Hydrogen in nominally anhydrous silicate minerals Quantification methods, incorporation mechanisms and geological applications

Sammanfattning: The aim of this thesis is to increase our knowledge and understanding of trace water concentrations in nominally anhydrous minerals (NAMs). Special focus is put on the de- and rehydration mechanisms of clinopyroxene crystals in volcanic systems, how these minerals can be used to investigate the volatile content of mantle rocks and melts on both Earth and other planetary bodies (e.g., Mars). Various analytical techniques for water concentration analysis were evaluated.The first part of the thesis focusses on rehydration experiments in hydrogen gas at 1 atm and under hydrothermal pressures from 0.5 to 3 kbar on volcanic clinopyroxene crystals in order to test hydrogen incorporation and loss from crystals and how their initial water content at crystallization prior to dehydration may be restored. The results show that extensive dehydration may occur during magma ascent and degassing but may be hindered by fast ascent rates with limited volatile loss. De- and rehydration processes are governed by the redox-reaction OH- + Fe2+ ↔ O2- + Fe3+ + ½ H2. Performing rehydration experiments at different pressures can restore the water contents of clinopyroxene at various levels in the volcanic systems. Subsequently water contents of magmas and mantle sources can be deduced based on crystal/melt partition coefficients. This thesis provides examples from the Canary Islands, Merapi volcano in Indonesia and the famous Nakhla meteorite. Using NAMs as a proxy for magmatic and mantle water contents may provide a very good method especially for planetary science where sample material is limited.The thesis’ second part focusses on analytical methods to measure the concentration of water in NAMs. Specifically the application of Raman spectroscopy and proton-proton scattering are tested. The hydrated mineral zoisite is thoroughly analyzed in order to be used as an external standard material. Polarized single crystal spectra helped to determine the orientation of the OH-dipole in zoisite. Further, Transmission Raman spectroscopy and a new method for the preparation of very thin samples for proton-proton scattering were developed and tested. The results provide new possibilities for the concentration analysis of water in NAMs such as three dimensional distribution and high spatial resolution.