Jurkovic.indd 223 � AB STRA CT In the Saski Rad barite-siderite ore deposit, Hg-tetrahedrite is the main ore mineral, pyrite and some others are only accessories. Two tetrahedrite samples (fresh and weathered) have been analysed in detail: major and minor compo- nents, constituent trace elements, REE, and δ34SCDT values. The following microconstituents have been detected: Ni 71 ppm (in fresh sample) and 70 ppm (in weathered sample); Co 113 and 90 ppm; Cd 27 and 20 ppm; W 20 and 5 ppm, Bi 2500 and 1613 ppm; Se >100 and 72 ppm and Au 11 and 9 ppm. These values have been compared with the only currently available analysis of Hg-tetrahedrite from the Duboki Vagan near Kreševo in the Mid-Bosnian Schist Mts. (MBSM) carried out by JURKOVIĆ et al. (2010): Ni 266.2 ppm; Co 63.5 ppm, Cd 319.6 ppm; Bi 1466.0 ppm; Au 38.96 ppm which also agrees with our analysis of Hg-tetrahedrite from the Brixlegg barite deposit in Tyrol, Aus- tria: Co 234.4 ppm; Cd 160.5 ppm; W 6.7 ppm; Sn 1.0 ppm; Bi 909.1 ppm; Se > 100 ppm and Au 2.3 ppm. The δ34SCDT isotope values of six tetrahedrites from the Saski Rad are on average –10.11‰, those of three tetrahe- drites from the Duboki Vagan –10,05‰ and of the tetrahedrite from the Brixlegg deposit –1.60‰. The ΣREE content is lower in two analysed tetrahedrites from the Saski Rad deposit (10 ppm) compared to the tet- rahedrite from Duboki Vagan (15 ppm) and the tetrahedrite from Brixlegg (17.4 ppm). The analysed barite sample from the Saski Rad deposit does not contain microconstituents typical of Hg-tetrahedrite. The distribution and genetic signifi cance of some trace elements, tetrahedrite microconstituents, REE and siderite isomorphic components in the seven most important genetic and paragenetic types of ore deposits in the MBSM and South-Eastern Bosnia have been commented upon. Keywords: Mercurian tetrahedrite, content of Co, Ni, W, Cd, Se, Ag and Au, sulphur isotope compositions, Saski Rad and Rad barite-siderite deposits, Palaeozoic, Mid-Bosnia Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad barite–siderite deposit in the Mid-Bosnian Schist Mts. � Ivan B. Jurković1, Vesnica Garašić1 & Ivan M. Jurković2 1 Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, 10000 Zagreb, Croatia 2Vladimira Ruždjaka 25, 10000 Zagreb, Croatia doi: 104154/gc.2011.19 Geologia Croatica 64/3 223–237 7 Figs. 11 Tabs. Zagreb 2011 Geologia CroaticaGeologia Croatica 1. INTRODUCTION In the framework of the Variscan metallogeny in the Mid- Bosnian Schist Mts. (MBSM) and South-Eastern (SE) Bos- nia, particular attention has been paid to the problem of tet- rahedrites, the main ore minerals of numerous barite and barite-siderite ore deposits (JURKOVIĆ, 1956; JURKOVIĆ et al., 2010). Two completely different tetrahedrite types have been discovered: a) an initial, older type without mercury charac- terised by positive δ34SCDT values ranging from +3.28 to +4.0‰ (KUBAT et al., 1979/80; JURKOVIĆ et al., 2010); and b) a second, younger type mercury-bearing tetrahedrite, characterised by strongly negative δ34SCDT values ranging from –4.95 to –15.40‰ (JURKOVIĆ et al., 1997). Geologia Croatica 64/3Geologia Croatica 224 At present, 16 quantitative chemical analyses of tetra- hedrite samples from the MBSM have been performed and published (POECH, 1900; VESELY, 1921; JURKOVIĆ, 1956, 1960, 1986; JURKOVIĆ & MIKO, 1997; JURKOVIĆ et al., 1997). These analyses included only eight major con- stitutive elements: Cu, Fe, Zn, Hg, Ag, Sb, As and Bi (rarely Au). Tetrahedrite samples have been taken from the follow- ing barite and barite-siderite ore deposits: two older tetrahe- drite samples (without mercury) from Trošnik (2) and 14 younger Hg-tetrahedrite samples from Maškara (5), Saski Rad (2), Sabiljine Pećine (1), Zlatarica (1), Točak (1), Ko- stajnica (1), Duboki Vagan (1), Dubrave (1), Vidici (1). Che- mical