We applied geochemical (ICP-MS, WD-XRF, GFAAS, and AMA 254) and mineralogical (EPMA) studies of 137 samples to ore mineralization from Middle-Triassic sediment-hosted Zn-Pb (Mississippi Valley-type MVT) and Lower Zechstein sediment-hosted stratiform (SSC) Cu-Ag (Kupferschiefer-type) deposits in Poland. They contain a number of trace elements which are not recovered during the ore processing. Only Cu, Ag, Pb, Ni, Re, Se, Au, and PGE are extracted from Cu-Ag deposits while Zn and Pb are the only elements produced from Zn-Pb deposits. Zn-Pb deposits contain Cd, Ag, Ga, and Ba in slightly elevated concentrations and have potential to be mineral resources. This applies to a lesser extent to other trace elements (Bi, As, Hf, Tl, Sb, Se, and Re). However, only Cd and Ag show high enrichment factors indicative of potential for recovery. The bulk-rock analyses reveal strong correlations between Zn and Cd and Se, As and Mo, and weaker correlations between Ag and Cd, as well as Ga and Zn. Electron microprobe analyses of sphalerite revealed high concentrations of Cd (≤2.6 wt%) and Ag (≤3300 ppm). Zn-Pb deposits have fairly significant estimated resources of Ga and Sc (>1000 tons) and Cd (>10,000 tons). The Cu-Ag deposits have element signatures characterized by high values of Co, V, Ni, and Mo and much lower of Bi, As, Cd, Hg, Mo, Sb, and Tl. Bulk-rock analyses show strong correlations between Se and V; As and Co; Bi and Re; and weaker correlations between, for example, Cu and Mo; V, Ni, Ag and Mo; and Ni, V, and Co and Ni. The EPMA determinations reveal strong enrichments of Ag in Cu sulfides (geerite ≤ 10.1 wt %, chalcocite ≤ 6.28 wt %, bornite ≤ 3.29 wt %, djurleite ≤ 9080 ppm, yarrowite ≤ 6614 ppm, and digenite ≤ 3545 ppm). Silver minerals and alloys, as well as the native Ag and Au, were recorded in the Cu-Ag ores. Large resources of Co, V, and Ni (>100,000 tons) and Sc and Mo (>10,000 tons) are notable in Cu-Ag deposits. A number of trace elements, classified as critical for the economy of the European Union, including Ga and Ba (to a lesser extent Hf, Nb, and Sc) in Zn-Pb deposits, and Co and V in the Cu-Ag deposits, may eventually be recovered in the future from the studied deposits if proper ore-processing circuits and increasing demand are favorable.
As part of the research subject of the Polish Geological Survey, funded by NFOŚiGW, a research project was carried out at PGI-NRI in 2015–2018. Its main task was quantitative and qualitative identification of elements accompanying the main ore and associated elements, including critical ones, and mineralogical identification of their main carriers in metallic ore deposits documented after World War II, representing the main metallogenic formations in Poland. The research focused mainly on drill cores from historical survey boreholes, rarely samples from open-pits and deep mines, representing: Mesozoic Zn-Pb ores, Lower Zechstein Cu-Ag ores, Mesoproterozoic Fe-Ti-V ores, Mo-Cu-W porphyry ores, stratiform Sn ores in the Sudetes, Variscan vein and metasomatic Au-As polymetallic ores, and Cenozoic Ni ores. The PIG-PIB Chemical Laboratory performed analytical work (ICP-MS, WD-XRF, GF-ASS), which allowed quantitative identification of approximately 60 chemical elements. In addition, complementary mineralogical and petrographic studies of the trace element carriers were carried out using a polarizing microscope and an electron microprobe (CAMECA SX-100). Before sampling, metal ore-bearing intervals were examined for the content of chemical elements using a portable spectrometer (Olympus XRF Delta). The results indicate the presence of numerous elements in studied deposits, including those currently regarded as critical for the European Union economy. The collected materials allowed both developing detailed geochemical and mineralogical characteristics of ores from individual deposits and identifying critical elements. They show a clear correlation with the main ore metals, and their resources can be a matter of interest in terms of raw materials.
On the basis of geochemical whole-rock and mineralogical point analyses, the concentrations of V and Co were determined in magnetite-ilmenite oxide ores, associated with sulphides, at the Krzemianka and Udryn deposits in the Mesoproterozoic Suwałki Anorthosite Massif (SAM) in NE Poland. EPMA analyses showed that the main carrier of vanadium was magnetite (mean = 0.42 wt%) and, to a lesser extent, ilmenite (mean = 0.14 wt%) and minor Al-spinels (mean = 0.04 wt%). In turn, cobalt was found mainly in the form of isomorphic substitutions in magmatic sulphides such as pentlandite (mean = 4.41 wt% Co), pyrrhotite (mean = 0.16 wt%), and chalcopyrite (mean = 0.11 wt%). Moreover, Co-enrichments were also recognized in the secondary sulphides, such as pyrite and bravoite, replacing pyrrhotite (means = 1.6 and 2.7 wt% Co, respectively), and in the form of different thiospinels ((Fe, Ni) (Co, Ni)2S4), mainly siegenite (mean = 22.0 wt% Co), replacing pyrrhotite and pentlandite. Vanadium cations were substituted in Fe, Ti oxide minerals in place of Fe + 3 cations, and in the case of cobalt, Fe + 2 cations were substituted in sulphides and thiospinels. Vanadium and cobalt showed high Person’s correlation coefficients (r = 0.70), indicating their close spatial coexistence and a common source, which was parental anorthosite-norite magma of the SAM suites. The common magma genesis of magnetite-ilmenite and sulphide mineralization was also confirmed by the very similar shapes of the curves of REE content in the oxide-sulphide ores in relation to chondrite, in which negative Eu anomalies and positive Sm anomalies are clearly visible. Although the average contents of vanadium and cobalt were low (arithmetic means = 960 ppm, and 122 ppm, respectively), the resources of these metals were estimated to be large due to the enormous reserves of magnetite-ilmenite ores hosted by the SAM. However, the Fe-Ti-V ores associated with Fe, Ni, Co, and Cu sulphides were considered to be sub-economic because of their depth of occurrence (mainly 1.0 km below the surface level); their metal contents, which were usually too low; and additionally the fact that the location is in a highly environmentally protected landscape and lake area.
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