Structural complexity of simple Fe 2O 3 at high pressures and temperatures
Abstract
Although chemically very simple, Fe 2O 3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe 2O 3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe 2O 3. Decomposition of Fe 2O 3 and Fe 3O 4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe 5O 7 and Fe 25O 32 phases with release of oxygen. Lastly, our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.
- Authors:
-
[1];
[1];
- Univ. of Bayreuth, Bayreuth (Germany)
- Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
- Univ. of Bayreuth, Bayreuth (Germany); European Synchrotron Radiation Facility, Grenoble (France)
- European Synchrotron Radiation Facility, Grenoble (France)
- Univ. of Chicago, Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- OSTI Identifier:
- 1238292
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 02, 2016; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical physics; structural properties
Citation Formats
Bykova, Elena, Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S. V., Liermann, H. -P., Kupenko, I., Chumakov, A. I., Ruffer, R., Hanfland, M., and Prakapenka, V. Structural complexity of simple Fe2O3 at high pressures and temperatures. United States: N. p., 2016.
Web. doi:10.1038/ncomms10661.
Bykova, Elena, Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S. V., Liermann, H. -P., Kupenko, I., Chumakov, A. I., Ruffer, R., Hanfland, M., & Prakapenka, V. Structural complexity of simple Fe2O3 at high pressures and temperatures. United States. doi:10.1038/ncomms10661.
Bykova, Elena, Dubrovinsky, L., Dubrovinskaia, N., Bykov, M., McCammon, C., Ovsyannikov, S. V., Liermann, H. -P., Kupenko, I., Chumakov, A. I., Ruffer, R., Hanfland, M., and Prakapenka, V. Thu .
"Structural complexity of simple Fe2O3 at high pressures and temperatures". United States. doi:10.1038/ncomms10661. https://www.osti.gov/servlets/purl/1238292.
@article{osti_1238292,
title = {Structural complexity of simple Fe2O3 at high pressures and temperatures},
author = {Bykova, Elena and Dubrovinsky, L. and Dubrovinskaia, N. and Bykov, M. and McCammon, C. and Ovsyannikov, S. V. and Liermann, H. -P. and Kupenko, I. and Chumakov, A. I. and Ruffer, R. and Hanfland, M. and Prakapenka, V.},
abstractNote = {Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Lastly, our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.},
doi = {10.1038/ncomms10661},
journal = {Nature Communications},
number = 02, 2016,
volume = 7,
place = {United States},
year = {2016},
month = {2}
}
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Works referenced in this record:
The 57 Fe Synchrotron Mössbauer Source at the ESRF
journal, May 2012
- Potapkin, Vasily; Chumakov, Aleksandr I.; Smirnov, Gennadii V.
- Journal of Synchrotron Radiation, Vol. 19, Issue 4
Experimental evidence for the existence of iron-rich metal in the Earth's lower mantle
journal, March 2004
- Frost, Daniel J.; Liebske, Christian; Langenhorst, Falko
- Nature, Vol. 428, Issue 6981
Zeta-Fe2O3 – A new stable polymorph in iron(III) oxide family
journal, October 2015
- Tuček, Jiří; Machala, Libor; Ono, Shigeaki
- Scientific Reports, Vol. 5, Issue 1
Single-crystal X-ray diffraction at megabar pressures and temperatures of thousands of degrees
journal, December 2010
- Dubrovinsky, L.; Boffa-Ballaran, T.; Glazyrin, K.
- High Pressure Research, Vol. 30, Issue 4
In situ X-ray observation of phase transformation in Fe2O3 at high pressures and high temperatures
journal, October 2005
- Ono, Shigeaki; Ohishi, Yasuo
- Journal of Physics and Chemistry of Solids, Vol. 66, Issue 10
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
Crossover from melting to dissociation of CO2 under pressure: Implications for the lower mantle
journal, September 2011
- Litasov, Konstantin D.; Goncharov, Alexander F.; Hemley, Russell J.
- Earth and Planetary Science Letters, Vol. 309, Issue 3-4
Pressure-Induced Hydrogen Bond Symmetrization in Iron Oxyhydroxide
journal, October 2013
- Xu, Weiming; Greenberg, Eran; Rozenberg, Gregory Kh.