compositions were obtained through various analytical techniques: a) quantitative wet chemical analyses (5 sam- ples); b) the PIXE method with scanning proton microprobe (5 samples); and c) atomic absorption spectrophotometry (AAS) and ICP–AES after Br2–HCl digestion (6 samples). The analytical data obtained from these 16 tetrahedrite samples, demonstrate signifi cant differences resulting from a) the distance of the ore deposit from the long and deep Voljevac fault; b) the stratigraphic level (age) of the host rock; c) the type of the host rock (carbonates or metaclas- tics); d) being overprinted (or not) by ascending mercury- bearing fl uids. The average values of Hg, Fe, Zn and As in the tetrahe- drite samples from the barite-siderite deposits of the four most important ore regions of the MBSM are represented in Table 1. Evidently, the mercury content in the tetrahedrite crystal lattice depends on the distance of the deposit from the Voljevac fault. The Maškara vein (No 6) and the Mračaj vein (No 46) are the biggest and the richest Hg-tetrahedrite ore deposits in the MBSM. The Maškara vein is 2 km and the Mračaj vein only 0.5 km away from the fi rst order Volje- vac fault. The values of the same elements in tetrahedrites from the Gemericum (Slovakia) (CAMBEL-JURKOVSKY et al., 1985) and from the Brixegg, Tyrol (Austria) (LUKAS, 1971; GSTREIN, 1983; FRIMMEL and PAPESH, 1990) are included in Table 1 for comparison. Our initial detailed study of the tetrahedrite genesis in the MBSM and SE Bosnia, demanded additional, more pre- cise analytical methods which ensure the determination of Au intergrowths and microconstituents in the tetrahedrite samples such as Ni, Co, Cd, Sn, W, Se, Te, another 31 trace elements and 14 rare earth elements. The fi rst such determi- nation has been done on Hg-tetrahedrite from the Duboki Vagan deposit (D-VAGT sample) in which the following mi- croconstituents have been detected: 266 ppm Ni, 63.5 ppm Co, <0.5 ppm W, 313 ppm Cd, <1.0 ppm Sn, <0.5 ppm Se and 39 ppm Au (JURKOVIĆ et al., 2011). In this paper, our objectives are to investigate in great detail the chemical composition of Hg-tetrahedrite from the smaller barite-siderite deposits Saski Rad and Rad. They pre- sent the south-eastern prolongation of the Maškara ore depo- sit, the biggest Hg-tetrahedrite deposit in the MBSM, located in the Silurian–Devonian (S,D) metaclastic rocks, 9 km SE of the town of Gornji Vakuf. In order to elucidate its genesis, Hg-tetrahedrites will be compared with Hg-tetrahedrite sam- ples from other Maškara vein type deposits; the Duboki Vagan (Kreševo) and Brixlegg (Tyrol) barite deposits. 2. GEOLOGICAL SETTING 2.1. Geology of the Gornji Vakuf area The Gornji Vakuf area is situated in the middle part of the south-western Mid-Bosnian Schist Mts. (Fig. 1.a). Fig. 1.b presents a simplifi ed geological map, compiled from data published by SOFILJ & ŽIVANOVIĆ (1979) and SOFILJ et al. (1980). The oldest rocks of the area are chlorite-sericite schists and sericite-chlorite-quartz schists, locally interlayered by metasandstones and, in the area of Gromilica, by quartzites. Table 1: Average values (in wt.%) of Hg, Fe, Zn and As in the crystal lattices of tetrahedrite samples from the barite-siderite deposits located in the four most important regions of the Mid-Bosnian Schist Mountains (MBSM) (JURKOVIĆ et al., 1997). Abbreviations: lm = limestone; do = dolomite; sch = meta- clastic rocks (phyllite, metasandstone); S = Silurian; D = Devonian; n = number of analysed tetrahedrite samples; nmrs = numerous; av = average value; rg = range; V. Fault = Voljevac Fault. Ore district n Hg wt. % Fe wt. % Zn wt. % As wt. % Host rock Age Distance to Voljevac fault Sabiljine Pećine NW of the Gornji Vakuf 1 av rg 7.35 1.10 4.17 2.04 lm (do) D2 0.5–1 km Maškara – Saski Rad SE of Gornji Vakuf 8 av rg 