Abstract

Skarn iron deposits, as representative examples of Co-rich magmatic-hydrothermal deposits, are attracting increasing attention due to rising cobalt demand worldwide. However, the specific Co enrichment mechanisms and metallogenic processes in skarn deposits remain elusive. This study presents high-precision in situ U–Pb geochronological data for garnet from skarns, major and trace element analyses of sulfarsenides and sulfides, and X-ray mapping in the Galinge deposit. The Galinge skarn iron deposit formed at 237.1 ± 0.3 Ma (garnet U–Pb dating), during which time the region was in the post-collisional stage. During this period, the crust was thickened, causing delamination of the lithospheric mantle, which further led to the upwelling of asthenospheric materials and partial melting of the lower crust. As the resultant mixed magma ascended, it reacted with carbonate strata to form skarn deposits. Cobalt shows two occurrence modes in the Galinge deposit: independent cobalt minerals such as skutterudite and cobaltite, and isomorphic substitution of Co with other metals in ore minerals (arsenopyrite, pyrrhotite, sphalerite, pyrite, magnetite, and chalcopyrite). Our results revealed that arsenopyrite is the most cobalt-enriched ore mineral in the Galinge deposit, with an average Co content of 34,077 ppm. Other minerals generally contain insignificant Co contents of less than 500 ppm, including sphalerite (471 ppm) > pyrite (194 ppm) > pyrrhotite (145 ppm) > alabandite (∼100 ppm) > magnetite (7 ppm) > chalcopyrite (2 ppm). In arsenopyrite, cobalt and nickel replace iron in accordance with the inverse correlation between the concentrations of cobalt and nickel (wt%) and that of iron. In pyrite and chalcopyrite, a portion of the isomorphic cobalt substitutes for Fe or Cu. The weak correlation between Co (ppm) and Cu or Fe (wt%) indicates that only isomorphic cobalt is carried out by substituting Fe or Cu. The negative correlation between Co + Fe and Zn or Mn suggests that cobalt and iron replace Zn or Mn in sphalerite and alabandite. No evidence of element substitution was observed in pyrrhotite. Our study highlights that during the early mineralization stage, cobalt in the magmatic-hydrothermal fluids migrated in the form of CoCl42-. Subsequently, under the influence of an increase in pH, CoCl42- reacts with H3AsO30 to form CoAs3 (skutterudite). With the continuous precipitation of arsenides and sulfarsenides, the As/S (reduced) ratio decreased, leading to the CoAs3 (skutterudite) changing to CoAsS (cobaltite).

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