Partitioning of Ru, Rh, Pd, Re, Ir and Pt between liquid metal and silicate at high pressures and high temperatures - Implications for the origin of highly siderophile element concentrations in the Earth’s mantle

The apparent overabundance of the highly siderophile elements (HSEs: Pt-group elements, Re and Au) in the mantles of Earth, Moon and Mars has not been satisfactorily explained. Although late accretion of a chondritic component seems to provide the most plausible explanation, metal–silicate equilibration in a magma ocean cannot be ruled out due to a lack of HSE partitioning data suitable for extrapolations to the relevant high pressure and high temperature conditions. We provide a new data set of partition coefficients simultaneously determined for Ru, Rh, Pd, Re, Ir and Pt over a range of 3.5–18 GPa and 2423–2773 K. In multianvil experiments, molten peridotite was equilibrated in MgO single crystal capsules with liquid Fe-alloy that contained bulk HSE concentrations of 53.2–98.9 wt% (XFe = 0.03–0.67) such that oxygen fugacities of IW − 1.5 to IW + 1.6 (i.e. logarithmic units relative to the iron-wüstite buffer) were established at run conditions. To analyse trace concentrations of the HSEs in the silicate melt with LA-ICP-MS, two silicate glass standards (1–119 ppm Ru, Rh, Pd, Re, Ir, Pt) were produced and evaluated for this study. Using an asymmetric regular solution model we have corrected experimental partition coefficients to account for the differences between HSE metal activities in the multicomponent Fe-alloys and infinite dilution. Based on the experimental data, the P and T dependence of the partition coefficients (D) was parameterized.The partition coefficients of all HSEs studied decrease with increasing pressure and to a greater extent with increasing temperature. Except for Pt, the decrease with pressure is stronger below ∼6 GPa and much weaker in the range 6–18 GPa. This change might result from pressure induced coordination changes in the silicate liquid. Extrapolating the D values over a large range of potential P–T conditions in a terrestrial magma ocean (peridotite liquidus at P ⩽ 60–80 GPa) we conclude that the P–T-induced decrease of D would not have been sufficient to explain HSE mantle abundances by metal–silicate equilibration at a common set of P–T-oxygen fugacity conditions. Therefore, the mantle concentrations of most HSEs cannot have been established during core formation. The comparatively less siderophile Pd might have been partly retained in the magma ocean if effective equilibration pressures reached 35–50 GPa. To a much smaller extent this could also apply to Pt and Rh providing that equilibration pressures reached ⩾60 GPa in the late stage of accretion. With most of the HSE partition coefficients at 60 GPa still differing by 0.5–3 orders of magnitude, metal–silicate equilibration alone cannot have produced the observed near-chondritic HSE abundances of the mantles of the Earth as well as of the Moon or Mars. Our results show that an additional process, such as the accretion of a late veneer composed of some type of chondritic material, was required. The results, therefore, support recent hybrid models, which propose that the observed HSE signatures are a combined result of both metal–silicate partitioning as well as an overprint by late accretion.