Xenotime-(Gd), ideally GdPO4, is a new mineral of the xenotime group. It was discovered at the Zimná Voda REE–U–Au occurrence near Prakovce, Western Carpathians, Slovakia. It forms rare crystal domains (≤20 μm, usually ≤10 μm in size) in Gd-rich xenotime-(Y) crystals (≤100 μm in size), in association with monazite-group minerals, uraninite, fluorapatite and uranyl arsenates–phosphates. The hydrothermal REE–U–Au mineralisation occurs in a quartz–muscovite vein, hosted in Palaeozoic phyllites near exocontact with Permian granites. The density is 5.26 g/cm3, based on calculated average empirical formula and unit-cell parameters. The average chemical composition (n = 6) measured by electron microprobe is as follows (wt.%): P2O5 30.1, As2O5 0.5, SiO2 0.2, UO2 0.3, Y2O3 15.7, (La, Ce, Pr, Nd)2O3 0.5, Sm2O3 5.7, Eu2O3 1.4, Gd2O3 29.2, Tb2O3 3.9, Dy2O3 10.4, Ho2O3 0.4, (Er, Tm, Yb, Lu)2O3 2.1, (Ca, Fe, Pb, Mn, Ba)O 0.1, total 100.5. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.37Y0.32Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Tm0.01Nd0.01…)Σ1.01(P0.98As0.01Si0.01)O4. The empirical formula of the Gd-richest composition is: (Gd0.38Y0.31Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Nd0.01Ho0.01…)Σ1.01(P0.98As0.01Si0.01)O4. The ideal formula is GdPO4. The xenotime-type structure has been confirmed by micro-Raman spectroscopy and a Fast Fourier-Transform pattern using HRTEM. Xenotime-(Gd) is tetragonal, space group I41/amd, a = 6.9589(5) Å, c = 6.0518(6) Å, V = 293.07(3) Å3 and Z = 4. The new mineral is named as an analogue of xenotime-(Y) and xenotime-(Yb) with Gd dominant among the REE. The middle REE enrichment of xenotime-(Gd) is shared with the associated monazite-(Gd) and Gd-rich hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing minerals is a product of selective complexing and enrichment in MREE in low-temperature hydrothermal fluids by alteration of uraninite, brannerite and fluorapatite on a micro-scale. The existence of xenotime-(Gd) and monazite-(Gd) is the first naturally documented dimorphism among REE phosphates. In addition, xenotime-(Gd) is only the third approved Gd-dominant mineral, after lepersonnite-(Gd) and monazite-(Gd).

This work is an investigation of the assemblages of supergene minerals occurring in hydrothermal REE–U–Au quartz-vein mineralisation at the Prakovce-Zimná Voda site, Slovakia. Heterogeneous uranyl arsenates and minor phosphates of the autunite group (nováčekite, kahlerite, threadgoldite, autunite, arsenuranospathite and chistyakovaite) together with scorodite and Sb–Bi-rich philipsbornite–segnitite-series minerals formed by oxidising fluids during decomposition and leaching of primary hypogene uraninite, brannerite and base-metal sulfides and sulfosalts. A progressive change of pH from acidic to near-neutral due to the gradual consumption of sulfides resulted in the formation of late phosphuranylite, pharmacosiderite and arseniosiderite. Goethite and other Fe oxides represent the latest hydrous ferric mineral phases and were formed after most of the As was already fixed in Fe arsenates. Antimony and Bi were taken up only into philipsbornite–segnitite and suggest unusual conditions during this process. X-ray absorption spectroscopy indicates that Sb in the philipsbornite–segnitite is fully oxidised (0.1–0.4 apfu Sb5+, octahedral coordination on the G site). Pentavalent Sb together with the presence of ferric oxides and arsenates and uranyl minerals suggest oxidative conditions during weathering. This study also indicates that hydrous ferric arsenates are dominant and stable secondary minerals in a supergene environment in a quartz vein rich in Fe and As accompanied by elevated concentrations of U, Pb, Sb, Bi, S, P, Ca and Ba under oxidising conditions.

