Abstract
We performed in situ infrared spectroscopic measurements of OH bands in a forsterite single crystal between −194 and 200 °C. The crystal was synthesized at 2 GPa from a cooling experiment performed between 1,400 and 1,275 °C at a rate of 1 °C per hour under high silica-activity conditions. Twenty-four individual bands were identified at low temperature. Three different groups can be distinguished: (1) Most of the OH bands between 3,300 and 3,650 cm−1 display a small frequency lowering (<4 cm−1) and a moderate broadening (<10 cm−1) as temperature is increased from −194 to 200 °C. The behaviour of these bands is compatible with weakly H-bonded OH groups associated with hydrogen substitution into silicon tetrahedra; (2) In the same frequency range, two bands at 3,617 and 3,566 cm−1 display a significantly anharmonic behaviour with stronger frequency lowering (42 and 27 cm−1 respectively) and broadening (~30 cm−1) with increasing temperature. It is tentatively proposed that the defects responsible for these OH bands correspond to H atoms in interstitial position; (3) In the frequency region between 3,300 and 3,000 cm−1, three broad bands are identified at 3,151, 3,178 and 3,217 cm−1, at −194 °C. They exhibit significant frequency increase (~20 cm−1) and broadening (~70 cm−1) with increasing temperature, indicating moderate H bonding. These bands are compatible with (2H)Mg defects. A survey of published spectra of forsterite samples synthesized above 5 GPa shows that about 75 % of the incorporated hydrogen belongs to type (1) OH bands associated with Si substitution and 25 % to the broad band at 3,566 cm−1 (type (2); 3,550 cm−1 at room temperature). The contribution of OH bands of type (3), associated to (2H)Mg defects, is negligible. Therefore, solubility of hydrogen in forsterite (and natural olivine compositions) cannot be described by a single solubility law, but by the combination of at least two laws, with different activation volumes and water fugacity exponents.
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Acknowledgments
This work was supported by the ANR grant (NT09-566853) provided to J. Ingrin. We thank Jed Mosenfelder and an anonymous reviewer for useful comments to the manuscript. We thank EU for the funding of Liu Jia during his stay in Lille through the LiSUM project from the Erasmus Mundus External Cooperation Window program.
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Ingrin, J., Liu, J., Depecker, C. et al. Low-temperature evolution of OH bands in synthetic forsterite, implication for the nature of H defects at high pressure. Phys Chem Minerals 40, 499–510 (2013). https://doi.org/10.1007/s00269-013-0587-3
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DOI: https://doi.org/10.1007/s00269-013-0587-3