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Hydrogen diffusion in spinel grain boundaries and consequences for chemical homogenization in hydrous peridotite

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Abstract

Hydrogen can be stored in the structure of nominally anhydrous minerals as point defects, and these impurities substantially modify many physical properties of Earth’s mantle minerals. However, mantle rocks are composed of mineral grains separated by grain boundaries and interphase grains boundaries. Therefore, as a potential hydrogen reservoir, grain boundaries should be given proper attention. Here, I report an experimental investigation into hydrogen diffusion through grain boundaries in polycrystalline aggregates. Sintering and diffusion experiments were performed using a gas-medium high-pressure vessel at under pressure of 300 MPa and over a temperature range of 900–1,250°C. The diffusion assembly consisted of a polycrystalline cylinder of aluminous spinel + olivine crystals with a talc cylinder as the main hydrogen source. A Ni capsule was used to buffer the oxygen fugacity at Ni–NiO. Experimental durations varied from 5 min to 5 h. The presence of hydrogen in the crystals was measured by Fourier-transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the characteristic distance. The absence or presence of hydrogen recorded by the ‘hydrogen sensor’ olivines embedded in the aggregate allows the estimation of bounds on this characteristic distance. Results presented here suggest that hydrogen effective diffusion coefficients are only one order of magnitude faster (~10−9 m2s−1 at 1,000°C) than in an olivine single crystal along the [100] axis. Resulting diffusion coefficients for hydrogen in grain boundary are four orders of magnitude faster than in a single crystal, but this diffusivity is not fast enough to affect hydrogen mobility in mantle rocks with grain sizes greater than ~1 mm. Thus, very limited chemical homogenization would occur using grain boundaries diffusion in mantle hydrous peridotite for incompatible and volatile element, such as hydrogen.

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Acknowledgments

SD is thankful to Takehiko Hiraga and Tony Withers for numerous and enthusiastic discussions at the very early stage of the project, as well as to Bruce Watson and two reviewers for helpful comments. Christophe Nevado and Doriane Delmas are thanked for providing high-quality thin sections. Joel Oustry is thanked for his precious assistance and patience in the mechanical workshop. Electron microprobe analyses were carried out with the help of Claude Merlet and Bernard Boyer at the Electron Microprobe Lab ‘SUD’, and FTIR analyses were performed with the help of David Maurin at the Lab. Colloids, Verre et Nanomateriaux, both facilities located at Université Montpellier 2, France. CNRS supported this study trough INSU and its SEDIT 2008 program.

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  1. Geosciences Montpellier UMR 5243, Université Montpellier 2 and CNRS, Place Eugène Bataillon, 34095, Montpellier Cedex 5, France

    Sylvie Demouchy

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Correspondence to Sylvie Demouchy.

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Communicated by T. L. Grove.

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Demouchy, S. Hydrogen diffusion in spinel grain boundaries and consequences for chemical homogenization in hydrous peridotite. Contrib Mineral Petrol 160, 887–898 (2010). https://doi.org/10.1007/s00410-010-0512-4

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