Garnet and scheelite as indicators of multi-stage tungsten mineralization in the Huangshaping deposit, southern Hunan province, China

Abstract

The Huangshaping W–Mo–Pb–Zn deposit in southern Hunan province, south China, contains multiple generations of garnet and scheelite in skarn and sulfide–carbonate altered rocks. Optical characteristics and chondrite-normalized rare earth element (REEN) patterns obtained by in situ laser ablation–inductively coupled plasma–mass spectrometry analysis were used to distinguish different generations of garnet and scheelite. These data show a clear correspondence of garnet REEN patterns to major element zonation, with HREEs (e.g., Gd–Lu) being depleted overall. Coarse-grained garnets in the Huangshaping deposit have extreme HREE depletions and significant LREE (e.g., La–Eu) enrichment, particularly for Ce, Pr, and Nd. This indicates that REEs in these garnets are the result of coupled substitutions: [Ca2+]VIII− 1[REE3+]VIII+1 and [Fe2+]IV +1[Al3+]IV − 1. Medium-grained garnets have REEN patterns showing significant LREE enrichment and depleted HREEs, with high Sn contents. This suggests that substitution of REEs in these garnets occurs as [Ca2+]VIII−1[REE3+]VIII+1[Sn4+]IV−1[Al3+]IV+1. The fact that medium-grained garnets have high Sn contents indicates mineralizing fluids were oxidizing, which is consistent with significant positive Eu anomalies. However, hump-shaped REEN patterns for garnet rims suggest substitution by: [Ca2+]VIII−2[Na+]VIII+1[REE3+]VIII+1, where Nd–Tb are preferentially incorporated into the garnet lattice over other REEs.Group-1a scheelite has black cores in cathodoluminescence images, and REEN patterns showing extreme LREE enrichment and HREE depletion. Group-1b scheelite has cores with fine oscillatory zoning and enriched LREEs with depleted HREEs, similar to the REEN patterns of Group-2a scheelite that occur as rims with bright CL surrounding both Group-1a and 1b scheelite. The substitution mechanism for REEs in these three types of scheelite is: [Ca2+]VIII−3[ ]VIII+1[REE3+]VIII+2, with [ ] being a Ca site vacancy. The influence of REE speciation in the hydrothermal fluid dominates the REEN patterns of these types of scheelite. However, for Group-2b bright rims of scheelite, REEs are incorporated as: [Ca2+]VIII−2[Na+]VIII+1[REE3+]VIII+1, similar to the garnet rims. Finally, scheelite Mo contents and δEu values that decrease from Group-1a to 2b support a temporal decrease in oxygen fugacity of the mineralizing fluids.Ratios of Y/Ho and Mo contents that decrease from Group-1a and 1b to Group-2a and 2b scheelites are similar to those in porphyry-related skarn W (Mo) and quartz vein Au–W deposits, respectively. Our studies also suggest that all these scheelites in this deposit formed from magmatic fluids. At the Huangshaping deposit, medium-grained garnets associated with Group-1a scheelite precipitated from evolved magmatic fluids during prograde metamorphism, as indicated by their complementary Y/Ho ratios. Paragentically younger scheelite, particularly Group-2b, may have formed from dilute magmatic fluids that underwent large-scale hydrothermal circulation. The characteristics of Group-1b and 2a scheelite likely reflect a transitional environment and fluid mixing during tungsten mineralization in the polymetallic Huangshaping deposit.