of Earth and Planetary Materials
journal, May 2006


Magma redox and structural controls on iron isotope variations in Earth's mantle and crust
journal, July 2014


UV-vis absorption of the transition metal-doped SiO2–B2O3–Na2O glasses
journal, August 2007


Multi-technique equation of state for Fe 2 SiO 4 melt and the density of Fe-bearing silicate melts from 0 to 161 GPa : EQUATION OF STATE FOR Fe
journal, October 2012

  • Thomas, Claire W.; Liu, Qiong; Agee, Carl B.
  • Journal of Geophysical Research: Solid Earth, Vol. 117, Issue B10
  • DOI: 10.1029/2012JB009403

The effect of composition on UV–vis–NIR spectra of iron doped glasses in the systems Na2O/MgO/SiO2 and Na2O/MgO/Al2O3/SiO2
journal, March 2007


Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts
journal, September 2005

  • Jackson, William E.; Farges, Francois; Yeager, Mark
  • Geochimica et Cosmochimica Acta, Vol. 69, Issue 17
  • DOI: 10.1016/j.gca.2005.01.008

The density and compressibility of CaO–FeO–SiO2 liquids at one bar: Evidence for four-coordinated Fe2+ in the CaFeO2 component
journal, November 2013


Seismic Evidence for Partial Melt at the Base of Earth's Mantle
journal, September 1996


Fe2+?Fe3+ ordered distribution in chromite spinels
journal, November 1992

  • Chen, Y. L.; Xu, B. F.; Chen, J. G.
  • Physics and Chemistry of Minerals, Vol. 19, Issue 4
  • DOI: 10.1007/BF00202316

Redox reactions during temperature change in soda-lime–silicate melts doped with copper and iron or copper and manganese
journal, October 2006


The effect of bulk composition on the speciation of water in submarine volcanic glasses
journal, May 1992


Site distribution of iron in staurolite
journal, May 1972


57FE Mössbauer spectroscopy studies of Tektites from Khon Kaen, Ne Thailand
journal, February 2013

  • Costa, B. F. O.; Klingelhöfer, G.; Alves, E. I.
  • Hyperfine Interactions, Vol. 224, Issue 1-3
  • DOI: 10.1007/s10751-013-0769-x

Infrared and thermogravimetric study of high pressure consolidation in alkoxide silica gel powders
journal, November 1997


Distribution of cations at two tetrahedral sites in Ca2MgSi2O7-Ca2Fe3+AlSiO7 series synthetic melilite and its relation to incommensurate structure
journal, February 2013


Redox equilibria and coordination of Fe2+ and Fe3+ in silicate glasses from 57Fe mossbauer spectroscopy
journal, December 1987


Determination of the iron oxidation state in basaltic glasses using XANES at the K-edge
journal, July 2005


The coordination number of ferrous ions in silicate glasses
journal, December 1972


Analysis of Mössbauer spectra of silicate glasses using a two-dimensional Gaussian distribution of hyperfine parameters
journal, January 1996

  • Alberto, H. V.; Pinto da Cunha, J. L.; Mysen, B. O.
  • Journal of Non-Crystalline Solids, Vol. 194, Issue 1-2
  • DOI: 10.1016/0022-3093(95)00463-7

Structure and density of basaltic melts at mantle conditions from first-principles simulations
journal, October 2015

  • Bajgain, Suraj; Ghosh, Dipta B.; Karki, Bijaya B.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9578

Electronic transitions of iron in almandine-composition glass to 91 GPa
journal, July 2016

  • Dorfman, Susannah M.; Dutton, Sian E.; Potapkin, Vasily
  • American Mineralogist, Vol. 101, Issue 7
  • DOI: 10.2138/am-2016-5606

The oxidation state of Fe in MORB glasses and the oxygen fugacity of the upper mantle
journal, May 2011

  • Cottrell, Elizabeth; Kelley, Katherine A.
  • Earth and Planetary Science Letters, Vol. 305, Issue 3-4
  • DOI: 10.1016/j.epsl.2011.03.014

A Study of Na 2 O-TiO 2 -SiO 2 Glasses by Infrared Spectroscopy
journal, May 1974


Mineral Mössbauer spectroscopy: Correlations between chemical shift and quadrupole splitting parameters
journal, December 1994


Advanced analyses of 57Fe Mössbauer data of alumino-silicate glasses
journal, November 2007


57 Fe Mössbauer spectroscopy of tektites
journal, July 1999

  • Rossano, S.; Balan, E.; Morin, G.
  • Physics and Chemistry of Minerals, Vol. 26, Issue 6
  • DOI: 10.1007/s002690050216

Electronic structure of iron in magnesium silicate glasses at high pressure
journal, December 2012

  • Gu, Chen; Catalli, Krystle; Grocholski, Brent
  • Geophysical Research Letters, Vol. 39, Issue 24
  • DOI: 10.1029/2012GL053950

Nuclear resonant spectroscopy
journal, January 2004


Spin crossover and iron-rich silicate melt in the Earth’s deep mantle
journal, April 2011

  • Nomura, Ryuichi; Ozawa, Haruka; Tateno, Shigehiko
  • Nature, Vol. 473, Issue 7346
  • DOI: 10.1038/nature09940