Genetic significance of trace elements in hydrothermal quartz from the Xiangzhong metallogenic province, South China

Despite the Xiangzhong metallogenic province being globally the most important ore-concentrated area of antimony (Sb) mineralization, the genesis of Sb-(Au-W) deposits in this region is still under debate. In this study, trace element compositions of hydrothermal quartz from four representative Sb-(Au-W) deposits (Xikuangshan, Woxi, Banxi, and Zhazixi) in the Xiangzhong metallogenic province have been investigated to constrain the origin of ore-forming fluids and physiochemical conditions of Sb mineralization. The fsLA-ICP-MS data indicate that Li, B, Na, Al, P, K, and Sb are relatively enriched in quartz, probably mainly incorporated into the quartz crystal lattice, and dominated by the coupled substitution of (Al3+, Sb3+, B3+) + (Li+, Na+, K+, H+) ↔ Si4+ and (Al3+, Sb3+, B3+) + P5+ ↔ 2Si4+. In the Xikuangshan Sb deposit, charge-neutrality conditions of cations reveal that (Al3+, Sb3+) + Li+ ↔ Si4+ is the most important substitution mechanism in quartz from early-stage Sb mineralization (quartz-stibnite veins), whereas (Al3+, Sb3+) + (Li+ + H+) ↔ Si4+ may control the trace element contents in quartz from late-stage Sb mineralization (calcite-quartz-stibnite veins). The relatively high Al content and the low variability in trace element content suggest that quartz from the Xikuangshan Sb deposit may have precipitated from a relatively acidic and stable ore-forming fluid. Combined with the high Sr and Rb contents of quartz, a plausible explanation is that acidic hydrothermal fluids promoted water–rock reaction that dissolved large amounts of Sr and Rb, resulting in the high Al, Rb, and Sr contents in crystallized quartz from the Xikuangshan Sb deposit. In contrast, the relatively low but inhomogeneous Al content indicates that quartz from the Woxi and Banxi Sb-(Au-W) deposits may have precipitated from a less acidic ore-forming fluid and supports the idea of fluid mixing. More importantly, the relatively high contents of Rb, Ge, and Ti in quartz from the Woxi and Banxi Sb-(Au-W) deposits, combined with the low Al and Sr contents, imply that magmatic-hydrothermal systems possibly contributed to the ore-forming fluids. Based on the trace element compositions of quartz, two major types of Sb deposits were identified in the Xiangzhong metallogenic province: the giant Xikuangshan epithermal deposit in which the ore-forming fluids are relatively acidic, stable and have experienced water–rock reaction, generally similar to the Qinglong Sb deposit in the Youjiang metallogenic province. The second type is the orogenic-type deposit represented by the Woxi Sb-Au-W deposit, including the Banxi Sb deposit, where the ore-forming fluids have undergone fluid mixing and relatively weak water–rock reaction, and may have been joined by a small amount of magmatic-hydrothermal fluids. Together with the recently published Sb mineralization ages (149–144 Ma) of the Woxi Sb-Au-W deposit, it supports the idea that this type of Sb deposit is related to the Mesozoic magmatism. The Zhazixi Sb-W deposit shows transitional features between these two types of Sb deposits.