Characteristics of Cu isotopes from chalcopyrite-rich black smoker chimneys at Brothers volcano, Kermadec arc, and Niuatahi volcano, Lau basin

We analysed primary chalcopyrite from modern seafloor ‘black smoker’ chimneys to investigate high-temperature hydrothermal Cu isotope fractionation unaffected by metamorphism. Samples came from nine chimneys collected from Brothers volcano, Kermadec arc, and Niuatahi volcano, Lau backarc basin. This is the first known study of Cu isotopes from submarine intraoceanic arc/backarc volcanoes, with both volcanoes discharging significant amounts of magmatic volatiles. Our results (n = 22) range from δ⁶⁵Cu = −0.03 to 1.44 ± 0.18 ‰ (2 sd), with the majority of samples between ∼0.00 and 0.50 ‰. We interpret this cluster (n = 17) of lower δ⁶⁵Cu values as representing a mantle source for the chimney Cu, in agreement with δ⁶⁵Cu values for mantle rocks. The few higher δ⁶⁵Cu values (>0.90 ‰) occur (1) within the same chimneys as lower values, (2) randomly distributed within the chimneys (i.e. near the top and bottom, interior and exterior), and (3) within chalcopyrite of approximately the same age (<1 year). This suggests the higher δ⁶⁵Cu values are not related to oxidation by mixing with ambient seawater, but to isotopic variation within the vent fluids over a relatively short time. Theoretical studies demonstrate significant isotopic fractionation can occur between aqueous and vapourous complexing species. When combined with evidence for periodic release of magmatic volatiles at Brothers, we believe vapour transport of Cu is responsible for the observed isotopic fractionation. When compared to global δ⁶⁵Cu data for primary chalcopyrite, volcanic arc chimneys are most similar to porphyry copper deposits that also form from magmatic-hydrothermal processes in convergent tectonic settings.