- Physical Review Letters, Vol. 111, Issue 17
Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6
journal, June 2015
- Lavina, Barbara; Meng, Yue
- Science Advances, Vol. 1, Issue 5, Article No. e1400260
Discovery of the recoverable high-pressure iron oxide Fe4O5
journal, October 2011
- Lavina, B.; Dera, P.; Kim, E.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 42
Static compression of ?-Fe2O3: linear incompressibility of lattice parameters and high-pressure transformations
journal, October 2003
- Liu, H.; Caldwell, W. A.; Benedetti, L. R.
- Physics and Chemistry of Minerals, Vol. 30, Issue 9
Determination of high-pressure phase equilibria of Fe2O3 using the Kawai-type apparatus equipped with sintered diamond anvils
journal, February 2009
- Ito, E.; Fukui, H.; Katsura, T.
- American Mineralogist, Vol. 94, Issue 2-3
Nature of the High-Pressure Transition in Hematite
journal, October 2002
- Badro, James; Fiquet, Guillaume; Struzhkin, Viktor V.
- Physical Review Letters, Vol. 89, Issue 20
Effect of high pressure on the crystal structure and electronic properties of magnetite below 25 GPa
journal, January 2012
- Glazyrin, K.; McCammon, C.; Dubrovinsky, L.
- American Mineralogist, Vol. 97, Issue 1
The structure of the metallic high-pressure Fe 3 O 4 polymorph: experimental and theoretical study
journal, October 2003
- Dubrovinsky, L. S.; Dubrovinskaia, N. A.; McCammon, C.
- Journal of Physics: Condensed Matter, Vol. 15, Issue 45
Adiabatic temperature profile in the mantle
journal, November 2010
- Katsura, Tomoo; Yoneda, Akira; Yamazaki, Daisuke
- Physics of the Earth and Planetary Interiors, Vol. 183, Issue 1-2
Novel high pressure monoclinic Fe 2 O 3 polymorph revealed by single-crystal synchrotron X-ray diffraction studies
journal, August 2013
- Bykova, Elena; Bykov, Maxim; Prakapenka, Vitali
- High Pressure Research, Vol. 33, Issue 3
Nonstoichiometry of the perovskite-type oxide La1−xSrxCrO3−δ
journal, March 1984
- Mizusaki, Junichiro; Yamauchi, Shigeru; Fueki, Kazuo
- Solid State Ionics, Vol. 12, p. 119-124
Phase transition boundary between B1 and B8 structures of FeO up to 210GPa
journal, April 2010
- Ozawa, Haruka; Hirose, Kei; Tateno, Shigehiko
- Physics of the Earth and Planetary Interiors, Vol. 179, Issue 3-4
Redox freezing and melting in the Earth’s deep mantle resulting from carbon–iron redox coupling
journal, March 2011
- Rohrbach, Arno; Schmidt, Max W.
- Nature, Vol. 472, Issue 7342
Evidence for deep mantle circulation from global tomography
journal, April 1997
- van der Hilst, R. D.; Widiyantoro, S.; Engdahl, E. R.
- Nature, Vol. 386, Issue 6625
Subducted banded iron formations as a source of ultralow-velocity zones at the core–mantle boundary
journal, March 2005
- Dobson, David P.; Brodholt, John P.
- Nature, Vol. 434, Issue 7031
Breakdown of the Mott-Hubbard State in : A First-Order Insulator-Metal Transition with Collapse of Magnetism at 50 GPa
journal, June 1999
- Pasternak, M. P.; Rozenberg, G. Kh.; Machavariani, G. Yu.
- Physical Review Letters, Vol. 82, Issue 23
Phase equilibria in partially open systems under pressure: the decomposition of stoichiometric GeO 2 oxide
journal, December 2003
- Brazhkin, Vadim V.; Voloshin, Roman N.; Lyapin, A. G.
- Physics-Uspekhi, Vol. 46, Issue 12
Boninite-like volcanic rocks in the 3.7–3.8 Ga Isua greenstone belt, West Greenland: geochemical evidence for intra-oceanic subduction zone processes in the early Earth
journal, April 2002
- Polat, A.; Hofmann, A. W.; Rosing, M. T.
- Chemical Geology, Vol. 184, Issue 3-4
The oxidation state of the mantle and the extraction of carbon from Earth’s interior
journal, January 2013
- Stagno, Vincenzo; Ojwang, Dickson O.; McCammon, Catherine A.
