Within the Variscan Karkonosze pluton (NE Bohemian Massif), the Szklarska Poręba Huta quarry hosts multistage post-magmatic mineralisation disseminated in aplogranites, pegmatites, and quartz veins, comprising W-Sn-Mo-Bi and Th-Nb-REE assemblages. In this study, diverse Bi sulphides, sulphosalts, and chalcogenides were identified and characterised, and trace-element compositions of associated base-metal sulphides were determined to reconstruct the crystallisation sequence and metal distribution during hydrothermal fluid evolution.LA-ICP-MS data reveal strong geochemical contrasts between base-metal sulphides from aplogranites and quartz veins. The mineralisation records a transition from late-magmatic to hydrothermal conditions, defining three successive, partly overlapping stages within a mineralising continuum. Early aplogranite-hosted mineralisation was dominated by pyrite–pyrrhotite, accompanied by W-Sn-Mo minerals, other base-metal sulphides, bismuthinite, and bismuth. Pyrite from this stage shows high enrichment in Mo, W, As, Co, and Ni, with progressive Ni depletion relative to Co as temperature decreases. Subsequent quartz-vein mineralisation was initially characterised by abundant W-Sn-Mo minerals associated with Fe-sulphides, which show continued Ni depletion followed by a decrease in Co availability. With progressive cooling, chalcopyrite and sphalerite became dominant, incorporating Cd, Ag, In, and Sn from the mineralising fluids. Bismuth and bismuthinite were also present, accompanied by the crystallisation of rare Pb-Bi-Ag sulphosalts. The late stage was characterised by various Cu-Bi sulphosalts, Bi chalcogenides, and a second generation of base-metal sulphides.Paragenetic and trace-element data indicate that base-metal sulphides and Bi-bearing phases crystallised over a broad temperature range from ≥ 400 to ∼200 °C during progressive cooling and fluid fractionation, reflecting changes in fS2 and redox state. These parameters controlled the distribution of base and critical metals among successive mineral assemblages throughout the system evolution. The Szklarska Poręba–Huta mineralisation provides new insights into the mechanisms responsible for the development of CRM-bearing granite-related mineralising systems in the Bohemian Massif and Central Europe.

In this work, we evaluated the biological and geological contributions to the formation and preservation of the oxidation zones in & Lcaron;ubietov & aacute;-Podlipa, & Lcaron;ubietov & aacute;-Sv & auml;todu & scaron;n & aacute;, Poniky-Farbi & scaron;te and & Scaron;pania Dolina-Piesky. This case study highlights the importance of the biological contribution to weathering processes of ore deposits. It may be extended to other similar sites in order to assess the magnitude of biological input. Using U-Pb dating, secondary minerals from Podlipa were dated to 22 +/- 6 and 19 +/- 4 Ma (Lower Miocene). At this time, this region experienced deep weathering under a humid and warm climate and tectonic quiescence. The isotopic (O, H) composition of the secondary minerals shows that they formed from Lower Miocene meteoric water under surface temperatures. The delta C-13(PDB) values in malachite (-19 to -17 parts per thousand) document a biological source of C, from soil CO2. The delta O-18(VSMOW) values of the PO4 groups in the accessory fluorapatite in the host rocks (1.8 +/- 1.7 parts per thousand, 1 sigma) and pseudomalachite in the oxidation zone (12.1 +/- 2.9 parts per thousand, 1 sigma) show substantial biological P input into the oxidation zone. A biogenic source of both C and P agrees well with the palaeoclimatic constraints based on the radiometric dating. The oxidation zones at Podlipa, Sv & auml;todu & scaron;n & aacute; and Farbi & scaron;te are contemporaneous with kaolin crusts in the same area; they were all preserved only where they were covered by young (14-12 Ma) volcanic rocks and exposed recently by erosion. The other oxidation zones in the Tatric and Veporic units, if they existed, were destroyed by the Pliocene uplift of these units. The oxidation zone at Piesky is younger, dated to 2.5 Ma (Early Pleistocene) when the global temperatures in interglacials were similar to the present, decreasing in glacials by similar to 4 degrees C. The different climate at this time is manifested by scattered delta C-13 values, reflecting surface temperature and vegetation fluctuations at this time.

