Distribution of In, Sn, Ga, Ge, and other critical metals in sulfide ores from epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposit (Kosovo): Insights from mineralogy and geochemistry

This work presents a mineralogical and geochemical study of sulfide ores from the epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposit, which is located in the central part of the Kizhnica-Hajvalia-Badovc ore field, in the Trepça Mineral Belt (TMB) in Kosovo. Badovc is an example of one of many base-metal Pb–Zn–Ag deposits associated with the Serbo-Macedonian metallogenic province. There are three types of ores, the first two associated with polymetallic epithermal IS veins (massive-banded Pb–Zn–Sb and rhodochrosite-stibnite breccia) and disseminated ores associated with listvenites, which are hydrothermally altered mafic and ultramafic rocks. The mineralogy of these ores was described using EPMA in combination with reflected and transmitted light microscopy. The mineralogy of massive-banded Pb–Zn–Sb and rhodochrosite-stibnite breccia ores is relatively limited: sphalerite + rhodochrosite-siderite + pyrite/marcasite ± Pb–Sb sulfosalts ± stibnite. Listvenite Pb–Zn–Sb–Ni ores are more mineralogically variable due to the multi-stage formation of these rocks and the overprint of polymetallic mineralization. Apart from typical base-metal sulfides such as sphalerite, pyrite, galena, and chalcopyrite, the listvenite ores contain Fe–Mn carbonates, quartz, and Ni–Fe ± As ± Sb association (gersdorffite, ullmannite, millerite, and Ni–Fe thiospinels), Sn minerals (stannite and cassiterite). The LA-ICP-MS technique was used to determine critical metals occurring as minor and trace elements and substitution mechanisms in sphalerite, pyrite, stibnite, chalcopyrite and stibnite. The main critical metals, such as In, Sn, Ga, and Ge, are hosted by sphalerite in all types of ores. The highest concentrations of tin in sphalerite are observed in massive-banded Pb–Zn–Sb ores, which substitutes within the 3Zn2+ ↔ 2(Cu, Ag)+ + Sn4+ mechanism. The highest concentrations of indium are observed in sphalerites from listvenites, indicating the 2Zn2+ ↔ Cu+ + In3+ substitution. Low-temperature sphalerites from rhodochrosite-stibnite breccia exhibit elevated concentrations of Ga, Ge, and Ag, which incorporate into the structure through 2Zn2+ ↔ (Ag, Cu)+ + Ga3+, and 3Zn2+ ↔ 2(Cu, Ag)+ + Ge4+ mechanisms. The specific crystallization temperatures using GGIMFis for sphalerite are: 248–332 °C for massive-banded Pb–Zn–Sb ores, 208 °C for rhodochrosite-stibnite breccia, and 2112–344 °C for listvenite Pb–Zn–Sb–Ni ores. Additionally, stibnite from Badovc exhibits substitutions such as As3+ ↔ Sb3+ and (Cu+ + Ag+) + Pb2+ ↔ Sb3+ + □, and can incorporate various monovalent elements other than copper, including Ag+ and Tl+. Studies of epithermal listvenite-associated Badovc Pb–Zn–Sb–Ni deposits suggest that similar deposits spread across the Balkans may hold considerable prospectivity.