The behavior of Fe and S isotopes in porphyry copper systems: Constraints from the Tongshankou Cu-Mo deposit, Eastern China

Iron isotopes have been widely applied to trace mineralization processes of magmatic-hydrothermal ore systems, yet the application of Fe isotopes in porphyry Cu deposits (PCDs) is still restricted by the lack of understanding of its behaviors during hydrothermal alteration and ore formation processes. In this study, Fe isotope systematics in whole-rocks and Fe-bearing minerals coupled with S isotope compositions of Fe-sulfides are investigated for the early Cretaceous Tongshankou porphyry Cu-Mo deposit from Eastern China. The results show that altered ore-hosting granodiorite porphyries display a small delta Fe-56 variation (0.04 parts per thousand to 0.17 parts per thousand) with an average of 0.10 +/- 0.08 parts per thousand (2SD, n = 10), indistinguishable from the values for global igneous rocks. The delta Fe-56 of magnetite (0.22 parts per thousand) and biotite (-0.08 parts per thousand to 0.12 parts per thousand) from the altered porphyries are also within the delta Fe-56 ranges of those from global igneous rocks. These results indicate that hydrothermal fluids have negligible effect on Fe isotope compositions of the porphyry host rocks, likely due to the insignificant contributions of fluid-derived iron relative to the total Fe budget of the host rocks. The Fe-sulfides in the porphyry system record geochemical and iron isotopic characteristics of the ore-forming fluids. Specifically, chalcopyrites show large Fe isotope variations with delta Fe-56 ranging from -0.60 parts per thousand to 0.61 parts per thousand. The calculated Fe isotope compositions of ore-forming fluids based on the chalcopyrite delta Fe-5(6) are thus not uniform and fall in the range from -0.69 +/- 0.18 parts per thousand to 0.52 +/- 0.18 parts per thousand (2SD). On the other hand, pyrites exhibit a delta Fe-56 variation between -0.48 parts per thousand and 0.40 parts per thousand and show distinct Fe isotopic characteristics for disseminated and vein-type pyrite. The delta Fe-56 for disseminated pyrites are consistently higher than whole-rock values, ranging from 0.14 parts per thousand to 0.40 parts per thousand, likely reflecting equilibrium Fe isotopic exchange between pyrite and dissolved Fe in fluid. By contrast, delta Fe-56 for pyrites in veins are highly variable (-0.48 parts per thousand to 0.34 parts per thousand) and show an inverse correlation with the chalcopyrite delta Fe-56. These observations, in concert with S isotope data, have been interpreted to reflect pyrite formation through the FeS pathway, whereas the wide range in delta Fe-56 for pyrite may record isotopic change from initial FeS-fluid equilibrium towards pyrite-fluid equilibrium due to different extent of reaction upon precipitation. Additionally, when compared to sulfides formed by non-magmatic, low-temperature processes, the sulfides in our study exhibit a relatively narrow range of delta Fe-56 and delta S-34, implying a high-temperature magmatic origin for both elements. Overall, our study demonstrates that the coupling of Fe and S isotopes could be a useful tool for tracking the processes of sulfide mineralization in porphyry-related deposits. (C) 2019 Elsevier Ltd. All rights reserved.