The partitioning of Cu and Ag between minerals and silicate melts during partial melting of planetary silicate mantles

Abstract

Geochemical and cosmochemical reservoirs show Cu/Ag variations from 500 to 40,000. To understand magmatic Cu–Ag fractionation and origins of such large Cu/Ag variations, we have measured the partition coefficients of Cu and Ag between minerals and silicate melts (DCu,AgMin/SM) relevant for partial melting of the silicate mantles of Earth, Mars, and the Moon. The experiments were conducted at 1–3 GPa, 1300–1600 °C, and oxygen fugacity ∼2–5 log units below the FMQ buffer. The results show that DCuMin/SM are 0.034–0.109 for olivine, 0.011–0.044 for orthopyroxene, and 0.046–0.092 for clinopyroxene; DAgMin/SM are 0.003–0.012 for orthopyroxene and 0.037–0.093 for clinopyroxene. These DCu,AgMin/SM values increase mainly with increasing pressure and are oxygen fugacity-independent. DAgMin/SM are 0.0005–0.0017 for olivine, which do not show measurable dependence on P–T, oxygen fugacity, or silicate composition. One pair of DCu,AgMin/SM values are 0.0037 and 0.0004 for garnet, respectively; 0.15 and 0.005 for spinel, respectively. These results indicate that Ag is more incompatible than Cu in all mantle minerals. Our DCu,AgMin/SM combined with previous sulfide–silicate melt partition coefficients of Cu and Ag imply that although sulfides host large fractions of planetary mantle Cu and Ag, silicate minerals can be also important Cu and Ag reservoirs, particularly when sulfides occur as monosulfide solid solutions. The application of our DCu,AgMin/SM to various melting models demonstrates that Cu–Ag fractionation occurs during partial melting of the silicate mantles of Earth, Mars, and the Moon; however, the modeled Cu/Ag ratios in basalts agree with their mantle source Cu/Ag ratios within 50% relative. Therefore, the superchondritic but similar Cu/Ag ratios of ∼3000–4000 in mid-ocean ridge basalts, arc basalts, mantle plume-related oceanic island basalts and plateau basalts, and the bulk silicate Earth (BSE) reflect homogeneous distribution of Cu/Ag in Earth’s mantle and limited Cu–Ag fractionation during slab dehydration/melting in subduction zones. However, components with chondritic Cu/Ag ratios (∼600–2300) may exist in the mantle sources of Hawaii oceanic island lavas. The Cu/Ag ratios (∼500–1100) in the Martian basalts and bulk silicate Mars (BSMars) are chondritic, but the Cu/Ag ratio (∼15,000–40,000) in the bulk silicate Moon (BSMoon) is strongly superchondritic. Such largely different Cu/Ag ratios in different planetary reservoirs cannot be explained by magmatic Cu–Ag fractionation, solar nebular process, or core-formation process. We propose that different degrees of planetary melting and evaporation provide a solution because Ag is more volatile than Cu during silicate melt evaporation. The chondritic Cu/Ag ratios in the BSMars could be explained by limited evaporation of planetesimals that delivered Mars’ moderately volatile elements, and the superchondritic Cu/Ag ratios in the BSE may be due to Earth’s accretion of planetesimals with partial evaporative loss of Cu and Ag. However, high degrees of evaporative Cu and Ag loss during the Moon-formation are required to explain the strongly superchondritic Cu/Ag ratios in the BSMoon. Accordingly, Cu/Ag ratios in the bulk silicate planets may provide new insights into the nature of their building blocks.