5.14 (3.69–7.58) 4.29 (2.80–5.77) 0.24 (tr – 0.72) 3.82 (1.50–5.84) sch S,D 0.5–2 km Dusina, Deževice Kostajnica 5 av rg 1.62 (0.63–3.40) 1.89 (0.82–3.40) 3.64 (0.77–6.18) 3.05 (0.43–5.41) do (lm) D2 10–15 km Kreševo, Tarčin 5 av rg 1.95 (0.33–3.80) 2.27 (0.52–4.15) 3.01 (1.21–4.64) 1.97 (1.41–2.73) do (lm) D2 15–20 km Trošnik, Fojnica 3 av rg 0.29 (0.03–0.63) 6.77 (6.00–7.42) 2.24 (1.82–2.41) 1.05 (0.90–1.20) do (sch) S,D >20 km MBSM 22 av rg 3.07 (0.03–7.58) 3.74 (0.52–7.42) 2.09 (tr. 6.18) 2.77 (0.43–5.84) JURKOVIĆ et al. (1997, 2010) Rudnány, Gemericum, Slovakia nmrs av rg 9.70 (0.0–19.80) 2.59 (0.2–5.8) 0.79 (0.1–4.0) 4.87 (2.3–4.7) CAMBEL & JURKOVSKY (1985), RADVANEC et al. (2004) Brixlegg, Tyrol Austria nmrs av rg 1.80 (0.0–15.0) 2.60 (2.5–3.0) 5.40 (4.0–6.0) 6.20 (5.0–6.0) LUKAS (1971), GSTREIN (1983), FRIMMEL & PAPESH (1990) Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 225 In the area of the Cvrče Village and in the Desna Valley younger rocks and slates occur. The area near Krugljača is characterised by the occurrence of sandy sericite-chlorite schists and schistose sandstones. Limestone and dolomite lenses are very rare. All these rocks are attributed to the Sil- urian–Devonian metamorphic rocks of greenschist facies (S,D in Fig. 1.b). In the Mt. Vranica area, the Silurian–Devonian complex is tectonically covered by Devonian limestones with subor- dinate dolomites. The lowest part, found only in the Suvodol valley, is built up by the fossiliferous Lower Devonian platy limestones (D1). The Middle Devonian consists of zoogene, massive and rarely bedded limestones and subordinate do- lomites (D1,2). On the geological map, Prozor Sheet, Car bon i- ferous rocks have not been registered, although ŽIVA NOVIĆ (1972) presumes that younger parts of the Silurian–Devonian complex may belong to the Lower Carboniferous. Shallow subvolcanic rhyolite (denoted as X in the Fig. 1.b) intrusions and extrusions are numerous. JURKOVIĆ et al. (2010) proved by 87Sr/86Sr ratio that they represent an S-type granitoid magma as previously assumed by MAJER & GARAŠIĆ, 2001. They are mostly transformed into meta- Figure 1: a) Position of the Mid-Bosnian Schist Mountains (MBSM) inside the Republic of Bosnia and Herzegovina; b) Simplifi ed geological map of the Gornji Vakuf area from the Prozor sheet compiled by SOFILJ & ŽIVANOVIĆ (1979). Positions of the 47 ore occurrences, their parageneses, strike and dip are marked by JURKOVIĆ et al. (1994). The Maškara ore deposit is denoted by the number 6, Rad by number 7 and Saski Rad by number 8. Colours are according to the Commission for the Geological Map of the World (CGMW) and the International Commission on Stratigraphy (ICS) (CMYK colour code, 2008). Abbreviations: S,D – Upper Silurian–Lower Devonian schist complex; D1 – Lower Devonian; D1,2 (D) – Middle Devonian carbonate complex; mD1,2 – marbleized limestones; X – rhyolite; X’ – metarhyolite; nq – quartzkeratophyre; P3 – Upper Permian sediments; T1,2 – Lower and Middle Triassic; gf – fl u- vioglacial placers; Ore occurrences: Nos 1–15 (in Fig. 1.b) = siderite ± barite + tetrahedrite (in S,D); Nos 16–24 = barite ± siderite + tetrahedrite (S,D); Nos 25–40 = barite ± tetrahedrite (D1,2); Nos 41–43 = bartie ± tetrahedrite (P3–D1,2 thrust/fault zone); Nos 44–46 = siderite ± barite + tetrahedrite (P3–S,D thrust/ fault zone); No 47 = metamorphogenic quartz deposit (S,D). Geologia Croatica 64/3Geologia Croatica 226 rhyolites (denoted as X’ in the Fig. 1.b) by Variscan regional metamorphism. Keratophyres (nq), are much rarer, younger than (meta)rhyolites and belong to the Permian. Upper Permian formations are unconformably underlain by older Palaeozoic rocks: breccias, conglomerates, porous limestones ± gypsum, coloured subgraywackes, subarkoses, siltstones. The Lower Triassic (T1) is composed of siltstones and limestones, and the Middle Triassic (T2) by limestones, do- lomites and a volcanic-sedimentary formation. 