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The interplay between twinning and cation inversion in MgAl2O4-spinel: Implications for a nebular thermochronometer

  • Venkateswara Rao Manga , Krishna Muralidharan and Thomas J. Zega
Published/Copyright: July 27, 2022
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American Mineralogist
From the journal American Mineralogist Volume 107 Issue 8

Abstract

We report a first-principles-based thermodynamic investigation of the interplay between cation inversion and twinning in MgAl2O4 spinel (MAS). We examine the atomic-scale structure of (111) twins and characterize the local octahedral and tetrahedral distortions. We observe that the asymmetric nature of polyhedral distortions about the (111) twin plane causes anisotropy in cation inversion energies near the planar fault. The predicted enthalpies and entropies of inversion reveal that in comparison to the Kagome layer, the anti-site occupancies of Al and Mg, i.e., cation inversion, on the mixed-cation-layer near the twin boundary are more favorable and stable in the entire range of temperature of twin stability. Structurally, such a stable inversion is necessitated by the minimization in the polyhedral distortions, especially by the octahedral distortion, which exhibits a reduction of four orders of magnitude relative to the polyhedra with no inversion. The fundamental understanding obtained on the thermodynamics of the twin-cation inversion interplay in conjunction with the kinetics of inversion was used as a basis for developing a thermochronometer for deducing the temperature of twinning in MAS. This work serves as an important steppingstone for experimental characterization of MAS structures within a host of Earth and planetary materials. In the case of the latter, our results enable the use of planar faults, such as twins, as important markers for deducing the physical and chemical landscape that MAS experienced in its evolution and transport within the solar protoplanetary disk.

Keywords: Spinel twins; cation inversion; thermodynamics; order parameter; nebular thermo-chronometer

Acknowledments and Funders

Research supported by the NASA Emerging Worlds Program (NNX15AJ22G and 80NSSC19K0509). Resources supporting this work were provided by the NASA High-End Computing (HEC) Program through the NASA Advanced Supercomputing (NAS) Division at Ames Research Center. The authors also acknowledge the high-performance computing facility at the University of Arizona. The authors are thankful to Prajkta Mane for valuable discussions about twins in perovskite and spinel phases.

  1. Manuscript handled by Simon Redfern

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Received: 2020-10-27
Accepted: 2021-07-29
Published Online: 2022-07-27
Published in Print: 2022-08-26

© 2022 Mineralogical Society of America

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https://doi.org/10.2138/am-2021-7874
Keywords for this article
Spinel twins; cation inversion; thermodynamics; order parameter; nebular thermo-chronometer

Articles in the same Issue

  1. Estimating kaolinite crystallinity using near-infrared spectroscopy: Implications for its geology on Earth and Mars
  2. The interplay between twinning and cation inversion in MgAl2O4-spinel: Implications for a nebular thermochronometer
  3. The effect of fluorine on reaction-rim growth dynamics in the ternary CaO-MgO-SiO2 system
  4. Seeing through metamorphic overprints in Archean granulites: Combined high-resolution thermometry and phase equilibrium modeling of the Lewisian Complex, Scotland
  5. Interphase misorientation as a tool to study metamorphic reactions and crystallization in geological materials
  6. Trace element partitioning between olivine and melt in lunar basalts
  7. Solving the iron quantification problem in low-kV EPMA: An essential step toward improved analytical spatial resolution in electron probe microanalysis—Fe-sulfides
  8. Zircon geochronological and geochemical insights into pluton building and volcanic-hypabyssal-plutonic connections: Oki-Dōzen, Sea of Japan—A complex intraplate alkaline volcano
  9. Using cathodoluminescence to identify oscillatory zoning of perthitic K‑feldspar from the equigranular Toki granite
  10. Influence of intensive parameters and assemblies on friction evolution during piston-cylinder experiments
  11. Formation process of Al-rich calcium amphibole in quartz-bearing eclogites from The Sulu Belt, China
  12. Helvine-danalite mineralogy of the Dulong Sn-Zn polymetallic deposit in southeast Yunnan, China
  13. Native gold enrichment process during growth of chalcopyrite-lined conduits within a modern hydrothermal chimney (Manus Basin, PNG)
  14. Pliniusite, Ca5(VO4)3F, a new apatite-group mineral and the novel natural ternary solid-solution system pliniusite–svabite–fluorapatite
  15. Heamanite-(Ce), (K0.5Ce0.5)TiO3, a new perovskite supergroup mineral found in diamond from Gahcho Kué, Canada
  16. A revised analysis of ferrihydrite at liquid helium temperature using Mössbauer spectroscopy
  17. First find of merrillite, Ca3(PO4)2, in a terrestrial environment as an inclusion in lower-mantle diamond
  18. New Mineral Names: Hydrous Minerals
  19. Book Review
  20. Past to Present. (2020) Edited by Beth N. Orcutt, Isabelle Daniel, and Rajdeep Dasgupta.
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