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• CH 4 was generated by the thermal decomposition of the carbonaceous wall-rocks. • CH 4 added, which contributed to the system from oxidized to reduced conditions. • Ore elements were deposited via fluid boiling process. High f O 2 conditions characterize the majority of global porphyry copper deposits and contain highly oxidized minerals, such as magnetite and anhydrite. In contrast, the No. 1 porphyry Cu–Au deposit in the Xiongcun district (Tibet, China) has abundant pyrrhotite, reduced fluids (CH 4 ≫ CO 2), and a relative lack of highly oxidized minerals, which are indicative of low f O 2 conditions. Scanning electron microscopy, fluid inclusion, C–H–O–He–Ar isotopes, and whole-rock organic carbon contents and isotope analysis were used to constrain the evolution of ore-forming fluid, the origin of CH 4 and metal deposition mechanisms for the No. 1 deposit. The He–Ar isotopic compositions (3He/4He = 0.11–0.96 Ra, 40Ar/36Ar = 418.7–2920.2) suggest that the ore-forming fluids predominantly derived from crust source with minor mantle input. The H–O isotopic analysis results (δ18O H2O = −1.8 to +5.2‰, δD = −106 to −89.9‰) indicate that the ore-forming fluids were derived from a magmatic source that mixed with some meteoric waters. The element compositions of zircons and fluid/melt inclusions from the mineralized Middle Jurassic quartz diorite porphyry reveal that the primary magma was characterized by high log f O 2 (>NNO) conditions. The quartz diorite porphyry intruded into the carbon-bearing wall rocks produced abundant CH 4 by thermal decomposition of organic matter (δ13C CH4 = −26.3 to −28.5‰), which changed the redox state of the porphyry copper system from oxidized to reduced condition. Ore elements were deposited via fluid boiling as a consequence of the rapid decrease in temperature and pressure. [ABSTRACT FROM AUTHOR]

• Initial ore-forming fluids were low-salinity, CO 2 -rich, single-phase fluids. • The fluids evolved from magmatic in origin to meteoric water-dominated. • Fluid immiscibility was the prime factor resulting in chalcopyrite precipitation. • Fluid-cooling was probably responsible for molybdenite precipitation. The No. 2 porphyry Cu–Au deposit in the Xiongcun district forms part of the Gangdese porphyry copper belt of Tibet. This study clarifies the fluid evolution and ore precipitation mechanisms of the magmatic-hydrothermal system that formed the deposit by combining the results of fluid inclusion petrography, microthermometry, scanning electron microscope-cathodoluminescence imaging, and stable isotope analyses of multiple quartz-dominated veins. Four distinct sets of quartz-dominated veins and eight generations of quartz (Q1–Q8) within the veins were identified, namely from early to late, early barren quartz veins (V1) comprised of equigranular CL-bright Q1 quartz, quartz–pyrite–chalcopyrite ± magnetite veins (V2) containing early equigranular CL-bright Q1 quartz and later CL-gray or CL-dark Q2–3 (Q2 + Q3) quartz grains intergrown with Cu–Fe sulfides, quartz–molybdenite ± pyrite ± chalcopyrite veins (V3) comprised of quartz grains (Q4–Q6) characterized by subhedral comb-like textures with well-developed oscillatory growth zoning, and late quartz veins (V4) containing CL-gray Q7 quartz with euhedral growth zones and later CL-dark Q8 quartz. Fluid inclusions in these veins can be classified into six types: B40, B40H, B80, B15H, B15H+, and B15. The B40 and B40H inclusions; B80 inclusions; and B15, B15H, and B15H+ inclusions contain vapor bubbles occupying 30–60 vol%, >70 vol%, and 5–25 vol%, respectively; in addition, B15H, B15H+, and B40H inclusions contain transparent daughter minerals (halite, and in some cases, sylvite). Raman spectra showed that CO 2 is only present in B40 and B80 inclusions. In the Q1 quartz in V1 and V2 veins, the dominant type of inclusions is B40, which have homogenization temperatures (Th) of 278 °C–389 °C (peaking at 310 °C–330 °C) and salinities of 2.0–12.8 wt% NaCl equiv. In Q2–3 quartz in V2 veins, all inclusion types were observed. These were trapped at temperatures of approximately 325 °C–340 °C and had salinities of 1.8–69.7 wt% NaCl equiv. In V3 veins, only B15H and B15 inclusions were observed, which had Th values of 171 °C–320 °C (peaking at 240 °C–260 °C) and 173 °C–317 °C (peaking at 210 °C–230 °C) and salinities of 28.7–33.9 wt% NaCl equiv and 5.6–23.1 wt% NaCl equiv, respectively. In V4 veins, only B15 inclusions were observed. Primary B15 inclusions in V4 veins yielded Th values of 166 °C–229 °C (peaking at 170 °C–200 °C) and salinities of 5.1–17.1 wt% NaCl equiv. The 3He/4He and 40Ar/36Ar ratios of the fluid inclusions exhibited the ranges of 0.08–0.84 Ra and 451.3–1567.8, respectively, and the δ18O fluid and δD fluid values varied from −3.2‰ to 5.8‰ and −92.8‰ to −80.3‰, respectively. By integrating all results from the fluid inclusion, cathodoluminescence, and isotopic analyses, we conclude that the initial ore-forming fluids of the No. 2 deposit were low-salinity, CO 2 -rich single-phase fluids of magmatic origin. Subsequently, fluid immiscibility developed in the initial ore-forming fluids, generating hypersaline liquid and low-salinity vapor phases and leading to the separation of a CO 2 phase plus chalcopyrite precipitation from the fluids. As meteoric water was injected into the hydrothermal system, the ore-forming fluids gradually evolved to become meteoric water-dominated, low temperature, low-salinity, and CO 2 -poor; in addition, fluid-cooling due to the meteoric water input resulted in molybdenite precipitation. [ABSTRACT FROM AUTHOR]