Preliminary chemical and mineralogical characterization of tailings from base metal sulfide deposits in Serbia and North Macedonia

Tailings of old mines often contain metals, which were not of economic interest or could not be recovered with the existing technology at the time of active mining. This is especially true for metals that often occur as by-products in Cu-Pb-Zn-(Ag-Au) ores as Sb, Mo, Ge, and In. A fundamental characterization of some tailings is presented in terms of their mineralogy and content of valuable metals which could be extracted to finance a possible remediation and improve the supply of the EU with critical metals. Tailings from active and abandoned mines in Serbia (Bor, porphyry Cu/Au; Krivelj, porphyry Cu/Au; Blagodat, hydrothermal Pb-Zn; Lece, epithermal Au; Rudnik, hydrothermal/skarn Pb-Zn) and North Macedonia (Sasa, Pb-Zn; Probištip, Pb-Zn; Bučim, porphyry Cu; Lojane, fault-bound vein-type low-temperature As, Sb, Cr at the contact of rhyolite and serpentinite) were studied. Analysis for major and trace elements used a multi-method approach (lithium borate fusion and ICP-MS/OES analysis, gravimetric analysis, instrumental neutron activation analysis, total digestion ICP-OES, infrared spectroscopy) with mineral identification by scanning electron microscopy. Concentrations of the major commodity elements (Cu, Pb, Zn, Au, Ag) varies within several orders of magnitude depending on mineralogy and ore type. Critical metals (Co, Ga, Ge, Sb) contents are low with some exceptions. Some tailings contain moderate to elevated potentially toxic element levels (As, Cd, Pb, Tl). For the sample from Probištip which yielded the highest valuable metal concentrations (>5000 ppm Pb, 4020 ppm Zn), a heavy mineral concentrate of the sand size fraction (0.06 mm to 0.5 mm) was produced and analyzed by SEM and LA-ICP-MS for additional rare phases and trace elements. In all tailings studied, additional milling would be needed to separate ore from gangue minerals. Increasing metal prices might facilitate feasibility studies for some of the localities in the future, despite the limited quantitative information about the characterized tailings.