Tracing metal source of copper-rich tungsten mineralization: Evidence from individual fluid inclusion analysis of the Huangsha Cu-rich W deposit in South China

The Huangsha Cu-rich W deposit, located in the northeast part of the Nanling region, is a typical large-size wolframite-quartz vein-type W deposit with considerable reserves of copper. Wolframite and chalcopyrite usually distribute in the same quartz veins, while field and petrographic observation show that wolframite commonly precipitates earlier than coexisting quartz and sulfides. Veined quartz can be divided into three successive generations (Q1, Q2, and Q3) based on SEM-CL imaging, and only Q2 is strictly coeval with chalcopyrite and other sulfides. Primary two-phase aqueous (type Lw) fluid inclusions are identified from wolframite with homogenization temperatures of 292 to 327 degrees C and salinities of 6.9 to 9.9 wt% NaCl equiv. Pseudosecondary two-phase aqueous (type Lq) and vapor-rich (type Vq) fluid inclusions are recognized from Q2, supporting the occurrence of fluid immiscibility. Homogenization temperatures of type Lq inclusions in Q2 range from 200 to 258 degrees C with salinities of 4.3 to 7.7 wt% NaCl equiv. LA-ICP-MS analysis shows that all inclusions contain Na and K as the major cations. For all the detected elements, type Lw inclusions in wolframite have higher concentration ratios X/Na than type Lq inclusions to varying degrees. The ore-forming fluid in both W and Cu mineralization stages share the same characteristics of high B concentrations, consistent Rb/Cs ratios and evolving nature of ore metals, indicating that W and Cu were sourced from the same magmatic fluid but precipitated in different mineralization stages. The variation of fluid Sr concentration likely indicates fluid-rock interaction during precipitation of wolframite, whereas the deposition of chalcopyrite is possibly influenced by fluid cooling and immiscibility. Compared with typical porphyry Cu systems and W/Sn mineralized systems worldwide, the ore-forming fluid in the W mineralization stage at Huangsha shows considerably higher mineralization potential of Cu, which is consistent with the geological fact. The Cu contents in initial W oreforming fluids may serve as an indicator in identifying Cu-rich W deposits.