Diffusion of hydrogen in olivine grain boundaries and implications for the survival of water-rich zones in the Earth's mantle
Nominally anhydrous minerals (NAMs) of Earth's mantle can contain hydrogen as atomic impurity in their crystal structures. This hydrogen substantially modifies many physical properties of Earth's mantle rocks. Also, the Earth's deep interior is made of rocks where minerals are separated by nanometer-scale interfaces call grain boundaries and interphase boundaries. These grain boundaries should carefully be considered as a potential hydrogen reservoir as well. I report here an experimental investigation of hydrogen diffusion through grain boundaries in olivine polycrystalline aggregates. Hot-press and diffusion experiments were performed using a gas-medium high-pressure vessel at a confining pressure of 300 MPa, over a temperature range of 1000-1200 °C. The diffusion assembly consisted of a dense polycrystalline cylinder of natural olivine from San Carlos (Arizona) mixed with olivine singles crystals of millimeter size. This mixture was couple with a talc cylinder. Ni capsule were used to buffer the oxygen fugacity at Ni-NiO level. Experiment durations varied from 3 min to 4 h. The presence of hydrogen in the sample was quantified using Fourier transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the length of polycrystalline solid affected by the diffusion of hydrogen. The absence or presence of hydrogen was recorded by the large olivines behaving here as “hydrogen sensor”, which are implanted in the aggregate. The results indicate that effective hydrogen diffusivity which includes grain boundaries effect in olivine aggregate is barely one order of magnitude faster than hydrogen diffusion in an olivine single crystal with a diffusivity ∼ 8.5 × 10- 10 m2 s- 1 at 1000 °C and only twice faster ∼ 2.1 × 10- 9 m2 s- 1 at 1200 °C. Calculations of the diffusion data in relation to the Arrhenius Law, yield an activation energy of ∼ 70 ± 10 kJ mol- 1. From these effective diffusivities and combined with published diffusion data for olivine single crystals, hydrogen diffusion in grain boundaries is extracted and yield diffusivities almost three order of magnitude faster (∼ 5 × 10- 6 m2 s- 1 at 1200 °C) than in an olivine single crystal at the equivalent high temperature. On geological scales and for coarse-grain rocks, hydrogen diffusivity in grain boundaries is not fast enough to compete with lattice diffusion. The relative large grain size of mantle rocks will ensure a very limited hydrogen transport by effective diffusion, and a good conservation of water-rich zones in the Earth's mantle.