Oxygen Vacancy Substitution Linked to Ferric Iron in Bridgmanite at 27 GPa

Ferric iron can be incorporated into the crystal structure of bridgmanite by either oxygen vacancy substitution (MgFeO2.5 component) or charge-coupled substitution (FeFeO3 component) mechanisms. We investigated the concentrations of MgFeO2.5 and FeFeO3 in bridgmanite in the MgO-SiO2-Fe2O3 system at 27 GPa and 1700–2300 K using a multianvil apparatus. The FeFeO3 content increases from 1.6 to 7.6 mol.% and from 5.7 to 17.9 mol.% with and without coexistence of (Mg,Fe)O, respectively, with increasing temperature from 1700 to 2300 K. In contrast, the MgFeO2.5 content does not show clear temperature dependence, that is, ~2–3 and < 2 mol.% with and without the coexistence of (Mg,Fe)O, respectively. Therefore, the presence of (Mg,Fe)O enhances the oxygen vacancy substitution for Fe3+ in bridgmanite. It is predicted that Fe3+ is predominantly substituted following the oxygen vacancy mechanism in (Mg,Fe)O-saturated Al-free bridgmanite when Fe3+ is below ~0.025 pfu, whereas the charge-coupled mechanism occurs when Fe3+ > 0.025 pfu.