Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6
Abstract
The iron-oxygen system is the most important reference of rocks’ redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe4O5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe3O4, and Fe2O3. Combining synthesis at high pressure and temperature with micro- diffraction mapping, we have identified yet another distinct iron oxide, Fe5O6. The new compound, which has an orthorhombic structure, was obtained in the pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe5O6, Fe4O5, and h-Fe3O4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe5O6, along with FeO and Fe4O5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geo- chemical importance. Here, we are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe5O6, Fe4O5, and h-Fe3O4—in a narrow compositional range (0.75 < Fe/O < 1.0). New, finelymore »
- Authors:
-
- Univ. of Nevada, Las Vegas, NV (United States)
- Carnegie Inst. of Washington, Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Univ. of Nevada, Las Vegas, NV (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1332704
- Grant/Contract Number:
- NA0001982
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Science Advances
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 5; Related Information: http://advances.sciencemag.org/content/suppl/2015/06/23/1.5.e1400260.DC1; Journal ID: ISSN 2375-2548
- Publisher:
- AAAS
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 58 GEOSCIENCES; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; high pressure; iron oxide; extreme conditions synthesis; mantle phases; redox equilibria; planetary interiors; microdiffraction
Citation Formats
Lavina, Barbara, and Meng, Yue. Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6. United States: N. p., 2015.
Web. doi:10.1126/sciadv.1400260.
Lavina, Barbara, & Meng, Yue. Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6. United States. https://doi.org/10.1126/sciadv.1400260
Lavina, Barbara, and Meng, Yue. Fri .
"Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6". United States. https://doi.org/10.1126/sciadv.1400260. https://www.osti.gov/servlets/purl/1332704.
@article{osti_1332704,
title = {Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe5O6},
author = {Lavina, Barbara and Meng, Yue},
abstractNote = {The iron-oxygen system is the most important reference of rocks’ redox state. Even as minor components, iron oxides can play a critical role in redox equilibria, which affect the speciation of the fluid phases chemical differentiation, melting, and physical properties. Until our recent finding of Fe4O5, iron oxides were assumed to comprise only the polymorphs of FeO, Fe3O4, and Fe2O3. Combining synthesis at high pressure and temperature with micro- diffraction mapping, we have identified yet another distinct iron oxide, Fe5O6. The new compound, which has an orthorhombic structure, was obtained in the pressure range from 10 to 20 GPa upon laser heating mixtures of iron and hematite at ~2000 K, and is recoverable to ambient conditions. The high-pressure orthorhombic iron oxides Fe5O6, Fe4O5, and h-Fe3O4 display similar iron coordination geometries and structural arrangements, and indeed exhibit coherent systematic behavior of crystallographic parameters and compressibility. Fe5O6, along with FeO and Fe4O5, is a candidate key minor phase of planetary interiors; as such, it is of major petrological and geo- chemical importance. Here, we are revealing an unforeseen complexity in the Fe-O system with four different compounds—FeO, Fe5O6, Fe4O5, and h-Fe3O4—in a narrow compositional range (0.75 < Fe/O < 1.0). New, finely spaced oxygen buffers at conditions of the Earth’s mantle can be defined.},
doi = {10.1126/sciadv.1400260},
journal = {Science Advances},
number = 5,
volume = 1,
place = {United States},
year = {Fri Jun 26 00:00:00 EDT 2015},
month = {Fri Jun 26 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
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
Nuclear forward scattering and first-principles studies of the iron oxide phase
journal, July 2014
- Kothapalli, Karunakar; Kim, Eunja; Kolodziej, Tomasz
- Physical Review B, Vol. 90, Issue 2
In situ observation of the breakdown of magnetite (Fe3O4) to Fe4O5 and hematite at high pressures and temperatures
journal, September 2012
- Woodland, A. B.; Frost, D. J.; Trots, D. M.
- American Mineralogist, Vol. 97, Issue 10
Fe4O5 and its solid solutions in several simple systems
journal, October 2013
- Woodland, A. B.; Schollenbruch, K.; Koch, M.
