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Natural cubic perovskite, Ca(Ti,Si,Cr)O3–δ, a versatile potential host for rock-forming and less-common elements up to Earth’s mantle pressure

  • Sergey N. Britvin , Natalia S. Vlasenko , Andrey Aslandukov , Alena Aslandukovа , Leonid Dubrovinsky , Liudmila A. Gorelova , Maria G. Krzhizhanovskaya , Oleg S. Vereshchagin ORCID logo , Vladimir N. Bocharov , Yulia S. Shelukhina , Maksim S. Lozhkin , Anatoly N. Zaitsev and Fabrizio Nestola ORCID logo
Published/Copyright: September 29, 2022
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American Mineralogist
From the journal American Mineralogist Volume 107 Issue 10

Abstract

Perovskite, CaTiO3, originally described as a cubic mineral, is known to have a distorted (orthorhombic) crystal structure. We herein report on the discovery of natural cubic perovskite. This was identified in gehlenite-bearing rocks occurring in a pyrometamorphic complex of the Hatrurim Formation (the Mottled Zone), in the vicinity of the Dead Sea, Negev Desert, Israel. The mineral is associated with native α-(Fe,Ni) metal, schreibersite (Fe3P), and Si-rich fluorapatite. The crystals of this perovskite reach 50 μm in size and contain many micrometer-sized inclusions of melilitic glass. The mineral contains significant amounts of Si substituting for Ti (up to 9.6 wt% SiO2), corresponding to 21 mol% of the davemaoite component (cubic perovskite-type CaSiO3), in addition to up to 6.6 wt% Cr2O3. Incorporation of trivalent elements results in the occurrence of oxygen vacancies in the crystal structure; this is the first example of natural oxygen-vacant ABO3 perovskite with the chemical formula Ca(Ti,Si,Cr)O3–δ (δ ~0.1). Stabilization of cubic symmetry (space group Pm3̅m) is achieved via the mechanism not reported so far for CaTiO3, namely displacement of an O atom from its ideal structural position (site splitting). The mineral is stable at atmospheric pressure to 1250 ± 50 °C; above this temperature, its crystals fuse with the embedded melilitic glass, yielding a mixture of titanite and anorthite upon melt solidification. The mineral is stable upon compression to at least 50 GPa. The a lattice parameter exhibits continuous contraction from 3.808(1) Å at atmospheric pressure to 3.551(6) Å at 50 GPa. The second-order truncation of the Birch-Murnaghan equation of state gives the initial volume V0 equal to 55.5(2) Å3 and room temperature isothermal bulk modulus K0 of 153(11) GPa. The discovery of oxygen-deficient single perovskite suggests previously unaccounted ways for incorporation of almost any element into the perovskite framework up to pressures corresponding to those of the Earth’s mantle.

Keywords: Cubic perovskite; site splitting; disordered oxygen vacancies; davemaoite; mantle; high pressure; pyrometamorphism; Dead Sea Transform

Funding statement: This research was financially supported by the Russian Science Foundation, grant 18-17-00079. High-pressure studies were performed at the PETRA III storage ring at DESY, a member of the Helmholtz Association (HGF). The authors acknowledge the Resource Center of X‑ray diffraction studies, “Geomodel” Resource Centre, Centre for Microscopy and Microanalysis, Nanophotonics Resource Center and Interdisciplinary Resourse center of Nanotechnology of Saint-Petersburg State University for the access to instrumental and computational resources.

Acknowledgments

The authors are indebted to Mikhail Murashko and Yevgeny Vapnik for the loan of the specimens of cubic perovskite. We are thankful to Associate Editor G.D. Gatta for editorial handling of the manuscript and to the Crystal Structures Editor for corrections of crystallographic data. The constructive suggestions and invaluable linguistic support of the referees, Roger Mitchell and an anonymous reviewer, are gratefully acknowledged.

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Received: 2021-06-19
Accepted: 2021-09-29
Published Online: 2022-09-29
Published in Print: 2022-10-26

© 2022 Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8186
Keywords for this article
Cubic perovskite; site splitting; disordered oxygen vacancies; davemaoite; mantle; high pressure; pyrometamorphism; Dead Sea Transform

Articles in the same Issue

  1. Experimentally derived F, Cl, and Br fluid/melt partitioning of intermediate to silicic melts in shallow magmatic systems
  2. Spectroscopic study on the local structure of sulfate ( S O 4 2 − ) incorporated in scorodite (FeAsO4·2H2O) lattice: Implications for understanding the Fe(III)-As(V)- S O 4 2 − -bearing minerals formation
  3. Oxidation of arcs and mantle wedges by reduction of manganese in pelagic sediments during seafloor subduction
  4. Raman scattering and Cr3+ luminescence study on the structural behavior of δ-AlOOH at high pressures
  5. Jadeite and related species in shocked meteorites: Limitations on inference of shock conditions
  6. Pressure-induced C23–C37 transition and compression behavior of orthorhombic Fe2S to Earth’s core pressures and high temperatures
  7. Estimating ferric iron content in clinopyroxene using machine learning models
  8. Pyradoketosite, a new, unexpected, polymorph of Ag3SbS3 from the Monte Arsiccio mine (Apuan Alps, Tuscany, Italy)
  9. Pyrite geochemistry and its implications on Au-Cu skarn metallogeny: An example from the Jiguanzui deposit, Eastern China
  10. Synthesis of ferrian and ferro-saponites: Implications for the structure of (Fe,Mg)-smectites formed under reduced conditions
  11. Natural cubic perovskite, Ca(Ti,Si,Cr)O3–δ, a versatile potential host for rock-forming and less-common elements up to Earth’s mantle pressure
  12. Nazarovite, Ni12P5, a new terrestrial and meteoritic mineral structurally related to nickelphosphide, Ni3P
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  14. Tracing structural relicts of the ikaite-to-calcite transformation in cryogenic cave glendonite
  15. Oxygen-fugacity evolution of magmatic Ni-Cu sulfide deposits in East Kunlun: Insights from Cr-spinel composition
  16. New Mineral Names
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