2.2. Ore deposits of the Gornji Vakuf area In the Gornji Vakuf area JURKOVIĆ et al. (1994) have regi- stered 47 ore occurrences (Fig. 1.b) of the following genetic types: 1) Sedimentary gold deposits: a) Quaternary gold-bear- ing fl uvial deposits; b) gold-bearing Diluvial terraces; and c) Uppermost Pleistocene (Wuerm) glacial formations (RU- ECKER, 1896; JURKOVIĆ, 1951; RADUSINOVIĆ, 1960; JURKOVIĆ et al., 1994). 2) Hydrothermal ore deposits (Nos 1–46 in Fig. 1.b): a) The Maškara vein type, containing siderite, barite and Hg-tetrahedrite, located SE of Gornji Vakuf in metapelites and metapsammites of the lower parts of the Silurian–Dev- onian complex (Nos 1–15); b) The Cvrče-Borova Ravan type, containing barite, siderite and Hg-tetrahedrite, located in metaclastic rocks of the higher parts of the Silurian–Dev- onian complex (Nos 16–24); c) The Sabiljine Pećine type, containing only barite, while Hg-tetrahedrite is a very sub- ordinate or even accessory mineral. This type is located in the partly dolomitised Middle Devonian limestones, (Nos 25–43); and d) The Mračaj type, which is characterised by a barite-siderite-Hg-tetrahedrite paragenesis. This type is located along the Voljevac fault zone (the tectonic contact between the Upper Permian and Lower Palaeozoic) (Nos 44–46). 3) Metamorphogenic quartz deposit (No 47 in Fig. 1.b) The research here is restricted to ore occurrences situ- ated in the triangular area between the western slopes of the Vrbas river, western banks of the river Desna and eastern banks of the river Dragučina, a western tributary of the Vr- bas river. There are hydrothermal ore deposits of the Maškara paragenetic type (Nos 5–15 in Fig. 1.b) and the Cvrče-Bor- ova Ravan paragenetic type (Nos 16–24) present in this (~60 km2) area. Taking into consideration two published detailed studies of the Maškara vein (KATZER, 1907; JURKOVIĆ, 1960), research samples were selected from the old medieval and Austrian mines Rad and Saski Rad, which are a prolonga- tion of the Maškara vein. 2.3. General characteristics of the Maškara vein type From 15 ore occurrences (Nos 1–15) attributed to this para- genetic type, the biggest one is the Maškara vein (Nos 6). It is 250 to 350 m long, vertically over 110 m high, 0.1 to 1.0 m thick, dipping 75°/40–60°. This vein produced 8.0 tons of crude ore with 25% of Hg-tetrahedrite. The average content of Hg-tetrahedrite was 9–15 vol.% or 10–16 wt.% in barite crude ore and 20–60 vol.% or 15–65 wt.% in siderite crude ore (KATZER, 1907; JURKOVIĆ, 1960). The Rad (No 7) and Saski Rad (No 8) are ore occurrences which belong to the Maškara genetic type. The quantitative relationship of the main constituent elements in the Hg-tetrahedrite of the Rad and Saski Rad deposits is very similar to that in the Hg-tetrahedrite from the Maškara deposit, indicating that these deposits might represent the broken parts of the Maškara ore vein. The Maškara vein lies at the absolute al- titudes of +820 to +930 m, the Rad deposit at an altitude of +1000 m, and the Saski Rad deposit at +1070 m. On the western banks of the river Desna (a tributary of the Vrbas river), the other ore deposits belonging to the Ma š ka ra paragenetic type are located: Desna (No 9 in the Fig. 1.b), Da- ganj Creek (No 10), Valice Village (No 11), Valice Mlinovi (No 12) and Kulentaš (No 15). In these deposits, siderite is the main mineral with sin- gle Hg-tetrahedrite grains, net-like aggregates or interrupted interlayers of tetrahedrite. Barite is abundant, but subordi- nate. Ore occurrences Nos 10 and 11 contain an increased quantity of quartz ± pyrite and a decreased amount of tetra- hedrite (JURKOVIĆ et al., 1994). All these veined ore oc- currences stretch NNE–SSW or NE–SW with a very