Control of magmatic halogen composition and redox state on the zonation of metal mineralization across active continental margins: Perspectives from the world-class South China metallogenic province

Abstract

Active continental margins are the major sites of continental magmatism and associated hydrothermal ore deposits with a broad metal spectrum. Mineralization across active continental margins typically displays spatial zonation, with porphyry copper-(molybdenum‑gold) deposits in volcanic arcs and tin- and tungsten-dominated mineralization occurring further inland in a back-arc setting. Particularly, tin and tungsten commonly form separate deposits in back-arc regions, even though both metals exhibit similar lithophile behavior. The key factors governing this metallogenic zonation remain unclear. The world-class South China metallogenic province hosts over 50 % of the global tungsten resources, along with a significant amount of tin and copper resources distributed in different mineralization belts, making it an ideal location in which to study regional metal zonation. Here, we comprehensively integrate a very large dataset of the halogen volatile composition (F, Cl) and oxygen fugacity of granites related to tin, tungsten, and copper mineralization in the South China continental margin. Our compilation, derived from a substantial collection of zircon, apatite, mica, and whole-rock geochemistry data, suggests that lateral variations in granite magmatism (away from the trench), transitioning from chlorine-rich and oxic to fluorine-rich and reduced conditions, exert the primary control on copper versus tin‑tungsten mineralization in the arc and back-arc regions, respectively. Differences in oxygen fugacity have a minor impact on the decoupling of tin and tungsten mineralization despite tin granites being universally reduced (ΔFMQ = −1.8 to −0.1, where FMQ is the fayalite-magnetite-quartz redox buffer) and tungsten granites having a broader redox range (ΔFMQ = −1.5 to +1.2). Instead, the disparity in fluorine content plays a more crucial role in controlling the spatial separation of tin and tungsten mineralization observed in the back-arc setting. Nd-Hf and He-Ar isotopic modeling calculations suggest that magmas linked to tin mineralization have a more pronounced involvement of F-rich mantle components compared to those associated with tungsten. Elevated fluorine (ca. 650–8000 ppm) in tin-associated magmas allowed an extreme degree of magmatic differentiation and delayed fluid exsolution due to high H₂O solubility in F-rich silicate melts, ensuring Sn enrichment in highly evolved melts. In contrast, early fluid exsolution under less F-rich conditions (ca. 100–700 ppm) led to early tin loss from the melts, ultimately resulting in tungsten-dominant mineralization. This work emphasizes the combined influence of halogen composition and redox state on the regional mineralization zonation in world-class metallogenic provinces, providing vectors for global metal exploration in both past and currently active continental margins.