Magmatic–Hydrothermal Evolution at the Barren Wushan Pluton, Southeast China: Insight into Controls on Mineralization Potential

Abstract A-type granites typically exhibit enrichment and mineralization of critical metals such as molybdenum and tin, essential for emerging technologies. However, the key factors influencing their mineralization potential remain elusive. The scarcity of studies on barren systems impedes the understanding of this question. Here, a detailed melt and fluid inclusion study was conducted on the barren Wushan pluton to reconstruct its magmatic evolution and magmatic–hydrothermal transition and explore the factors controlling the metallogenic potential of Mo and Sn in A-type granites. The Wushan pluton displays apparent lithological zoning consisting of two major phases, i.e., medium-grained seriate to porphyritic alkali feldspar granite and fine-grained porphyritic granite. Miarolitic cavities are widely developed in each lithofacies. The silicate melt inclusions from two granitic phases are rhyolitic, with moderate F contents (0.06–0.53 wt %) and depleted H2O contents (2.0–3.5 wt %). Melt inclusions show a wide range of incompatible element contents, such as Cs (9–1977 μg/g) and Rb (268–2601 μg/g), suggesting that Wushan has undergone a high degree of magma evolution. Mo behaves incompatibly in the magmatic evolution, and its content is enriched with the increasing degree of fractional crystallization, but remains constant after the Cs content exceeds 50 μg/g. Rayleigh fractionation model suggests that a large amount of Mo is extracted from fluid exsolution, which restrains Mo from further enrichment. In contrast, Sn behaves as a mildly incompatible element during the entire magmatic evolution history. The contents of Sn increase slowly compared to the trend of Mo, and the maximum contents reach ~30 μg/g in the highly evolved melts. The separation and crystallization of Sn-bearing minerals such as biotite, magnetite, and titanite inhibit the enrichment of Sn. Intermediate-density (ID-type) fluid inclusions hosted in the miarolitic quartz, representing the initial fluid exsolving from magma, display high Mo but low Sn concentrations. Constrained from two assemblages of coexisting ID-type fluid and melt inclusions, the fluid/melt partition coefficients of metals are obtained, with DMo, fluid/melt at 16–19, while DSn, fluid/melt is only about 1. The comparison between Mo-mineralized and barren intrusions worldwide shows that the metal contents in melts and fluids are not fundamentally different. The mineralized intrusions are characterized by the lower melt viscosity and the development of apophyses, both of which facilitate the extraction of metals and fluids from large magma chambers, followed by their concentration into a small rock volume. Consequently, it appears that physical and structural conditions rather than chemical compositions play a crucial role in the Mo mineralization process. Enrichment of Sn in melts is necessary but not decisive for Sn mineralization, whereas Sn enrichment in the initial exsolving fluid determines the Sn mineralization potential of a given granitic system. Compared to Sn enrichment in source melting and fractional crystallization which commonly enhance final Sn fertility in the highly evolved melts, the efficiency of Sn partitioning between melt and fluid plays a fundamental role in converting melt fertility into Sn-enriched fluids and thereby high mineralization potential of the magmatic–hydrothermal system. Our findings suggest a prospect for Mo exploration in the coastal A-type granite belt in South China, while the potential for Sn mineralization is expected to be limited.