Effects of temperature, silicate melt composition, and oxygen fugacity on the partitioning of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide phases and silicate melt

Abstract

In order to assess the role of sulfide in controlling the ore metal budgets and fractionation during magmatic genesis and differentiation, the partition coefficients (D) of V, Mn, Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between sulfide liquid (SL), monosulfide solid solution (MSS), and basaltic to rhyolitic melts (SM) were determined at 900–1200°C, 0.5–1.5GPa, and oxygen fugacity (fO2) ranging from ∼FMQ−2 to FMQ+3, in a piston-cylinder apparatus. The DSL/SM values range from 0.4 to 2 for V, 0.5 to 3 for Mn, 80 to 580 for Co, 2300 to 18,000 for Ni, 800 to 4600 for Cu, 1 to 11 for Zn, 20 to 180 for As, 4 to 230 for Mo, 450 to 1600 for Ag, 5 to 24 for Sn, 10 to 80 for Sb, 0.03 to 0.16 for W, 2000 to 29,000 for Au, 24 to 170 for Pb, and 830 to 11,000 for Bi; whereas the DMSS/SM values range from 0.04 to 10 for V, 0.5 to 10 for Mn, 70 to 2500 for Co, 650 to 18,000 for Ni, 280 to 42,000 for Cu, 0.1 to 80 for Zn, 0.2 to 30 for As, 1 to 820 for Mo, 20 to 500 for Ag, 0.2 to 220 for Sn, 0.1 to 40 for Sb, 0.01 to 24 for W, 10 to 2000 for Au, 0.03 to 6 for Pb, and 1 to 350 for Bi. Both DMSS/SM and DSL/SM values generally increase with decreasing temperature or decreasing FeOtot content in silicate melt, except for Mo, DMSS/SM and DSL/SM of which show a clear decrease with decreasing temperature. At given temperature and FeOtot content, high oxygen fugacity appears to lead to a significant decrease in DMSS/SM of Au, Bi, Mo, and potentially As. The partitioning data obtained experimentally in this study and previous studies were fitted to an empirical equation that expresses the DMSS/SM and/or DSL/SM of a given element as a function of temperature, oxygen fugacity, and FeOtot content of the silicate melt:log(DSL/SMorDMSS/SM=d+a·10,000/T+b·(ΔFMQ)+c·log(FeOmelt)in which T is temperature in K, FeOmelt denotes wt% FeOtot in silicate melt, and ΔFMQ denotes log fO2 relative to the fayalite–magnetite–quartz (FMQ) oxygen buffer. The application of this equation to natural samples of basaltic to rhyolitic composition yields DMSS/SM and DSL/SM values that agree with the measured values within ±0.5 log units for most of the elements, indicating the validity of the application of this equation to natural systems. Our partitioning data imply that sulfide liquid saturation in low-temperature intermediate to felsic melts causes a strong depletion in Cu, Au, Bi, and potentially Ag in the silicate melt, whereas MSS saturation may cause a depletion in Cu and potentially Au. Other elements including W, Zn, As, Mo, Sn, Sb, and Pb are much less or not affected by the saturation of sulfide liquid or MSS. These results place important constrains on the potential of magmas in forming porphyry-type ore deposits and the origin of the observed variability in metal ratios in porphyry-type ore deposits.