Home Physical Sciences A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra
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A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra

  • Marcus Silva EMAIL logo , Earl F. O’Bannon and Quentin Williams
Published/Copyright: July 30, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 8

Abstract

The Raman and infrared spectra of kernite [Na2B4O6(OH)2·3H2O] have been characterized up to ~25 and 23 GPa, respectively, to explore pressure-induced changes in a structurally novel mineral that contains mixed coordination borate groups (threefold and fourfold), as well as both hydroxyl groups and water molecules. BO3 and BO4 vibrational modes are characterized in both the Raman and infrared spectra of kernite, and reassignments of some modes are made based on observed pressure shifts. Under compression to ~25 GPa, kernite undergoes three phase transitions: one initiates near ~2.5 GPa, the second occurs at ~7.0 GPa, and the third near 11.0 GPa. The first transition is characterized by a loss of both a subset of the Na-associated modes and a sharp OH peak, and it is fully reversible. The second transition is characterized by the loss of most of the BO3 modes, some of the BO4 modes at ~7 GPa, and further broadening of the H2O and OH peaks. This transition is partially reversible on decompression, but the Raman spectra indicate that the high-pressure structure and its reversion products are likely disordered. The third transition is characterized by the loss of most of the Raman and infrared modes, and it is not reversible on decompression. The decompression products from ~25 GPa have markedly different infrared and Raman spectra from the starting material, and appear to involve different bonding environments of boron than are present in the starting materials: thus, pressure treatment of boron-rich materials may generate novel quenchable structures. Notably, the BO3 groups in kernite are destabilized under compression, with the BO4 groups appearing to be more stable under compression. This shift in coordination may be endemic among borate glasses and crystalline borates under compression. The coordination conversion (and its products on decompression) is likely to highly depend on the detailed topology of the starting materials. Commonalities and differences between the threefold to fourfold transitions in borate systems relative to those in carbonate systems are presented. Our results, combined with prior shock data, indicate that kernite, which may be representative of low-temperature borate minerals, can persist during impact events with peak shock pressures less than ~33 GPa, and the primary polyborate structural units involved in early ribose stabilization would thus survive most impact conditions.

Keywords: Kernite; boron; high pressure; vibrational spectroscopy

Acknowledgments

We thank R.L. Frost, two anonymous reviewers, and the associate editor (M. Mookherjee) for helpful comments that improved the quality of the manuscript. We also thank Dan Sampson for invaluable technical assistance with the Raman and infrared spectrometers. Work partially supported by NSF through EAR-1215745 and -1620423, and COMPRES, the Consortium for Materials Properties Research in Earth Sciences under NSF Cooperative Agreement EAR 11-57758. A portion of this work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

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Received: 2017-07-10
Accepted: 2018-04-10
Published Online: 2018-07-30
Published in Print: 2018-08-28

© 2018 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Electron channeling to achieve the full potential of mineralogy
  3. The inverse problem of unpolarized infrared spectroscopy of geological materials: Estimation from noisy random sampling of a quadratic form
  4. The distribution of lead and thallium in mantle rocks: Insights from the Balmuccia peridotite massif (Italian Alps)
  5. Sulfide partial melting and chalcopyrite disease: An experimental study
  6. Nanoscale partitioning of Ru, Ir, and Pt in base-metal sulfides from the Caridad chromite deposit, Cuba
  7. Stability of Al-bearing superhydrous phase B at the mantle transition zone and the uppermost lower mantle
  8. Origin of the fluorine- and beryllium-rich rhyolites of the Spor Mountain Formation, Western Utah
  9. The mantle source of thermal plumes: Trace and minor elements in olivine and major oxides of primitive liquids (and why the olivine compositions don’t matter)
  10. The effects of ferromagnetism and interstitial hydrogen on the equation of states of hcp and dhcp FeHx: Implications for the Earth’s inner core age
  11. Accurate predictions of microscale oxygen barometry in basaltic glasses using V K-edge X-ray absorption spectroscopy: A multivariate approach
  12. Electrical cell assembly for reproducible conductivity experiments in the multi-anvil
  13. A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra
  14. Discreditation of bobdownsite and the establishment of criteria for the identification of minerals with essential monofluorophosphate (PO3F2–)
  15. Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a new Cl-rich silicate mineral from the Allende meteorite: An alteration phase in a Ca-Al-rich inclusion
  16. MSA Distinguished Lecturer Series
  17. An accessory mineral and experimental perspective on the evolution of the early crust
  18. Letter
  19. POLARIO, a computer program for calculating refractive indices from chemical compositions
  20. Book Review
  21. Book Review
  22. Erratum
  23. Erratum
https://doi.org/10.2138/am-2018-6253
Keywords for this article
Kernite; boron; high pressure; vibrational spectroscopy

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Electron channeling to achieve the full potential of mineralogy
  3. The inverse problem of unpolarized infrared spectroscopy of geological materials: Estimation from noisy random sampling of a quadratic form
  4. The distribution of lead and thallium in mantle rocks: Insights from the Balmuccia peridotite massif (Italian Alps)
  5. Sulfide partial melting and chalcopyrite disease: An experimental study
  6. Nanoscale partitioning of Ru, Ir, and Pt in base-metal sulfides from the Caridad chromite deposit, Cuba
  7. Stability of Al-bearing superhydrous phase B at the mantle transition zone and the uppermost lower mantle
  8. Origin of the fluorine- and beryllium-rich rhyolites of the Spor Mountain Formation, Western Utah
  9. The mantle source of thermal plumes: Trace and minor elements in olivine and major oxides of primitive liquids (and why the olivine compositions don’t matter)
  10. The effects of ferromagnetism and interstitial hydrogen on the equation of states of hcp and dhcp FeHx: Implications for the Earth’s inner core age
  11. Accurate predictions of microscale oxygen barometry in basaltic glasses using V K-edge X-ray absorption spectroscopy: A multivariate approach
  12. Electrical cell assembly for reproducible conductivity experiments in the multi-anvil
  13. A vibrational spectroscopic study of kernite to 25 GPa: Implications for the high-pressure stability of borate polyhedra
  14. Discreditation of bobdownsite and the establishment of criteria for the identification of minerals with essential monofluorophosphate (PO3F2–)
  15. Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a new Cl-rich silicate mineral from the Allende meteorite: An alteration phase in a Ca-Al-rich inclusion
  16. MSA Distinguished Lecturer Series
  17. An accessory mineral and experimental perspective on the evolution of the early crust
  18. Letter
  19. POLARIO, a computer program for calculating refractive indices from chemical compositions
  20. Book Review
  21. Book Review
  22. Erratum
  23. Erratum
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