Characterization of the cobalt content in zinc ore from Zinkgruvan, Sweden

Abstract: Zinkgruvan is a stratiform Zn-Pb-Ag deposit located in the Bergslagen ore district in south central Sweden. Elevated concentrations of cobalt have been detected in zinc ore from the mine. Cobalt is one of EU’s critical raw materials, since cobalt is mainly mined in politically unstable countries like Congo and is an important metal needed in batteries for modern technology, e.g., electrical cars. However, elevated contents of cobalt can also cause problems during smelting of zinc ore and lower the value of zinc concentrates. Knowledge of the mineralogical deportment of cobalt is in this context critical, since accessory cobalt minerals could potentially be separated from zinc concentrates, whereas lattice-bound cobalt in sphalerite will follow the latter throughout the processing chain. In this study, the mineralogical distribution in zinc ore from three different main areas of Zinkgruvan (Knalla, Nygruvan and Westfield) has been investigated using optical microscopy, whole rock lithogeochemistry, Scanning Electron Microscope (SEM), Electron Microprobe Analysis (EMPA), Quantitative Target Mineralogy (QanTmin) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). The different datasets have been integrated in order to provide quantitative data on cobalt deportment in the samples, and for defining geochemical proxies that can be used to predict the cobalt deportment using only whole rock assay data. For the majority of the samples of this study, the cobalt content in sphalerite is higher than what has been reported in earlier studies of Zinkgruvan and are among the highest globally. In addition, this study provides the first account of high levels of lattice-bound cobalt in pyrrhotite at Zinkgruvan, for some samples being even higher than in sphalerite. Thus, the pyrrhotite could also potentially be separated from the zinc concentrate in order to dispose of some of the cobalt in the samples.  However, for the samples on which cobalt deportment calculations have been made, the results of the calculations suggest that for 50% of the samples most of the whole rock cobalt is lattice-bound to sphalerite, which is by far the predominant mineral in the zinc ore. For the remaining 50% of the samples most of the whole rock cobalt is bound to the cobalt mineral safflorite, which locally forms an important accessory mineral. No sample has the majority of the whole rock cobalt in pyrrhotite, reflecting the generally minor contents of this mineral in the zinc ore. In general, there is more lattice-bound cobalt in pyrrhotite and sphalerite in samples from Westfield and more cobalt bound to cobalt minerals in samples from Knalla. Samples from Nygruvan have very low whole rock cobalt contents altogether and contain no cobalt minerals. These spatial variations support ore genetic zonation models presented by earlier studies, with increasing Zn/Pb ratios and decreasing cobalt content in zinc ore from proximal to distal, in relation to an old hydrothermal vent zone at Knalla. However, the high cobalt and cadmium contents found at Westfield could imply that the vent zone might be more widespread than assumed by earlier studies.