Abstract
We report for the first time the formation of a HP-PdF2-type FeCl2 phase (space group Pa3), through high pressure-temperature (P-T) reactions in the hydrous systems (Mg0.6Fe0.4)SiO3–H2O–NaCl and FeO2H– NaCl in a laser-heated diamond-anvil cell up to 108 GPa and 2000 K. Applying single-crystal X‑ray difraction (XRD) analysis to individual submicrometer-sized grains, we have successfully determined the crystal structure of the as-synthesized FeCl2 phase, in agreement with our theoretical structure search results. In situ high P-T XRD data revealed the substitution of Cl for OH(O) in such a cubic Pa3 structure, demonstrating that this topology is a potential host for both H and Cl in the deep Earth. The chemical analysis of the recovered sample showed that the post-perovskite phase contains considerable amounts of Na2O and Fe2O3. The coexistence of the cubic FeCl2 phase and post-perovskite suggests that the lowermost mantle could be a potential reservoir of Cl. The possible presence of volatiles such as H and Cl in the deep lower mantle would impact the composition and iron valence state of the post-perovskite phase.
Funding statement: The authors acknowledge the support from the National Natural Science Foundation of China (NSFC) (Grant No: 41902033, 41574080, 11774015, and U1530402). This work was performed at HPCAT (Sector 16) and GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. HPCAT operations are supported by DOE-NNSA’s Office of Experimental Sciences. GeoSoilEnviroCARS is supported by the National Science Foundation-Earth Sciences (EAR-1634415) and Department of Energy-GeoSciences (DE-FG02-94ER14466). The Advanced Photon Source is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Portions of this work were performed at the beamline 15U1 of the Shanghai Synchrotron Radiation Facility (SSRF).
References cited
Barnes, J.D., and Straub, S.M. (2010) Chorine stable isotope variations in Izu Bonin tephra: Implications for serpentinite subduction. Chemical Geology, 272, 62–74.10.1016/j.chemgeo.2010.02.005Search in Google Scholar
Bonifacie, M., Jendrzejewski, N., Agrinier, P., Humler, E., Coleman, M., and Javoy, M. (2008) The chlorine isotope composition of Earth’s mantle. Science, 319, 1518–1520.10.1126/science.1150988Search in Google Scholar PubMed
Boulard, E., Guyot, F., Menguy, N., Corgne, A., Auzende, A.L., Perrillat, J.P., and Fiquet, G. (2018) CO2-induced destabilization of pyrite-structured FeO2Hx in the lower mantle. National Science Review, 5, 870–877.10.1093/nsr/nwy032Search in Google Scholar
Dorfman, S.M., Meng, Y., Prakapenka, V.B., and Duffy, T.S. (2013) Effects of Fe-enrichment on the equation of state and stability of (Mg,Fe)SiO3 perovskite. Earth and Planetary Science Letters, 361, 249–257.10.1016/j.epsl.2012.10.033Search in Google Scholar
Du, X., Wang, Z., Wang, H., Iitaka, T., Pan, Y., Wang, H., and Tse, J.S. (2018) Structures and stability of iron halides at the Earth’s mantle and core pressures: Implications for the missing halogen paradox. ACS Earth and Space Chemistry, 2, 711–719.10.1021/acsearthspacechem.8b00034Search in Google Scholar
Fei, Y., Ricolleau, A., Frank, M., Mibe, K., Shen, G., and Prakapenka, V. (2007) Toward an internally consistent pressure scale. Proceedings of the National Academy of Sciences, 104, 9182–9186.10.1073/pnas.0609013104Search in Google Scholar PubMed PubMed Central
Ford, S.R., Garnero, E.J., and McNamara, A.K. (2006) A strong lateral shear velocity gradient and anisotropy heterogeneity in the lowermost mantle beneath the southern Pacific. Journal of Geophysical Research: Solid Earth, 111, B03306.10.1029/2004JB003574Search in Google Scholar
