Partitioning of copper between olivine, orthopyroxene, clinopyroxene, spinel, garnet and silicate melts at upper mantle conditions

Abstract

Previously published Cu partition coefficients (DCu) between silicate minerals and melts cover a wide range and have resulted in large uncertainties in model calculations of Cu behavior during mantle melting. In order to obtain true DCumineral/melt values, this study used Pt95Cu05 alloy capsules as the source of Cu to experimentally determine the DCu between olivine (ol), orthopyroxene (opx), clinopyroxene (cpx), spinel (spl), garnet (grt) and hydrous silicate melts at upper mantle conditions. Three synthetic silicate compositions, a Komatiite, a MORB and a Di70An30, were used to produce these minerals and melts. The experiments were conducted in piston cylinder presses at 1.0–3.5GPa, 1150–1300°C and oxygen fugacities (fO2) of from ∼2log units below to ∼5log units above fayalite–magnetite–quartz (FMQ). The compositions of minerals and quenched melts in the run products were measured with EMP and LA-ICP-MS. Attainment of equilibrium is verified by reproducible DCu values obtained at similar experimental conditions but different durations. The results show that DCu for ol/, opx/, spl/ and possibly cpx/melt increase with increasing fO2 when fO2>FMQ+1.2, while DCu for cpx/ and spl/melt also increase with increasing Na2O in cpx and Fe2O3 in spinel, respectively. In the investigated P–T–fO2 conditions, the DCumineral/melt values are 0.04–0.14 for ol, 0.04–0.09 for opx, 0.02–0.23 for cpx, 0.19–0.77 for spl and 0.03–0.05 for grt. These results confirm that Cu is highly incompatible (DCu<∼0.2) in all the silicate minerals and oxides of the upper mantle with the exception of the high-Fe spinel, in which Cu is moderately incompatible (DCu=0.4–0.8) and thus Cu will be enriched in the derived melts during mantle partial melting and magmatic differentiation if sulfide is absent. These experimental DCu values are used to assess the controls on Cu behavior during mantle melting. The model results suggest that MORBs and most arc basalts must form by sulfide-present melting at relatively reduced conditions, while high Cu (>70ppm) arc basalts may form at oxidized, sulfide-absent conditions, which is consistent with the possibility of some high fO2 regions present in the arc mantle.