- Contributions to Mineralogy and Petrology, Vol. 166, Issue 6
Mise en évidence de CaF2e4O6 et détermination des structures cristallines des ferrites de calcium CaFe2+nO4+n(n = 1, 2, 3): nouvel exemple d'intercroissance
journal, November 1980
- Evrard, O.; Malaman, B.; Jeannot, F.
- Journal of Solid State Chemistry, Vol. 35, Issue 1
New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team
journal, July 2015
- Meng, Yue; Hrubiak, Rostislav; Rod, Eric
- Review of Scientific Instruments, Vol. 86, Issue 7
Synthesis and Microdiffraction at Extreme Pressures and Temperatures
journal, January 2013
- Lavina, Barbara; Dera, Przemyslaw; Meng, Yue
- Journal of Visualized Experiments, Issue 80
Isothermal compression of magnetite to 320 KB
journal, March 1974
- Mao, Ho-Kwang; Takahashi, Taro; Bassett, William A.
- Journal of Geophysical Research, Vol. 79, Issue 8
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
Mantle Oxidation State and Its Relationship to Tectonic Environment and Fluid Speciation
journal, April 1990
- Wood, B. J.; Bryndzia, L. T.; Johnson, K. E.
- Science, Vol. 248, Issue 4953
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
The Redox State of Earth's Mantle
journal, May 2008
- Frost, Daniel J.; McCammon, Catherine A.
- Annual Review of Earth and Planetary Sciences, Vol. 36, Issue 1
Carbon speciation in the asthenosphere: Experimental measurements of the redox conditions at which carbonate-bearing melts coexist with graphite or diamond in peridotite assemblages
journal, November 2010
- Stagno, Vincenzo; Frost, Daniel J.
- Earth and Planetary Science Letters, Vol. 300, Issue 1-2
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
Microscopic properties to macroscopic behaviour: The influence of iron electronic state
journal, January 2006
- McCAMMON, Catherine
- Journal of Mineralogical and Petrological Sciences, Vol. 101, Issue 3
High-Fe (Mg, Fe)O inclusion in diamond apparently from the lowermost mantle
journal, October 2014
- Wirth, R.; Dobrzhinetskaya, L.; Harte, B.
- Earth and Planetary Science Letters, Vol. 404
The system Fe-Si-O: Oxygen buffer calibrations to 1,500K
journal, March 1983
- Myers, J.; Eugster, H. P.
- Contributions to Mineralogy and Petrology, Vol. 82, Issue 1
A redetermination of the fayalite-magnetite-quartz equilibrium between 650 degrees and 850 degrees C
journal, May 1978
- Hewitt, D. A.
- American Journal of Science, Vol. 278, Issue 5
Iron-water reaction at high pressure and temperature, and hydrogen transport into the core
journal, March 2005
- Ohtani, Eiji; Hirao, Naohisa; Kondo, Tadashi
- Physics and Chemistry of Minerals, Vol. 32, Issue 1
Formation of iron hydride and high-magnetite at high pressure and temperature
journal, August 2004
- Saxena, Surendra K.; Liermann, Hanns-Peter; Shen, Guoyin
- Physics of the Earth and Planetary Interiors, Vol. 146, Issue 1-2
Generation of methane in the Earth's mantle: In situ high pressure-temperature measurements of carbonate reduction
journal, September 2004
- Scott, H. P.; Hemley, R. J.; Mao, H. -k.
- Proceedings of the National Academy of Sciences, Vol. 101, Issue 39
Stability of magnesite and its high-pressure form in the lowermost mantle
journal, January 2004
- Isshiki, Maiko; Irifune, Tetsuo; Hirose, Kei
- Nature, Vol. 427, Issue 6969
Novel high-pressure structures of MgCO3, CaCO3 and CO2 and their role in Earth's lower mantle
journal, August 2008
- Oganov, Artem R.; Ono, Shigeaki; Ma, Yanming
- Earth and Planetary Science Letters, Vol. 273, Issue 1-2
Magnesite formation from MgO and CO2 at the pressures and temperatures of Earth's mantle
journal, July 2013
- Scott, H. P.; Doczy, V. M.; Frank, M. R.
