103 Annales Universitatis Paedagogicae Cracoviensis Studia Naturae, 3: 103–122, 2018, ISSN 2543-8832 DOI: 10.24917/25438832.3.8 Erika Remešicová1, Peter Andráš2*, Radmila Kučerová3 1Nábrežie armádneho generála L. Svobodu 5, 812 49 Bratislava 1 Bratislava, Slovakia 2Faculty of Natural Sciences, Matej Bel University, Tajovského 40, 974 01 Banská Bystrica, Slovakia, *peter.andras@umb.sk 3Technical University Ostrava, Ostrava – Poruba, Czechia Environmental characteristics of the mining area affected by sulphide minerals and acidification (Banská Štiavnica, Slovakia) Introduction The presence of sulphides in heaps and tailing ponds connected with the oxidation and subsequent acidification represents risk for the environment. Iron sulphates and H2SO4 are formed during reaction of the sulphides, air, and water. Fe2+ may be consequently oxidized and produce more acids. Bacteria have an important role in this process that significantly accelerates the oxidation (Ledin, Pedersen, 1996). The oxidation of the sulphides is a natural process, although naturally taking place much slower in geological time periods (Akcil, Koldas, 2006; Moreno, Neretnieks, 2006; Lottermoser, 2007; Jennings et al., 2008). Acidification removes mould, Ca, and Mg from the soils, mobilizes metals, and reduces the sorption capacity of the upper horizon causing its gradual destruction. Water entering the mining areas can enhance the oxidation process and pose a significant risk of acid mine water (AMD) formation. The metals released from AMD both to the surface water and ground- water are dangerous, particularly because of bioaccumulation, through which they are further spread into the food chain (Salomons, 1995; Thornton, 1996; Bell et al., 2001; Marqués et al., 2001; Šottník, 2005). Some of the mining waste pond sites may seem harmless, without producing AMD and become a source of contamination in few years or decades after the termination of mining operations and revegetation (Younger, Wolkersdorfer, 2004). The aim of this study was to examine the environmental characteristics of the min- ing area affected by sulphide minerals and acidification (Banská Štiavnica, Slovakia). Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 104 Study area, materials and methods Banská Štiavnica is situated in the southern part of Central Slovakia and belongs to the Protected Landscape Area Štiavnické Vrchy Mts. In the past, Banská Štiavnica be- longed to the most important Ag- and Pb- Zn- deposits of Europe. Areas of interest in this study are the tailing pond Sedem Žien and nearby hydroquartzite quarry Šobov. The deposit is situated in Neovolcanic rocks (diorite, andesite, rhyolite, and younger basalts). The dominant vein minerals are quartz, carbonates, sphalerite, galena, pyrite, chalcopyrite, hematite, gold, argentite, and stephanite (Koděra, 1963). The tailing pond was intentionally built according to the project of the mining company Banský projekt Košice (Križáni, Andráš, 2008). The pond is 44 m deep with the volume of 2.5 million cubic meters (Masarovičová et al., 2007). The area of the tailing pond is approx. 22 ha, and the dam of the pond consists of mine waste rocks and local soils. The pond is filled with mud from the flotation treatment plant of gale- na-sphalerite ore (Masarovičová et al., 2007). The tailing pond was in operation from 1963 until 1994. During the reclamation, the plain of the pond was covered with 2–3 Fig. 1. Localisation of the sampling points. S1 – 3: soil samples; R1 – 3: rock samples; W1 – 3: water samples (Maps source: Google earth) Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 105 meters of waste rocks coming from galena-sphalerite