- Nature, Vol. 493, Issue 7430
Electronic and magnetic structures of the postperovskite-type Fe2O3 and implications for planetary magnetic records and deep interiors
journal, March 2009
- Shim, S. -H.; Bengtson, A.; Morgan, D.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 14
High-pressure structural studies of hematite
journal, January 2002
- Rozenberg, G. Kh.; Dubrovinsky, L. S.; Pasternak, M. P.
- Physical Review B, Vol. 65, Issue 6
Magnesium silicate perovskite and effect of iron oxidation state on its bulk sound velocity at the conditions of the lower mantle
journal, May 2014
- Glazyrin, K.; Boffa Ballaran, T.; Frost, D. J.
- Earth and Planetary Science Letters, Vol. 393
New developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design
journal, May 2002
- Belsky, Alec; Hellenbrandt, Mariette; Karen, Vicky Lynn
- Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3
BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements
journal, December 2012
- Kantor, I.; Prakapenka, V.; Kantor, A.
- Review of Scientific Instruments, Vol. 83, Issue 12, Article No. 125102
Solid oxygen
journal, November 2004
- Freiman, Yu. A.; Jodl, H. J.
- Physics Reports, Vol. 401, Issue 1-4
Preliminary reference Earth model
journal, June 1981
- Dziewonski, Adam M.; Anderson, Don L.
- Physics of the Earth and Planetary Interiors, Vol. 25, Issue 4
High-pressure structural behavior of -Fe2O3 studied by single-crystal X-ray diffraction and synchrotron radiation up to 25 GPa
journal, November 2011
- Schouwink, P.; Dubrovinsky, L.; Glazyrin, K.
- American Mineralogist, Vol. 96, Issue 11-12
Portable double-sided laser-heating system for Mössbauer spectroscopy and X-ray diffraction experiments at synchrotron facilities with diamond anvil cells
journal, December 2012
- Kupenko, I.; Dubrovinsky, L.; Dubrovinskaia, N.
- Review of Scientific Instruments, Vol. 83, Issue 12
A study of the crystal structure of Fe 2 O 3 in the pressure range up to 65 GPa using synchrotron radiation
journal, March 1991
- Olsen, J. Staun; Cousins, C. S. G.; Gerward, L.
- Physica Scripta, Vol. 43, Issue 3
High-pressure phase transition of hematite, Fe2O3
journal, August 2004
- Ono, Shigeaki; Kikegawa, Takumi; Ohishi, Yasuo
- Journal of Physics and Chemistry of Solids, Vol. 65, Issue 8-9
Perovskite-like Mn 2 O 3 : A Path to New Manganites
journal, December 2012
- Ovsyannikov, Sergey V.; Abakumov, Artem M.; Tsirlin, Alexander A.
- Angewandte Chemie International Edition, Vol. 52, Issue 5
Global tomographic images of mantle plumes and subducting slabs: insight into deep Earth dynamics
journal, August 2004
- Zhao, Dapeng
- Physics of the Earth and Planetary Interiors, Vol. 146, Issue 1-2
Synthesis and recovery of bulk Fe 4 O 5 from magnetite, Fe 3 O 4 . A member of a self-similar series of structures for the lower mantle and transition zone
journal, April 2014
- Guignard, J.; Crichton, W. A.
- Mineralogical Magazine, Vol. 78, Issue 2
Works referencing / citing this record:
Perovskite-like Mn 2 O 3 : A Path to New Manganites
journal, December 2012
- Ovsyannikov, Sergey V.; Abakumov, Artem M.; Tsirlin, Alexander A.
- Angewandte Chemie International Edition, Vol. 52, Issue 5
High-Pressure Phase Transformations in TiPO 4 : A Route to Pentacoordinated Phosphorus
journal, October 2016
- Bykov, Maxim; Bykova, Elena; Hanfland, Michael
- Angewandte Chemie International Edition, Vol. 55, Issue 48
High-Pressure Synthesis of a Nitrogen-Rich Inclusion Compound ReN 8 ⋅ x N 2 with Conjugated Polymeric Nitrogen Chains
journal, June 2018
- Bykov, Maxim; Bykova, Elena; Koemets, Egor
- Angewandte Chemie International Edition, Vol. 57, Issue 29
Static compression of ?-Fe2O3: linear incompressibility of lattice parameters and high-pressure transformations
journal, October 2003
- Liu, H.; Caldwell, W. A.; Benedetti, L. R.