- American Mineralogist, Vol. 98, Issue 7
High pressure single-crystal micro X-ray diffraction analysis with GSE_ADA/RSV software
journal, August 2013
- Dera, Przemyslaw; Zhuravlev, Kirill; Prakapenka, Vitali
- High Pressure Research, Vol. 33, Issue 3
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
Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
- Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
- High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
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
In situ structure determination of the high-pressure phase of Fe 3 O 4
journal, February 1999
- Fei, Yingwei; Frost, Daniel J.; Mao, Ho-Kwang
- American Mineralogist, Vol. 84, Issue 1-2
Equation of state of magnetite and its high-pressure modification: Thermodynamics of the Fe-O system at high pressure
journal, March 2000
- Haavik, Camilla; Stølen, Svein; Fjellvåg, Helmer
- American Mineralogist, Vol. 85, Issue 3-4
Carbon speciation in the asthenosphere: Experimental measurements of the redox conditions at which carbonate-bearing melts coexist with graphite or diamond in peridotite assemblages
journal, November 2010
- Stagno, Vincenzo; Frost, Daniel J.
- Earth and Planetary Science Letters, Vol. 300, Issue 1-2
High-Fe (Mg, Fe)O inclusion in diamond apparently from the lowermost mantle
journal, October 2014
- Wirth, R.; Dobrzhinetskaya, L.; Harte, B.
- Earth and Planetary Science Letters, Vol. 404
Iron hydride formed by the reaction of iron, silicate, and water: Implications for the light element of the Earth's core
journal, July 1995
- Yagi, Takehiko; Hishinuma, Takahiro
- Geophysical Research Letters, Vol. 22, Issue 14
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
Generation of methane in the Earth's mantle: In situ high pressure-temperature measurements of carbonate reduction
journal, September 2004
- Scott, H. P.; Hemley, R. J.; Mao, H. -k.
- Proceedings of the National Academy of Sciences, Vol. 101, Issue 39
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
Synthesis and Microdiffraction at Extreme Pressures and Temperatures
journal, October 2013
- Lavina, Barbara; Dera, Przemyslaw; Meng, Yue
- Journal of Visualized Experiments, Issue 80
Works referencing / citing this record:
Chemical Reactions Between Fe and H 2 O up to Megabar Pressures and Implications for Water Storage in the Earth's Mantle and Core
journal, February 2018
- Yuan, Liang; Ohtani, Eiji; Ikuta, Daijo
- Geophysical Research Letters, Vol. 45, Issue 3
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, Vol. 130, Issue 29
A Room‐Temperature Verwey‐type Transition in Iron Oxide, Fe 5 O 6
journal, January 2020
- Ovsyannikov, Sergey V.; Bykov, Maxim; Medvedev, Sergey A.
- Angewandte Chemie, Vol. 132, Issue 14
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
Niobium Doping in BiVO 4 : Interplay Between Effective Mass, Stability, and Pressure
journal, February 2019
- Sarker, Hori Pada; Rao, Pratap M.; Huda, Muhammad N.
- ChemPhysChem, Vol. 20, Issue 5
Ferrous Iron Under Oxygen‐Rich Conditions in the Deep Mantle
journal, February 2019
- Boulard, E.; Harmand, M.; Guyot, F.
- Geophysical Research Letters, Vol. 46, Issue 3
Effect of Fe 3+ on Phase Relations in the Lower Mantle: Implications for Redox Melting in Stagnant Slabs
journal, December 2019
- Sinmyo, Ryosuke; Nakajima, Yoichi; McCammon, Catherine A.
- Journal of Geophysical Research: Solid Earth, Vol. 124, Issue 12
FeO2 and FeOOH under deep lower-mantle conditions and Earth’s oxygen–hydrogen cycles
journal, June 2016
- Hu, Qingyang; Kim, Duck Young; Yang, Wenge
- Nature, Vol. 534, Issue 7606
Structural complexity of simple Fe2O3 at high pressures and temperatures
journal, February 2016
- Bykova, E.; Dubrovinsky, L.; Dubrovinskaia, N.
- Nature Communications, Vol. 7, 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
Stability and nature of the volume collapse of ε-Fe2O3 under extreme conditions
journal, November 2018
- Sans, J. A.; Monteseguro, V.; Garbarino, G.