mine and partially of waste from the Šobov quarry on which was spread a layer of dam soils (Masarovičová et al., 2007). Sampling sites for soil material were as follows: sample 1 S1 – soil forming the second terrace of the pond’s dam; S2 – soil from the fourth terrace of the pond’s dam; and, S3 – soil from the surface of the top plane of the tailings pond. Rock samples were selected as follows: R1 – the rock material from the lower part of the Šobov quarry; R2 – rock material from the upper parts of the Šobov quarry; and, R3 – Pb-Zn ore. The analysed soils were sampled from the upper layer (20 cm) of the soil. At the sampling points of the water, pH, conductivity (Eh), dissolved oxygen and total dissolved solids of the samples were measured. The Šobov quarry is situated in the southwest direction from the pond. The deposit is formed by secondary quartz with dispersed pyrite. The tailing pond, Sedem Žien, and the Šobov quarry fulfil the technical and legislative requirements for categorisa- tion in the group of permanent environmental burdens (Masarovičová et al., 2007; SAZP.sk, 2015). Three sampling sites for each type of sample are presented in figure 1. The follow- ing water sampling sites were selected: water sample 1 (W1) – red coloured drainage percolating Sedem Žien tailing pond; water sample 2 (W2) – transparent drainage percolating tailing pond; and water sample 3 (W3) – accumulated drainage from hy- droquartzite quarry Šobov. The mineralogical composition of the pulverised soils and rocks samples was de- termined by X-ray diffraction analysis (XRD) using a Philips X’Pert Pro Multipur- pose X-ray Diffractometer, and the mineral morphology of the samples was studied by scanning electron microscope FEI XL 30. The concentrations of macro elements (Ca, Mg, Na, K) and metals (Fe, Al, Pb, Zn, Mn, Co, Cr, Ni, Cu) were measured in rock, soil, and water samples. The soils and rocks samples were moistened with 5 ml of HF to dissolve the silicates and with 1.5 mL of HClO4 to oxidize of the organic matter. The resulting compound was dried for 2 days at 150°C to dry salts. After the addition of 3.75 mL of 37% HCl and 1.25 mL of 69% HNO3 the samples were evaporated for 1 hour and mixed with distilled water. Analyses of metals and macro elements were realised by atomic absorption spectrom- etry using a Fast Sequential Atomic Adsorption Spectrometer Varian AA240 FS. The measurement of anions in the water was carried out with use of ion chroma- tography. Measuring F-, Cl- and sulphates (SO4)2- was performed by a Dionex ICS- 1000 Ion Chromatography System. The rinse pH (soil reaction) was measured in a suspension of 5 g soil sample in 25 ml of distilled water. A similar procedure was chosen for the determination of paste pH, which was measured in a suspension of 5 g soil in 25 ml of 1 M KCl after 1 hour of mixing in a magnetic stirrer. Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 106 Determination of isotopes of selected elements (carbon, oxygen, deuterium, sul- phur, nitrogen) is crucial in identifying the origin of the elements. δ13C represents the ratio between carbon isotopes 13C/12C, δ18O represents the ratio between 18O/16O, δ34S is 34S/32S ratio, and δD is the ratio of deuterium to light hydrogen 2H/1H (Mook, 2001; ŠGÚDŠ, 2012). Isotope measurements of sulphur (δ 14S) were carried out in all samples. The measurement of deuterium isotopes (δ D or δ 2H) and oxygen (δ 18O) was made in water samples, and carbon isotopes (δ 13C) measurements were made in rock and soil samples. In order to measure the isotopes of sulphur and carbon, solid samples were weighted in tin capsules and mixed with a catalyst of vanadium