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Experimental constraints on hydrogen diffusion in garnet

  • Julien Reynes
  • Michael Jollands
  • Jörg Hermann
  • Trevor Ireland
Original Paper

Abstract

The incorporation mechanisms and diffusional loss of hydrogen in garnet have been experimentally investigated. A suite of gem-quality hydrous spessartine- and grossular-rich garnets were analysed by Fourier transform infrared spectroscopy (FTIR) and by ion microprobe (SHRIMP-SI) to determine the calibration coefficients for quantification of FTIR data. The excellent agreement between measured absorption and OH/O indicates that the same molar extinction coefficient can be used for spessartine and grossular. The coefficient of 14400 l mol− 1 cm− 2 proposed by Maldener et al. (Phys Chem Miner 30:337–344, 2003) seems the most appropriate for both minerals. A grossular with 6.4% andradite and 1.6% almandine containing 834 ppm H2O, and an almost pure spessartine with 282 ppm H2O, were selected for diffusion experiments. 1.5-mm cubes of garnets were heated between 12 h and 10 days at 1 atm under various temperature (750–1050 °C) and oxygen fugacity (\({f_{{{\text{O}}_2}}}\)) conditions, (ΔQFM + 15.2 to − 3.0). Diffusion profiles were acquired from sections through the cubes using FTIR, with a deconvolution algorithm developed to assess peak-specific behaviour. Different families of peaks have been identified based on their diffusive behaviour, representing hydrogen incorporated in different H-bearing defects. A dominant, fast, strongly \({f_{{{\text{O}}_2}}}\)-dependent oxidation-related diffusion mechanism is proposed \(\left( {\{ {{\text{M}}^{2+}}+{{\text{H}}^+}\} +\frac{1}{4}{{\text{O}}_2}={{\text{M}}^{3+}}+\frac{1}{2}{{\text{H}}_2}{\text{O}}} \right)\) (M=Fe, Mn) with a relatively low activation energy (158 ± 19 kJ mol− 1). This diffusion mechanism is likely restricted by availability of ferrous iron in grossular. At low oxygen fugacity, this diffusion mechanism is shut off and the diffusivity decreased by more than three orders of magnitude. A second, slower hydrogen diffusion mechanism has been observed in minor bands, where charge balance might be maintained by diffusion of cation vacancies, with much higher activation energy (≈ 200–270 kJ mol− 1). Spessartine shows clear differences in peak retentivity suggesting that up to four different H sites might exist. This opens exciting opportunities to use hydrogen diffusion in garnet as speedometer. However, it is essential to constrain the main diffusion mechanisms and the oxygen fugacity in the rocks investigated to obtain timescales for metamorphic or igneous processes.

Keywords

Hydrogen diffusion FTIR Water in garnet Grossular Spessartine Deconvolution Water quantification 

Notes

Acknowledgements

D. Scott and D. Clark are thanked for help with experiments and P. Holden and J. Avila for assistance at the SHRIMP. We are grateful to Y. Zhang and an anonymous reviewer for their careful reviews, which helped us to improve our manuscript, and H. Keppler for editorial handling. This work was financially supported by the Australian Research Council (DP140100622) and the Swiss National Science Foundation (200021_169062).

Supplementary material

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Supplementary material 2 (PDF 14506 KB)
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Supplementary material 3 (XLSX 15 KB)

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Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institut für GeologieUniversität BernBernSwitzerland
  2. 2.Research School of Earth SciencesThe Australian National UniversityActonAustralia
  3. 3.Institute of Earth SciencesUniversity of LausanneLausanneSwitzerland

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