The Baiyinnuo’er skarn deposit is one of the largest Zn-Pb deposits in northeastern China, with 32.74 million metric tons (Mt) resources averaging 5.44% Zn, 2.02% Pb, and 31.36 g/t Ag. The deposit formed in three stages: the preore stage (prograde skarn minerals with minor magnetite), the synore stage (sulfides and retrograde skarn minerals including calcite and minor quartz), and the postore stage (late veins composed of calcite, quartz, fluorite, and chlorite; cutting the above mineral assemblages). In this study we analyzed the composition of single fluid inclusions using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to (1) determine the composition of the fluids and the evolution through the stages, (2) infer the fluid and metal sources, and (3) explore the metal deposition mechanisms. The preore fluids trapped in pyroxene have higher homogenization temperatures (432°–504°C), higher salinity (36.5–46.1 wt % NaCl equiv), and higher concentrations of Zn (~0.9 wt %), Pb (~1.4 wt %), and other elements (e.g., Na, K, Li, As, Rb, Sr, Cs, Ba, Cl, and Br) than synore mineralizing fluids (<370°C, <10 wt % NaCl equiv, ~450 ppm Zn, and ~290 ppm Pb). The postore fluids show lower temperatures (<250°C) and a rather dilute composition (<4 wt % NaCl equiv, ~33 ppm Zn, and ~24 ppm Pb). Geochemically, the fluids of all paragenetic stages in Baiyinnuo’er have magmatic signatures based on the element mass ratios, including elevated K/Na, Zn/Na, and Rb/Na ratios, lower Ca/K ratios, and combined Cl/Br-Na/K ratios, which are distinctively different from basinal brines. Inclusion fluids in preore stage show little variation in composition between ~510° and ~430°C, indicative of a closed cooling system. In contrast, the major components of the syn- and postore fluids, including Cl, Na, and K, decrease and correlate with a drop of homogenization temperatures from ~370° to ~200°C, indicating a dilution by mixing with groundwater. The Baiyinnuo’er mineralizing fluids (trapped in sphalerite) have higher Ca/K mass ratios (avg ~0.78) than other proximal magmatic hydrothermal systems (0.06–0.52) but lower than that of the distal El Mochito skarn (avg ~6.4), probably reflecting a gradually weakened magmatic signal away from the causative intrusions. The metal contents in preore fluids are significantly higher than those in synore fluids, but no mineralization occurred. This confirms that the early fluids were, although enriched in metals, not responsible for ore precipitation, most likely due to their high temperature and high salinities. One important factor controlling Zn-Pb mineralization was mixing with groundwater, which resulted in temperature decrease and dilution that significantly reduced the metal solubility, thereby promoting metal deposition. Another main driving force was the interaction with carbonate wall rock that buffered the acidity generated during the breakdown of Zn and (Pb)-Cl complexes and the precipitation of sulfides. Phase separation occurred in both the preore and the early part of the synore stages, but no evidence indicated that it caused metal deposition. The prograde minerals and retrograde minerals (including ore minerals) coexisting in the same samples could have been caused by two (or more) successive pulses of hydrothermal fluids released from residual melts of a progressively downward crystallizing magma. Each fluid produced a series of proximal high-temperature prograde to distal low-temperature assemblages, with the lower temperature assemblages of later fluids overprinting the higher temperature assemblages at most locations.

Recognized large occurrences of fluid-deposited graphite displaying high crystallinity were previously restricted to high-temperature environments (mainly granulite facies terranes). However, in the extensively mined Borrowdale deposit (UK), the mineralogical assemblage, notably the graphite-epidote intergrowths, shows that fully ordered graphite precipitated during the propylitic hydrothermal alteration of the volcanic host rocks. Fluids responsible for graphite deposition had an average X CO2/(XCO2 + X CH4) ratio of 0.69, thus indicating temperatures of ~500 °C at the fayalite-magnetite-quartz buffered conditions. Therefore, this is the first reported evidence indicating that huge concentrations of highly crystalline graphite can precipitate from moderate-temperature fluids. \u