pentox- ide (V2O5). For the sulphur isotopes measurements, precipitation of barium sulphate (BaSO4) from the water samples was needed. The pH value of the samples was adapted to a value of 1 by the application of HCl. After adding 4 g of NaCl, the samples were boiled for 5 min, and consequently BaCl2 was added to the solution until a sufficient amount of BaSO4 was precipitated. Water samples measured for deuterium and oxide isotopes were filtered before analysis through a 0.2 µm membrane. Deuterium and ox- ygen were measured by a laser absorption spectroscope Laser Water Isotope Analyser OA-ICOS DLT-100 from Los Gatos Research, and isotopes C and N were measured by a mass spectrometry analyser Flash HT Plus Elemental Analyser connected to the instrument Delta V Advantage Isotope Ratio Mass spectrometer from Thermo Sci- entific. Isotopes are reported using the conventional δ notation relative to Canyon Diablo Troilite (V-CDT) for 34S, Vienna Standard Mean Ocean Water (V-SMOW) for D and 18O, and Vienna Pee Dee Belemnite (VPDB) for 13C (Ďurza, 2007). Tab. 1. Quantitative representation of the minerals in studied rock samples Sample ang anh ank ant cal clc ccp fsp gn ms po py qtz toz sp R1 + + ++ ++++ + R2 + * + ++ ++ +++ ++ R3 + + + + + +++ ++ +++ +++ ++++ Explanatory notes: from + mild representation, to ++++ dominant representation, * traces of the mineral; ang – anglesite, anh – anhydride, ank – ankerite, cal – calcite, clc – clinochlore, ccp – chalcopyrite, fsp – feldspar, gn – galena, ms – muscovite, po – pyrrhotite, py – pyrite, qtz – quartz, toz – topaz, sp – sphalerite Soil samples were analysed for the availability of metals and macro elements by single chemical extraction adapted from Tipping et al. (2003). The extraction of soil samples with grain size ≤ 2 mm was performed with 0.43 M HNO3. Triplicates of each soil at a ratio of 2 g air dried soil to 20 ml of extractant were mixed by end-over-end shaking for 2 hours and filtered through a 0.2 µm membrane. Samples were then ana- lysed using AAS Varian AA240 FS equipment. Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 107 Results Mineralogical characteristics of the rock samples XRD and SEM analyses of the rock samples’ mineralogical compositions showed that silica with sulphide minerals predominate in the samples. Sample R3 represents sphalerite-galena ore. XRD analysis confirmed the presence of the following sulphide minerals in the next samples: R1 – pyrrhotite, chalcopyrite, and sphalerite; in R2 – pyrite; and, in R3 – pyrite, pyrrhotite, chalcopyrite, galena, and sphalerite (Fig. 2; Tab. 1). SEM analysis enabled us to distinguish the following in sample R1: quartz – SiO2, fine-grained pyrite – FeS2 in the quartz matrix, galena – PbS, sphalerite – ZnS, anatase – TiO2 and zircon – ZrSiO4 (Appendix 1 – Fig. I). SEM analysis identified the following in sample R2: quartz, anatase, topaz, anhydride, and pyrite (FeS2; Appendix 1 – Fig. II). In rock sample R3 the following were identified: quartz, ankerite, clino- chlore, dolomite, pyrite, galena, sphalerite, and chalcopyrite (Appendix 1 – Fig. III). Mineralogical characteristics of the soil samples XRD analysis of soil samples confirmed the presence of the following minerals: quartz, albite, biotite, calcite, clinochlore, illite, ilmenite, jarosite, kaolinite, muscovite, and orthoclas (Fig. 3; Tab. 2). Fig. 2. The mineralogical composition of rock samples determined by XRD; Explanatory notes: ang – anglesite, anh – anhydride, ank – ankerite, cal – calcite, clc – clinochlore, ccp – chalcopyrite, fsp – feldspar, gn – galena, ms – muscovite, po – pyrrhotite, py – pyrite, qtz – quartz, toz – topaz, sp – sphalerite Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 108 Tab. 2. Quantitative representation of the minerals in studied soil samples Sample ab bt cal clc ill ilm jrs kln ms or qtz S1 ++ + ++ + ++ +++ S2 + + ++ + + ++ +++ S3 ++ + + + + ++ ++ +++ Explanatory notes: from + mild representation, to ++++ dominant representation, * traces of the mineral; Abbreviation of minerals as in figure 3 Tab. 3. AAS analysis of rock and soil samples Sample CaO MgO Na2O K2O Al2O3 Fe2O3 Mn Pb Co Cr Cu Ni Zn [mg.kg-1] R1 0.23 0.13 0.08 0.35 1.61 4.67 0.04 82.48 4.96 531 9.71 173 137 R2 0.27 0.10 0.12 4.65 22.47 75.82 0.01 0.5 mg.L-1, which is current Slovak limit concentration for waters resulting from the extraction of the ores Government Regulation 269/2010 Coll.). Differences in pH values between water percolating the tailing and quarry may be caused by more rapid weathering of disulphides than monosulphides, which could explain a slower oxidation of galena – PbS and sphalerite – ZnS in the tailing pond in comparison to pyrite – FeS2 dispersed in the quartz. Another reason for the differences in pH may be the presence of acidophilic sulphide-oxidizing bacteria (Acidithiobacillus ferrooxidans (Temple & Colmer) Kelly & Wood), which was previously found in the drainage water from Šobov quarry (Šlauková, Bella, 2006; Bella et al., 2010). The limiting factor for the oxidation is the transformation of Fe2+ to Fe3+, which is very slow in abiotic condi- tions with pH above 5 (Šottník, 2005). Interpretation of the geochemistry of stable isotopes (D, O, C, N, S) is complicated because of the fact that the minerals created by different processes may have the same isotopic composition and minerals created by same process; however, under differ- ent conditions, they may have significantly different isotopic compositions. Therefore, waters which percolate rocks and soils affected by the composition of ore minerals reflect all of the mentioned aspects. Variations in the isotopic composition of the nat- ural material are the result of isotope exchange reactions and kinetic isotope effects (Hladíková, 1988; Rollinson, 1988). Sulphur in natural materials can have various sources, and its isotopic composi- tion may reflect different processes that material overcame. In the tailing pond Sedem Žien, the main sources of sulphur are hydrothermal sulphides of mined polymetallic (Pb-Zn) ore and dispersed pyrite from the nearby Šobov quarry. Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 113 It is known that δ34S values in the surrounding of Banská Štiavnica are relatively homogeneous, and close to zero. Such values indicate the sulphur origin from sedi- mentary rocks (Sakai et al., 1982; Chaussidon et al., 1989). The negative δ 34S value in sample W3 (-2.19) is typical for the sulphur originating from the sulphides (Newman et al., 1991). The isotopic composition of sulphur in the solid samples (δ34S -1.48 to 4.48‰) mainly reflects the isotopic balance of the sulphides of the main Pb-Zn hy- drothermal mineralization in the ore field of Banská Štiavnica as well as the isotopic characteristics of sulphur in pyrite dispersed in the hydroquartsite mined in the vicin- ity of the tailing pond. The homogeneity of the composition indicates a magmatic origin of ores and a meteoric origin of the waters (Kantor, 1979; Burian et al., 1985). δ34S values of drain- age waters of the tailings pond correspond to the range of values for sulphur originat- ing in Central Europe from atmospheric precipitation (+3‰ to 5‰; Newman et al., 1991). Regarding the oxidation of sulphides, many studies on the effects of the isotopic composition have been done. The results of studies