Sulphur-oxidising autotrophic bacterial communities in deep biosphere from weathered ore samples from active gold mine Hodruša-Hámre, Slovakia were analysed using cultivation approach followed by DNA extraction, PCR amplification and 16S rRNA gene analyses. Indirect measurement of pH changes in cultivation media evidenced the presence of acidophilic bacteria with active production of acids. The decrease of pH was observed at the beginning of isolation and later pH in range of 1.5 – 2 was maintained in both, sulphuric acid and thiosulphate, media. The presence of homogenous population of gram-negative rods was proved by Gram staining. Molecular analyses have revealed that the population of sulphur-oxidising bacteria in gold mine is dominated by a single species of Aciditiobacillus genus, identified as A. albertensis, suggesting the low level of autotrophic bacteria diversity in deep deposits. For the first time this species was isolated from weathered rocks of a gold mine subsurface environment.

Interest in the Ruska Polyana subalkaline rare-metal granite is due to a wide range of their accessory minerals. There are few studies of accessory minerals of these granites and their chemical composition and the paper is aimed at filling this gap and identifying the main concentrations of rare elements in the granites. Granites samples from deep wells, drilled in the southeastern area of rare-metal mineralization of the Ruska Polyana massif (Ruska Polyana Village) are investigated by scanning electron microscope JEOLJSM-6700F with EDS JED-2300 (M. P Semenenko Institute of Geochemistry, Mineralogy and Ore Formation of the NAS of Ukraine, Kyiv) rnicroanalyzer JEOL JXA-8200 (Technical Center of the National Academy of Sciences of Ukraine, Kyiv) and microprobe JEOL JXA-8530F (The Earth Science Institute of the Slovak Academy of Sciences, Banska Bystrica). The Ruska Polyana granites contain accessory minerals zircon, thorite, fluorapatite, xenotime-(Y), monazite-(Ce), columbite-(Fe), ilmenorutile, rutile, ilmenite, gadolinite-(Y), (hingganite-(Y)) (?), synchisite-(Ce), bastnaesite-(Y), parisite-(Ce) (?), fluorite. This paper discusses their chemical composition. The composition of the accessory minerals of the Ruska Polyana granites is generally similar to that of rare-metal granites of the late phases of the magmatic activity of the Korosten complex. The presence of fluids has caused post-magmatic granite alteration, which resulted in formation a two-stage rare-metal mineralization. Zircon-apatite-xenotime-monazite-gadolinite-columbite-ilmenite association is typical of the early stage, and the late stage is characterized by fluorite-synchisite-parisite-bastnaesite-ilmenorutile associations.

The neutral mine drainage system at Eubietova in Slovakia is overwhelmingly dominated by copper (17 ppm in the most concentrated aqueous sample) and sulfate and almost devoid of iron (0.7 ppb in the most concentrated aqueous sample). This mine drainage is generated by oxidative dissolution of chalcopyrite (CuFeS2), as confirmed by sulfur isotopes, and its neutral nature is maintained by buffering via the primary carbonates. The rich oxidation zone, composed of abundant libethenite (Cu-2(PO4)(OH)), pseudomalachite (Cu-5(PO4)(2)(OH)4), and malachite (Cu-2(CO3)(OH)(2)), appears to play only a passive and negligible role in the mine drainage generation. The copper- and sulfate-laden water is discharged through the lowermost adits in the ore field; inside the adits, blue gel covers the stream and converts slowly to crystalline langite (Cu-4(SO4)(OH)(6)center dot 2H(2)O). X-ray absorption spectroscopy on Cu K edge showed that the local structure inside the gel is similar to that in langite. Calculation of saturation indices showed supersaturation with respect to sulfates (langite, brochantite (Cu-4(SO4 )(OH)(6))), malachite, and copper arsenates and phosphates. Arsenates and phosphates were not found and do not form, probably because of kinetic hindrance. The solubility product of langite was estimated as log K-sp = 17.73. Outside of the adits, transmission electron microscopy showed redox cycling of copper via the formation of nanocrystals of native copper on rock-forming sheet silicates. The copper concentrations are naturally attenuated, being reduced by a factor of 100 once the mine drainage reaches the Hutna river, about 1 km away from the discharge site. Sulfur isotopes document that no copper sulfides are precipitating; copper must be removed from the contaminated water in the form of sulfates or carbonates. The natural attenuation could be responsible for the enrichment of hyporheic sediments with copper whose mineralogy and geochemistry is unknown but its size is estimated to several metric tonnes of copper.

