The importance of sulfur for the behavior of highly-siderophile elements during Earth’s differentiation

Abstract

The highly siderophile elements (HSEs) are widely used as geochemical tracers for Earth’s accretion and core formation history. It is generally considered that core formation strongly depleted the Earth’s mantle in HSEs, which were subsequently replenished by a chondritic late veneer. However, open questions remain regarding the origin of suprachondritic Ru/Ir and Pd/Ir ratios that are thought to be characteristic for the primitive upper mantle. In most core-formation models that address the behavior of the HSEs, light elements such as S entering the core have not been taken into account and high P–T experimental data for S-bearing compositions are scarce. Here we present a comprehensive experimental study to investigate the effect of increasing S concentration in the metal on HSE metal–silicate partitioning at 2473K and 11GPa. We show that the HSEs become less siderophile with increasing S concentrations in the metal, rendering core-forming metal less efficient in removing the HSEs from the mantle if S is present. Furthermore, we investigated the FeS sulfide–silicate partitioning of the HSEs as a function of pressure (7–21GPa) and temperature (2373–2673K). The sulfide–silicate partition coefficient for Pt increases strongly with P, whereas those for Pd, Ru and Ir all decrease. The combined effect is such that above ∼20GPa Ru becomes less chalcophile than Pt, which is opposite to their behavior in the metal–silicate system where Ru is always more siderophile than Pt. The newly determined experimental results are used in a simple 2-stage core formation model that takes into account the effect of S on the behavior of the HSEs during core formation. Results of this model show that segregation of a sulfide liquid to the core from a mantle with substantial HSE concentrations plays a key role in reproducing Earth’s mantle HSE abundances. As Ru and Pd are less chalcophile than Pt and Ir at high P–T, some Ru and Pd remain in the mantle after sulfide segregation. Addition of the late veneer then raised the concentrations of all HSE to their current levels. Suprachondritic Ru/Ir and Pd/Ir ratios of the mantle can thus be explained by a combination of sulfide segregation together with the addition of a late veneer without the need to invoke unknown chondritic material.