Home A cotunnite-type new high-pressure phase of Fe2S
Article
Licensed
Unlicensed Requires Authentication

A cotunnite-type new high-pressure phase of Fe2S

  • Kenta Oka , Shigehiko Tateno , Yasuhiro Kuwayama , Kei Hirose ORCID logo , Yoichi Nakajima ORCID logo , Koihiro Umemoto , Noriyoshi Tsujino and Saori I. Kawaguchi ORCID logo
Published/Copyright: July 2, 2022
Become an author with De Gruyter Brill
Author Information
American Mineralogist
From the journal American Mineralogist Volume 107 Issue 7

Abstract

We examined pressure-induced phase transitions in Fe2S based on high-pressure and high-temperature X‑ray diffraction measurements in a laser-heated diamond-anvil cell. Fe2S is not stable at ambient pressure but is known to form above 21 GPa with the Fe2P-type (C22) structure. Our experiments demonstrate a novel phase transition in Fe2S from the C22 to C23 phase with the Co2P-type cotunnite structure above ~30 GPa. The experiments also reveal a transformation from the C23 to C37 (Co2Si-type) phase above ~130 GPa. While the C23 and C37 structures exhibit the same crystallographic symmetry (orthorhombic Pnma), the coordination number of sulfur increases from nine in C23 to ten in C37. Such a sequence of pressure-induced phase transitions in Fe2S, C22 → C23 → C37, are similar to those of Fe2P, while they are not known in oxides and halogens that often adopt the C23 cotunnite-type structure. The newly found cotunnite-type Fe2S phase could be present in solid iron cores of planets, including Mars.

Keywords: Iron sulfide; high pressure; high temperature; core; phase transition; cotunnite-type structure; Mars; Physics and Chemistry of Earth’s Deep Mantle and Core

Acknowledgments and Funding

Synchrotron XRD measurements were performed at beamline BL10XU, SPring-8 (proposals nos. 2008B0099, 2018B0072, 2019A0072, and 2021A0072). First principles calculations were performed at Global Scientific Information and Computing Center at the Tokyo Institute of Technology. This work was supported by the JSPS grants nos. 16H06285 and 21H04968 to K.H.

References cited

Baroni, S., de Gironcoli, S., Dal Corso, A., and Giannozzi, P. (2001) Phonons and related crystal properties from density-functional perturbation theory. Reviews of Modern Physics, 73, 515–558.10.1103/RevModPhys.73.515Search in Google Scholar

Bazhanova, Z.G., Roizen, V.V., and Oganov, A.R. (2017) High-pressure behavior of the Fe-S system and composition of the Earth’s inner core. Uspekhi Fizicheskih Nauk, 187, 1105–1113.10.3367/UFNe.2017.03.038079Search in Google Scholar

Chabot, N., Wollack, E.A., Klima, R.L., and Minitti, M.E. (2014) Experimental constraints on Mercury’s core composition. Earth and Planetary Science Letters, 390, 199–208.10.1016/j.epsl.2014.01.004Search in Google Scholar

Dekura, H., Tsuchiya, T., Kuwayama, Y., and Tsuchiya, J. (2011) Theoretical and experimental evidence for a new post-cotunnite phase of titanium dioxide with significant optical absorption. Physical Review Letters, 107, 045701.10.1103/PhysRevLett.107.045701Search in Google Scholar

Dera, P., Lavina, B., Borkowski, L.A., Prakapenka, V.B., Sutton, S.R., Rivers, M.L., Downs, R.T., Boctor, N.Z., and Prewitt, C.T. (2008) High-pressure polymorphism of Fe2P and its implications for meteorites and Earth’s core. Geophysical Research Letters, 35, 1–6.10.1029/2008GL033867Search in Google Scholar

Dera, P., Lavina, B., Borkowski, L.A., Prakapenka, V.B., Sutton, S.R., Rivers, M.L., Downs, R.T., Boctor, N.Z., and Prewitt, C.T. (2009) Structure and behavior of the barringerite Ni end-member, Ni2P, at deep Earth conditions and implications for natural Fe-Ni phosphides in planetary cores. Journal of Geophysical Research, 114, B03201.10.1029/2008JB005944Search in Google Scholar