of the effects of oxidation in the presence of phototrophic bacteria diverge, but the oxidation in the presence of chem- otrophic bacteria shows clearer results. Kaplan-Rittenberg (1964) demonstrated the effect of oxidation in the presence of bacteria Thiobacillus concretivorus, as did Kelly & Harrison, when changes reached the range of -18‰ (ŠGÚDŠ, 2010). Isotopes 18O compose, in comparison with 16O, just a small part of oxygen, and their ratio helps to provide information about origins of the waters (Hoefs, 1987). The dependence between δ18O and δD ‰ values in the water indicates formation in the conditions of isotopic equilibrium. The isotopic composition of the δD values in the drainage water (δD 42.73 to -74.78‰) and of δ18O (-6.11 to -10.17‰) corresponds, according to Taylor (1974), Sheppard (1981), and Rollinson (1988), to meteoric water. Conclusion The studied area is contaminated by heavy metals (mainly by Fe, Pb, Zn, and Cu) and acidified. From the mineralogical point of view, the rock material is rich in quartz and sulphide minerals, which has an important influence on the chemical composition of soils and waters. The isotope study proved the meteoric origin of the waters, and sulphide origin of the sulphur in the waters. References Act No. 220 Coll. on the Conservation and Use of Agricultural Land (2004). Zákon č. 220/2004 Z. z. O ochrane a využívaní poľnohospodárskej pôdy a o zmene zákona č. 245/2003 Z. z. o integrovanej prevencii a kontrole znečisťovania životného prostredia a o zmene a doplnení niektorých zákonov. [In Slovak] Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 114 Akcil, A., Koldas, S. (2006). Acid Mine Drainage (AMD): causes. treatment and case studies. Journal of Cleaner Production, 14, 1139–1145. DOI: 10.1016/j.jclepro.2004.09.006 Bell, F.G., Bullock, S.E.T., Halbichc, T.F.J., Lindsay, P. (2001). Environmental impacts associated with an abandoned mine in the Witbank Coalfield, South Africa. International Journal of Coal Geology, 45, 195–216. DOI: 10.1016/S0166-5162(00)00033-1 Bella, P., Gaál, Ľ., Grego. J. (2010). Hydrotermálne kvarcitové jaskyne v lome Šobov pri Banskej Štiavnici. Slovenský Kras – Acta Carsologica Slovaca, 48(10), 19–30. [In Slovak] Burian, J., Slavkay, M., Štohl, J., Tőzsér, J., (1985). Metalogenéza neovulkanitov Slovenska. Bratislava: Alfa, 269. [In Slovak] Craig, H. (1961). Isotopic variations in meteoric waters. Science, 133, 1702–1703. DOI: 10.1016/0012- 821X(89)90042-3 Čurlík, J., Kolesár, M., Ďurža, O., Hiller, E. (2015). Dandelion (Taraxacum officinale) and agrimony (Agri- monia eupatoria) as indicators of geogenic contamination of flysch soils in Eastern Slovakia. Archives of Environmental Contamination and Toxicology, 69(2). DOI: 10.1007/s00244-015-0206-z Ďurža, O. (2007). Využitie pôdnej magnetometrie pri štúdiu kontaminácie pôd ťažkými kovmi. Acta Environmentalica Universitatis Comenianae, 15(1), 5–15. [In Slovak] Hladíková, J. (1988). Základy geochemie stabilních izotopů lehkých prvků. Brno: Univerzita Jana Evange- listy Purkině, 96. [In Czech] Hoefs, J. (1987). Stable Isotope Geochemistry. Berlin Heidelberg: Springer-Verlag, 241. Chaussidon, M., Albarede, F., Sheppard, S.M.F. (1989). Sulphur isotope variations in the mantle from iron microprobe analyses of micro-sulphide inclusions. Earth and Planetary Science Letters, 92, 144–156. IAEA – International Atomic Energy Agency. Global network of isotops in precipitation. http://www- naweb.iaea.org/napc/ih/IHS_resources_gnip.html Jennings, S.R., Neumann, D.R., Blicker, P.S. (2008). Acid mine drainage and effects on fish health and ecol- ogy: a review. Montana, Bozeman: Reclamation Research Group