The potassium silicate (K-silicate) alteration zone is the main ore contributor in porphyry copper deposits worldwide. Knowledge of element behaviors in the alteration and mineralization processes is essential for an improved understanding of porphyry copper mineralization, but they are still not well understood. In this study, we reacted synthetic Cl-rich fluids, containing K, Na, Cu, Mo, Zn, etc., with andesite in a complex experimental system to simulate the shallow porphyry copper mineralization process. We aimed to bridge the gap between simple experimental studies and complex natural systems and to evaluate the contribution of sulfate reduction to porphyry ore formation and its relationship with early alkali metasomatism. The results show that increasing temperature (from 300 to 500 °C) enhances the K-silicate alteration by promoting ion-exchange reactions, and the K-feldspar is mainly formed by the transformation of plagioclase via a dissolution-reprecipitation processes. The low-salinity vapor phase has a stronger capacity for K-silicate alteration than the liquid phase at similar temperatures. In addition, increasing temperature from 300 to 500 °C favors sulfate reduction to further enhance metal sulfide precipitation. The limited availability of reduced sulfur in the fluid causes preferential precipitation of Cu-(Mo) sulfides, while most of the Zn is soluble in the fluid, and Cu precipitation as sulfides in the vapor is much more efficient than in the coexisting liquid. The overlap between the K-silicate alteration zone and the mineralization triggered by sulfate reduction in porphyry copper deposits is controlled by several concomitant factors, e.g., relatively high temperature (e.g., at 400–500 °C), vapor formation, and decompression. Moreover, K-silicate alteration would further promote mineralization by changing fluid compositions, e.g., removing K from the fluid.

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