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

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 textl textmol_textH2textO^-1 textcm^-2text{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 textl textmol_textH2textO^-1 textcm^-2text{l},text{mol}_{{text{H}_2}text{O}}^{-1},text{cm}^{-2}; stishovite ε = 485,000 ± 109,000 textl textmol_textH2textO^-1 textcm^-2text{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.