Fluid evolution and mineralizing process of the Bawang Fe-Zn-Sn deposit, Danchi Fold-and-Thrust belt, South China

The Bawang deposit, a newly discovered Fe-Zn-Sn deposit occurred in the paleokarst in the Youjiang Basin, South China, offers an excellent opportunity to understand the ore-forming process and genesis of this unique tin mineralization, thus enriching the tin mineralization theories. Mineralogy, X-ray photoelectron spectroscopy (XPS), and laser ablation-inductively coupled plasma-mass (LA-ICP-MS) analysis were performed on sphalerite to investigate the fluid evolution and mineralizing process of the Bawang deposit. The formation of the deposit involved hydrothermal-cassiterite-sulfides and oxidation periods. The hydrothermal-cassiterite-sulfides period is dominated by the mineralization of Zn- (stage 1), Sn- (stage 2), and Sb- (stage 3) in order. Three types of sphalerite were identified in these hydrothermal stages. Mineralogical studies and spectrum data show that the massive sphalerite in stage 1 (Sp1) is euhedral coarse-grained and characterized by high Fe contents (9.67–15.69 wt%), with obvious pyrrhotite blebs, pyrite laths, stannite and/or chalcopyrite solid solutions. The sphalerite with 5.56–11.31 wt% Fe contents in stage 2 (Sp2) occurs as fine-grained, euhedral to subhedral crystals (15–50 μm) and coexists with cassiterite, arsenopyrite, and quartz. The sphalerite in stage 3 (Sp3) is characterized by low Fe content (0.59–2.99 wt%) and is generally micro-fine-grained (10–25 μm) associated with stibnite, sulfosalts, and carbonates. LA-ICP-MS analyses of sphalerite suggest that Sp1 and Sp2 have similar characteristics and are enriched in Fe, Cu, Sn, Ga, and Cd, whereas Sp3 is enriched in Sb, Pb, Ag, Bi, and Tl. The principal component analysis (PCA), boxplots, and bivariate plots of trace elements from sphalerite, combined with previous Raman spectroscopy data for fluid inclusions and H-O-Cd isotopic compositions, indicate two types of ore-forming fluids were involved in the mineralization of the Bawang deposit. The early Fe-Zn-Sn-Cu-In-rich fluids originated from granitic magma and underwent Zn- and Sn-dominated mineralization in order in a slowly cooling closed system. The later hydrothermal fluids with the addition of oil field brine were enriched in Sb, Pb, Ag, and Bi elements in the Sb-sulfosalts-carbonates stage in an open system with a drop in temperature. The mineralization process of the Bawang deposit can be concluded as follows: The early ore-forming fluids derived from an inferred concealed intrusion infilled into the paleokarst (below 350 m of the altitude) and caused the massive euhedral ferroan sphalerite (stage 1) to precipitate. The deposition of sphalerite decreased sulfur fugacity (fS2) in a slowly cooling closed system, and increased relative oxygen fugacity (fO2) which promoted cassiterite to precipitate in stage 2. The foreign hydrothermal fluids lowered the temperatures of residual ore-forming fluids due to the addition of oil field brine. Then the Pb-Sb sulfides and Pb-Sb-Ag-Bi-bearing sulfosalts (stage 3) crystallized at shallow depths (350 to 500 m of the altitude).