The southwest Guizhou Province, China, contains numerous sediment-hosted Au deposits with Au reserves greater than 700 tonnes. To date, the source of ore fluids that formed the Guizhou sediment-hosted Au deposits is controversial, hampering the formulation of genetic models. In this study, we selected the Shuiyindong and Jinfeng Au deposits, the largest strata-bound and fault-controlled deposits in Guizhou, respectively, for detailed research on pyrite chemistry and S isotope composition using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS), respectively.
Petrography and pyrite chemistry studies distinguished five generations of pyrite. Among these, pre-ore pyrite 2 and ore pyrite are the most abundant types in the deposits. Pre-ore pyrite 2 is anhedral to euhedral and with ~2,639 ppm As and wider ranges of Cu, Sb, and Pb (<~22–4,837 ppm, <~6 to 532 ppm, and <~4 to 1,344 ppm, respectively). Gold in pre-ore pyrite 2 is below the detection limit of LA-ICP-MS (~2 ppm). Pre-ore pyrite 2 is interpreted to have a sedimentary (syngenetic or diagenetic) origin. Ore pyrite commonly rims the four identified pre-ore pyrites or occurs as individual, anhedral to euhedral crystals. Ore pyrite is enriched in Au (~641 ppm), As (~9,147 ppm), Cu (~1,043 ppm), Sb (~188 ppm), Hg (~43 ppm), and Tl (~22 ppm) in both deposits. Ore pyrite formed mainly by sulfidation of Fe in Fe-bearing host rocks, mainly Fe dolomite, and As, Cu, Sb, Hg, and Tl, also in ore fluids, were incorporated into ore pyrite.
In situ δ34S isotope ratios for pre-ore pyrite 2 and ore pyrite were measured by LA-MC-ICP-MS. Pre-ore pyrite 2 from Shuiyindong and Jinfeng deposits resulted in δ34S values ranging from −0.8 to +3.4‰ and from 5.1 to 10.5‰, respectively. Analyses of ore pyrite from the Shuiyindong have δ34S values that vary from −3.3 to +2.5‰, with a median of 0.7‰; analyses of ore pyrite from the Jinfeng range from 8.9 to 11.2‰, with a median at 10.3‰. Available bulk and in situ δ34S data in the literature for pre-ore pyrites 1 and 2 and ore-related sulfide minerals including ore pyrite, arsenopyrite, and late ore-stage stibnite, realgar, orpiment, and cinnabar from several Guizhou sediment-hosted Au deposits were compiled for comparison. Pre-ore-stage pyrites from Guizhou sediment-hosted Au deposits have a broad range of δ34S values, from −33.8 to + 17.9‰ (including in situ and available bulk δ34S data). Ore-related sulfide minerals in all Guizhou sediment-hosted Au deposits, except Jinfeng, have very similar δ34S values, and most data plot between ~−5 and +5‰. In the Jinfeng deposit, the ore-related sulfide minerals exhibit δ34S values ranging from 1.9 to 18.1‰, with most data plotting between 6 and 12‰.
The broad range of S isotope compositions for the sedimentary pyrites (pre-ore pyrites 1 and 2) indicate that S in these pre-ore pyrites was most likely generated by bacterial reduction from marine sulfate. The narrow range of δ34S values (~−5–+5‰) for ore-related sulfide minerals in all Guizhou sediment-hosted Au deposits, excepting the Jinfeng deposit, suggests that the deposits may have formed in response to a single widespread metallogenic event. As the S isotope fractionation between hydrothermal fluids and sulfide minerals in a sulfide-dominated system is small (<2‰) at ~250°C, the initial ore fluids that formed the Guizhou sediment-hosted Au deposits would have had δ34S values similar to the ore-related sulfide minerals, between ~−5 and +5‰. At Jinfeng, initial ore fluids may have mixed with local fluids with heavier δ34S, possibly basin brine (δ34Sbasin brine >18‰), resulting in elevated δ34S values of ore-related sulfide minerals and especially late ore-stage sulfide minerals.
Although few igneous rocks are exposed in the mining area around these deposits, there is evidence of magmatic activity ~20 km away. Furthermore, gravity and magnetic geophysical investigations indicate the presence of a pluton ~5 km below the surface of the Shuiyindong district. Based on in situ S isotope results and recent data indicating proximal intrusions, we interpret a deep magmatic S source for the ore fluids that formed the Guizhou sediment-hosted Au deposits. However, as the age for Au mineralization of Guizhou sediment-hosted Au deposits is still debated, the mineralization-magma connection remains hypothetical. Identifying an ore fluid source and time frame for Guizhou Au mineralization continues to be a critically important research goal for this district.