Hanyu, T., Shimizu, K., Ushikubo, T., Kimura, J.I., Chang, Q., Hamada, M., Ito, M., Iwamori, H., and Ishikawa, T. (2019) Tiny droplets of ocean island basalts unveil Earth’s deep chlorine cycle. Nature Communications, 10, 4–10.10.1038/s41467-018-07955-8Search in Google Scholar PubMed PubMed Central
Hiraga, T., Anderson, I.M., and Kohlstedt, D.L. (2004) Grain boundaries as reservoirs of incompatible elements in the Earth’s mantle. Nature, 427, 699–703.10.1038/nature02259Search in Google Scholar PubMed
Hirose, K., Takafuji, N., Sata, N., and Ohishi, Y. (2005) Phase transition and density of subducted MORB crust in the lower mantle. Earth and Planetary Science Letters, 237, 239–251.10.1016/j.epsl.2005.06.035Search in Google Scholar
Hohenberg, P., and Kohn, W. (1964) Inhomogeneous electron gas. Physical Review, 136, B864–B871.10.1103/PhysRev.136.B864Search in Google Scholar
Hu, Q., Kim, D.Y., Yang, W., Yang, L., Meng, Y., Zhang, L., and Mao, H.-K. (2016) FeO2 and FeOOH under deep lower-mantle conditions and Earth’s oxygen–hydrogen cycles. Nature, 534, 241–244.10.1038/nature18018Search in Google Scholar PubMed
Jang, B.G., Kim, D. Y., and Shim, J.H. (2017) Metal-insulator transition and the role of electron correlation in FeO2. Physical Review B, 95, 075144.10.1103/PhysRevB.95.075144Search in Google Scholar
John, T., Scambelluri, M., Frische, M., Barnes, J.D., and Bach, W. (2011) Dehydration of subducting serpentinite: Implications for halogen mobility in subduction zones and the deep halogen cycle. Earth and Planetary Science Letters, 308, 65–76.10.1016/j.epsl.2011.05.038Search in Google Scholar
Kabsch, W. (2010) XDS. Acta Crystallographica, D66, 125–132.10.1107/97809553602060000835Search in Google Scholar
Kendrick, M.A., Hémond, C., Kamenetsky, V.S., Danyushevsky, L., Devey, C.W., Rodemann, T., Jackson, M.G., and Perfit, M.R. (2017) Seawater cycled throughout Earth’s mantle in partially serpentinized lithosphere. Nature Geoscience, 10, 222–228.10.1038/ngeo2902Search in Google Scholar
Kim, B., Kim, K., and Min, B.I. (2014) Universal metastability of the low-spin state in Co2+ systems: Non-Mott type pressure-induced spin-state transition in CoCl2. Physical Review B, 89, 115131.10.1103/PhysRevB.89.115131Search in Google Scholar
Koemets, E., Yuan, L., Bykova, E., Glazyrin, K., Ohtani, E., and Dubrovinsky, L. (2020) Interaction between FeOOH and NaCl at extreme conditions: synthesis of novel Na2FeCl4OHx compound. Minerals, 10, 51.10.3390/min10010051Search in Google Scholar
Koemets, E., Leonov, I., Bykov, M., Bykova, E., Chariton, S., Aprilis, G., Fedotenko, T., Clément, S., Rouquette, J., Haines, J., and others (2021) Revealing the complex nature of bonding in the binary high-pressure compound FeO2. Physical Review Letters, 126, 106001.10.1103/PhysRevLett.126.106001Search in Google Scholar PubMed
Kohn, W., and Sham, L.J. (1965) Self-consistent equations including exchange and correlation effects. Physical Review, 140, A1133–A1138.10.1103/PhysRev.140.A1133Search in Google Scholar
Kresse, G., and Furthmüller, J. (1996) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 6, 15–50.10.1016/0927-0256(96)00008-0Search in Google Scholar
Lazić, P., Armiento, R., Herbert, F.W., Chakraborty, R., Sun, R., Chan, M.K.Y., Hartman, K., Buonassisi, T., Yildiz, B., and Ceder, G. (2013) Low intensity conduction states in FeS2: Implications for absorption, open-circuit voltage and surface recombination. Journal of Physics Condensed Matter, 25, 465801.10.1088/0953-8984/25/46/465801Search in Google Scholar PubMed
Liu, J., Hu, Q., Young Kim, D., Wu, Z., Wang, W., Xiao, Y., Chow, P., Meng, Y., Prakapenka, V.B., Mao, H.-K., and others (2017) Hydrogen-bearing iron peroxide and the origin of ultralow-velocity zones. Nature, 551, 494–497.10.1038/nature24461Search in Google Scholar PubMed