The beryllium silicate minerals phenakite and bertrandite have been identified in granitic pegmatite dykes of the beryl-columbite subtype of Variscan age (~340−355 Ma), associated with S- to I-type granitic rocks of the Tatric Superunit, Western Carpathians (Slovakia). The two beryllium silicates and associated minerals were characterised by electron microprobe analysis, back-scattered electron petrography and cathodoluminescence imagery, X-ray diffraction and micro-Raman techniques. Phenakite and bertrandite form euhedral-to-anhedral crystals and aggregates in irregular domains and veinlets replacing primary magmatic beryl. A detailed textural study revealed a close genetic association of phenakite and bertrandite with secondary fine-grained quartz, K-feldspar and muscovite. Locally, clay phyllosilicate minerals, (with compositions similar to those of Fe-dominant hydrobiotite, beidellite, nontronite and saponite) occur as the youngest minerals. During the post-magmatic (hydrothermal) stage of the pegmatites, infiltration of aqueous K-bearing fluids at T ≈ 200–400°C resulted in the breakdown of magmatic beryl to secondary assemblages containing phenakite and bertrandite.

Two contrasting reaction coronae were developed around rare earth element (REE) accessory phosphates in Variscan metagranitic rocks, which have been overprinted by Alpine blastomylonitisation from the Fabova Hol'a Massif, in the Veporic Unit, Western Carpathians, Central Slovakia. The Th–U–Pb total EPMA age determination of primary magmatic monazite-(Ce) from the metagranite indicates a Carboniferous (Mississippian, Tournaisian) age of 355 ± 1.9 Ma. Monazite-(Ce) breakdown resulted in impressive, though common, fluorapatite ± Th-silicate + allanite-(Ce) + clinozoisite coronae. The alteration of xenotime-(Y) produced a novel type of secondary coronal micro-texture consisting of a massive fluorapatite mantle zone and tiny satellite crystals of hellandite-(Y) [(Ca,REE)4Y2Al□2(B4Si4O22)(OH)2] and hingganite-(Y) [Y2□Be2Si2O8(OH)2] of ~1–5 μm, and rarely ≤10 μm in size. The localised occurrence of Y–B–Be silicates, which are associated closely with other secondary minerals, suggests the involvement of B and Be during the metasomatic alteration transformation of xenotime-(Y). General reactions for monazite-(Ce) and xenotime-(Y) decomposition, including the fluids involved, can be written as follows: Mnz + (Ca, Fe, Si, Al and F)-rich fluid → FAp + Ht + Aln + Czo; Xtm + (Ca, Fe, Si, Al, F, B and Be)-rich fluid → FAp + Hld + Hin + Czo.

The granitic rocks underwent Early Cretaceous burial metamorphism under greenschist- to lower amphibolite-facies P–T conditions. Subsequently, Alpine post-collisional uplift and exhumation of the Veporic Unit, starting from the Late Cretaceous epoch, was accompanied by a retrograde tectono-metamorphic overprint; the activity of external fluids, caused the formation of secondary coronae minerals around monazite-(Ce) and xenotime-(Y). A portion of B (± Be) should have been liberated from the metagranite feldspars, micas, or xenotime-(Y) enriched in (Nb,Ta)BO4 (schiavinatoite or béhierite) components. However, the principal source of B and Be in fluids necessary for the production of hellandite and hingganite, was probably of external origin from adjacent magmatic, metamorphic, or sedimentary rocks (Permian granites, rhyolites and sedimentary rocks, and Palaeozoic metapelites).

The SC-3 speleothem from Szczelina Chochołowska Cave, located in the Tatra Mountains, was studied in detail. U-series dating and age–depth modeling allowed us to constrain the period of speleothem growth to between approximately 330 and 200 ka, that is, during Marine Isotope Stages (MIS) 9–7. The complementary use of stable isotope analyses, petrographic studies, and trace element analyses allowed the identification of warm and wet climatic conditions that were favorable for speleothem growth during MIS 9e and MIS 9c. Unfavorable climatic periods included the cold glacial conditions of MIS 8 and the MIS 9/MIS 8 transition. The breaks in the growth of the SC-3 stalagmite were most likely connected with a reduction in precipitation in MIS 9a and extreme hydrologic events during MIS 8. Comparisons with other European records suggest that the climatic variability recorded in the speleothem from the Tatra Mountains is not only a record of local environmental conditions but can also be linked to European climatic patterns during both interglacial and glacial intervals. This makes our study the northernmost paleoclimatic record for the whole Carpathian range and one of the very few records from those periods worldwide.

