Fe isotope fractionation caused by phase transition of FeS and implications for Fe isotope signatures of the mantle and core

Iron is the most important component of the cores of terrestrial planets, and iron sulfide (FeS) is one of the preferred candidates present in these cores. FeS is also ubiquitous in Earth’s crust, peridotites, and extraterrestrial samples. Knowledge of the phase stability of FeS and Fe isotope fractionation between FeS phases and mantle silicates is of great importance for understanding the interior of the Earth and terrestrial planets. In this study, first-principles methods were used to study the pressure-dependent phase stability of FeS and equilibrium Fe isotope fractionation in FeS, hexagonal close-packed (hcp) Fe, and mantle silicates at the pressure of Earth’s interior. FeS underwent four phase transitions at 0 K. The first is the transition from FeS I to FeS II at 2.8 GPa, the second from FeS II to FeS III at 7.5 GPa, the third from FeS III to FeS VI at 74.2 GPa, and the fourth from FeS VI to FeS VII at 122.2 GPa. Apart from the fact that the transition from FeS I to FeS II causes negligible Fe isotope fractionation, other phase transitions can cause measurable Fe isotope fractionation at corresponding pressures along the geotherm. Fe isotopes exhibit measurable fractionation between FeS and mantle silicates under mantle pressure–temperature conditions. Each phase was more enriched in heavy Fe with increasing depth in the pressure range of 7.5–90 GPa. If the silicate mantle is enriched in heavy Fe relative to the core or Fe has negligible isotope fractionation between them under the core-mantle boundary (CMB) conditions of the Earth, the Fe2+/(Fe2++Mg) in (Fe2+, Mg)SiO3 post-perovskite is less than 50%. At the temperature–pressure conditions of Earth’s core, equilibrium Fe isotope fractionation between hcp Fe and FeS VII can be neglected. FeS III is more likely to exist in the Martian core relative to FeS VI.