Loubeyre, P., LeToullec, R., Wolanin, E., Hanfland, M., and Hausermann, D. (1999) Modulated phases and proton centring in ice observed by X-ray diffraction up to 170 GPa. Nature, 397, 503–506.10.1038/17300Search in Google Scholar
Mao, H., Hu, Q., Yang, L., Liu, J., Kim, D.Y., Meng, Y., Zhang, L., Prakapenka, V.B., Yang, W., and Mao, W.L. (2017) When water meets iron at Earth’s core-mantle boundary. National Science Review, 4, 870–878.10.1093/nsr/nwx109Search in Google Scholar
Meng, Y., Hrubiak, R., Rod, E., Boehler, R., and Shen, G. (2015) New developments in laser-heated diamond anvil cell with in situ synchrotron X-ray diffraction at High Pressure Collaborative Access Team. The Review of Scientific Instruments, 86, 072201.10.1063/1.4926895Search in Google Scholar PubMed
Nishi, M., Kuwayama, Y., Tsuchiya, J., and Tsuchiya, T. (2017) The pyrite-type high-pressure form of FeOOH. Nature, 547, 205–208.10.1038/nature22823Search in Google Scholar PubMed
Oganov, A.R., Lyakhov, A.O., and Valle, M. (2011) How evolutionary crystal structure prediction works—and why. Accounts of Chemical Research, 44, 227–237.10.1021/ar1001318Search in Google Scholar PubMed
Perdew, J.P., Burke, K., and Ernzerhof, M. (1996) Generalized gradient approximation made simple. Physical Review Letters, 77, 3865–3868.10.1103/PhysRevLett.77.3865Search in Google Scholar PubMed
Prakapenka, V.B., Kubo, A., Kuznetsov, A., Laskin, A., Shkurikhin, O., Dera, P., Rivers, M.L., and Sutton, S.R. (2008) Advanced flat top laser heating system for high pressure research at GSECARS: Application to the melting behavior of germanium. High Pressure Research, 28, 225–235.10.1080/08957950802050718Search in Google Scholar
Ren, Y., Stutzmann, E., van der Hilst, R.D., and Besse, J. (2007) Understanding seismic heterogeneities in the lower mantle beneath the Americas from seismic tomography and plate tectonic history. Journal of Geophysical Research, 112, 1–15.10.1029/2005JB004154Search in Google Scholar
Roberge, M., Bureau, H., Bolfan-Casanova, N., Raepsaet, C., Surble, S., Khodja, H., Auzende, A.L., Cordier, P., and Fiquet, G. (2017) Chlorine in wadsleyite and ring-woodite: An experimental study. Earth and Planetary Science Letters, 467, 99–107.10.1016/j.epsl.2017.03.025Search in Google Scholar
Rozenberg, G.K., Pasternak, M.P., Gorodetsky, P., Xu, W.M., Dubrovinsky, L.S., Le Bihan, T., and Taylor, R.D. (2009) Pressure-induced structural, electronic, and magnetic phase transitions in FeCl2 studied by X-ray diffraction and resistivity measurements. Physical Review B, 79, 214105.10.1103/PhysRevB.79.214105Search in Google Scholar
Scambelluri, M., and Philippot, P. (2001) Deep fluids in subduction zones. Lithos, 55, 213–227.10.1016/S0024-4937(00)00046-3Search in Google Scholar
Scambelluri, M., Piccardo, G., Philippot, P., Robbiano, A., and Negretti, L. (1997) High salinity fluid inclusions formed from recycled seawater in deeply subducted alpine serpentinite. Earth and Planetary Science Letters, 148, 485–499.10.1016/S0012-821X(97)00043-5Search in Google Scholar
Sharp, Z.D., Shearer, C.K., McKeegan, K.D., Barnes, J.D., and Wang, Y.Q. (2010) The chlorine isotope composition of the Moon and implications for an anhydrous mantle. Science, 329, 1050–1053.10.1126/science.1192606Search in Google Scholar PubMed
Sheldrick, G.M. (2007) A short history of SHELX. Acta Crystallographica, A64, 112–122.Search in Google Scholar
Tschauner, O., Huang, S., Greenberg, E., Prakapenka, V.B., Ma, C., Rossman, G.R., Shen, A.H., Zhang, D., Newville, M., Lanzirotti, A., and Tait, K. (2018) Ice-VII inclusions in diamonds: Evidence for aqueous fluid in Earth’s deep mantle. Science, 359, 1136–1139.10.1126/science.aao3030Search in Google Scholar PubMed
