Three water sites in upper mantle olivine and the role of titanium in the water weakening mechanism

[1] Infrared spectroscopy on synthetic olivines has established that there are at least four different mechanisms by which hydrogen is incorporated into the crystal structure. Two mechanisms occur in the system MgO-SiO2-H2O associated with silicon and magnesium vacancies, respectively. A third mechanism is associated with trivalent cation substitution, commonly Fe in natural olivine, while the fourth mechanism, which is the one most prevalent in natural olivines from the spinel-peridotite facies of the Earth’s upper mantle, is associated with Ti [Berry et al., 2005]. Here first principles calculations based on density functional theory are used to derive the structure and relative energies of the two defects in the pure MgO-SiO2-H2O system, and possible hydrogen-bearing and hydrogen-free point defects in Ti-doped forsterite. Calculated structures are used to compare the predicted orientation of the O-H bonds with the experimentally determined polarization. The energies are used to discuss how different regimes of chemical environment, temperature (T), pressure (P), and both water content and water fugacity ( fH2O), impact on which of the different hydroxyl substitution mechanisms are thermodynamically stable. We find that given the presence of Ti impurities, the most stable mechanism involves the formation of silicon vacancies containing two protons charge balanced by a Ti cation occupying an adjacent octahedral site. This mechanism leads to the water-mediated formation of silicon vacancies. As silicon is known to be the most slowly diffusing species in olivine, this provides a credible explanation of the observed water weakening effect in olivine.