Raman spectroscopy was used to investigate the lead–antimony sulfosalts minerals: boulangerite (Pb5Sb4S11), jamesonite (FePb4Sb6S14), robinsonite (Pb4Sb6Sl3) and zinkenite (Pb9Sb22S42). Raman bands of the investigated minerals that have interconnected SbS3 pyramids are found between 375 and 50cm−1. The stretching and bending modes of SbS3 groups occur between 375 and 175cm−1 in boulangerite, 350 and 180cm−1 in jamesonite, 350 and 175cm−1 in robinsonite and zinkenite. The investigated minerals show approximate similarities in their spectral features with those of minerals containing pyramidal SbS3 groups.

Rare Cu–Bi sulphosalt, hodrusite, occurs in the Rozalia vein (levels X–XIV of the Rozalia mine, Hodrusa-Hamre ore deposit near Banska Stiavnica, central Slovakia) in two unusual morphological forms. The first type are brownish bronze thin acicular striated crystals, up to 3 mm long, in drusy cavities of quartz–hematite gangue, which are usually grouped into chaotic or irregular aggregates. The second hodrusite type comprises flattened columnar aggregates, up to 1.5 cm long, overgrown by hematite in quartz gangue. These aggregates are distinctly striated with brownish bronze colour and metallic lustre. Abundant W- and Al-rich hematite, chalcopyrite, kaolinite/dickite, siderite, baryte, rare bismuthinite and kupcikite were found in the association. The earliest columnar aggregates of hodrusite are locally substantially replaced by bismuthinite; these hodrusite–bismuthinite aggregates are further intensively pushed back by hematite displaying W- and Al-rich zones. Acicular crystals of hodrusite in gangue cavities were later than bismuthinite and hematite and their formation was related to remobilisation of Cu and Bi from earlier altered gangue. Powder X-ray diffraction data and chemical composition of both hodrusite types are similar; their unit-cell parameters were refined (monoclinic space group C2/m) as: a 17.552(5), b 3.905(1), c 27.167(9) A, β 92.44(3) o

Abstract The Štiavnica Stratovolcano in Central Slovakia is the largest volcano in the Neogene to Quaternary Carpathian volcanic arc. A large caldera, an extensive subvolcanic intrusive complex and a resurgent horst with late stage rhyolite volcanites are the most characteristic features. The results of new K-Ar and Rb-Sr isotope dating using more sophisticated methodical approaches have changed our view on the timing of volcanic and intrusive activity. K-Ar dating of groundmass fractions combined with Rb-Sr isochron dating in the cases of possible rejuvenation has provided highly reliable results. The lifespan of the stratovolcano is apparently shorter than assumed earlier. Evolution of the stratovolcano took place in five stages during the Early Badenian to beginning of Early Pannonian time: (1) construction of the extensive andesite stratovolcano during the interval 15.0-13.5 Ma; (2) denudation of the volcano concluded with the initial subsidence of a caldera and the contemporaneous emplacement of a subvolcanic intrusive complex of diorite, granodiorite, granodiorite porphyries and quartz-diorite porphyries during the interval 13.5-12.9 Ma; (3) subsidence of the caldera and its filling by differentiated andesites during the interval 13.1-12.7 Ma - volcanic activity overlapping with the emplacement of the youngest intrusions; (4) renewed explosive and effusive activity of less differentiated andesites during the interval 12.7-12.2 Ma; (5) uplift of the resurgent horst in the central part of the caldera accompanied by rhyolite volcanic/intrusive activity during the interval 12.2-11.4 Ma. Extensive epithermal mineralization was contemporaneous with the uplift of the resurgent horst and rhyolite volcanic activity and continued till 10.7 Ma