steep dip. They are short, shallow and very thin veins (from 0.1 to 0.2 m thick). Their outcrops lie at altitudes of +1100 m, hosted by the rocks of the lower part of the Silurian–Devo- nian complex (phyllite and similar rocks). The Laznice ore occurrence (No 13) at +1200 m altitude, and Crkvice (No 14) at +950 m, represent an open jointing system (width 0.1–1.0–3.0 m) which is only partly fi lled with clay gangue, Fe and Mn hydroxides, ankerite, calcite and ore fragments. In the Cvrče-Borova Ravan area, at altitudes of +1050– +1350 m, similar ore occurrences have been discovered, characterised by barite as the dominant ore mineral, whereas siderite ± quartz are subordinate minerals. Hg-tetrahedrite is scarce or very subordinate. The following ore deposits and occurrences belong to this paragenetic type: Ladina Voda (No 16), Kašli Brdo (No 17), Djamuš Brdo (No 18), Cvrče Village (No 19), Cvrče-Zaganj (No 20), Borova Ravan-Bos- njačica (No 22) and Borova Ravan (No 23). All these veins strike NNW–SSE or NW–SE, dipping towards the NE/25– 45°. They are all very thin (Nos 19 and 23 are 0.05–0.10 m thick), only the Djamuš Brdo vein (No 18) is somewhat thicker (0.10–0.40 m). All ore occurrences are hosted by metasandstones and schists are attributed to the higher parts of the Silurian–Devonian complex. ŽIVANOVIĆ (1972) claims that these rocks belong to the Lower Carboniferous. At Borova Ravan-Guvnanica (No 21) and Ričica (No 24) fragments of ore were only discovered in blocks and not in associated outcrops. Mineralization of the Maškara vein type occurred inside a system of tensional fi ssures and joints of variable lengths, widths and depths. The ore occurrences strike mostly NNW–SSE Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 227 and dips towards the ENE with very different angles. The other extensive system, 3.5 km long, has been registered be- tween the Vrbas and Desna rivers (N–S strike, dip towards the E). In higher levels of the ore deposits, barite predominates over subordinate Hg-tetrahedrite, whereas in the lower lev- els siderite and Hg-tetrahedrite (± quartz) predominate. Within the geological column, a vertical zonation of the whole Silurian–Devonian complex was also observed. In the lower parts of the complex, siderite with subordinate barite and quartz are common, whereas in the higher parts, barite with subordinate siderite and tetrahedrite are common. The relationships between tetrahedrite, barite and side- rite in Maškara-Saski Rad vein described by KATZER (1907) are shown in Fig 2. 3. THE MAIN GENETIC AND PARAGENETIC TYPES OF MINERAL OCCURRENCES ESTABLISHED IN THE MBSM AND SE BOSNIA The following main genetic and paragenetic types of mineral occurrences have been established in the MBSM and SE Bosnia: Ia) The oldest nonmetallic occurrences are numerous Variscan synorogenic and postorogenic sterile, monomine- ralic quartz veins and irregular quartz bodies located in the Busovača, Fojnica, Kiseljak, and Kreševo area (KATZER, 1926; JURKOVIĆ, 1956; HRVATOVIĆ, 1996). Ib) The oldest metallic ore deposits, Mačje Jame iron ore deposits (JURKOVIĆ, 1956) and Vranjska Rijeka (JUR- KOVIĆ and HRVATOVIĆ, unpublished) are located west of the town of Busovača. These deposits are formed at T = 350– 400°C and P = 3–5 kbars (MAJER et al., 1991). The main minerals are siderite and ankerite (50–90 wt.%), with mag- netite, haematite, albite, Ti-oxides (10–30 wt.%). This fi rst phase is followed by a very subordinate pneumatolytic phase with quartz, pyrite, arsenopyrite (5–10 wt.%) associated with cassiterite (0.024 wt.%), and ferberite (0.012 wt.%). The mineralization in these two ore deposits is completed by a weak hydrothermal phase which consists of Cu, Zn, Fe, As, Bi (cosalite), Sb-sulphides and sulphosalts. The crude ore contains 10 ppm Ag, 0.33 ppm Au, 0.7 wt.% Cu, 0.6 wt.