Dewaele, A., and Torrent, M. (2013) Equation of state of α-Al2O3. Physical Review B, 88064107.10.1103/PhysRevB.88.064107Search in Google Scholar

Dreibus, G., and Palme, H. (1996) Cosmochemical constraints on the sulfur content in the Earth’s core. Geochimica et Cosmochimica Acta, 60, 1125–1130.10.1016/0016-7037(96)00028-2Search in Google Scholar

Dreibus, G., and Wänke, H. (1985) Mars, a volatile-rich planet. Meteoritics, 20, 367–381.Search in Google Scholar

Dumberry, M., and Rivoldini, A. (2015) Mercury’s inner core size and core-crystallization regime. Icarus, 248, 254–268.10.1016/j.icarus.2014.10.038Search in Google Scholar

Ellner, M., and Mittemeijer, E.J. (2001) The reconstructive phase transformation β-Co2P → α-Co2P and the structure of the high-temperature phosphide β-Co2P. Zeitschrift für Anorganische und Allgemeine Chemie, 627, 2257.10.1002/1521-3749(200109)627:9<2257::AID-ZAAC2257>3.0.CO;2-WSearch in Google Scholar

Errandonea, D., Santamaría-Perez, D., Vegas, A., Nuss, J., Jansen, M., Rodríguez-Hernandez, P., and Muñoz, A. (2008) Structural stability of Fe5Si3 and Ni2Si studied by high-pressure X-ray diffraction and ab initio total-energy calculations. Physical Review B, 77, 094113.10.1103/PhysRevB.77.094113Search in Google Scholar

Fei, Y., Bertka, C.M., and Finger, L.W. (1997) High-pressure iron-sulfur compound, Fe3S2, and melting relations in the system Fe-FeS at high pressure. Science, 275, 1621–1623.10.1126/science.275.5306.1621Search in Google Scholar PubMed

Fei, Y., Li, J., Bertka, C.M., and Prewitt, C.T. (2000) Structure type and bulk modulus of Fe3S, a new iron-sulfur compound. American Mineralogist, 85, 1830–1833.10.2138/am-2000-11-1229Search in Google Scholar

Fiquet, G., Auzende, A.L., Siebert, J., Corgne, A., Bureau, H., Ozawa, H., and Garbarino, G. (2010) Melting of peridotite to 140 gigapascals. Science, 329, 1516–1518.10.1126/science.1192448Search in Google Scholar PubMed

Geller, S., and Wolontis, V.M. (1955) The crystal structure of Co2Si. Acta Crystallographica, 8, 83–87.10.1107/S0365110X55000352Search in Google Scholar

Giannozzi, P., Gironcoli, S., Pavone, P., and Baroni, S. (1991) Ab initio calculation of phonon dispersions in semiconductors. Physical Review B, 43, 7231–7242.10.1103/PhysRevB.43.7231Search in Google Scholar PubMed

Giannozzi, P., Baroni, S., Bonini, N., Calandra, M., Car, R., Cavazzoni, C., Ceresoli, D., Chiarotti, G.L., Cococcioni, M., Dabo, I., and others (2009) QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. Journal of Physics, Condensed Matter, 21, 395502.10.1088/0953-8984/21/39/395502Search in Google Scholar PubMed

Gu, T., Fei, Y., Wu, X., and Qin, S. (2014) High-pressure behavior of Fe3P and the role of phosphorus in planetary cores. Earth and Planetary Science Letters, 390, 296–303.10.1016/j.epsl.2014.01.019Search in Google Scholar

Haines, J., Léger, J.M., and Schulte, O. (1998) High-pressure isosymmetric phase transition in orthorhombic lead fluoride. Physical Review B, 57, 7551–7555.10.1103/PhysRevB.57.7551Search in Google Scholar

Harder, H., and Schubert, G. (2001) Sulfur in Mercury’s core? Icarus, 151, 118–122.10.1006/icar.2001.6586Search in Google Scholar

Helffrich, G. (2017) Mars core structure—concise review and anticipated insights from InSight. Progress in Earth and Planetary Science, 4, 24.10.1186/s40645-017-0139-4Search in Google Scholar