- Nature Communications, Vol. 9, Issue 1
Altered chemistry of oxygen and iron under deep Earth conditions
journal, January 2019
- Liu, Jin; Hu, Qingyang; Bi, Wenli
- Nature Communications, Vol. 10, Issue 1
Stability and anisotropy of (FexNi1−x)2O under high pressure and implications in Earth’s and super-Earths’ core
journal, January 2018
- Huang, Shengxuan; Wu, Xiang; Qin, Shan
- Scientific Reports, Vol. 8, Issue 1
Cation, magnetic, and charge ordering in MnFe 3 O 5
journal, January 2018
- Hong, K. H.; Arevalo-Lopez, A. M.; Coduri, M.
- Journal of Materials Chemistry C, Vol. 6, Issue 13
Gold nanorods as a high-pressure sensor of phase transitions and refractive-index gauge
journal, January 2019
- Runowski, Marcin; Sobczak, Szymon; Marciniak, Jędrzej
- Nanoscale, Vol. 11, Issue 18
Multimode scanning X-ray diffraction microscopy for diamond anvil cell experiments
journal, February 2019
- Hrubiak, Rostislav; Smith, Jesse S.; Shen, Guoyin
- Review of Scientific Instruments, Vol. 90, Issue 2
Unraveling the structure and bonding evolution of the newly discovered iron oxide
journal, August 2018
- Lu, Cheng; Amsler, Maximilian; Chen, Changfeng
- Physical Review B, Vol. 98, Issue 5
Sunlight-driven water splitting using hematite nanorod photoelectrodes
journal, January 2018
- Souza, Flavio L.
- Anais da Academia Brasileira de Ciências, Vol. 90, Issue 1 suppl 1
Pressure tuning of charge ordering in iron oxide
text, January 2018
- Ovsyannikov, Sergey; Bykov, Maxim; Bykova, Elena
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
High-pressure synthesis of a nitrogen-rich inclusion compound $ReN_{8}·xN_{2}$ with conjugated polymeric nitrogen chains
text, January 2018
- Bykov, Maxim; Bykova, Elena; Koemets, Egor
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
A Room‐Temperature Verwey‐type Transition in Iron Oxide, Fe 5 O 6
journal, January 2020
- Ovsyannikov, Sergey V.; Bykov, Maxim; Medvedev, Sergey A.
- Angewandte Chemie International Edition, Vol. 59, Issue 14
Pressure tuning of charge ordering in iron oxide
journal, October 2018
- Ovsyannikov, Sergey V.; Bykov, Maxim; Bykova, Elena
- Nature Communications, Vol. 9, Issue 1
Effect of Fe3+ on Phase Relations in the Lower Mantle: Implications for Redox Melting in Stagnant Slabs
text, January 2019
- Sinmyo, Ryosuke; Nakajima, Yoichi; McCammon, Catherine A.
- FID GEO
Effect of Fe3+ on Phase Relations in the Lower Mantle : Implications for Redox Melting in Stagnant Slabs
text, January 2019
- Sinmyo, Ryosuke; Nakajima, Yoichi; McCammon, Catherine A.
- University of Bayreuth
Structural complexity of simple Fe2O3 at high pressures and temperatures
journal, February 2016
- Bykova, E.; Dubrovinsky, L.; Dubrovinskaia, N.
- Nature Communications, Vol. 7, 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
Altered chemistry of oxygen and iron under deep Earth conditions
journal, January 2019
- Liu, Jin; Hu, Qingyang; Bi, Wenli
- Nature Communications, Vol. 10, Issue 1
Stability and anisotropy of (FexNi1−x)2O under high pressure and implications in Earth’s and super-Earths’ core
journal, January 2018
- Huang, Shengxuan; Wu, Xiang; Qin, Shan
- Scientific Reports, Vol. 8, Issue 1
Discovery of Fe7O9: a new iron oxide with a complex monoclinic structure
journal, September 2016
- Sinmyo, Ryosuke; Bykova, Elena; Ovsyannikov, Sergey V.
- Scientific Reports, Vol. 6, Issue 1