% As, 15 to >230 ppm Bi and to 25 ppm Se. The copper-bear- ing Sinjakovo siderite deposit, located west of the town of Jajce, also belongs to this genetic type (VASILJEVIĆ, 1972). BARTALSKY (1991) discovered an almost identical genetic and paragenetic type of ore in the Gemericum (Slo- vakia). RADVANEC et al. (2004) consider that this is the oldest Slovakian deposit generated at T = 330–380°C and P = 2–4 kbars. II) The Vrtlasce ore deposit is a small, but parageneti- cally very interesting ore type, located east of the town of Fojnica. Siderite, ankerite and subordinate albite are the main minerals, but the pneumatolytic phase with cassiterite, stan- nite and molybdenite is clearly noticeable (JURKOVIĆ, 1956; 1958). The hydrothermal phase with 0.02 wt.% Cu, 2.2 wt.% Pb, and 5.0 wt.% Zn is very well developed. This deposit having >300 ppm Ag was a very good supply of sil- ver for the Saxon miners in the Middle Ages. Due to the re- duction of Bi and Se, the content of gold was only 0.07 g/t. The silver bearing minerals were galena, boulangerite and other Pb-antimonides. III) Numerous quartz veins (the longest of which is 1500 m) with silver-bearing sphalerite, antimonite, and Pb- antimonides as the main ore minerals, comprise the Čemer- nica genetic type, located northwest, northeast and east of the town of Fojnica (KATZER, 1926; JURKOVIĆ, 1956, 1962; JURKOVIĆ et al., 1999). Entire ore reserves (300.000 t) contain 5.9 wt.% Zn, 4.0 wt.% Sb, and 114 g/t Ag. The Au content is only 0.01 g/t, Bi and Se occur in trace amounts. In the Čemernica “Main vein”, RAMOVIĆ (1956) discov- ered ferberite with 74 wt.% WO4; 18 wt.% Fe and 6.2 wt.% Mn. IV) The Bakovići gold-bearing pyrite veins with 10–20 wt.% SiO2, 5–10 wt.% of Mn-siderite and 50–75 wt.% of gold-bearing pyrite are the richest gold deposits in Bosnia and Herzegovina. The average gold content in the Bakovići ore deposit is 21 g/t Au and 13 g/t Ag. The source of gold in this deposit is presently unknown (JURKOVIĆ, 1995). V) Barite ± siderite veins and irregular replacement bod- ies with 1–10 (max.15 wt.%) of Fe, Cu, Zn, Pb, and Sb sul- phides and sulphosalts characterized by positive δ34SCDT (0.0 to +5‰), are predominantly located in SE Bosnia, rarely in the MBSM (RAMOVIĆ, 1957, 1976; JEREMIĆ, 1963; KULE NOVIĆ, 1987; JURKOVIĆ et al., 2010). An identical morphologic and paragenetic type of polysulphide-bearing barite deposits has been found in the Petrova and Trgovska gora Mts. in Croatia (JURKOVIĆ, 1958) and in NW Bosnia (ŠIFTAR, 1988, 1990) but only sporadically in the MBSM (JURKOVIĆ, 1956; JURKOVIĆ et al., 2010). Small quan- tities of Sb-tetrahedrite do not contain mercury in the crystal lattice, being also characterized by a positive δ34SCDT. This type of barite deposit with the polysulphide group of ore mine rals, has been formed at moderate temperatures of 140°C as determinated by the fl uid inclusion studies of BLEČIĆ (1983). Figure 2: The relationships between tetrahedrite, barite and siderite in Maškara-Saski Rad vein described by KATZER (1907). Siderite gangue con- tains richer tetrahedrite masses then the barite gangue. Captions: p = phy- llite, s = siderite; b = barite; t = tetrahedrite; q = quartz. Geologia Croatica 64/3Geologia Croatica 228 VI) The youngest group of ore deposits consists exclu- sively of two morphologic groups of Hg-tetrahedrite-bearing barite deposits. The fi rst morphologic type are quartz-sider- ite-barite vein deposits; the Maškara-Saski Rad type, rich in Hg-tetrahedrite. Barite crude ore contains 10–16 wt.% of Hg-tetrahedrite, whereas siderite crude ore is richer and con- tains 20–65 wt.% of Hg-tetrahedrite (KATZER, 1907). All other ore minerals are only accessories or occur in micro- scopic dimensions. The second morphological type, the Kreševo type, are barite ± calcite ± quartz irregular replace- ment bodies with a very low content of Hg-tetrahedrite (traces or 1 to 5 wt.