Trace Element Distributions in the Zn-Pb (Mississippi Valley-Type) and Cu-Ag (Kupferschiefer) Sediment-Hosted Deposits in Poland

Abstract

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.

EMPA, XRD, and Raman Characterization of Ag-Bearing Djurleite from the Lubin Mine, Lower Silesia, Poland

“…The chemical composition of djurleite in this study is similar to other in previously published data. However, the average content of Ag in the studied djurleite is higher than that published the authors of [7] (mean Ag content = 0.33 wt.%) and [6] (mean Ag content = 0.1 wt.%).…”

“…Kucha [5] confirmed the optical properties of djurleite and classified this mineral as one of the main Cu minerals in the Kupferschiefer stratum in Poland. Moreover, some chemical data for djurleite, based on EPMA, were previously presented [6,7].…”

A rare indium-bearing mineral (Zn-In-Cu-Fe sulphide) from the Stara Kamienica Schist Belt (Sudetes, SW Poland).

“…Chem i cal anal y ses in ac cor dance with stan dard pro cedures were car ried out in the Chem i cal Lab o ra tory of the Pol ish Geo log i cal In sti tute -Na tional Re search In sti tute in the pe riod 2016-2018. In dium, like most of the trace el e ments from rock sam ples of the Stara Kamienica Schist Belt, was de ter mined by In duc tively Cou pled Plasma Mass Spec trom e try (ICP-MS) (see Mikulski et al, 2020a for the method ap plied). The low est detec tion limit of in dium ICP-MS method de ter mi na tion was 0.05 ppm (Mikulski et al, 2020a).…”

“…In dium, like most of the trace el e ments from rock sam ples of the Stara Kamienica Schist Belt, was de ter mined by In duc tively Cou pled Plasma Mass Spec trom e try (ICP-MS) (see Mikulski et al, 2020a for the method ap plied). The low est detec tion limit of in dium ICP-MS method de ter mi na tion was 0.05 ppm (Mikulski et al, 2020a). De tailed min er al og i cal and pet ro log i cal in ves ti ga tion with pho to graphic doc u men ta tion of the cas sit er ite-sul phide min eral iza tion was car ried out on a NICON ECLIPSE LV100 POL micro scope with NIS-El e ments soft ware while quan ti ta tive measure ments were made us ing an elec tron microprobe (EMPA) CAMECA SX-100, pre ceded by pre lim i nary stud ies us ing an elec tron mi cro scope LEO-1430 (ZEISS) with EDS de tec tor.…”

Influence of Genetic Processes on Geochemistry of Fe-oxy-hydroxides in Supergene Zn Non-Sulfide Deposits

“…These minerals are rarely pure; on the contrary, they often contain elevated contents of economically significant metals (e.g., Zn, Pb, Co, REEs, Sc, Ga, Ge, In, V), as well as deleterious elements (i.e., Hg, Cd, Cr), and more common cations (i.e., Ca, Mn, Si and Mg). All these elements freely circulate in groundwater and can be adsorbed and/or incorporated in FeO/OH as a consequence of the high specific surface areas of their particles and strong affinities for the surface-binding heavy metals [5][6][7][8][9][10][11]. The mechanism accounting for "metallic impurities" incorporation into/onto the FeO/OH is not always straightforward but depends on several parameters in the system precipitating the minerals.…”