Incorporation mechanism of Fe and Al into bridgmanite in a subducting mid-ocean ridge basalt and its crystal chemistry

The compositional difference between subducting slabs and their surrounding lower-mantle can yield the difference in incorporation mechanism of Fe and Al into bridgmanite between both regions, which should cause heterogeneity in physical properties and rheology of the lower mantle. However, the precise cation-distribution has not been examined in bridgmanites with Fe- and Al-contents expected in a mid-ocean ridge basalt component of subducting slabs. Here we report on Mg_0.662Fe_0.338Si_0.662Al_0.338O₃ bridgmanite single-crystal characterized by a combination of single-crystal X-ray diffraction, synchrotron ⁵⁷Fe-Mössbauer spectroscopy and electron probe microanalysis. We find that the charge-coupled substitution ^AMg²⁺ + ^BSi⁴⁺ ↔ ^AFe³⁺(high-spin) + ^BAl³⁺ is predominant in the incorporation of Fe and Al into the practically eightfold-coordinated A-site and the sixfold-coordinated B-site in bridgmanite structure. The incorporation of both cations via this substitution enhances the structural distortion due to the tilting of BO₆ octahedra, yielding the unusual expansion of mean <A–O> bond-length due to flexibility of A–O bonds for the structural distortion, in contrast to mean <B–O> bond-length depending reasonably on the ionic radius effect. Moreover, we imply the phase-transition behavior and the elasticity of bridgmanite in slabs subducting into deeper parts of the lower mantle, in terms of the relative compressibility of AO₁₂ (practically AO₈) and BO₆ polyhedra.