Hirao, N., Kawaguchi, S.I., Hirose, K., Shimizu, K., Ohtani, E., and Ohishi, Y. (2020) New developments in high-pressure X-ray diffraction beamline for diamond anvil cell at SPring-8. Matter and Radiation at Extremes, 5, 018403.10.1063/1.5126038Search in Google Scholar

Hirose, K., Tagawa, S., Kuwayama, Y., Sinmyo, R., Morard, G., Ohishi, Y., and Genda, H. (2019) Hydrogen limits carbon in liquid iron. Geophysical Research Letters, 46, 5190–5197.10.1029/2019GL082591Search in Google Scholar

Inerbaev, T.M., Sagatov, N., Sagatova, D., Gavryushkin, P.N., Akilbekov, A.T., and Litasov, K.D. (2020) Phase stability in nickel phosphides at high pressures. ACS Earth and Space Chemistry, 4, 1978–1984.10.1021/acsearthspacechem.0c00181Search in Google Scholar

Kamada, S., Ohtani, E., Terasaki, H., Sakai, T., Takahashi, S., Hirao, N., and Ohishi, Y. (2014) Equation of state of Fe3S at room temperature up to 2 megabars. Physics of the Earth and Planetary Interiors, 228, 106–113.10.1016/j.pepi.2013.11.001Search in Google Scholar

Khan, A., and Connolly, J.A.D. (2008) Constraining the composition and thermal state of Mars from inversion of geophysical data. Journal of Geophysical Research, 113, E07003.10.1029/2007JE002996Search in Google Scholar

Koch-Müller, K., Fei, Y., Wirth, R., and Bertka, C.M. (2002) Characterization of high-pressure iron-sulfur compounds. 33rd Lunar and Planetary Science Conference, Abstract 1424.Search in Google Scholar

Methfessel, M., and Paxton, A. (1989) High-precision sampling for Brillouin-zone integration in metals. Physical Review. B, Condensed Matter, 40, 3616–3621.10.1103/PhysRevB.40.3616Search in Google Scholar

Mori, Y., Ozawa, H., Hirose, K., Sinmyo, R., Tateno, S., Morard, G., and Ohishi, Y. (2017) Melting experiments on Fe–Fe3S system to 254 GPa. Earth and Planetary Science Letters, 464, 135–141.10.1016/j.epsl.2017.02.021Search in Google Scholar

Nakajima, Y., Araki, S., Kinoshita, D., Hirose, K., Tateno, S., Kawaguchi, S.I., and Hirao, N. (2020) New pressure-induced phase transition to Co2Si-type Fe2P. American Mineralogist, 105, 1752–1755.10.2138/am-2020-7574Search in Google Scholar

Oka, K., Hirose, K., Tagawa, S., Kidokoro, Y., Nakajima, Y., Kuwayama, Y., Morard, G., Coudurier, N., and Fiquet, G. (2019) Melting in the Fe-FeO system to 204 GPa: Implications for oxygen in Earth’s core. American Mineralogist, 104, 1603–1607.10.2138/am-2019-7081Search in Google Scholar

Ozawa, H., Hirose, K., Suzuki, T., Ohishi, Y., and Hirao, N. (2013) Decomposition of Fe3S above 250 GPa. Geophysical Research Letters, 40, 4845–4849.10.1002/grl.50946Search in Google Scholar

Perdew, J., Burke, K., and Ernzerhof, M. (1996) Generalized gradient approximation made simple. Physical Review Letters, 78, 1396–1396.10.1103/PhysRevLett.77.3865Search in Google Scholar PubMed

Rivoldini, A., Van Hoolst, T., Verhoeven, O., Mocquet, A., and Dehant, V. (2011) Geodesy constraints on the interior structure and composition of Mars. Icarus, 213, 451–472.10.1016/j.icarus.2011.03.024Search in Google Scholar

Rundqvist, S., Hede, A., Rundqvist, S., Varde, E., and Westin, G. (1960) The structures of Co2P, Ru2P and related phases. Acta Chemica Scandinavica, 14, 1961–1979.10.3891/acta.chem.scand.14-1961Search in Google Scholar