Yoshino, T., and Jaseem, V. (2018) Fluorine solubility in bridgmanite: A potential fluorine reservoir in the Earth’s mantle. Earth and Planetary Science Letters, 504, 106–114.10.1016/j.epsl.2018.10.009Search in Google Scholar
Yuan, H., and Zhang, L. (2017) In situ determination of crystal structure and chemistry of minerals at Earth’s deep lower mantle conditions. Matter and Radiation at Extremes, 2, 117–128.10.1016/j.mre.2017.01.002Search in Google Scholar
Yuan, L., Ohtani, E., Ikuta, D., Kamada, S., Tsuchiya, J., Naohisa, H., Ohishi, Y., and Suzuki, A. (2018) Chemical reactions between Fe and H2O up to megabar pressures and implications for water storage in the Earth’s mantle and core. Geophysical Research Letters, 45, 1330–1338.10.1002/2017GL075720Search in Google Scholar
Yuan, H., Zhang, L., Ohtani, E., Meng, Y., Greenberg, E., and Prakapenka, V.B. (2019) Stability of Fe-bearing hydrous phases and element partitioning in the system MgO–Al2O3–Fe2O3–SiO2–H2O in Earth’s lowermost mantle. Earth and Planetary Science Letters, 524, 115714.10.1016/j.epsl.2019.115714Search in Google Scholar
Zhang, L., Yuan, H., Meng, Y., and Mao, H. (2019) Development of high-pressure multi-grain X-ray diffraction for exploring the Earth’s interior. Engineering, 5, 441–447.10.1016/j.eng.2019.02.004Search in Google Scholar
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Articles in the same Issue
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- New Mineral Names: Alteration Products
- American Mineralogist thanks the 2021 reviewers
Articles in the same Issue
- Alumino-oxy-rossmanite from pegmatites in Variscan metamorphic rocks from Eibenstein an der Thaya, Lower Austria, Austria: A new tourmaline that represents the most Al-rich end-member composition
- Fluorine partitioning between quadrilateral clinopyroxenes and melt
- Multi-stage magma evolution recorded by apatite and zircon of adakite-like rocks: A case study from the Shatanjiao intrusion, Tongling region, Eastern China
- The physical and chemical evolution of magmatic fluids in near-solidus silicic magma reservoirs: Implications for the formation of pegmatites
- Texture, geochemistry, and geochronology of titanite and pyrite: Fingerprint of magmatic-hydrothermal fertile fluids in the Jiaodong Au province
- Polytypism in semi-disordered lizardite and amesite by low-dose HAADF-STEM
- Peralkalinity in peraluminous granitic pegmatites. I. Evidence from whewellite and hydrogen carbonate in fluid inclusions
- Peralkalinity in peraluminous granitic pegmatites. II. Evidence from experiments on carbonate formation in spodumene-bearing assemblages
- Ab initio study of structural, elastic and thermodynamic properties of Fe3S at high pressure: Implications for planetary cores
- Removal of barite from zircon using an aqueous solution of diethylenetriaminepentaacetic acid and potassium carbonate
- Improving grain size analysis using computer vision techniques and implications for grain growth kinetics
- Crystal chemistry of arsenian pyrites: A Raman spectroscopic study
- Formation of the Maoniuping giant REE deposit: Constraints from mineralogy and in situ bastnäsite U-Pb geochronology
- Amphibole as a witness of chromitite formation and fluid metasomatism in ophiolites
- Ferro-papikeite, ideally NaFe2 2+(Fe32+Al2)(Si5Al3)O22(OH)2, a new orthorhombic amphibole from Nordmark (Western Bergslagen), Sweden: Description and crystal structure
- Letter
- HP-PdF2-type FeCl2 as a potential Cl-carrier in the deep Earth
- New Mineral Names: Alteration Products
- American Mineralogist thanks the 2021 reviewers