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Thermal and combined high-temperature and high-pressure behavior of a natural intermediate scapolite

  • Paolo Lotti ORCID logo , G. Diego Gatta ORCID logo , Lara Gigli , Hannes Krüger , Volker Kahlenberg , Martin Meven , Davide Comboni , Sula Milani , Marco Merlini and Hanns-Peter Liermann
Published/Copyright: January 30, 2024
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American Mineralogist
From the journal American Mineralogist Volume 109 Issue 2

Abstract

A natural intermediate member of the scapolite solid solution {Me47; chemical formula: (Na1.86Ca1.86K0.23Fe0.01)(Al4.36Si7.64)O24[Cl0.48(CO3)0.48(SO4)0.01]}, with the unusual I4/m space group, has been studied at various temperatures and combined high-T and high-P by means of in situ single-crystal and powder X-ray diffraction, using both conventional and synchrotron X-ray sources. In addition, single-crystal neutron diffraction data were collected at ambient-T and 685 °C. A fit of the experimental V-T data with a thermal equation of state yielded a thermal expansion coeficient at ambient conditions: αV25°C = 1/V0·(∂V/∂T)P,25°C = 1.74(3)·10–5 K–1. A comparative analysis of the elastic behavior of scapolite based on this study and previous high-T XRD data suggests that a thorough re-investigation of the diferent members of the marialite-meionite solid solution is needed to fully understand the role of crystal chemistry on the thermal behavior of these complex nonbinary solid solutions. The experimental data obtained within the full temperature range of analysis at ambient pressure confirm that the investigated sample always preserves the I4/m space group, and possible implications on the metastability of I4/m intermediate scapolite are discussed. Neutron difraction data show that no significant Si and Al rearrangement among the T sites occurs between 25 and 685 °C. The combined high-T and high-P data show that at 650 °C and between 10.30(5) and 10.71(5) GPa a phase transition toward a triclinic polymorph occurs, with a positive Clapeyron slope (i.e., dP/dT > 0). A comprehensive description of the atomic-scale structure deformation mechanisms induced by temperature and/or pressure, including those leading to structural instability, is provided based on single-crystal structure refinements.

Keywords: Scapolite; temperature; pressure; phase transition; synchrotron X-ray diffraction; neutron diffraction; Microporous materials: Crystal-chemistry; properties; and utilizations

‡ Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

Acknowledgments and Funding

An anonymous reviewer is thanked for the competent and useful comments that improved the manuscript. We are grateful to Renato Pagano for providing the scapolite sample from his private mineralogical collection. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA-III and beamtime was allocated for proposal I-20170565 EC. The research has been supported by the project CALIPSOplus under the Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. ELETTRA Sincrotrone Trieste is acknowledged for the provision of beamtime and synchrotron facilities at the MCX beamline. Part of this work is based upon experiments performed at the HEiDi instrument operated jointly by RWTH Aachen University and Forschungszentrum Jülich within the JARA-FIT collaboration at the Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany.

The authors acknowledge the support by the Italian Ministry of Education (MIUR) through the project “PRIN2017—Mineral reactivity, a key to understand large-scale processes” (2017L83S77). P.L. and G.D.G. acknowledge the University of Milan for financial support through the project “Piano di Sostegno alla Ricerca 2021”.

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Received: 2023-02-06
Accepted: 2023-06-08
Published Online: 2024-01-30
Published in Print: 2024-02-26

© 2024 by Mineralogical Society of America

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  2. Thermal and combined high-temperature and high-pressure behavior of a natural intermediate scapolite
  3. Crystal structure, hydrogen bonding, and high-pressure behavior of the hydroxide perovskite MgSi(OH)6: A phase relevant to deep subduction of hydrated oceanic crust
  4. Equilibrium Sn isotope fractionation between aqueous Sn and Sn-bearing minerals: Constrained by first-principles calculations
  5. Raman spectroscopic investigation of selected natural uranyl sulfate minerals
  6. Modified magnetite and hydrothermal apatite in banded iron-formations and implications for high-grade Fe mineralization during retrogressive metamorphism
  7. Apatite trace element composition as an indicator of ore deposit types: A machine learning approach
  8. Identifying serpentine minerals by their chemical compositions with machine learning
  9. Crystal habit (tracht) of groundmass pyroxene crystals recorded magma ascent paths during the 2011 Shinmoedake eruption
  10. Reconstructing diagenetic mineral reactions from silicified horizons of the Paleoproterozoic Biwabik Iron Formation, Minnesota
  11. Mannardite as the main vanadium-hosting mineral in black shale-hosted vanadium deposits, South China
  12. Molybdenite-bearing vugs in microgranite in the Preissac pluton, Québec, Canada: Relicts of aqueous fluid pockets?
  13. The equilibrium boundary of the reaction Mg3Al2Si3O12 + 3CO2 = Al2SiO5 + 2SiO2 + 3MgCO3 at 3–6 GPa
  14. Discussion
  15. Comment on Lee et al. (2022) “Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis”— Concerning opal
  16. Reply
  17. On “Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis”—Reply to de Jong
  18. American Mineralogist thanks the Reviewers for 2023
https://doi.org/10.2138/am-2023-8962
Keywords for this article
Scapolite; temperature; pressure; phase transition; synchrotron X-ray diffraction; neutron diffraction; Microporous materials: Crystal-chemistry; properties; and utilizations

Articles in the same Issue

  1. Crystal chemistry and thermodynamic properties of zircon structure-type materials
  2. Thermal and combined high-temperature and high-pressure behavior of a natural intermediate scapolite
  3. Crystal structure, hydrogen bonding, and high-pressure behavior of the hydroxide perovskite MgSi(OH)6: A phase relevant to deep subduction of hydrated oceanic crust
  4. Equilibrium Sn isotope fractionation between aqueous Sn and Sn-bearing minerals: Constrained by first-principles calculations
  5. Raman spectroscopic investigation of selected natural uranyl sulfate minerals
  6. Modified magnetite and hydrothermal apatite in banded iron-formations and implications for high-grade Fe mineralization during retrogressive metamorphism
  7. Apatite trace element composition as an indicator of ore deposit types: A machine learning approach
  8. Identifying serpentine minerals by their chemical compositions with machine learning
  9. Crystal habit (tracht) of groundmass pyroxene crystals recorded magma ascent paths during the 2011 Shinmoedake eruption
  10. Reconstructing diagenetic mineral reactions from silicified horizons of the Paleoproterozoic Biwabik Iron Formation, Minnesota
  11. Mannardite as the main vanadium-hosting mineral in black shale-hosted vanadium deposits, South China
  12. Molybdenite-bearing vugs in microgranite in the Preissac pluton, Québec, Canada: Relicts of aqueous fluid pockets?
  13. The equilibrium boundary of the reaction Mg3Al2Si3O12 + 3CO2 = Al2SiO5 + 2SiO2 + 3MgCO3 at 3–6 GPa
  14. Discussion
  15. Comment on Lee et al. (2022) “Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis”— Concerning opal
  16. Reply
  17. On “Reexamination of the structure of opal-A: A combined study of synchrotron X-ray diffraction and pair distribution function analysis”—Reply to de Jong
  18. American Mineralogist thanks the Reviewers for 2023
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