Origin of Fe3+ in Fe-containing, Al-free mantle silicate perovskite

Abstract

We have studied the ferrous (Fe2+) and ferric (Fe3+) iron concentrations in Al-free Fe containing Mg-silicate perovskite (Mg-Pv) at pressure (P), temperature (T), and oxygen fugacity (fO2) conditions related to the lower mantle using a thermodynamic model based on ab initio calculations. We consider the oxidation reaction and the charge disproportionation reaction, both of which can produce Fe3+ in Mg-Pv. The model shows qualitatively good agreement with available experimental data on Fe3+/ΣFe (ΣFe = total Fe in system), spin transitions, and equations of state. We predict that under lower-mantle conditions Fe3+/ΣFe determined by the charge disproportionation is estimated to be 0.01–0.07 in Al-free Mg-Pv, suggesting that low Al Mg-Pv in the uppermost pyrolitic mantle (where majoritic garnet contains most of the Al) and in the harzburgitic heterogeneities throughout the lower mantle contains very little Fe3+. We find that the volume reduction by the spin transition of the B-site Fe3+ leads to a minimum Fe3+/ΣFe in Mg-Pv at mid-mantle pressures. The model shows that configurational entropy is a key driving force to create Fe3+ and therefore Fe3+ content is highly temperature sensitive. The temperature sensitivity may lead to a maximum Fe3+/ΣFe in Mg-Pv in warm regions at the core–mantle boundary region, such as Large Low Shear Velocity Provinces (LLSVPs), potentially altering the physical (e.g., bulk modulus) and transport (e.g., thermal and electrical conductivities) properties of the heterogeneities.