An electron microprobe study of Y-REE-Th phosphate, silicate and Nb-Ta-Y-REE accessory-mineral assemblages revealed the compositional variations and evolution in post-orogenic, hypersolvus Permian A-type metagranite from Turčok, in the Gemeric Unit, of the Western Carpathians, eastern Slovakia. Prismatic zircon I and allanite-(Ce) are primary magmatic phases. However, the late-magmatic to early-subsolidus processes led to the formation of a more complex younger assemblage: bipyramidal zircon II, xenotime-(Y), thorite, gadolinite-hingganite-(Y), Nb-Ta-Y-REE oxide phases [fergusonite-(beta)/ samarskite-(Y), aeschynite/polycrase-(Y), and Nb-rich rutile?] and possibly monazite-(Ce). However, monazite-(Ce) and the partial alteration of allanite-(Ce), xenotime-(Y) and the Nb-Ta-Y-REE minerals are probably connected with a younger Alpine metamorphic overprint of the granite. Thorite appears as a solid solution in the thorite-xenotime-zircon series; it is also enriched in Al. Fergusonite-(beta)/ samarskite-(Y) and especially aeschynite/polycrase-(Y) show increased P, Si and Al contents.

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.

Silicate minerals enriched in V, Cr and Mn including garnets and epidote-supergroup members, in association with amphiboles, albite, hyalophane, titanite, chamosite, sulfides and other minerals occur in Devonian black shales near Čierna Lehota in the Strážovské vrchy Mountains, Slovakia. The garnets have high concentrations of V, Cr and Mn (up to 17 wt.% V2O3, ≤11 wt.% Cr2O3 and ≤ 21 wt.% MnO) and several compositional types. Vanadian-chromian grossular (Grs 1) usually preserves primary metamorphic oscillatory zoning, whereas solid solutions between goldmanite (Gld 2A,B), V- and Cr-rich grossular and spessartine (Grs 2A,B, Sps 2) form irregular domains or crystals with variable zoning. Dominant substitutions in the garnets include CaMn–1 and (V,Cr)Al–1, resulting in coupled Ca(V,Cr)Mn–1Al–1. Epidote-supergroup minerals occur as abundant anhedral crystals with variable compositional zoning. Nearly all crystals have a complete zoning sequence beginning with REE-rich allanite-(La), followed by mukhinite and by V- and Cr-rich clinozoisite to mukhinite and V- and Cr-poor clinozoisite. In common with garnets, the epidote-supergroup minerals are enriched in V, Cr and Mn (<7 wt.% V2O3, <5 wt.% Cr2O3 and <3 wt.% MnO). Lanthanum is the dominant REE (up to 11.5 wt.% La2O3) in allanite-(La). The composition of epidote-supergroup minerals is controlled by REEFe2+(CaAl)–1, REEMg(CaAl)–1, REEMn2+(CaAl)–1 and REEFe2+(CaFe3+)–1 substitutions introducing REE, together with VAl–1 and CrAl–1 substitutions. The negative Ce and slightly positive Eu anomalies displayed in chondrite-normalized patterns and enrichment in V, Cr and Mn are ascribed to the geochemical properties of the protolith. The minerals investigated exhibit multi-stage evolution: (1) presumed low-grade greenschist-facies metamorphism; and (2) development of V- and Cr-rich zones in both garnet- and epidote-supergroup minerals which result from late-Variscan contact metamorphism due to granitic intrusion of the Suchý Massif. Decreased temperature following the metamorphic peak probably resulted in the formation of REE-, V- and Cr-poor clinozoisite and secondary garnet.

A combination of zircon (U–Th)/He (ZHe), apatite fission track (AFT) and apatite (U–Th)/He (AHe) dating methods is applied to constrain the metamorphic and exhumation history of the Tatric part of the Branisko Mountains in the Western Carpathians. ZHe ages from the basement samples prove the basement experienced a very low-grade to low-grade Eo-Alpine metamorphic overprint in mid-Cretaceous times. Miocene AFT and AHe ages found in the basement and in the Palaeogene sediments conclusively demonstrate that the Branisko Mts experienced a ‘mid-Miocene thermal event’. This thermal event had a regional character and was related to magmatic and/or burial heating that exposed the sediment and basement samples to ~ 120–130°C and ~ 100–190°C, respectively.

A new lichenized fungus, Lecanora microloba Śliwa & Flakus, is described from the subnival belt of the Polish Tatra Mountains. It is characterized by small, saxicolous thalli with minutely lobulate marginal areoles and mostly broadly sessile and constantly pale coloured apothecia that are grouped predominantly in the centre of the thallus. Anatomically the species is distinguished by coarse granules in the epithecium which are distinctly bright in polarized light. The species contains gyrophoric and usnic acids, zeorin and an unknown terpene as secondary metabolites.