Structure and titanium distribution of feiite characterized using synchrotron single-crystal X-ray diffraction techniques

A solid solution of the mineral feiite (Fe3TiO5) was recently discovered in a shock-induced melt pocket of the Shergotty martian shergottite. It is particularly interesting for its potential as an indicator of pressure-temperature (P-T) and oxygen fugacity in martian crustal and mantle material. To date, complete crystallographic analysis of feiite has not been conducted, as the mineral was previously analyzed by electron backscatter diffraction on micrometer-size grains (Ma et al. 2021). Here we report a convergent crystal-structure model for feiite based on synchrotron single-crystal X-ray diffraction data collected on three grains of feiite synthesized at 12 GPa and 1200 degrees C. Feiite adopts the CaFe3O5 structure type (Cmcm, Z = 4), which is composed of two octahedral M1 and M2 sites and one trigonal prismatic M3 site (M = metal) in a ratio of 1:2:1. The three feiite grains with composition Ti0.46-0.60Fe3.54-3.40O5 were best modeled by substituting Ti4+ into only the octahedral M2 site, accounting for 30% of this site. Comparisons of the measured average bond lengths in the coordination polyhedra with the optimized Ti4+-O, Fe2+-O, and Fe3+-O bond lengths suggest that ferrous iron occupies the trigonal M3 site, while iron is mixed valence in the octahedral M1 and M2 sites. The Ti4+ and Fe3+ content constrained by our crystal-chemical analyses suggests that at least similar to 30% of the available iron must be ferric (i.e., Fe3+/Fe-total = 0.3) for the sample synthesized at 12 GPa and 1200 degrees C and higher P-T conditions may be needed to form the end-member feiite (Fe32+TiO5)