Origin of the Early Cambrian Huayuan carbonate-hosted Zn-Pb orefield, South China: Constraints from sulfide trace elements and sulfur isotopes

Abstract

The Huayuan Zn-Pb orefield in the southeastern Yangtze Craton contains over 20 Mt Zn + Pb metal resource @ 4%, including several large, Lower Cambrian carbonate-hosted deposits classified as Mississippi Valley-Type (MVT). The source of zinc and lead and the ore-forming processes involved are still unclear. Trace elements and sulfur isotope compositions of sulfides from the large-scale Limei and Danaopo Zn-Pb deposits in the orefield favor a fluid-mixing metallogenic hypothesis. Alteration/mineralization occurred in three stages (S1-S3), forming pale-yellow sphalerite (S1: Sp1), yellow–brown sphalerite and pyrite (S2: Sp2-Py2), and galena-pyrite (S3: Gn-Py3).Syn-sedimentary fine-grained pyrite (Py1) in the Lower Cambrian Qingxudong Formation (Fm.) algal limestone has high Co, Ni, and As concentrations, whereas hydrothermal Py2 and Py3 in sulfide-calcite veins are rich in Zn and Pb, respectively. All the pyrites have low Co/Ni ratios (<2), indicating that the Fe, Co, and Ni are from a sedimentary source. Sphalerites from Limei and Danaopo are rich in Cd, Cl, and Ge but poor in Fe, Mn, and Co. They were formed under low-medium temperature (134–236 °C; determined by the concentrations of Mn, Fe, Ga, Ge, In, and Sb) and in an acidic and low-fO2 hydrothermal system, which are consistent with typical MVT ores. Lower Cambrian algal limestone (δ34SΣS = 34.3–34.4‰) contributed most sulfur to the ore sulfides (δ34S = 29.3–37.2‰). Meanwhile, the Lower Cambrian Niutitang Fm. Pb-Zn-rich black shale is likely the main ore metal source, but its limited sulfate content may not be able to provide sufficient sulfur. We propose a mixing between metal-rich brines leached from the basal Niutitang Fm. black shale with H2S-rich fluid resulting from thermochemical sulfate reduction (TSR) of the Qingxudong algal limestone formation, thus destabilizing the base metal chloride complexes and precipitating the Zn-Pb ores.