Altered chemistry of oxygen and iron under deep Earth conditions

Liu, Jin; Hu, Qingyang; Bi, Wenli; Yang, Liuxiang; Xiao, Yuming; Chow, Paul; Meng, Yue; Prakapenka, Vitali B.; Mao, Ho-Kwang; Mao, Wendy L.

doi:10.1038/s41467-018-08071-3

Title: Altered chemistry of oxygen and iron under deep Earth conditions

Journal Article · Fri Jan 11 00:00:00 EST 2019 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-08071-3· OSTI ID:1493416

^[1];

^[2]; Bi, Wenli ^[3];

^[4]; Xiao, Yuming ^[5]; Chow, Paul ^[5]; Meng, Yue ^[5]; Prakapenka, Vitali B. ^[6]; Mao, Ho-Kwang ^[7]; Mao, Wendy L. ^[8]

Center for High Pressure Science and Technology Advanced Research, Beijing (China); Stanford Univ., CA (United States)
Center for High Pressure Science and Technology Advanced Research, Beijing (China)
Argonne National Lab. (ANL), Argonne, IL (United States); University of Illinois at Urbana-Champaign, Urbana, IL (United States)
Carnegie Inst. of Washington, Washington, DC (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Chicago, IL (United States)
Center for High Pressure Science and Technology Advanced Research, Beijing (China); Carnegie Inst. of Washington, Washington, DC (United States)
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

A drastically altered chemistry was recently discovered in the Fe-O-H system under deep Earth conditions, involving the formation of iron superoxide (FeO2Hx with x = 0 to 1), but the puzzling crystal chemistry of this system at high pressures is largely unknown. Here we present evidence that despite the high O/Fe ratio in FeO2Hx, iron remains in the ferrous, spinpaired and non-magnetic state at 60–133 GPa, while the presence of hydrogen has minimal effects on the valence of iron. The reduced iron is accompanied by oxidized oxygen due to oxygen-oxygen interactions. The valence of oxygen is not -2 as in all other major mantle minerals, instead it varies around -1. This result indicates that like iron, oxygen may have multiple valence states in our planet’s interior. Our study suggests a possible change in the chemical paradigm of how oxygen, iron, and hydrogen behave under deep Earth conditions.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); National Natural Science Foundation of China (NSFC)

Grant/Contract Number:: AC02-76SF00515; FG02-99ER45775; FG02-94ER14466; AC02-06CH11357

OSTI ID:: 1493416

Alternate ID(s):: OSTI ID: 1493910

Journal Information:: Nature Communications, Vol. 10, Issue 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 30 works

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References (61)

