Distribution of Co, Te, Se in porphyry copper systems: A case study of the Tonglvshan deposit, Eastern China

Porphyry copper systems contain porphyry Cu, skarn, carbonate-replacement and epithermal deposits, and presently supply nearly all the Te and Se, and have the potential to produce Co as by-product in the future. However, few studies have investigated the distribution of Co, Te, and Se in the specific porphyry-skarn deposit. Detailed mineralogical and geochemical analyses were conducted to investigate the distribution of Co, Te, and Se across porphyry, skarn, and carbonate-replacement ore types in the Tonglvshan porphyry-skarn Cu-Fe-Au deposit, Eastern China. The early sulfide stage in three ore types is characterized by Co-bearing pyrite (Py1a, Co up to 1.3 wt%) + droplet-like tetradymite ± hessite ± cattierite. The texture transition from coarse-grained, pore-free to porous Py1a in porphyry and skarn type ores suggests a shift from stable physico-chemical conditions to gentle fluid boiling, resulting in the precipitation of Co- and Te-bearing minerals. In contrast, fine-grained euhedral Py1a in carbonate-replacement type ores implies rapid cooling from high-temperature fluid interaction with marble.

The late sulfide stage, which only occurs in skarn and carbonate-replacement type ores, is characterized by Co-rich pyrite (Py2) + carrollite + hessite + Bi-sulfosalts. In skarn type ores, tetradymite-kawazulite solid solution (TKSS) + hessite + native Te + naumannite reflects intense boiling, leading to an increase in fO₂ and pH that precipitates Py2b (Co up to 19.2 wt%) and carrollite, while Te and Se may precipitate through vapor phase condensation. Conversely, the presence of fine-grained carrollite, zoned Py2a, sphalerite, and galena in carbonate-replacement type ore suggests that rapid cooling and increasing pH, resulting from fluid mixing, played a significant role in the precipitation Co and Te. Furthermore, the porous texture resulting from coupled dissolution-reprecipitation (CDR) during the late sulfide stage also provided favorable conditions for the formation of micro-nano sized critical metal particles.