Seto, Y., Nishio-Hamane, D., Nagai, T., and Sata, N. (2010) Development of a software suite on X-ray diffraction experiments. The Review of High Pressure Science and Technology, 20, 269–276.10.4131/jshpreview.20.269Search in Google Scholar

Stewart, A.J., and Schmidt, M.W. (2007) Sulfur and phosphorus in the Earth’s core: the Fe-P-S system at 23 GPa. Geophysical Research Letters, 34, L13201.10.1029/2007GL030138Search in Google Scholar

Stewart, A.J., Schmidt, M.W., van Westrenen, W., and Liebske, C. (2007) Mars: a new core-crystallization regime. Science, 316, 1323–1325.10.1126/science.1140549Search in Google Scholar PubMed

Tateno, S., Ozawa, H., Hirose, K., Suzuki, T., I-Kawaguchi, S., and Hirao, N. (2019) Fe2S: the most Fe-rich iron sulfide at the Earth’s inner core pressures. Geophysical Research Letters, 46, 11944–11949.10.1029/2019GL085248Search in Google Scholar

Terasaki, H., Rivoldini, A., Shimoyama, Y., Nishida, K., Urakawa, S., Maki, M., Kurokawa, F., Takubo, Y., Shibazaki, Y., Sakamaki, T., and others (2019) Pressure and composition effects on sound velocity and density of core-forming liquids: implication to core compositions of terrestrial planets. Journal of Geophysical Research: Planets, 124, 2272–2293.10.1029/2019JE005936Search in Google Scholar

Thompson, S., Komabayashi, T., Breton, H., Suehiro, S., Glazyrin, K., Pakhomova, A., and Ohishi, Y. (2020) Compression experiments to 126 GPa and 2500 K and thermal equation of state of Fe3S: implications for sulphur in the Earth’s core. Earth and Planetary Science Letters, 534, 116080.10.1016/j.epsl.2020.116080Search in Google Scholar

Tsujino, N., Nishihara, Y., Nakajima, Y., Takahashi, E., Funakoshi, K.-I., and Higo, Y. (2013) Equation of state of γ-Fe: Reference density for planetary cores. Earth and Planetary Science Letters, 375, 244–253.10.1016/j.epsl.2013.05.040Search in Google Scholar

Vanderbilt, D. (1990) Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Physical Review. B, Condensed Matter, 41, 7892–7895.10.1103/PhysRevB.41.7892Search in Google Scholar

Wallace, D.C. (1972) Thermodynamics of Crystals. Wiley.10.1119/1.1987046Search in Google Scholar

Wu, X., and Qin, S. (2010) First-principles calculations of the structural stability of Fe2P. Journal of Physics: Conference Series, 215, 012110.10.1088/1742-6596/215/1/012110Search in Google Scholar

Wu, Z., Wentzcovitch, R.M., Umemoto, K., Li, B., Hirose, K., and Zheng, J.D. (2008) Pressure-volume-temperature relations in MgO: an ultrahigh pressure-temperature scale for planetary sciences applications. Journal of Geophysical Research, 113, B06204.10.1029/2007JB005275Search in Google Scholar

Yoder, C.F., Konopliv, A.S., Yuan, D.N., Standish, E.M., and Folkner, W.M. (2003) Fluid core size of Mars from detection of the solar tide. Science, 300, 299–303.10.1126/science.1079645Search in Google Scholar PubMed

Zhang, Q., Wu, X., and Qin, S. (2011) In situ high-pressure X-ray diffraction experiments and ab initio calculations of Co2P. Chinese Physics B, 20, 066101 066101.10.1088/1674-1056/20/6/066101Search in Google Scholar

Zhao, Z., Liu, L., Zhang, S., Yu, T., Li, F., and Yang, G. (2017) Phase diagram, stability and electronic properties of an Fe–P system under high pressure: a first principles study. RSC Advances, 7, 15986–15991.10.1039/C7RA01567DSearch in Google Scholar

Zharkov, V.N., and Gudkova, T.V. (2005) Construction of Martian interior model. Solar System Research, 39, 343–373.10.1007/s11208-005-0049-7Search in Google Scholar
Received: 2021-01-09
Accepted: 2021-07-21
Published Online: 2022-07-02
Published in Print: 2022-07-26

