Iron, boron, and sulfur isotope constraints on the ore-forming process of subseafloor replacement-style volcanogenic massive sulfide systems

The well-preserved Ashele subseafloor replacement -style volcanogenic massive sulfide (VMS) deposit in the Central Asian Orogenic Belt comprises two stages of Cu mineralization, i.e., early massive sulfides dominated by colloform and euhedral pyrite intergrown with chalcopyrite and sphalerite, which were replaced by late vein -dominated chlorite-chalcopyrite assemblages. In this study, a combined systematic Fe, B, and S isotope investigation was first applied to investigate the sulfide precipitation processes and the relative proportion of fluid sources in different alteration and mineralization stages of the Ashele deposit. Boron isotopes of Mg -rich tourmaline (811B from -5.57%0 to -2.73%0, average (avg.) -4.23%0) indicate significant seawater (similar to 19%) participated during the formation of massive sulfides. A two -component mixing model is used to estimate the contribution of seawater and igneous sulfur to the total sulfur budget, and the results show the increasing contribution of magmatic sulfur from the early (35%) to late (76%) stages. In addition, 856Fe values of pyrite gradually increase from the massive ore (-0.46%0 to -0.02%0, avg. -0.24%0), quartzpyrite (-0.09%0 to 0.07%0, avg. -0.01%0), chlorite-chalcopyrite-quartz-pyrite (0%0 to 0.21%0, avg. 0.08%0) to the quartz-sericite zone (-0.02%0 to 0.29%0, avg. 0.14%0), which is likely related to the different extent of isotopic exchange and formation temperature, and could be used in the exploration of VMS systems. The new two -stage ore -forming model shows that in the early stage, rapid mixing of hydrothermal fluid from underlying magma chamber with abundant cold seawater led to rapid deposition of pyrite and associated Cu mineralization under relatively oxidized condition, and long-term hydrothermal activities in relatively closed systems would promote the formation of upper massive ores, which resulted in an equilibrium system between pyrite, chalcopyrite, and associated fluid with wide ranges of 856Fe in pyrite (-0.46%0 to -0.02%0) and chalcopyrite (-1.56%0 to -0.49%0). The late hydrothermal activities in relatively open system would contribute to stringer sulfides or stockworks underlying the massive ore in relatively reduced conditions with heavier Fe isotope compositions in pyrite (-0.09%0 to 0.29%0) and chalcopyrite (-0.60%0 to -0.04%0). Overall, our study demonstrates that the coupling of B, Fe, and S isotopes could be a useful tool to indicate long-term subseafloor infilling and replacement processes for subseafloor replacementtype VMS deposits, which are the prerequisite to form large -tonnage VMS deposits.