Hydrogen-bearing iron peroxide and the origin of ultralow-velocity zones Liu, Jin; Hu, Qingyang; Young Kim, Duck Nature, Vol. 551, Issue 7681 https://doi.org/10.1038/nature24461	journal	November 2017
Coordination of iron in oxide glasses through high-resolution K-edge spectra: Information from the pre-edge Calas, G.; Petiau, J. Solid State Communications, Vol. 48, Issue 7 https://doi.org/10.1016/0038-1098(83)90530-6	journal	November 1983
First-principles studies of the electronic properties of native and substitutional anionic defects in bulk iron pyrite Hu, Jun; Zhang, Yanning; Law, Matt Physical Review B, Vol. 85, Issue 8 https://doi.org/10.1103/PhysRevB.85.085203	journal	February 2012
Phonon density of states of Fe $_{2}$ O $_{3}$ across high-pressure structural and electronic transitions Lin, Jung-Fu; Tse, John S.; Alp, Esen E. Physical Review B, Vol. 84, Issue 6 https://doi.org/10.1103/PhysRevB.84.064424	journal	August 2011
Dehydrogenation of goethite in Earth’s deep lower mantle Hu, Qingyang; Kim, Duck Young; Liu, Jin Proceedings of the National Academy of Sciences, Vol. 114, Issue 7 https://doi.org/10.1073/pnas.1620644114	journal	January 2017
FeO2 and FeOOH under deep lower-mantle conditions and Earth’s oxygen–hydrogen cycles Hu, Qingyang; Kim, Duck Young; Yang, Wenge Nature, Vol. 534, Issue 7606 https://doi.org/10.1038/nature18018	journal	June 2016
Elastic Anomalies in a Spin-Crossover System: Ferropericlase at Lower Mantle Conditions Wu, Zhongqing; Justo, João F.; Wentzcovitch, Renata M. Physical Review Letters, Vol. 110, Issue 22 https://doi.org/10.1103/PhysRevLett.110.228501	journal	May 2013
Synchrotron Mossbauer spectroscopic study of ferropericlase at high pressures and temperatures Lin, J. -F.; Gavriliuk, Alexander. G.; Sturhahn, W. American Mineralogist, Vol. 94, Issue 4 https://doi.org/10.2138/am.2009.3108	journal	April 2009
When Density Functional Approximations Meet Iron Oxides Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang Journal of Chemical Theory and Computation, Vol. 12, Issue 10 https://doi.org/10.1021/acs.jctc.6b00640	journal	September 2016
Oxidation state and coordination of Fe in minerals: An Fe K- XANES spectroscopic study Wilke, Max; Farges, François; Petit, Pierre-Emmanuel American Mineralogist, Vol. 86, Issue 5-6 https://doi.org/10.2138/am-2001-5-612	journal	May 2001
Toward an internally consistent pressure scale Fei, Y.; Ricolleau, A.; Frank, M. Proceedings of the National Academy of Sciences, Vol. 104, Issue 22 https://doi.org/10.1073/pnas.0609013104	journal	May 2007
Electronic Transitions in Perovskite: Possible Nonconvecting Layers in the Lower Mantle Badro, J. Science, Vol. 305, Issue 5682 https://doi.org/10.1126/science.1098840	journal	July 2004
GEOCHEMISTRY: The Paradox of Mantle Redox McCammon, C. Science, Vol. 308, Issue 5723 https://doi.org/10.1126/science.1110532	journal	May 2005
New developments in laser-heated diamond anvil cell with in situ synchrotron x-ray diffraction at High Pressure Collaborative Access Team Meng, Yue; Hrubiak, Rostislav; Rod, Eric Review of Scientific Instruments, Vol. 86, Issue 7 https://doi.org/10.1063/1.4926895	journal	July 2015
Local structure and spin transition in ${Fe}_{2} O_{3}$ hematite at high pressure Sanson, Andrea; Kantor, Innokenty; Cerantola, Valerio Physical Review B, Vol. 94, Issue 1 https://doi.org/10.1103/PhysRevB.94.014112	journal	July 2016
Preparation, Properties and Structure of Cadmium Peroxide Hoffman, C. W. W.; Ropp, R. C.; Mooney, R. W. Journal of the American Chemical Society, Vol. 81, Issue 15 https://doi.org/10.1021/ja01524a008	journal	August 1959
Synthesis, Crystal Structure, and Electronic Properties of High-Pressure PdF ₂ -Type Oxides MO ₂ (M = Ru, Rh, Os, Ir, Pt) Shirako, Yuichi; Wang, Xia; Tsujimoto, Yoshihiro Inorganic Chemistry, Vol. 53, Issue 21 https://doi.org/10.1021/ic501770g	journal	October 2014
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Hydrogen-Bond Symmetrization Breakdown and Dehydrogenation Mechanism of FeO ₂ H at High Pressure Zhu, Sheng-cai; Hu, Qingyang; Mao, Wendy L. Journal of the American Chemical Society, Vol. 139, Issue 35 https://doi.org/10.1021/jacs.7b06528	journal	August 2017
The oxidation state of the mantle and the extraction of carbon from Earth’s interior Stagno, Vincenzo; Ojwang, Dickson O.; McCammon, Catherine A. Nature, Vol. 493, Issue 7430 https://doi.org/10.1038/nature11679	journal	January 2013