- Physics and Chemistry of Minerals, Vol. 30, Issue 9
Preliminary reference Earth model
journal, June 1981
- Dziewonski, Adam M.; Anderson, Don L.
- Physics of the Earth and Planetary Interiors, Vol. 25, Issue 4
Nonstoichiometry of the perovskite-type oxide La1−xSrxCrO3−δ
journal, March 1984
- Mizusaki, Junichiro; Yamauchi, Shigeru; Fueki, Kazuo
- Solid State Ionics, Vol. 12, p. 119-124
Crossover from melting to dissociation of CO2 under pressure: Implications for the lower mantle
journal, September 2011
- Litasov, Konstantin D.; Goncharov, Alexander F.; Hemley, Russell J.
- Earth and Planetary Science Letters, Vol. 309, Issue 3-4
Magnesium silicate perovskite and effect of iron oxidation state on its bulk sound velocity at the conditions of the lower mantle
journal, May 2014
- Glazyrin, K.; Boffa Ballaran, T.; Frost, D. J.
- Earth and Planetary Science Letters, Vol. 393
High-pressure phase transition of hematite, Fe2O3
journal, August 2004
- Ono, Shigeaki; Kikegawa, Takumi; Ohishi, Yasuo
- Journal of Physics and Chemistry of Solids, Vol. 65, Issue 8-9
In situ X-ray observation of phase transformation in Fe2O3 at high pressures and high temperatures
journal, October 2005
- Ono, Shigeaki; Ohishi, Yasuo
- Journal of Physics and Chemistry of Solids, Vol. 66, Issue 10
Global tomographic images of mantle plumes and subducting slabs: insight into deep Earth dynamics
journal, August 2004
- Zhao, Dapeng
- Physics of the Earth and Planetary Interiors, Vol. 146, Issue 1-2
Phase transition boundary between B1 and B8 structures of FeO up to 210GPa
journal, April 2010
- Ozawa, Haruka; Hirose, Kei; Tateno, Shigehiko
- Physics of the Earth and Planetary Interiors, Vol. 179, Issue 3-4
Adiabatic temperature profile in the mantle
journal, November 2010
- Katsura, Tomoo; Yoneda, Akira; Yamazaki, Daisuke
- Physics of the Earth and Planetary Interiors, Vol. 183, Issue 1-2
Solid oxygen
journal, November 2004
- Freiman, Yu. A.; Jodl, H. J.
- Physics Reports, Vol. 401, Issue 1-4
Evidence for deep mantle circulation from global tomography
journal, April 1997
- van der Hilst, R. D.; Widiyantoro, S.; Engdahl, E. R.
- Nature, Vol. 386, Issue 6625
Experimental evidence for the existence of iron-rich metal in the Earth's lower mantle
journal, March 2004
- Frost, Daniel J.; Liebske, Christian; Langenhorst, Falko
- Nature, Vol. 428, Issue 6981
Subducted banded iron formations as a source of ultralow-velocity zones at the core–mantle boundary
journal, March 2005
- Dobson, David P.; Brodholt, John P.
- Nature, Vol. 434, Issue 7031
Redox freezing and melting in the Earth’s deep mantle resulting from carbon–iron redox coupling
journal, March 2011
- Rohrbach, Arno; Schmidt, Max W.
- Nature, Vol. 472, Issue 7342
The oxidation state of the mantle and the extraction of carbon from Earth’s interior
journal, January 2013
- Stagno, Vincenzo; Ojwang, Dickson O.; McCammon, Catherine A.