Publication. MT. Kantor, J. (1979). Izotopové zloženie síry zo sulfidických vzoriek rudného obvodu Banská Štiavnica. Brati- slava: GÚDŠ, 181. [In Slovak] Kaplan, I.R., Rittenberg, S.C. (1964). Microbial fractionation of sulphur isotopes. Journal of General Mi- crobiology, 34, 195–212. Koděra, M. (1963). Gezetzmässigkeiten der zonalen verteilung der mineralization an des subvulkanis- chen lagestätte Banská Štiavnica und Hodruša. Symp. – Problems Postmagmatic Ore Deposition I. Prag, 184–189. [In German] Križáni, I., Andráš, P. (2008). Modelovanie perkolácie sedimentov háld a odkalísk banskoštiavnického rudného revíru. Mineralia Slovaca, 40, 59–72. [In Slovak] Ledin, M., Pedersen, K. (1996). The environmental impact of mine wastes – Roles of microorgan- isms and their significance in treatment of mine wastes. Earth-Science Reviews, 41, 67–108. DOI: 10.1016/0012-8252(96)00016-5 Lottermoser, B.G. (2007). Mine wastes: characterization. treatment and environmental impacts. 2nd ed. London: Springer, 304. Marqués, M.J., Martínez-Conde, E., Rovira, J.V., Ordóňez, S. (2011). Heavy metals pollutions of aquatic ecosystems in the vicinity of a recently closed undersround lead-zinc mine (Basque Country. Spain). Environmental Geology, 40, 1125–1137. DOI: 10.1007/s002540100314 Masarovičová, M., Slávik, I., Kovalková, J. (2007). ZoD- 04 - 184 / 06. dod. 1/07. Kompletný monitoring odkalísk SR (časť 5). Bratislava: STU. Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 115 McCarten, N. (1992). Community structure and habitat relations in a serpentine grasland in California. In: A.J.M. Baker, J. Proctor, R.D. Reeves (eds.), The vegetation of ultramafic serpentine soils. Proc. of the first international conference on serpentine ecology. University of California: Davis California, 207–211. Mook, W.G. (2001). Environmental Isotopes in the environmental cycle. Technical Documents in Hydrol- ogy, 1(30), 280. Moreno, L., Neretnieks, I. (2006). Long-term environmental impact of tailings deposits. Hydrometallurgy, 83, 176–183. DOI: 10.1016/j.hydromet.2006.03.052 Newman, L., Krouse, H.R., Grinenko, V.A. (1991). Suphur isotopic variations in the atmosphere. In: H.R. Krouse, V.A. Grinenko (eds.), Stable isotopes: Natural and Antropogenic Sulphur in the environment. Chichester: SCPE 43. John Wiley and Sons, 133–176. Rollinson, H. (1998). Using geochemical data. Evaluation–Presentation–Interpretation. Singapore: Long- ma Publishers, 352. Sakai, H., Casadevall, T.J., Moore, J.G. (1982). Chemistry and isotope rations of sulfur and volcanic gases at Kilauea volcano (Hawaii). Geochimica et Cosmochimica Acta, 46, 729–738. DOI: 10.1016/0016- 7037(82)90024-2 Salomons, W. (1995). Environmental impact of metals derived from mining activities: processes. predic- tions. prevention. Heavy metal aspects of mining pollution and its remediation. Journal of Geochem- ical Exploration, 52(1/2), 5–23. DOI: 10.1016/0375-6742(94)00039-E SAZP – Slovenská Agentúra Životného Prostredia. http://www.sazp.sk/public/index/go.php?id=1433 [In Slovak] Sheppard, S.M.F. (1981). Stable isotope geochemistry of fluids. Physics and Chemistry of the Earth, 13/14, 419–445. DOI: 10.1016/0079-1946(81)90021-5 ŠGÚDŠ – Štátny geologický ústav Dionýza Štúra (2012). Využitie environmentálních izotopov v hydroge- ológii. In: Geology.sk: Náhradné zdroje vody. Bratislava: http://www.geology.sk/nahradnezdrojevody/ page.php?15 [In Slovak] Šlauková, E., Bella, J. (2006). Izolácia baktérií rodu Acidithiobacillus z kyslých banských vôd zo skládky odvalov v Banskej Štiavnici-Šobov a ich charakterizácia. In: Ľ. Stašík, J. Činka, B. Antonická (eds.), Odpady 2006 – zborník prednášok z medzinárodnej konferencie (Spišská Nová Ves, 9. – 10. 