Primary Minerals and Age of The Hydrothermal Quartz Veins Containing U-Mo-(Pb, Bi, Te) Mineralization in the Majerská Valley near Čučma (Gemeric Unit, Spišsko-Gemerské Rudohorie Mts., Slovak Republic)

An occurrence of vein U-Mo mineralization is located in the Majerská valley near Čučma, about 7 km to the NNE of the district town of Rožňava (Eastern Slovakia). Mineralization is hosted in the acidic metapyroclastics of the Silurian Bystrý Potok Fm. (Gemeric Unit), and originated in the following stages: (I.) quartz I, fluorapatite I; (II.) quartz II, fluorapatite II, zircon, rutile chlorite, tourmaline; (III.) uraninite, molybdenite, U-Ti oxides; (IV.) pyrite I, ullmannite, gersdorffite, cobaltite; (Va.) galena, bismuth, tetradymite, joséite A and B, Bi3(TeS)2 mineral phase, (BiPb)(TeS) mineral phase, ikunolite; (Vb.) minerals of the kobellite–tintinaite series, cosalite; (VI.) pyrite II; (VII.) titanite, chlorite; and (VIII.) supergene mineral phases. The chemical in-situ electron-microprobe U-Pb dating of uraninite from a studied vein yielded an average age of around 265 Ma, corresponding to the Guadalupian Epoch of Permian; the obtained data corresponds with the age of Gemeric S-type granites. The age correlation of uraninite with the Gemeric S-type granites and the spatial connection of the studied mineralization with the Čučma granite allows us to assume that it is a Hercynian, granite-related (perigranitic) mineralization.

Mineralogická charakteristika granátického skarnu z lokality Trohanka pri Prakovciach (gemerikum, Slovenská republika)

Garnet skarn mineralization was recently studied at the Trohanka locality near Prakovce (Gemeric Unit, Eastern Slovakia). Ca-skarn forms lenticular bodies in green schist environment. It mainly consists of zonal garnets, pyroxenes, amphiboles and magnetite accumulations. Studied garnets are rich in andradite component (up to 89.95 mol. %) with minor grossular component (6.83 - 39.67 mol. %). Strong oscillatory zoning in andradite is caused by substitution of Fe3+ and Al3+. Most pyroxenes are rich in the hedenbergite component. In some cases, euhedral diopside crystals with marginal transition zones (composed of diopside with lower content of Mg2+ and higher content of Fe2+) were found in hedenbergite matrix. Amphiboles are dominantly represented by ferro-actinolite and ferro-hornblende in association with isolated euhedral crystals of ferro-tschermakite and ferro-pargasite. Indistinct chemical zonality of amphibole euhedral crystals is caused by presence of ferro-pargasite in the central parts and ferro-tschermakite in the peripheral parts of crystals.

Accessory minerals and evolution of tin-bearing S-type granites in the western segment of the Gemeric Unit (Western Carpathians)

The S-type accessory mineral assemblage of zircon, monazite-(Ce), fluorapatite and tourmaline in the cupolas of Permian granites of the Gemeric Unit underwent compositional changes and increased variability and volume due to intensive volatile flux. The extended S-type accessory mineral assemblage in the apical parts of the granite resulted in the formation of rare-metal granites from in-situ differentiation and includes abundant tourmaline, zircon, fluorapatite, monazite-(Ce), Nb–Ta–W minerals (Nb–Ta rutile, ferrocolumbite, manganocolumbite, ixiolite, Nb–Ta ferberite, hübnerite), cassiterite, topaz, molybdenite, arsenopyrite and aluminophosphates. The rare-metal granites from cupolas in the western segment of the Gemeric Unit represent the topaz–zinnwaldite granites, albitites and greisens. Zircon in these evolved rare-metal Li–F granite cupolas shows a larger xenotime-(Y) component and heterogeneous morphology compared to zircons from deeper porphyritic biotite granites. The zircon Zr/Hfwt ratio in deeper rooted porphyritic granite varies from 29 to 45, where in the differentiated upper granites an increase in Hf content results in a Zr/Hfwt ratio of 5. The cheralite component in monazite from porphyritic granites usually does not exceed 12 mol. %, however, highly evolved upper rare-metal granites have monazites with 14 to 20 mol. % and sometimes > 40 mol. % of cheralite. In granite cupolas, pure secondary fluorapatite is generated by exsolution of P from P-rich alkali feldspar and high P and F contents may stabilize aluminophosphates. The biotite granites contain scattered schorlitic tourmaline, while textural late-magmatic tourmaline is more alkali deficient with lower Ca content. The differentiated granites contain also nodular and dendritic tourmaline aggregations. The product of crystallization of volatile-enriched granite cupolas are not only variable in their accessory mineral assemblage that captures high field strength elements, but also in numerous veins in country rocks that often contain cassiterite and tourmaline. Volatile flux is documented by the tetrad effect via patterns of chondrite normalized REEs (T1,3 value 1.46). In situ differentiation and tectonic activity caused multiple intrusive events of fluid-rich magmas rich in incompatible elements, resulting in the formation of rare-metal phases in granite roofs. The emplacement of volatile-enriched magmas into upper crustal conditions was followed by deeper rooted porphyritic magma portion undergoing second boiling and re-melting to form porphyritic granite or granite-porphyry during its ascent.

