Variation of oxygen oxidation state at the base of Earth's lower mantle.

Iron and oxygen interactions control oxygen fugacity and thus most of the global geochemical processes (1, 2). Extreme pressures and temperatures (PT) characteristic for Earth's deep interior are known to drastically affect the chemistry of these elements and to promote the formation of oxides unstable at ambient conditions, such as the homologous series of nFeO*mFe2O3 and FeO2 (3-6). To elucidate the chemistry of oxygen and the crystal chemistry of iron-oxygen compounds in detail, we use in situ single-crystal X-ray diffraction and Mossbauer spectroscopy in diamond anvil cells along with 'density-functional theory plus dynamical mean-field theory' (DFT+DMFT) calculations. Here we report that at extreme P-T conditions the oxidation state of oxygen in FeO2 is equal to 1.5-, and in major phases that constitute the lower mantle and the core-mantle boundary (CMB), the value deviates from 2-. The crystal chemistries of Fe,Al-bearing silicate perovskite (bridgmanite, Brg) and post-perovskite (PPv) considerably change: iron enters an octahedral structural position, the amount of iron in pure iron silicate perovskite and post-perovskite can be larger than the amount of silicon, and the quantity of iron in co-existing Brg and PPv may be significantly different. The formation of an oxygen reservoir in Earth's lower mantle (3, 7) is one of many consequences that can influence the dynamics and chemistry of the CMB, and alteration of the oxidation state of oxygen at high pressure as shown in this work can considerably contribute to this process.