Siderite at lower mantle conditions and the effects of the pressure-induced spin-pairing transition Lavina, B.; Dera, P.; Downs, R. T. Geophysical Research Letters, Vol. 36, Issue 23 https://doi.org/10.1029/2009GL039652	journal	January 2009
Chemical Reactions Between Fe and H ₂ O up to Megabar Pressures and Implications for Water Storage in the Earth's Mantle and Core Yuan, Liang; Ohtani, Eiji; Ikuta, Daijo Geophysical Research Letters, Vol. 45, Issue 3 https://doi.org/10.1002/2017GL075720	journal	February 2018
Pressure-induced structural evolution of pyrite-type SiO2 Kuwayama, Yasuhiro; Hirose, Kei; Sata, Nagayoshi Physics and Chemistry of Minerals, Vol. 38, Issue 8 https://doi.org/10.1007/s00269-011-0431-6	journal	April 2011
Effects of the Electronic spin Transitions of iron in Lower Mantle Minerals: Implications for deep Mantle Geophysics and Geochemistry: spin Transition in Lower Mantle Lin, Jung-Fu; Speziale, Sergio; Mao, Zhu Reviews of Geophysics, Vol. 51, Issue 2 https://doi.org/10.1002/rog.20010	journal	April 2013
Inelastic x-ray scattering of dense solid oxygen: Evidence for intermolecular bonding Meng, Y.; Eng, P. J.; Tse, J. S. Proceedings of the National Academy of Sciences, Vol. 105, Issue 33 https://doi.org/10.1073/pnas.0805601105	journal	August 2008
MÖSsbauer Spectroscopy of Earth and Planetary Materials Dyar, M. Darby; Agresti, David G.; Schaefer, Martha W. Annual Review of Earth and Planetary Sciences, Vol. 34, Issue 1 https://doi.org/10.1146/annurev.earth.34.031405.125049	journal	May 2006
Linear response approach to the calculation of the effective interaction parameters in the $LDA + U$ method Cococcioni, Matteo; de Gironcoli, Stefano Physical Review B, Vol. 71, Issue 3 https://doi.org/10.1103/PhysRevB.71.035105	journal	January 2005
Unraveling the structure and bonding evolution of the newly discovered iron oxide ${FeO}_{2}$ Lu, Cheng; Amsler, Maximilian; Chen, Changfeng Physical Review B, Vol. 98, Issue 5 https://doi.org/10.1103/PhysRevB.98.054102	journal	August 2018
Iron Partitioning in Earth's Mantle: Toward a Deep Lower Mantle Discontinuity Badro, J. Science, Vol. 300, Issue 5620 https://doi.org/10.1126/science.1081311	journal	April 2003
Iron Partitioning and Density Changes of Pyrolite in Earth’s Lower Mantle Irifune, Tetsuo; Shinmei, Toru; McCammon, Catherine A. Science, Vol. 327, Issue 5962 https://doi.org/10.1126/science.1181443	journal	December 2009
High Pressure Collapse of Magnetism in F $e_{0.94}$ O: Mössbauer Spectroscopy Beyond 100 GPa Pasternak, M. P.; Taylor, R. D.; Jeanloz, R. Physical Review Letters, Vol. 79, Issue 25 https://doi.org/10.1103/PhysRevLett.79.5046	journal	December 1997
Unraveling the complexity of iron oxides at high pressure and temperature: Synthesis of Fe₅O₆ Lavina, Barbara; Meng, Yue Science Advances, Vol. 1, Issue 5, Article No. e1400260 https://doi.org/10.1126/sciadv.1400260	journal	June 2015
Unexpected 3+ valence of iron in FeO2, a geologically important material lying “in between” oxides and peroxides Streltsov, Sergey S.; Shorikov, Alexey O.; Skornyakov, Sergey L. Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-13312-4	journal	October 2017
Equation of state and spin crossover of (Mg,Fe)O at high pressure, with implications for explaining topographic relief at the core-mantle boundary Solomatova, Natalia V.; Jackson, Jennifer M.; Sturhahn, Wolfgang American Mineralogist, Vol. 101, Issue 5 https://doi.org/10.2138/am-2016-5510	journal	May 2016
The rise of oxygen in Earth’s early ocean and atmosphere Lyons, Timothy W.; Reinhard, Christopher T.; Planavsky, Noah J. Nature, Vol. 506, Issue 7488 https://doi.org/10.1038/nature13068	journal	February 2014
Discovery of the recoverable high-pressure iron oxide Fe4O5 Lavina, B.; Dera, P.; Kim, E. Proceedings of the National Academy of Sciences, Vol. 108, Issue 42 https://doi.org/10.1073/pnas.1107573108	journal	October 2011
Superionic and Metallic States of Water and Ammonia at Giant Planet Conditions Cavazzoni, C. Science, Vol. 283, Issue 5398 https://doi.org/10.1126/science.283.5398.44	journal	January 1999
Advanced flat top laser heating system for high pressure research at GSECARS: application to the melting behavior of germanium Prakapenka, V. B.; Kubo, A.; Kuznetsov, A. High Pressure Research, Vol. 28, Issue 3 https://doi.org/10.1080/08957950802050718	journal	September 2008
High-pressure studies with x-rays using diamond anvil cells Shen, Guoyin; Mao, Ho Kwang Reports on Progress in Physics, Vol. 80, Issue 1 https://doi.org/10.1088/1361-6633/80/1/016101	journal	November 2016
