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IR calibrations for water determination in olivine, r-GeO2, and SiO2 polymorphs

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Abstract

Mineral-specific IR absorption coefficients were calculated for natural and synthetic olivine, SiO2 polymorphs, and GeO2 with specific isolated OH point defects using quantitative data from independent techniques such as proton–proton scattering, confocal Raman spectroscopy, and secondary ion mass spectrometry. Moreover, we present a routine to detect OH traces in anisotropic minerals using Raman spectroscopy combined with the “Comparator Technique”. In case of olivine and the SiO2 system, it turns out that the magnitude of ε for one structure is independent of the type of OH point defect and therewith the peak position (quartz ε = 89,000 ± 15,000 \(\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}\)), but it varies as a function of structure (coesite ε = 214,000 ± 14,000 \(\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}\); stishovite ε = 485,000 ± 109,000 \(\text{l}\,\text{mol}_{{\text{H}_2}\text{O}}^{-1}\,\text{cm}^{-2}\)). Evaluation of data from this study confirms that not using mineral-specific IR calibrations for the OH quantification in nominally anhydrous minerals leads to inaccurate estimations of OH concentrations, which constitute the basis for modeling the Earth’s deep water cycle.

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Notes

  1. Parallelepipeds of olivine were additionally turned by 90°, and thereafter analyzed as per the defined procedure.

  2. Hydrogen interstitials; unambiguous defect association is uncertain to date (cf. Kronenberg 1994).

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Acknowledgments

The authors wish to thank B. Wunder, G. Berger, M. Kreplin, R. Schulz, H. Steigert, U. Schade and M. Schmidt for help with the experiments, sample preparation, X-ray diffraction, and synchrotron IR measurements. C. Schmidt and W. Heinrich are thanked for helpful comments and discussions. We are grateful to W. van Westrenen, who kindly provided sample WIM04. This project was supported by the Maier-Leibnitz-Laboratorium of LMU and TU München. Reviews of M. Rieder, M. M. Hirschmann and E. Libowitzky are greatly appreciated. Finally, thanks to C. R. Bina for help with the English.

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  1. Sylvia-Monique Thomas

    Present address: Department of Earth and Planetary Sciences, Northwestern University, Evanston, IL, 60208, USA

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  1. Deutsches GeoForschungsZentrum GFZ, Section 3.3 Chemistry and Physics of Earth Materials, Telegrafenberg, 14473, Potsdam, Germany

    Sylvia-Monique Thomas, Monika Koch-Müller, Dieter Rhede, Rainer Thomas & Richard Wirth

  2. Universität der Bundeswehr München, LRT 2, 85577, Neubiberg, Germany

    Patrick Reichart

  3. Institute of Geochemistry, Mineralogy and Ore Formation, National Academy of Science of Ukraine, Palladin Ave. 34, 03680, 22142, Kiev, Ukraine

    Stanislav Matsyuk

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Thomas, SM., Koch-Müller, M., Reichart, P. et al. IR calibrations for water determination in olivine, r-GeO2, and SiO2 polymorphs. Phys Chem Minerals 36, 489–509 (2009). https://doi.org/10.1007/s00269-009-0295-1

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