The age of sericite from the epithermal Au-Ag-base metal mineralization of the Banská Štiavnica deposit was de­ termined for the first time by the low-blank К/Ar method. Typical magmatic rocks of the central part of the Banská Štiavnica stratovolcano, which are associated with the ore mineralization were dated. The К/Ar ages of the older (II and III) and final <V) magmatic stages (granodiorite porphyry, quartz-diorite porphyry, biotite-amphibole andesite, rhyolite, perlite) lay in the narrow interval of values from 12.7 ± 0.4 to 11.4 ± 1.2 Ma. The age of the hydrothermal sericite ac­ cording to isochron calculation is equal to 12.1 ± 0.2 Ma. These age values overlap if we take into account the analytical error margins. The proximity in age of all the magmatic events does not allow us to make age correlations of ore min­ eralization with specific magmatic complexes and formations. The time interval of the rock and Au-Ag-base metal min­ eralization formation in the central part of the Banská Štiavnica stratovolcano does not exceed 1-2 Ma and is similar to the time intervals for other comparable epithermal structures in the world, for example, Emperor (Tavua Caldera, Fiji), Sleeper (U.S. A) and others.

The dump-fields Podlipa and Reiner at Lubietova abandoned Cu-(Ag) deposit is situated at the boundary of the village settlement. The heavy metal contamination of the technogenous sediments and soils at the investigated dump-field show irregular planar distribution. Also the heavy metal content in the surface water, drainage water and in the groundwater was studied both in the dry as well as during the rainy periods. The speciation of As and Sb showed that there are present both As3+, Sb3+ as well as the less toxic As5+ and Sb5+ species. In the sediments prevail As5+ and Sb5+ species while in the water is dominant the As3+ and Sb3+ form. The article also presents results of the plant tissue degradation study in heavy metal contaminated conditions and compares them with those from reference sites. The cementation process causes substitution of iron by copper. The technogenous sediments and the contaminated soil of the dump show only very limited acidification potential. The installation of the Fe-0-barrier seems to an acceptable solution for cleaning of the underground water. (c) 2011 Published by Elsevier B.V. Selection and/or peer review under responsibility of University of Bucharest, Faculty of Geography, Department of Regional Geography and Environment, Centre for Environmental Research and Impact Studies.

An interesting association of the Bi sulfosalts was identified in the Rozalia mine, Hodrusa–Hamre, Slovakia. Sulfosalts of the cuprobismutite series are the most common, and occur in paragenesis with other Bi sulfosalts, chalcopyrite and hematite. Members of the pavonite homologous series are associated with bismuthinite derivatives and quartz of the amethyst variety. Three members of the cuprobismutite homologous series and four members of the pavonite homologous series have been found in a hydrothermal base-metal mineralization in the Rozalia mine. Kupcikite has the structural formula (Cu 6.73 Fe 1.10 ) ∑7.83 (Bi 9.49 As 0.36 Ag 0.24 ) ∑10.09 (S 18.89 Se 0.13 ) ∑19.02 ; that of hodrusite is (Cu 7.69 Fe 0.38 ) ∑8.07 (Bi 11.22 As 0.34 Ag 0.53 ) ∑12.09 (S 21.99 Se 0.17 ) ∑22.16 , and that of cuprobismutite is (Cu 7.47 Fe 0.14 ) ∑7.61 (Bi 12.81 As 0.69 Ag 1.38 ) ∑14.88 (S 23.85 Se 0.22 ) ∑24.07 . Makovickyite has the structural formula Cu 1.14 Ag 0,99 Pb 0.13 Bi 5.07 S 8.94 Se 0.06 ; that of pavonite is Cu 0.43 Ag 0.82 Fe 0.03 Pb 0.19 Bi 2.84 S 4.96 Se 0.04 , that of dantopaite is Cu 2.29 Ag 3.68 Fe 0.12 Pb 1.32 Bi 12.02 S 21.85 Se 0.15 , that of benjaminite is Cu 1.13 Ag 2.26 Fe 0.16 Pb 0.76 Bi 6.51 S 11.91 Se 0.09, and that of mummeite is Cu 1.44 Ag 2.61 Fe 0.41 Pb 0.95 Bi 6.70 S 12.93 Se 0.07 . The associated sulfosalts are paděraite, berryite and members of the bismuthinite–aikinite series (bismuthinite, gladite, krupkaite, lindstromite, friedrichite and aikinite).