11. 2006). Spišská Nová Ves: Geológia PaB, 247–250. [In Slovak] Šottník, P. (2005). Pasívne čistenie kyslých banských vôd. Podporné materiály pre projektové vyučovanie. Zvyšovanie kvality odbornej prípravy v oblasti environmentálneho rizika odpadov ťažobného priemys- lu. JPD 3 2005/1-052. Ministerstvo školstva SR. [In Slovak] Taylor, H.P. (1974). The application of oxygen and hydrogen isotope studies to problems of hydrothermal alteration and ore deposition. Economic Geology, 843–883. DOI: 10.2113/gsecongeo.69.6.843 Thornton, I. (1996). Impacts of mining on the environment; some local. regional and global issues. Ap- plied Geochemistry, 11, 355–361. DOI: 10.1016/0883-2927(95)00064-X Tipping, E., Rieuwerts, J., Pan, G., Ashmore, M.R., Lofts, S., Hill, M.T.R., Farago M., Thornton, I. (2003). The solid-solution partitioning of heavy metals (Cu, Zn, Cd, Pb) in upland soils of England and Wales. Environmental Pollution, 125(2), 213–225. DOI: 10.1016/S0269-7491(03)00058-7 Younger, P.L., Wolkersdorfer, Ch. (2004). Mining impacts on the fresh water environment: technical and managerial guidelines for catchment scale management. Mine Water and the Environment, 23(1), 2–80. DOI: 10.1007/s10230-004-0028-0 Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 116 Appendix 1 Fig. I. Scanning electron micrographs showing mineral phases of the sample R1; a: qtz – quartz (SiO2) and ant – anatase (TiO2) phases with finely dispersed gn – galena (PbS); b: crystals of anatase; c: sp – sphalerite (ZnS) surrounded by quartz; d: other formations of anatase Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 117 Fig. II. Scanning electron micrographs of sample R2; a, d: qtz – quartz matrix with dispersed toz – topaz and anh – anhydride needles; b, c : inclusions of py – pyrite in the quartz, ant – anatase and anhydride with Si and Al impurities; e, f: penetration of the quartz, topaz, anatase and anhydride Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 118 Fig. III. Scanning electron micrographs of sample R3; a: py – pyrite and ccp – chalcopyrite inclusions surrounded by gn – galena; b: chalcopyrite, galena and sp – sphalerite; c: galena, sphalerite and chalcopy- rite inclusions among clc – clinochlore and dol – dolomite; d: small inclusions of galena and chalcopyrite in the in the sphalerite matrix; e: sphalerite and galena surrounded by qtz – quartz and intersected by dolomite veins. Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 119 Fig. IV. Scanning electron micrographs of the sample S1; bt – biotite; qtz – quartz; ms – muscovite; jrs – jarosite; cerium phosphate Fig. V. Scanning electron micrographs of the sample S2; a: brt – barite, qtz – quartz, jrs – jarosite, ill – il- lite; b: , qtz – quartz, jrs – jarosite, ill – illite; c: jrs – jarosite, or – orthoclace, clc – clinochlore Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 120 Fig. VI. Scanning electron micrographs of the sample S3; qtz – quartz, ms – muscovite, jrs+Pb – jarosite with Pb impurities, ilm – ilmenite, or-orthoclase Environm ental characteristics of the m ining area affected by sulphide m inerals and acidification (B anská Š tiavnica, S lovakia) 121 Abstract The area of Sedem Žien tailing pond and the nearby Šobov hydroquartzite quarry affected by mining ac- tivity were investigated by geochemical and mineralogical methods to determine the contaminating chem- ical compounds and study their availability. Degradation of the hydrothermal base mineralisation (galena, sphalerite, pyrite, pyrrhotite, and chalcopyrite) and of fine-grained pyrite oxidation, which forms impreg- nations in hydroquartzite, produce Acid Mine Drainage (AMD). The