© 2022 Mineralogical Society of America

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Mineral evolution heralds a new era for mineralogy
  3. MSA Review
  4. Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials
  5. A cotunnite-type new high-pressure phase of Fe2S
  6. Density determination of liquid iron-nickel-sulfur at high pressure
  7. On the paragenetic modes of minerals: A mineral evolution perspective
  8. Lumping and splitting: Toward a classification of mineral natural kinds
  9. Thermal expansion of minerals in the amphibole supergroup
  10. A multi-faceted experimental study on the dynamic behavior of MgSiO3 glass in the Earth’s deep interior
  11. Origin of β-cristobalite in Libyan Desert Glass: The hottest naturally occurring silica polymorph?
  12. Time-resolved Raman and luminescence spectroscopy of synthetic REE-doped hydroxylapatites and natural apatites
  13. Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis
  14. A first-principles study of water in wadsleyite and ringwoodite: Implication for the 520 km discontinuity
  15. Inclusions in calcite phantom crystals suggest role of clay minerals in dolomite formation
  16. Crystal-chemical reinvestigation of probertite, CaNa[B5O7(OH)4]·3H2O, a mineral commodity of boron
  17. Crystal structure determination of orthorhombic variscite2O and its derivative AlPO4 structure at high temperature
  18. Transformation of Fe-bearing minerals from Dongsheng sandstone-type uranium deposit, Ordos Basin, north-central China: Implications for ore genesis
  19. Vaterite in a decrepitated diamond-bearing inclusion in zircon from a stromatic migmatite in the Chinese Sulu ultrahigh-pressure metamorphic belt
  20. Oxygen diffusion in garnet: Experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures
  21. Oxidation state of iron and Fe-Mg partitioning between olivine and basaltic martian melts
https://doi.org/10.2138/am-2022-7959
Keywords for this article
Iron sulfide; high pressure; high temperature; core; phase transition; cotunnite-type structure; Mars; Physics and Chemistry of Earth’s Deep Mantle and Core

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Mineral evolution heralds a new era for mineralogy
  3. MSA Review
  4. Pauling’s rules for oxide-based minerals: A re-examination based on quantum mechanical constraints and modern applications of bond-valence theory to Earth materials
  5. A cotunnite-type new high-pressure phase of Fe2S
  6. Density determination of liquid iron-nickel-sulfur at high pressure
  7. On the paragenetic modes of minerals: A mineral evolution perspective
  8. Lumping and splitting: Toward a classification of mineral natural kinds
  9. Thermal expansion of minerals in the amphibole supergroup
  10. A multi-faceted experimental study on the dynamic behavior of MgSiO3 glass in the Earth’s deep interior
  11. Origin of β-cristobalite in Libyan Desert Glass: The hottest naturally occurring silica polymorph?
  12. Time-resolved Raman and luminescence spectroscopy of synthetic REE-doped hydroxylapatites and natural apatites
  13. Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis
  14. A first-principles study of water in wadsleyite and ringwoodite: Implication for the 520 km discontinuity
  15. Inclusions in calcite phantom crystals suggest role of clay minerals in dolomite formation
  16. Crystal-chemical reinvestigation of probertite, CaNa[B5O7(OH)4]·3H2O, a mineral commodity of boron
  17. Crystal structure determination of orthorhombic variscite2O and its derivative AlPO4 structure at high temperature
  18. Transformation of Fe-bearing minerals from Dongsheng sandstone-type uranium deposit, Ordos Basin, north-central China: Implications for ore genesis
  19. Vaterite in a decrepitated diamond-bearing inclusion in zircon from a stromatic migmatite in the Chinese Sulu ultrahigh-pressure metamorphic belt
  20. Oxygen diffusion in garnet: Experimental calibration and implications for timescales of metamorphic processes and retention of primary O isotopic signatures
  21. Oxidation state of iron and Fe-Mg partitioning between olivine and basaltic martian melts
Sign up now to receive a 20% welcome discount
Institutional Access
How does access work?
Have an idea on how to improve our website?
Please write us.
© 2025 De Gruyter Brill
Downloaded on 25.9.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2022-7959/html
Scroll to top button