Fluid inclusion LA-ICP-MS constraint on hydrothermal evolution of proximal cassiterite-bearing quartz veins in the giant Gejiu orefield: Implications for controls on metallogenic potential of granite-related skarn system

Sn and Cu are proposed to have their mineralization potential predetermined by their contents in initial fluids of granite-related magmatic-hydrothermal systems. However, it remains ambiguous whether the giant Sn-mineralized skarn system is applicable, and whether the Sn-Cu association in some deposits is predominantly determined by their initial metal contents. The Gejiu orefield is one of the most essential Sn-polymetallic districts worldwide, with proven resources of 3.27 million tons of tin, 3.25 million tons of copper, 4.29 million tons of lead and zinc, and >20 other metals with economic significance. Sn-polymetallic mineralization at Gejiu constitutes a composite skarn ore system that includes proximal skarn and related cassiterite-sulfide, greisen, and tourmaline-vein types. The Laochang Sn-polymetallic deposit hosts several largest skarn and cassiterite-sulfide orebodies in the eastern part of Gejiu. Recent exploitation at Laochang discovered Sn-mineralized quartz veins hosted in the concealed granite, providing a valuable opportunity to characterize the proximal magmatic-hydrothermal process of the mineralizing granitic system. Here, fluid inclusion analysis is carried out on these veins to discuss the fluid evolution, cassiterite precipitation mechanism and whether metal content in early proximal magmatic fluids determines the metal association and endowment in the deposit.

Based on the paragenesis of ore and gangue minerals, three hydrothermal stages are distinguished, including quartz-tourmaline stage (Stage I), cassiterite-arsenopyrite-quartz stage (Stage II) and late sulfide stage (Stage III). Fluid evolution controlling vein formation is constrained by microthermometry and LA-ICP-MS analysis of four fluid inclusions generations successively entrapped in quartz and cassiterite. The fluids involved during vein formation show an interplay between single-sourced magmatic fluids and meteoric water. The intermediate-density single phase fluid recorded at stage I quartz is derived from initial fluids directly exsolving from granitic magma. At stage II, fluid immiscibility occurred and the separated brines were entrapped in quartz and early-formed cassiterite. Along with cassiterite precipitation, brines were mixed with low-salinity and cooler meteoric water, leading to entrapment of low-salinity aqueous fluid in outer growth zones of cassiterite at stage II. The constructed fluid evolution history suggests that fluid immiscibility may have facilitated the nucleation of cassiterite crystals at the onset of deposition while mixing of magmatic fluid with meteoric water likely dominate later cassiterite mineralization.

Compared with the fluid dataset of barren and mineralized granitic systems worldwide, pre-ore fluids of the studied quartz veins are enriched in Sn, confirming that high Sn content in the initial magmatic fluid can serve as indicator to distinguish mineralized system. In contrast, although Cu mineralization is economically important in the Laochang deposit, predicted Cu contents in pre-ore proximal magmatic fluids are as low as those obtained from Cu-barren system. This implies introduction of Cu into the hydrothermal system from other sources.