Multistage fluid mixing events induced Sn polymetallic super-enrichment at Dulong in Yunnan Province, South China

Dulong Sn polymetallic deposit is a world-class skarn tin deposit situated at the Youjiang basin with a reserve of 0.4 Mt Sn at 0.56 %, 5.0 Mt Zn at 5.12 %, together with 7 kt In. The deposit predominantly occurs within the Neoproterozoic Xinzhaiyan Formation and is controlled by NS-trending faults. Based on elaborate field and petrographic observations, the Dulong Sn polymetallic deposit was divided into four mineralization stages: stage 1 (prograde stage), stage 2 (retrograde stage), stage 3 (quartz-sulfide stage) and stage 4 (carbonate stage). Tin mineralization primarily occurs as cassiterite during stage 2, with additional cassiterite-stannite formation noted in stage 3. Analysis of fluid inclusions across these stages reveals the evolutionary history of the mineralizing fluids and the precipitation mechanisms at Dulong. During stage 1, diopside hosts both daughter-bearing multiphase inclusions and vapor-rich inclusions. The daughter-bearing multiphase inclusions exhibit homogenization temperatures ranging from 510 to 574 °C and salinities between 44.7 and 49.6 wt% NaCl equiv., whereas the vapor-rich inclusions display homogenization temperatures of 573–586 °C and salinities from 2.9 to 4.0 wt% NaCl equiv., indicating a boiling fluid process. Cassiterite (stage 2) features primarily liquid-rich two-phase inclusions, with homogenization temperatures of 351–410 °C and salinities of 6.3–9.6 wt% NaCl equiv. These inclusions document the mixing of magmatic fluid with meteoric water, which is likely the principal mechanism driving initial tin mineralization. Similarly, the same type of inclusions is also recorded in cassiterite of stage 3. The homogenization temperature of the inclusions in cassiterite is 290–334 °C and the salinities of the inclusions is 3.4–8.4 wt% NaCl equiv. Comparatively, the temperature continued to decrease in stage 3, indicating that fluid mixing may have persisted during this stage which could also explain the occurrence of cassiterite and stannite in this stage. In addition, redox reaction where CO₂ and/or As (III) serve as oxidants may also be another mechanism to exact cassiterite from ore-forming fluid. Our Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) data suggests that cassiterite of the Dulong deposit involves a variety of complex substitutional mechanism. Due to the differing geochemical properties of the elements and variations in their concentrations, there is an indication that two phases distinct mineralizing fluids may have been present. The varying geochemical properties and concentrations of elements such as Nb, Ta, Zr, Fe, In, and Ga align with microthermometric results, indicating a reduction in magmatic hydrothermal fluid contribution and/or a transition from high to low temperatures in the hydrothermal system. This variation is also likely attributable to fluid mixing processes.