Stability of Fe2S and Fe12S7 to 125 GPa; implications for S-rich planetary cores

The Fe-FeS phase relations were explored in the 22 – 25 wt. % S compositional range using single crystal X-ray diffraction in a laser heated diamond anvil cell. At pressures up to 125 GPa and at high temperatures, Fe 2 S and Fe 12 S 7 were determined to co-crystallise. The novel Fe 12 S 7 compound adopts the Co 12 P 7 structure and Fe 2 S assumes the Fe 2 P-type structure. Applying these results to an Fe-FeS binary phase diagram exposes a complex series of FeS phase assemblages in the 16 – 25 wt. % S range, whereby minor changes in S content significantly affect the crystallisation sequence of Fe-S rich planetary cores. For core compositions S-rich of the Fe 2 S-Fe 12 S 7 eutectic, the small density difference between solid Fe 12 S 7 and Fe 2 S is likely to result in the formation of a core slush rather than a gravitationally stable inner core. Crystallisation of denser Fe 2 S at eutectic conditions could then result in gravitational settling of an Fe 2 S-rich inner core over time. As the Fe 2 P-type Fe 2 S has previously been identified forming at high temperatures to pressures as low as 22 GPa, the core crystallisation regimes determined here also elucidate that the Martian core sulfur composition must lie on the S-rich side of the Fe-Fe 3 S eutectic or even the S-rich side of the Fe 3 S-Fe 2 S eutectic to maintain a fully molten core.