Stable intermediate-spin ferrous iron in lower-mantle perovskite

The lower mantle is dominated by a magnesium- and iron-bearing mineral with the perovskite structure. Iron has the ability to adopt different electronic configurations, and transitions in its spin state in the lower mantle can significantly influence mantle properties and dynamics. However, previous studies aimed at understanding these transitions have provided conflicting results(1-4). Here we report the results of high-pressure (up to 110 GPa) and high-temperature (up to 1,000 K) experiments aimed at understanding spin transitions of iron in perovskite at lower-mantle conditions. Our Mossbauer and nuclear forward scattering data for two lower-mantle perovskite compositions demonstrate that the transition of ferrous iron from the high-spin to the intermediate-spin state occurs at approximately 30 GPa, and that high temperatures favour the stability of the intermediate-spin state. We therefore infer that ferrous iron adopts the intermediate-spin state throughout the bulk of the lower mantle. Our X-ray data show significant anisotropic compression of lower-mantle perovskite containing intermediate-spin ferrous iron, which correlates strongly with the spin transition. We predict spin-state heterogeneities in the uppermost part of the lower mantle associated with sinking slabs and regions of upwelling. These may affect local properties, including thermal and electrical conductivity, deformation (viscosity) and chemical behaviour, and thereby affect mantle dynamics.