Post-cumulus control on copper isotopic fractionation during oceanic intra-crustal magmatic differentiation

Unlike their eruptive counterparts, plutonic rocks often experience post-cumulus evolution prior to their final solidification. These processes have the potential to exert significant control on the distributions of elements and their isotopic compositions of plutonic rocks. However, our understanding in these effects remains limited, particularly for metal stable isotopes. Here, we carried out high-precision delta Cu-65 measurements for a suite of primitive to evolved cumulates from the Kane area, 23(o)N of Mid-Atlantic Ridge. Most mid-ocean ridge basalts (MORBs) exhibit uniformly bulk silicate Earth (BSE)-like delta Cu-65 of + 0.09 +/- 0.08 parts per thousand, indicating limited Cu isotopic fractionation in crustal magma reservoirs prior to melt extraction. However, our new Cu isotopic data on these cumulates show that large Cu isotopic variations (delta Cu-65 = -0.6 parts per thousand to + 0.9 parts per thousand) occur in variably evolved cumulates (MgO/total FeO < 3.0), while the most primitive cumulates (MgO/total FeO > 3.0) exhibit BSE-like delta Cu-65 (+0.06 +/- 0.06 parts per thousand). Petrological and geochemical observations indicate limited hydrothermal effects on Kane cumulate Cu isotopes. Modeling results indicate that the variable delta Cu-65 in Kane cumulates are unlikely to result from magmatic processes during the cumulus stage. Instead, the large Cu isotopic variation in Kane cumulates requires post-cumulus melt evolution involving fractionation between sulfide and intercumulus melts at relatively low temperatures. Textures and mineral chemistry indicate pervasive post-cumulus modifications of Kane cumulates by porous melt flow. Thermodynamic calculations indicate that intercumulus melts persist at temperatures even to 200 degrees C lower than the initial liquidus temperatures. Our data indicate that lower temperatures in the post-cumulus melt evolution and lower sulfide Ni contents result in lower sulfide-silicate melt Cu isotope fractionation factor (alpha(sulfide-melt)), then causing greater Cu isotopic variations in cumulates. We suggest that post-cumulus melt evolution reconcile both the Cu depletion and large Cu isotope fractionation in oceanic cumulates that are unexpected by a simple process of crystal accumulation from MORBs. This study highlights the essential role of post-cumulus evolution in controlling metal budget and their stable isotope fractionation during intra-crustal differentiation, which might also be applied to island arc and continental settings.