%) and high temperature, octahedral fl uorite. All other microscopically established minor miner- als are only accessories (JURKOVIĆ, 1987). Numerous fl uid inclusion studies revealed a strongly in- creased homogenisation temperature of 230–330°C (PALIN- KAŠ & JURKOVIĆ, 1994; JURKOVIĆ & PALINKAŠ, 1996; JURKOVIĆ & PALINKAŠ, 2002; JURKOVIĆ et al., 2002). In both types of Hg-tetrahedrite deposits, tetrahedrite is char- acterized by a strongly negative δ34SCDT. The position of the main genetic and paragenetic types of mineral occurrences are shown in Fig. 3. 4. ANALYTICAL METHODS Numerous thick opaque polished sections of the tetrahedrite samples were studied using refl ected polarized light. Thin- sections of barite and siderite samples were examined using transmitted polarized light. The information obtained en- abled separation of the fresh and weathered samples. Se- lected samples were crushed, hand-picked under binocular microscope and powdered in an agate mortar for chemical analysis. A relatively high Se content (>100 ppm) was determined for the fi rst time in the fresh Hg-tetrahedrite of the Saski Rad deposit in the MBSM. This led to similar analysis of the weathered Hg-tetrahedrite of Saski Rad deposit in order to confi rm a similar high Se content of Hg-tetrahedrite as a typical characteristic of this deposit. Major and trace elements were analysed by inductively coupled plasma (ICP) mass spectrometry – in ACME Ana- lytical Laboratories, (Vancouver) Ltd. in Canada. Sulphur and oxygen stable isotope compositions were determined at the Stable Isotope Laboratory of the University of Lausanne, using the Finnigan Mat Facility. The Saski Rad No 7 tetrahedrite sample has been ana- lyzed by atomic absorption spectrometry (AAS) and ICP– AES, after Br2HCL digestion, in the Croatian geological In- stitute in Zagreb (JURKOVIĆ et al., 1997), and Saski Rad No 8 tetrahedrite sample by PIXE method with scanning proton microprobe in the Institute Rudjer Bošković in Za- greb (JURKOVIĆ et al., 1997). 5. RESULTS 5.1. Analytical results of the fresh Hg-tetrahedrite (SAS–TET sample) Results of quantitative chemical analyses of Hg-tetrahedrite samples from the Saski Rad deposit, are presented in Table 2. The fi rst two analyses, performed in 1994 and 1997, contain only the major constituent elements (Cu, Fe, Mn, Zn, Hg, Ag, Sb, As, Bi, Te, S and Au), whereas minor and trace constituents (Ni, Co, W, Cd and Se) as defi ned by DUDA & REJL (1987) were not analysed. However, the third analysis shown in Table 2 results from the present work and contains major, minor and Figure 3: Positions of the most impor- tant genetic and paragenetic types of ore deposits in the MBSM area. Geolo- gycal map after SOFILJ & ŽIVANOVIĆ (1979). Legend: Q-Quaternary, M-Mio- cene, K-Cretaceous, J-Jurassic, T1,2-Lower and Middle Triassic, P3-Upper Permian, C1-Lower carboniferous, D-Devonian, S-pre-Devonian metamorphic rocks, LLL-Triasic diorite, minor gabbro, albi- te syenite, albite granite; nnn-Middle Tri- assic volcanic rocks (keratophyre, an- de site, dacite); +++ – Upper Palaeozoic rhyolites, metarhyolites. Positions of the ore deposits after JURKOVIĆ et al (1994). Typ es of ore deposits: � Bu so vača type; � Mačje Jame type; � Vranjska Rijeka ty pe; � Vrtlasce type;� Čemernica ty- pe; � Bakovići type; � SE Bosnia type; � Maškara – Saski Rad type; � Kreševo type; � Vilenica type. Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 229 trace elements, along with the rare earth elements (REE). This analysis represents the SAS–TET Hg-tetrahedrite sample. According to the analysis of the SAS-TET sample, the studied tetrahedrite represents a Cu-Sb-S tetrahedrite, in which Cu is isomorphically replaced by Fe (5.70 wt.%), Hg (3.81 wt.%), Zn (0.225 wt.%) and Ag (>0.03 wt.