The origin and ore-forming processes of the Qixiashan Pb-Zn-Ag deposit, South China: Constraints from LA-ICP-MS analysis of pyrite and sphalerite

The Qixiashan Pb-Zn-Ag deposit, located in the Nanjing-Zhenjiang area of the Middle-Lower Yangtze Metallogenic Belt (MLYB), is one of the largest Pb-Zn deposits in Eastern China. The middle Carboniferous carbonates of the Huanglong Formation are the main host rocks of orebodies. Whether this deposit is associated with magmatic activity or sedimentary exhalative deposit is still debated due to the poor constraints on the origin of the ore materials and metallogenic processes. To address this, we analyzed the compositions of pyrite and sphalerite from different mineralization stages and depths, and the distributions of minor and trace elements within the pyrite and sphalerite crystals, using in situ laser ablation-inductively coupled plasma-mass spectrometer and scanning electron microscope analyses. Four hydrothermal stages can be identified: the pre-ore pyrite stage (stage I); Pb-Zn-Py stage (stage II); Pb-Zn-Ag stage (stage III); and carbonate stage (stage IV). The sphalerite in the deposit is typically enriched in Fe, Mn, In, and Sn, and depleted in Ge and Cd. These results are characteristic of magmatic hydrothermal activity and indicate the mineralization was related to late Yan-shanian magmatic activity. The Co and Ni contents of pyrite, and the Fe, In, and Sn contents of sphalerite decrease from the early to late stages, suggesting that the temperature of the hydrothermal fluid decreased continuously. Variations in the Se content of pyrite suggest that the fO2 increased from stage I to stage II, then decreased during stage III. Detailed SEM and elemental maps show that stage-II sphalerite (Sph-1) and pyrite (Py-2) are oscillatory zoned, which we interpret to reflect pressure fluctuations and repeated local fluid phase separation during stage II. We also infer from the zoning and subsequent formation of Py-3 that magmatic hydro-thermal activity increased from stage I to II, then decreased from stage II to III. In addition, changes in the In, Sn, and Fe contents of sphalerite can be useful indicators of the upward migration of ore-forming fluid and can help during prospecting for related deep magmatic rocks.