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Hydrous wadsleyite crystal structure up to 32 GPa

  • Fei Wang ORCID logo , Elizabeth C. Thompson ORCID logo , Dongzhou Zhang ORCID logo , Jingui Xu , Ercan E. Alp and Steven D. Jacobsen ORCID logo
Published/Copyright: October 4, 2023
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American Mineralogist
From the journal American Mineralogist Volume 108 Issue 10

Abstract

Hydroxylation of wadsleyite, β-(Mg,Fe)2SiO4, is associated with divalent cation defects and well known to afect its physical properties. However, an atomic-scale understanding of the defect structure and hydrogen bonding at high pressures is needed to interpret the influence of water on the behavior of wadsleyite in the mantle transition zone. We have determined the pressure evolution of the wadsleyite crystal symmetry and structure, including all O∙∙∙O interatomic distances, up to 32 GPa using single-crystal X-ray difraction on two well-characterized, Fe-bearing (Fo90) samples containing 0.25(4) and 2.0(2) wt% H2O. Both compositions undergo a pressure-dependent monoclinic distortion from orthorhombic symmetry above 9 GPa, with the less hydrous sample showing a larger increase in distortion at increased pressures due to the diference in compressibility of the split M3 site in the monoclinic setting arising from preferred vacancy ordering at the M3B site. Although hydrogen positions cannot be modeled from the X-ray difraction data, the pressure evolution of the longer O1∙∙∙O4 distance in the structure characterizes the primary hydrogen bond length. We observe the hydrogen-bonded O1∙∙∙O4 distance shorten gradually from 3.080(1) Å at ambient pressure to about 2.90(1) Å at 25 GPa, being still much longer than is defined as strong hydrogen bonding (2.5–2.7 Å). Above 25 GPa and up to the maximum pressure of the experiment at 32.5 GPa, the hydrogen-bonded O1∙∙∙O4 distance decreases no further, despite the fact that previous spectroscopic studies have shown that the primary O-H stretching frequencies continuously drop into the regime of strong hydrogen bonding (<3200 cm–1) above ~15 GPa. We propose that the primary O1-H∙∙∙O4 hydrogen bond in wadsleyite becomes highly nonlinear at high pressures based on its deviation from frequency-distance correlations for linear hydrogen bonds. One possible explanation is that the hydrogen position shifts from being nearly on the long O1-O4 edge of the M3 site to a position more above O1 along the c-axis.

Keywords: Wadsleyite; mantle transition zone; hydrogen bond; water

Funding statement: This research was supported by the U. S. National Science Foundation (NSF) awards EAR-1853521 to S.D. Jacobsen and EAR-1725673 to E.C. Thompson. S.D.J. also acknowledges support from the Alexander von Humboldt Foundation. This work was performed at GeoSoilEnviroCARS (The University of Chicago, Sector 13), Advanced Photon Source (APS), Argonne National Laboratory. Geo-SoilEnviroCARS is supported by the National Science Foundation–Earth Sciences (EAR 1634415) and Department of Energy–GeoSciences (DE-FG02-94ER14466). This research used resources of the Advanced Photon Source, a U. S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Use of the COMPRES-GSECARS gas loading system was supported by COMPRES under NSF Cooperative Agreement EAR-1606856. Single-crystal diffraction experiments on beamline 13-BM-C were supported in part by the Partnership for Extreme Crystallography (PX^2) under NSF EAR-1661511.

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Received: 2021-11-06
Accepted: 2022-11-23
Published Online: 2023-10-04
Published in Print: 2023-10-26

© 2023 by Mineralogical Society of America

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https://doi.org/10.2138/am-2022-8380
Keywords for this article
Wadsleyite; mantle transition zone; hydrogen bond; water

Articles in the same Issue

  1. Heavy halogen compositions of lamprophyres derived from metasomatized lithospheric mantle beneath eastern North China Craton
  2. Compositional trends in Ba-, Ti-, and Cl-rich micas from metasomatized mantle rocks of the Gföhl Unit, Bohemian Massif, Austria
  3. Experimental determination of quartz solubility in H2O-CaCl2 solutions at 600–900 °C and 0.6–1.4 GPa
  4. The use of boron nitride to impose reduced redox conditions in experimental petrology
  5. Structures and transport properties of supercritical SiO2-H2O and NaAlSi3O8-H2O fluids
  6. Hydrologic regulation of clay-mineral transformations in a redoximorphic soil of subtropical monsoonal China
  7. Witness to strain: Subdomain boundary length and the apparent subdomain boundary density in large strained olivine grains
  8. Libyan Desert Glass: New evidence for an extremely high-pressure-temperature impact event from nanostructural study
  9. Crystal vs. melt compositional effects on the partitioning of the first-row transition and high field strength elements between clinopyroxene and silicic, alkaline, aluminous melts
  10. Microbially induced clay weathering: Smectite-to-kaolinite transformation
  11. Hydrous wadsleyite crystal structure up to 32 GPa
  12. Multiple fluid sources in skarn systems: Oxygen isotopic evidence from the Haobugao Zn-Fe-Sn deposit in the southern Great Xing’an Range, NE China
  13. Crocobelonite, CaFe23+(PO4)2O, a new oxyphosphate mineral, the product of pyrolytic oxidation of natural phosphides
  14. Tetrahedrite-(Ni), Cu6(Cu4Ni2)Sb4S13, the first nickel member of tetrahedrite group mineral from Luobusa chromite deposits, Tibet, China
  15. New Mineral Names: Heavy metal and minerals from China
  16. Book Review
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