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Hydrogen incorporation mechanism in the lower-mantle bridgmanite

  • Narangoo Purevjav , Naotaka Tomioka , Shigeru Yamashita , Keiji Shinoda , Sachio Kobayashi , Kenji Shimizu , Motoo Ito , Suyu Fu , Jesse Gu , Christina Hoffmann , Jung-Fu Lin and Takuo Okuchi ORCID logo EMAIL logo
Published/Copyright: May 31, 2024
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American Mineralogist
From the journal American Mineralogist Volume 109 Issue 6

Abstract

Bridgmanite, the most abundant mineral in the lower mantle, can play an essential role in deep-Earth hydrogen storage and circulation processes. To better evaluate the hydrogen storage capacity and its substitution mechanism in bridgmanite occurring in nature, we have synthesized high-quality single-crystal bridgmanite with a composition of (Mg0.88Fe0.052+Fe0.053+Al0.03)(Si0.88Al0.11H0.01)O3 at nearly water-saturated environments relevant to topmost lower mantle pressure and temperature conditions. The crystallographic site position of hydrogen in the synthetic (Fe,Al)-bearing bridgmanite is evaluated by a time-of-flight single-crystal neutron diffraction scheme, together with supporting evidence from polarized infrared spectroscopy. Analysis of the results shows that the primary hydrogen site has an OH bond direction nearly parallel to the crystallographic b axis of the orthorhombic bridgmanite lattice, where hydrogen is located along the line between two oxygen anions to form a straight geometry of covalent and hydrogen bonds. Our modeled results show that hydrogen is incorporated into the crystal structure via coupled substitution of Al3+ and H+ simultaneously exchanging for Si4+, which does not require any cation vacancy. The concentration of hydrogen evaluated by secondary-ion mass spectrometry and neutron diffraction is ~0.1 wt% H2O and consistent with each other, showing that neutron diffraction can be an alternative quantitative means for the characterization of trace amounts of hydrogen and its site occupancy in nominally anhydrous minerals.

Keywords: Bridgmanite; lower mantle; hydrogen substitution; neutron diffraction

† Present address: School of Earth and Environmental Sciences, Seoul National University, Seoul 08826, Korea.

‡ Pressent address: Department of Earth and Planetary Sciences, Harvard University, Cambridge, Massachusetts 02138, U.S.A.

Funding statement: This work was supported by the Japan Society for the Promotion of Science (Post-doctoral Fellowship for Research in Japan Grant Number P17331, and KAKENHI Grant Numbers 17H01172, 18K18795, 18H04468, 20H01965 and 21H04519). J.F.L. acknowledges support from the Geophysics Program and the Cooperative Studies of The Earth’s Deep Interior Program (CSEDI) of the National Science Foundation (EAR-2001381; EAR-1916941). A portion of this research at the Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. This work was supported in part by the Joint Use Program at IPM, by the Kochi Core Center Open Facility System (KOFS) under the MEXT foundation, and by the collaboration research project of Integrated Radiation and Nuclear Science, Kyoto University (R3148, R4011, and R5007).

Acknowledgments

We acknowledge E. Ito at IPM for technical suggestions in high-pressure synthesis, Y. Yachi at IPM for supporting EPMA analysis, I. Miyagi at National Institute of Advanced Industrial Science and Technology for providing natural amphibole standard for SIMS, X. Wang at SNS for supporting neutron data analysis, and Wenli Bi and Ercan Alp at Argonne National Laboratory for Mössbauer analysis.

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Received: 2022-06-20
Accepted: 2023-08-06
Published Online: 2024-05-31
Published in Print: 2024-06-25

© 2024 by Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8680
Keywords for this article
Bridgmanite; lower mantle; hydrogen substitution; neutron diffraction

Articles in the same Issue

  1. Perspectives
  2. Concerning tetrahedrites: How much to lump and how far to split?
  3. The space-time architecture variation of the shallow magmatic plumbing systems feeding the Campi Flegrei and Ischia volcanoes (Southern Italy) from halogen constraints
  4. Effect of chlorine substitution on the thermal stability of ferro-pargasite and thermochemical properties of ferro-chloro-hornblende
  5. Ilmenite phase transformations in suevite from the Ries impact structure (Germany) record evolution in pressure, temperature, and oxygen fugacity conditions
  6. The 34S/32S homogeneity of Chemical Vapor Transport (CVT) Reaction-synthesized pyrites
  7. Hydrogen incorporation mechanism in the lower-mantle bridgmanite
  8. Different structural behavior of MgSiO3 and CaSiO3 glasses at high pressures
  9. High-pressure phase transitions of Fe-bearing orthopyroxene revealed by Raman spectroscopy
  10. High P-T phase relations of Al-bearing magnetite: Post-spinel phases as indicators for P-T conditions of formation of natural samples
  11. Magnesio-ferri-hornblende, □Ca2(Mg4Fe3+)[(Si7Al)O22](OH)2, a new member of the amphibole supergroup
  12. A multivariate statistical approach for mineral geographic provenance determination using laser-induced breakdown spectroscopy and electron microprobe chemical data: A case study of copper-bearing tourmalines
  13. Characteristics of congruent dissolution of silicate minerals enhanced by chelating ligand under ambient conditions
  14. Pyrite stability and chalcophile element mobility in a hot Eocene forearc of the Pacific Rim Terrane, Vancouver Island, Canada
  15. Multi-wavelength Raman spectroscopy of natural nanostructured carbons
  16. A machine learning approach to discrimination of igneous rocks and ore deposits by zircon trace elements
  17. Book Review
  18. RIMG Volume 88: Diamond: Genesis, Mineralogy and Geochemistry
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