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Valence, spin states, and crystallographic sites of Fe in (Mg,Fe)SiO 3  perovskite were investigated using energy-domain  57 Fe-synchrotron Mössbauer spectroscopy and powder X-ray diffraction up to 86 GPa. The volumes of Fe 3+ -bearing perovskite in this study are slightly smaller than those of Mg endmember perovskite. Our Mössbauer data suggest that Fe 3+  prefers A sites coupled with Mg vacancies, which is consistent with previous data at ambient conditions. Fe 3+  in the A site remains in a high-spin state up to 86 GPa, and some fraction of the A site is occupied by Fe 2+  at pressures above 30 GPa. Fe 2+  in the A sites is also in a high-spin state up to 86 GPa. The coupled substitution from Mg 2+  to a highspin state of Fe 3+  and Mg 2+  vacancy would make the volume of perovskite smaller than that of Mg end-member perovskite. If the lower mantle is saturated in silica, perovskite containing high-spin Fe 3+  in A site has a higher density. Such silica oversaturated regions could sink by the density difference.

Chemistry and Mineralogy of Earth’s Mantle. The spin state of iron in Fe 3+ -bearing Mg-perovskite and its crystal chemistry at high pressure