The dump-field L'ubietova - Podlipa is situated at the boundary of the village settlement. The heavy metal contamination of the technogenous sediments and soils at the investigated dump-field show irregular planar distribution. Also the heavy metal content in the surface water, drainage water and in the groundwater was studied both in the dry as well as during the rainy periods. The cementation process causes substitution of iron by copper. Natural installation and development of plant species was observed at the old mine waste dumps, specific to the local chemical conditions such as low content of essential nutrients and high content of heavy metals. The individual parts of the plant tissues (roots, branches/stems, leaves/needles, flowers/fruits) are contaminated by heavy metals and tissues are damaged differently, respectively. The technogenous sediments and the contaminated soil of the dump show only very limited acid potential,

The results of scientific investigations of mineralogy, fluid inclusions and stable isotopes of epithermal precious and base metals ores at Biber, Rozalia and Terezia vein systems and subepithermal gold-quatrz ores at Svetozar vein system are discussed. The main physico-chemical parameters of oreforming process and the factors of metal concentration in ore determined.

The hydrometallurgical processing of complex concentrates represents an ecologically attractive alternative with respect to classical pyrometallurgical technologies. The leaching of gold from a mechanochemically pretreated CuPbZn complex sulfide concentrate of Slovak origin using ammonium thiosulfate was studied. Physicochemical transformations in the concentrate due to mechanical activation have an influence on the rate of extraction and the recovery of gold. It was possible to achieve 99% gold recovery within 45 min for a sample mechanically activated at an energy input of 403 kWh t−1. Only 54% of gold were recovered from the as-received concentrate in 120 min. Mechanical activation proved to be an appropriate pretreatment for this CuPbZn concentrate before extraction of gold into thiosulfate leaching solution.

The Banska Stiavnica Au-Ag base metals epithermal deposit is hosted within a Neogene-age volcanic caldera in central Slovakia. The caldera comprises a central granodiorite stock that has been capped by comagmatic andesite and rhyolite extrusions. The intrusive felsic rocks possess a close spatial and temporal relationship with the mineralization and associated hydrothermal alteration. To investigate the possible genetic link between magmatic and hydrothermal activity paragenetically constrained melt and fluid inclusions in magmatic quartz and vein minerals were studied, using microthermometric techniques. Primary melt inclusions in magmatic quartz from the granodiorite vary in composition from essentially silicate H2O- and Cl-rich melt with low-salinity fluid (8.3-9.6 wt % NaCl equiv) to high-density hypersaline brines (similar to 80 wt % NaCl equiv). Salinities of secondary fluid inclusions in magmatic quartz systematically decrease along the NaCl saturation curve toward lower temperatures and salinities equivalent to those determined for primary fluid inclusions in sphalerite and vein minerals (quartz, barite, fluorite) within the deposit (<400 degrees C, <12 wt % NaCl equiv). This systematic evolution in measured and calculated characteristics (temperature, pressure, salinity, and density) of the studied fluid inclusions indicates that exsolved magmatic brines and aqueous chloride solutions were the primitive precursors to the hydrothermal ore-forming fluids that produced epithermal mineralization upon mixing with meteoric waters in the near-surface environment.