Prediction of siderophile element metal-silicate partition coefficients to 20 GPa and 2800°C: the effects of pressure, temperature, oxygen fugacity, and silicate and metallic melt compositions

We report new metal-silicate partition coefficients for Ni, Co and P at 7.0 GPa (1650-1750°C), and Ni, Co, Mo, W and P at 0.8, 1.0 and 1.5 GPa (1300-1400°C). Guided by thermodynamics, all available metal-silicate partition coefficients, D( i), where i is Ni, Co, P, Mo and W, are regressed against 1/T, P/T, ln f(O ₂), ln(1 - X_s) ( X_S is mole fraction of S in metallic liquid) and nbo/t (non-bridging oxygen/tetrahedral cation ratio, a silicate melt compositional-structural parameter) to derive equations of the following form: ln D(i) = a ln f( O₂) + ( b/T) + ( cP/T) + d( nbo/t) + e ln(1 - X _S) + f . Expressions for solid metal-liquid silicate and liquid metal-liquid silicate partition coefficients are derived for S-free and S-bearing systems. We investigate whether Earth's upper-mantle siderophile element abundances can be reconciled with simple metal-silicate equilibrium. Sulfur-free metallic compositions do not allow a good fit. However, Ni, Co, Mo, W and P abundances in the upper mantle are consistent with simple metal-silicate equilibrium at mantle pressures and temperatures (27 GPa, 2200 K, ΔIW(iron-wüstite) = -0.15, nbo/t = 2.7 ; X _S = 0.15). Although these conditions are near the anhydrous peridotite solidus, they are well above the hydrous solidus and probably closer to the liquidus. A hydrous magma ocean and early mantle are consistent with predicted planetary accretion models. These results suggest that siderophile element abundances in Earth's upper mantle were established by liquid metal-liquid silicate equilibrium near the upper-mantle-lower-mantle boundary.