area is acidified and the components (soil, rock, water) are contaminated mainly by Pb, Zn, and Fe. The tailing pond dam forming soils have an acidic pH of 2.28–3.25, whereas the soil on the tailing pond surface is close neutral (pH 7.26). The leaching availability of the metals from the soil is up to 75%. The AMD from the hydroquartzite quarry is, in comparison with those percolating the tailing pond sediments, very acidic (pH 2.71) and contains high concentration of metals (Fe 311 mg.L-1, Zn 1690 µg.L-1, Cu 890 µg.L-1, Pb 126 µg.L-1). Key words: heavy metals, contamination, acidification, availability Received: [2018.07.11] Accepted: [2018.10.25] Charakterystyka środowiskowa obszaru górniczego skażonego minerałami siarczkowymi i zakwaszającymi (Banská Štiavnica, Słowacja) Streszczenie Za pomocą metod geochemicznych i mineralogicznych, zbadano obszar osadnika Sedem Žien i pobliskie- go kamieniołomu hydro-kwarcytu Šobov, dotkniętych działalnością górniczą, w celu określenia związków chemicznych zanieczyszczających te tereny i zbadania ich dostępności. Degradacja hydrotermalna oparta na mineralizacji (galena, sfaleryt, piryt, pirotyn i chalkopiryt) i utlenianiu drobnoziarnistego pirytu, której formy impregnują hydro-kwarcyt, produkuje kwaśne odcieki z  kopalń (AMD). Obszar jest zakwaszony, a  składniki lokalne (gleba, skała, woda) są zanieczyszczone, głównie przez Pb, Zn i  Fe. Zanieczyszczenia zapory osadnika tworzą gleby kwaśne (pH 2,28 - 3,25), natomiast zanieczyszczona gleba na powierzchni osadnika jest zbliżona do odczynu obojętnego (pH 7,26). Dostępność ługowania metali z  gleby wynosi tu aż do 75%. AMD z kamieniołomu hydro-kwarcytu, jest porównywalna z tymi przenikającymi, bardzo kwaśnymi (pH 2,71), zanieczyszczeniami sedymentacyjnymi osadnika i zawiera wysokie stężenia metali (Fe 311 mg.L-1, Zn 1690 µg.L-1, Cu 890 µg.L-1, Pb 126 µg.L-1). Słowa kluczowe: metale ciężkie, zanieczyszczenia, zakwaszenie, dostępność Information on the authors Erika Remešicová She studied environmental engineering during her master studies, and the field of her doctoral studies was environmental protection in the industry. During PhD. studies, she dedicated her research to mining landscape in Slovakia and to the possibilities of the decontamination of the acidic mine waters. Currently, she works at Water Research Institute in Slovakia at the Department of Groundwater Assessment. Peter Andráš https://orcid.org/0000-0002-5366-4041 He is a professor at the Department of Environment (Matej Bel University, Banská Bystrica). He is a geochem- ist, mineralogist, and environmentalist. He has worked for a long time as a research worker in the field of ore mineralogy, mineral deposits (mineralogy, isotope study, study of the ore origin etc.), and the impact of the mining activities on the environment. He gives lectures at several home universities and also abroad. He was a principal investigator in 7 grants and/or a member of the research team in 24 grant projects. He is an author of 11 monographs, 13 chapters in monographs, numerous current contents articles, and articles registered in WOS and SCOPUS databases. Er ik a R em eš ic ov á, P et er A nd rá š, R ad m ila K uč er ov á 122 Radmila Kučerová She is the associate professor at the Department of Environmental Engineering (Faculty of Mining and Geology, VŠB – Technical University of Ostrava). She is mainly concerned with biotechnologies. She is the author of 3 monographs, articles registered in WOS and SCOPUS databases, and numerous articles presented at domestic and foreign conferences. She was a principal investigator in 3 grants and a member of the research team in 19 grant projects.