- Nature, Vol. 493, Issue 7430
Stability of iron-bearing carbonates in the deep Earth’s interior
journal, July 2017
- Cerantola, Valerio; Bykova, Elena; Kupenko, Ilya
- Nature Communications, Vol. 8, Issue 1
Crystalline polymeric carbon dioxide stable at megabar pressures
journal, August 2018
- Dziubek, Kamil F.; Ende, Martin; Scelta, Demetrio
- Nature Communications, Vol. 9, Issue 1
Pressure tuning of charge ordering in iron oxide
journal, October 2018
- Ovsyannikov, Sergey V.; Bykov, Maxim; Bykova, Elena
- Nature Communications, Vol. 9, Issue 1
Penta- and hexa-coordinated beryllium and phosphorus in high-pressure modifications of CaBe2P2O8
journal, June 2019
- Pakhomova, Anna; Aprilis, Georgios; Bykov, Maxim
- Nature Communications, Vol. 10, Issue 1
Zeta-Fe2O3 – A new stable polymorph in iron(III) oxide family
journal, October 2015
- Tuček, Jiří; Machala, Libor; Ono, Shigeaki
- Scientific Reports, Vol. 5, Issue 1
BX90: A new diamond anvil cell design for X-ray diffraction and optical measurements
journal, December 2012
- Kantor, I.; Prakapenka, V.; Kantor, A.
- Review of Scientific Instruments, Vol. 83, Issue 12, Article No. 125102
Portable double-sided laser-heating system for Mössbauer spectroscopy and X-ray diffraction experiments at synchrotron facilities with diamond anvil cells
journal, December 2012
- Kupenko, I.; Dubrovinsky, L.; Dubrovinskaia, N.
- Review of Scientific Instruments, Vol. 83, Issue 12
Electronic and magnetic structures of the postperovskite-type Fe2O3 and implications for planetary magnetic records and deep interiors
journal, March 2009
- Shim, S. -H.; Bengtson, A.; Morgan, D.
- Proceedings of the National Academy of Sciences, Vol. 106, Issue 14
Discovery of the recoverable high-pressure iron oxide Fe4O5
journal, October 2011
- Lavina, B.; Dera, P.; Kim, E.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 42
Single-crystal X-ray diffraction at megabar pressures and temperatures of thousands of degrees
journal, December 2010
- Dubrovinsky, L.; Boffa-Ballaran, T.; Glazyrin, K.
- High Pressure Research, Vol. 30, Issue 4
Novel high pressure monoclinic Fe 2 O 3 polymorph revealed by single-crystal synchrotron X-ray diffraction studies
journal, August 2013
- Bykova, Elena; Bykov, Maxim; Prakapenka, Vitali
- High Pressure Research, Vol. 33, Issue 3
A study of the crystal structure of Fe 2 O 3 in the pressure range up to 65 GPa using synchrotron radiation
journal, March 1991
- Olsen, J. Staun; Cousins, C. S. G.; Gerward, L.
- Physica Scripta, Vol. 43, Issue 3
The structure of the metallic high-pressure Fe 3 O 4 polymorph: experimental and theoretical study
journal, October 2003
- Dubrovinsky, L. S.; Dubrovinskaia, N. A.; McCammon, C.
- Journal of Physics: Condensed Matter, Vol. 15, Issue 45
Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6
journal, June 2015
- Lavina, Barbara; Meng, Yue
- Science Advances, Vol. 1, Issue 5, Article No. e1400260
Synthesis and recovery of bulk Fe 4 O 5 from magnetite, Fe 3 O 4 . A member of a self-similar series of structures for the lower mantle and transition zone
journal, April 2014
- Guignard, J.; Crichton, W. A.
- Mineralogical Magazine, Vol. 78, Issue 2
Determination of high-pressure phase equilibria of Fe2O3 using the Kawai-type apparatus equipped with sintered diamond anvils
journal, February 2009
- Ito, E.; Fukui, H.; Katsura, T.
- American Mineralogist, Vol. 94, Issue 2-3
High-pressure structural behavior of -Fe2O3 studied by single-crystal X-ray diffraction and synchrotron radiation up to 25 GPa
journal, November 2011
- Schouwink, P.; Dubrovinsky, L.; Glazyrin, K.
- American Mineralogist, Vol. 96, Issue 11-12
Effect of high pressure on the crystal structure and electronic properties of magnetite below 25 GPa
journal, January 2012
- Glazyrin, K.; McCammon, C.; Dubrovinsky, L.
- American Mineralogist, Vol. 97, Issue 1
Climate engineering by mimicking natural dust climate control: the iron salt aerosol method
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- Oeste, Franz Dietrich; de Richter, Renaud; Ming, Tingzhen
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