Solid oxygen revisited Freiman, Yu. A.; Jodl, H. J.; Crespo, Yanier Physics Reports, Vol. 743 https://doi.org/10.1016/j.physrep.2018.03.003	journal	May 2018
Observation of an O8 molecular lattice in the ɛ phase of solid oxygen Lundegaard, Lars F.; Weck, Gunnar; McMahon, Malcolm I. Nature, Vol. 443, Issue 7108 https://doi.org/10.1038/nature05174	journal	September 2006
Experimental evidence for superionic water ice using shock compression Millot, Marius; Hamel, Sebastien; Rygg, J. Ryan Nature Physics, Vol. 14, Issue 3 https://doi.org/10.1038/s41567-017-0017-4	journal	February 2018
CONUSS and PHOENIX: Evaluation of nuclear resonant scattering data Sturhahn, W. Hyperfine Interactions, Vol. 125, Issue 1/4, p. 149-172 https://doi.org/10.1023/A:1012681503686	journal	March 2000
When water meets iron at Earth's core–mantle boundary Mao, Ho-Kwang; Hu, Qingyang; Yang, Liuxiang National Science Review, Vol. 4, Issue 6 https://doi.org/10.1093/nsr/nwx109	journal	September 2017
Compression of Ice to 210 Gigapascals: Infrared Evidence for a Symmetric Hydrogen-Bonded Phase Goncharov, A. F.; Struzhkin, V. V.; Somayazulu, M. S. Science, Vol. 273, Issue 5272 https://doi.org/10.1126/science.273.5272.218	journal	July 1996
Perovskite as a possible sink for ferric iron in the lower mantle McCammon, Catherine Nature, Vol. 387, Issue 6634 https://doi.org/10.1038/42685	journal	June 1997
Metal-insulator transition and the role of electron correlation in ${FeO}_{2}$ Jang, Bo Gyu; Kim, Duck Young; Shim, Ji Hoon Physical Review B, Vol. 95, Issue 7 https://doi.org/10.1103/PhysRevB.95.075144	journal	February 2017
Structural complexity of simple Fe2O3 at high pressures and temperatures Bykova, E.; Dubrovinsky, L.; Dubrovinskaia, N. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10661	journal	February 2016
The pyrite-type high-pressure form of FeOOH Nishi, Masayuki; Kuwayama, Yasuhiro; Tsuchiya, Jun Nature, Vol. 547, Issue 7662 https://doi.org/10.1038/nature22823	journal	July 2017
Density Functional Theory in Transition-Metal Chemistry: A Self-Consistent Hubbard $U$ Approach Kulik, Heather J.; Cococcioni, Matteo; Scherlis, Damian A. Physical Review Letters, Vol. 97, Issue 10 https://doi.org/10.1103/PhysRevLett.97.103001	journal	September 2006
Spin crossover and iron-rich silicate melt in the Earth’s deep mantle Nomura, Ryuichi; Ozawa, Haruka; Tateno, Shigehiko Nature, Vol. 473, Issue 7346 https://doi.org/10.1038/nature09940	journal	April 2011
Viscosity jump in the lower mantle inferred from melting curves of ferropericlase Deng, Jie; Lee, Kanani K. M. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-02263-z	journal	December 2017
Local Structure and Spin Transition in Fe2O3 Hematite at High-Pressure Sanson, Andrea; Kantor, Innokenty; Cerantola, Valerio arXiv https://doi.org/10.48550/arxiv.1602.06721	text	January 2016
Metal-Insulator Transition and the Role of Electron Correlation in FeO2 Jang, Bo Gyu; Kim, Duck Young; Shim, Ji Hoon arXiv https://doi.org/10.48550/arxiv.1606.09582	text	January 2016
Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach Kulik, Heather J.; Cococcioni, Matteo; Scherlis, Damian A. arXiv https://doi.org/10.48550/arxiv.cond-mat/0608285	text	January 2006
Structural dynamics of basaltic melt at mantle conditions with implications for magma oceans and superplumes Majumdar, Arnab; Wu, Min; Pan, Yuanming Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-18660-w	journal	September 2020
Nuclear resonant spectroscopy Sturhahn, Wolfgang Journal of Physics: Condensed Matter, Vol. 16, Issue 5 https://doi.org/10.1088/0953-8984/16/5/009	journal	January 2004
Computational searches for iron oxides at high pressures Weerasinghe, Gihan L.; Pickard, Chris J.; Needs, R. J. Journal of Physics: Condensed Matter, Vol. 27, Issue 45 https://doi.org/10.1088/0953-8984/27/45/455501	journal	October 2015
Pressure calibration of diamond anvil Raman gauge to 410 GPa Akahama, Yuichi; Kawamura, Haruki Journal of Physics: Conference Series, Vol. 215 https://doi.org/10.1088/1742-6596/215/1/012195	journal	March 2010
CO2-induced destabilization of pyrite-structured FeO2Hx in the lower mantle Boulard, Eglantine; Guyot, François; Menguy, Nicolas National Science Review, Vol. 5, Issue 6 https://doi.org/10.1093/nsr/nwy032	journal	March 2018
A linear response approach to the calculation of the effective interaction parameters in the LDA+U method Cococcioni, Matteo; de Gironcoli, Stefano arXiv https://doi.org/10.48550/arxiv.cond-mat/0405160	text	January 2004

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