Partitioning of highly siderophile elements between monosulfide solid solution and sulfide melt at high pressures

Base metal sulfides (Fe–Ni–Cu–S) are ubiquitous phases in mantle and subduction-related lithologies. Sulfides in the mantle often melt incongruently, which leads to the production of a Cu–Ni-rich sulfide melt and a solid residue called monosulfide solid solution (mss). Even though peridotite-hosted sulfides, which tend to be more Ni-rich, are likely completely molten at mantle potential temperatures, the same is not true for eclogite-hosted Ni-poor, Fe-rich sulfides. Because of this, solid crystalline mss may persist at higher pressures and equilibrate with co-existing sulfide melt along colder geotherms, like those associated with subduction zones. Because highly siderophile elements (HSE—Pt, Pd, Rh, Ru, Os, Ir, and Re) are known to fractionate as a result of mss/sulfide-melt equilibrium, the persistence of an mss/sulfide-melt assemblage to higher pressures may lead to the fractionation of these elements during the subduction process. In this contribution, we carried out an experimental investigation of the partitioning behavior of the HSE, as well as Cu and Ni, between mss and sulfide melt over a pressure and temperature range relevant to equilibration between Earth’s surface and transition zone depths (0.1 MPa to 14 GPa; 930–1530 \(^{\circ }\) ${}^{\circ }$ C), and variable Ni contents in sulfide. Results show that at higher pressures, the HSE are considerably less fractionated as a result of mss and sulfide melt equilibrium compared to lower pressure conditions. This is exemplified by a lowering of the \(D_{i}^\mathrm{mss/melt}\) $D_i^{\mathrm{mss}/\mathrm{melt}}$ for the more compatible HSE (Ru, Os, Ir, Rh and Re) from around 10 at 0.1 MPa to just above or below unity at 14 GPa. Moreover, the higher the Ni content of the bulk sulfide assemblage, the larger the degree of change in the magnitude of HSE fractionation seen over the pressure range studied. The exchange coefficient ( \(K_D^{\textrm{Ru}-\textrm{Pt}}\) $K_D^{\text{Ru}-\text{Pt}}$ ) between highly compatible HSE (Ru) and less compatible Pt illustrates a notable contrast. In the Ni-poor composition (E1), \(K_D^{\textrm{Ru}-\textrm{Pt}}\) $K_D^{\text{Ru}-\text{Pt}}$ changes from 27 at 0.1 MPa to 6 at 14 GPa. In contrast, the Ni-rich composition exhibits a broader range, with \(K_D^{\textrm{Ru}-\textrm{Pt}}\) $K_D^{\text{Ru}-\text{Pt}}$ ranging from 150 to 17 across the same pressure interval. Our results highlight key differences between experimental data obtained at lower and higher pressure, and how composition, namely the Ni content of sulfide, affects HSE partitioning behavior.