D/H exchange in pure and Cr-doped enstatite: implications for hydrogen diffusivity

Abstract

The kinetics of hydrogen diffusion in enstatite was studied by hydrogen–deuterium exchange experiments in the range of 1–5,000 bar and 700–850°C using synthetic single crystals of pure and Cr-doped enstatites. The OH- and OD-content in the samples was quantified after each thermal treatment with Fourier transformed infrared spectroscopy. H–D-exchange rates were measured parallel to the three crystallographic axes. In addition, in order to visualize diffusion profiles, OH and OD were mapped for some samples, utilizing synchrotron IR micro-spectroscopy. Hydrogen self-diffusivities derived from D/H exchange experiments at one atmosphere are very similar to the chemical diffusivity of hydrogen in natural Fe-bearing orthopyroxene, which was reported previously (Stalder and Skogby 2003) to exhibit a small, but significant anisotropy (D[001] > D[100] > D[010]). Activation energies are estimated to be 211 (±31) kJ/mol for diffusion parallel [100] and 185 (±28) kJ/mol for diffusion parallel [010]. Lattice diffusion of hydrogen is decelerated by more than one order of magnitude when Cr is dissolved in enstatite. In comparison to the chemical composition, pressure seems to have only a minor influence on hydrogen diffusion. Compared to other minerals in the Earth’s upper mantle, enstatite exhibits the highest activation energy for hydrogen diffusion, suggesting faster diffusion than in other mafic minerals at mantle temperatures, but slower diffusion at crustal conditions. Thus under upper mantle conditions, physical properties that are expected to be influenced by hydrogen mobility, such as electrical conductivity, may in enstatite be more intensely affected by the presence of hydrogen than in other upper mantle minerals.