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Ab initio study of water speciation in forsterite: Importance of the entropic effect

  • Tian Qin , Renata M. Wentzcovitch EMAIL logo , Koichiro Umemoto , Marc M. Hirschmann and David L. Kohlstedt
Published/Copyright: April 30, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 5

Abstract

In this ab initio study, we expand previous investigations of charge-balanced hydrous Mg ((2H)MgX) and Si ((4H)SiX) defects in forsterite, the Mg end-member of olivine, to address the relative stability of these two defects. First, we systematically search for (2H)MgX configurations to find possible defect states; second, we include the contribution of vibrational energy and defect configurational entropy in the calculation of formation energies of both defects; third, we address the effect of pressure and temperature simultaneously on their relative stability. Based on these considerations, we demonstrate that hydrous Mg defects ((2H)MgX) can be stabilized with respect to hydrous Si defects ((4H)SiX) at relevant mantle conditions and that configurational entropy and vibrational free energy play key roles in this stabilization. Our results reveal that water speciation in olivine is influenced by temperature and pressure. As mantle physical and chemical properties may be affected by the speciation of water in olivine, application of experimental results to the mantle should account for the temperature- and pressure-dependent changes in water speciation.

Keywords: Hydrous defects; olivine; nominally anhydrous minerals; ab initio calculations; thermodynamics; Water in Nominally Hydrous and Anhydrous Minerals

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

Acknowledgments

This work was supported by NSF/EAR grant 1161023. Computations were performed at the Minnesota Supercomputing Institute and at the Texas Advanced Computing Center (Stampede2) under an XSEDE allocation. We thank the Editor, Roland Stalder, and two anonymous reviewers for their constrictive comments that helped improve the clarity of the manuscript.

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Received: 2017-7-31
Accepted: 2018-1-22
Published Online: 2018-4-30
Published in Print: 2018-5-25

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2018-6262
Keywords for this article
Hydrous defects; olivine; nominally anhydrous minerals; ab initio calculations; thermodynamics; Water in Nominally Hydrous and Anhydrous Minerals

Articles in the same Issue

  1. Review
  2. Biosilica as a source for inspiration in biological materials science
  4. Ab initio study of water speciation in forsterite: Importance of the entropic effect
  6. Surface-modified phillipsite-rich tuff from the Campania region (southern Italy) as a promising drug carrier: An ibuprofen sodium salt trial
  8. Structure of low-order hemimorphite produced in a Zn-rich environment by cyanobacterium Leptolingbya frigida
  10. Formation of dolomite catalyzed by sulfate-driven anaerobic oxidation of methane: Mineralogical and geochemical evidence from the northern South China Sea
  12. Anisotropic growth of olivine during crystallization in basalts from Hawaii: Implications for olivine fabric development
  14. Melting experiments on Fe–Si–S alloys to core pressures: Silicon in the core?
  16. High-pressure phase behavior and equations of state of ThO2 polymorphs
  18. Mafic inputs into the rhyolitic magmatic system of the 2.08 Ma Huckleberry Ridge eruption, Yellowstone
  20. Toward the wider application of 29Si NMR spectroscopy to paramagnetic transition metal silicate minerals and glasses: Fe(II), Co(II), and Ni(II) silicates
  22. Equations of state and phase boundary for stishovite and CaCl2-type SiO2
  24. Insight on gem opal formation in volcanic ash deposits from a supereruption: A case study through oxygen and hydrogen isotopic composition of opals from Lake Tecopa, California, U.S.A
  26. Revisiting the crystal structure of dickite: X-ray diffraction, solid-state NMR, and DFT calculations study
  28. Temperature and pressure effects on the partitioning of V and Sc between clinopyroxene and silicate melt: Implications for mantle oxygen fugacity
  29. Letter
  30. Why natural monazite never becomes amorphous: Experimental evidence for alpha self-healing
  32. New Mineral Names
  33. Book Review
  34. Book Review: Glaciovolcanism on Earth and Mars: Products, Processes and Paleoenvironmental Significance
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