A compilation of copper isotopic compositions (δ65Cu) from supergene systems suggests distinct differences in the mean δ65Cu of Cu in leach cap (δ65Cu = −1.2 ± 3.5‰), enrichment zone (mean δ65Cu = +1.2 ± 4.2‰), and fluids (mean δ65Cu = +0.9 ± 1.3‰) relative to the high-temperature sulfides that comprise the primary ore (δ65Cu = +0.1 ± 0.6‰). These isotopic differences can be explained by the oxidative dissolution of primary ore minerals, such as chalcopyrite, and the subsequent precipitation of oxides in the near-surface system and of sulfides at depth. A dynamic mass balance model predicts the observed Cu isotopic compositions of the Cu reservoirs in nature and constrains the temporal isotopic evolution of supergene systems. From the model, these systems isotopically evolve to substantial extents over 500 ka to 5 Ma time scales. In relatively closed systems, percent-level loss of Cu from the solid (with δ65Cu values >>0‰) is possible, suggesting that supergene systems are important components of the global Cu cycle.
The study presents δ65Cu and δ97Mo isotope values from cogenetic chalcopyrite and molybdenite found in veins and breccias of the Dahutang W‐Cu‐Mo ore field in China. The samples span a 3–4 km range. Both isotopes show a significant degree of fractionation. Cu isotope values in the chalcopyrite range from −0.31‰ to +1.48‰, and Mo isotope values in the molybdenite range from −0.03‰ to +1.06‰. For the cogenetic sulfide veined samples, a negative slope relationship exists between δ65Cu and δ97Mo values, which suggest a similar fluid history. Rayleigh distillation models the vein samples' change in isotope values. The breccia samples do not fall on the trend, thus indicating a different source mineralization event. Measured fluid inclusion and δD and δ18O data from cogenetic quartz indicate changes in temperature, and mixing of fluids do not appear to cause the isotopic shifts measure. Related equilibrium processes associated with the partitioning of metal between the vapor‐fluid in the hydrothermal system could be the probable cause for the relationship seen between the two isotope systems.