First evidence for Permian-Triassic boundary volcanism in the Northern Gemericum: geochemistry and U-Pb zircon geochronology

Several magmatic events based on U-Pb zircon geochronology were recognized in the Permian sedimentary succession of the Northern Gemeric Unit (NGU). The Kungurian magmatic event is dominant. The later magmatism stage was documented at the Permian-Triassic boundary. The detrital zircon assemblages from surrounding sediments documented the Sakmarian magmatic age. The post-orogenic extensional/transtensional faulting controlled the magma ascent and its emplacement. The magmatic products are represented by the calc-alkaline volcanic rocks, ranging from basaltic metaandesite to metarhyolite, associated with subordinate metabasalt. The whole group of the studied NGU Permian metavolcanics has values for the Nb/La ratio at (0.44–0.27) and for the Nb/U ratio at (9.55–4.18), which suggests that they represent mainly crustal melts. Magma derivation from continental crust or underplated crust is also indicated by high values of Y/Nb ratios, ranging from 1.63 to 4.01. The new206U–238Pb zircon ages (concordia age at 269 ± 7 Ma) confirm the dominant Kungurian volcanic event in the NGU Permian sedimentary basin. Simultaneously, the Permian-Triassic boundary volcanism at 251 ± 4 Ma has been found for the first time. The NGU Permian volcanic activity was related to a polyphase extensional tectonic regime. Based on the new and previous U-Pb zircon ages, the bulk of the NGU Permian magmatic activity occurred during the Sakmarian and Kungurian. It was linked to the post-orogenic transpression/transtension tectonic movements that reflected the consolidation of the Variscan orogenic belt. The Permian-Triassic boundary magmatism was accompanied by extension, connected with the beginning of the Alpine Wilson cycle.

Alpine oxidation of lithium micas in Permian S-type granites (Gemeric unit, Western Carpathians, Slovakia)

Lithium micas of the zinnwaldite and phengite–Li-phengite series occur as characteristic minerals in Permian Li-F-(P) granites of the western Gemeric unit (Western Carpathians) accompanied by topaz, tourmaline, Nb, Ta, Ti, Sn oxides and aluminophosphates. The calculated Li2O contents of all the mica analysed, together with Rb2O and Cs2O were confirmed by LA-ICP-MS analyses for all the identified micas. Samples from three localities were investigated: two surficial (Surovec, Vrchsúl’ová); and one drill hole (Dlhá dolina). Zinnwaldite (polylithionite) occurs in the upper level of the Dlhá dolina granitic intrusion and in the nearby shallow satellite body of Surovec. The lower level porphyritic granites contain only siderophyllite. The Vrchsúl’ ová micas are closer in composition to Li-annite and siderophyllite. Dioctahedral micas are mostly phengites, although zinnwaldite-bearing granites are rich in late-crystallizing Li-phengite, which extensively replaces earlier zinnwaldite. The secondary Liphengite and phengite are interpreted as products of Alpine metamorphism during Cretaceous burial and subsequent exhumation of the Gemeric unit. Reactions are suggested explaining the formation of Li-phengite by reaction of zinnwaldite with phengite or with muscovite. All mica types were investigated by Mössbauer spectroscopy, which showed high degrees of oxidation (25–50% Fe3+ of total Fe) with the exception of zinnwaldite from Vrchsúl’ová, which may have preserved an original, reduced value of 10%. The metamorphic assemblage present permitted calculation of P-T-X conditions: T = 184°C, P = 320 MPa, with oxidation of siderophyllite to phengite + goethite and fO2 at ΔNN = 4.7, confirming the low-grade conditions of the Alpine metamorphism in agreement with previous estimates.

Re-Os and U-Th-Pb dating of the Rochovce granite and its mineralization (Western Carpathians, Slovakia)

The subsurface Rochovce granite intrusion was emplaced into the contact zone between two principal tectonic units (the Veporic Unit and the Gemeric Unit) of the Central Western Carpathians (CWC), Slovakia. The Cretaceous age of this granite and its Mo-W mineralization is shown using two independent methods: U-Pb on zircon and Re-Os on molybdenite. The studied zircons have a typical homogeneous character with oscillatory zoning and scarce restite cores. SHRIMP U-Pb data provide an age of 81.5 ± 0.7 Ma, whereas restite cores suggest a latest Neoproterozoic-Ediacaran age (~565 Ma) source. Zircon εHf(81) values -5.2 to + 0.2 suggest a lower crustal source, whereas one from the Neoproterozoic core εHf(565)= + 7.4 call for the mantle influenced old precursor. Two molybdenite- bearing samples of very different character affirm a genetic relation between W-Mo mineralization and the Rochovce granite. One sample, a quartz-molybdenite vein from the exocontact (altered quartz-sericite schist of the Ochtiná Formation), provides a Re-Os age of 81.4 ± 0.3 Ma. The second molybdenite occurs as 1-2 mm disseminations in finegrained granite, and provides an age of 81.6 ± 0.3 Ma. Both Re-Os ages are identical within their 2-sigma analytical uncertainty and suggest rapid exhumation as a consequence of post-collisional, orogen-parallel extension and unroofing. The Rochovce granite represents the northernmost occurrence of Cretaceous calc-alkaline magmatism with Mo-W mineralization associated with the Alpine-Balkan-Carpathian-Dinaride metallogenic belt.