An experimental study of fe–ni exchange between sulfide melt and olivine at upper mantle conditions: Implications for mantle sulfide compositions and phase equilibria

Abstract

The behavior of nickel in the Earth’s mantle is controlled by sulfide melt–olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity condi-tions. In this study, we constrain the Fe–Ni composition of molten sulfide in the Earth’s upper mantle via sulfide melt–olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt [Formula Presented] (atomic ratio) ranging from 0 to 0.94. Ni Ni+Fe To verify the approach to equilibrium and to explore the effect of fO2 on Fe–Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31–46, 1995), “zero time” experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite–magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ − 1 or more oxidized (suite 4). For the reduced (suites 1–3) experiments, Fe–Ni distribution coefficients [Formula Presented] are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of KD (21.1–25.2). Compared to previous determinations at 100 kPa, values of KD from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem attributable to differences in temperature and pressure between experimental studies. It may be related in part to the effects of metal/sulfur ratio in sulfide melt. Application of these results to the composition of molten sulfide in peri-dotite indicates that compositions are intermediate in composition (Xsulfide Ni ~ 0.4–0.6) in the shallow mantle at 50 km, becomes more Ni rich with depth as the O content of the melt diminishes, reaching a maximum (0.6–0.7) at depths near 80–120 km, and then becomes more Fe rich in the deeper mantle where conditions are more reduced, approaching (Xsulfide Ni ~ 0.28) > 140 km depth. Because Ni-rich sulfide in the shallow upper mantle melts at lower temperature than more Fe-rich compositions, mantle sulfide is likely molten in much of the deep continental lithosphere, including regions of diamond formation.