%) and also by mi- nor elements (71 ppm Ni, 113 ppm Co, 20 ppm W and 27 ppm Cd). Additionally, Sb is replaced by As (5.02%) and Bi (0.25 %), whereas S is replaced by Se (>100 ppm). This represents the fi rst discovery of selenium in the MBSM and SE Bosnia tetrahedrite samples. Au (11 ppm) is present in microcavities Table 2: Quantitative chemical analyses of Hg-tetrahedrites from the Saski Rad deposit. Abbrevations: (1) analysis performed by JURKOVIĆ et al. (1994); (2) analysis performed by JURKOVIĆ et al. (1997); (3) analysis performed for the present work (SAS–TET sample); M.a. – mechanical admixtures; Tr-El. – trace elements, MDL – method detection limit. The diff erence between 97.5% and 100% is attributed to unanalysed O2 and H2O+. tetrahedrite tetrahedrite tetrahedrite JURKOVIĆ et al., 1994 JURKOVIĆ et al., 1997 SAS–TET this work Main element Main element MDL MDL REE MDL Tr. El. MDL Admixture in tetrah. wt. % wt. % wt. % ppm wt. % ppm ppm ppm ppm % Cu 38.290 41.770 Cu 39.8100 0.001 La 9.30 0.10 Cr 20.0 10.00 BaSO4 0.0467 Fe 5.070 5.030 Fe 5.7010 0.010 Ce 0.60 0.10 Mo 7.3 1.00 SrSO4 0.0129 Zn 0.290 0.460 Zn 0.2249 0.010 Pr 0.05 0.02 Tl 91.9 0.10 CaCO3 0.3496 Mn n.a. n.a. Mn <0.0100 n.a. 0.010 Nd <0.30 0.30 Cs 0.2 0.10 MgCO3 0.0347 Hg 2.820 4.060 Hg 3.8120 0.001 Sm <0.05 0.05 Rb 1.2 0.10 Total 0.4439 Ag 0.140 0.149 Ag >0.0300 2.00 Eu <0.02 0.02 U 0.1 0.10 Ni n.a. n.a. Ni 0.0071 0.10 Gd 0.07 0.05 V 0.9 8.00 Co n.a. n.a. Co 0.0113 0.20 Tb 0.01 0.01 Zr 0.6 0.10 W n.a. n.a. W 0.0020 0.50 Dy 0.08 0.05 Y 0.3 0.10 Cd n.a. n.a. Cd 0.0027 0.10 Ho <0.02 0.02 Total 122.5 Sb 21.160 16.830 Sb 19.0300 0.001 Er 0.05 0.03 As 4.010 5.840 As 5.0200 0.010 Tm <0.01 0.01 Bi 0.232 0.247 Bi 0.2509 0.010 Yb <0.05 0.05 Te n.a. n.a. Te n.a. n.a. – Lu <0.01 0.01 S 25.440 23.340 S 22.6315 0.005 Total 10.16 Se n.a. n.a. Se >0.0100 0.50 CO3 2- n.a. n.a. CO3 2- 0.5151 Au 0.00218 n.a. Au (ppb) 0.00110 0.50* M.a. n.a. n.a. M.a. 0.4439 Tr-El. n.a. n.a. Tr-El. 0.0122 REE n.a. n.a. REE 0.0010 Total 97.450 97.730 Total 97.5170 Cation proportion Cu+Ag+Hg 0.61792 0.67894 Fe+Zn 0.09522 0.09772 Sb+Ag+Bi 0.22843 0.21736 S 0.79341 0.72792 Me2+ : Me3+ : S 3.12:1.3:3.47 3.57:1.3:3.5 Table 3: Sulphur isotope composition of six mercurian tetrahedrites from the Saski Rad deposit. Sample δ34SCDT Publication ‰ SAS-41. No 102/a –9.50 JURKOVIĆ et al., 1994 Saski Rad No 7 –10.69 JURKOVIĆ et al., 1997 Saski Rad. No 8 –9.68 JURKOVIĆ et al., 1997 SAS-41.No 102/b –9.90 this work S-RADT –10.30 this work SAS-TET –10.60 this work Geologia Croatica 64/3Geologia Croatica 230 and fi ssures of tetrahedrite. Only 9 trace elements (Cr, Mo, Tl, Cs, Rb, U, V, Zr and Y), among the 31 analysed, have been detected, accounting for 122.5 ppm in total. Among them Tl is the most abundant (91.9 ppm; accounting for 75% of the total). In the other analysed tetrahedrite samples from the MBSM, Tl was not detected. The REE values of the studied Hg-tetrahedrite are very low (10.16 ppm in total, Table 2). The δ34SCDT values of this Hg-tetrahedrite equal –10.60‰. There are six Hg-tetrahedrite samples from the Saski Rad deposit (Table 3), which have already been analysed for δ34SCDT values (three in this work). These values, ranging from –9.50‰ to –10.69‰ (average: –10.09‰), are in ac- cordance with 18 other values obtained from 18 different Hg-tetrahedrite samples over the whole Mid-Bosnian Schist Mts. (JURKOVIĆ et al., 1997), which range from –5.50‰ to –15.40‰ (average: –10.40‰). 5.2. Analytical results of weathered Hg-tetrahedrite (SAS-41 sample) Results of quantitative chemical analysis of one weathered Hg-tetrahedrite, grown inside the oxydised siderite from the Saski Rad deposit, are presented in Table 4. The elements V (15.00 ppm), Y (2.40 ppm), Rb (0.80 ppm), Zr (0.50 ppm) and U (0.40 ppm) have values barely above method deter- mination limit (MDL). All other trace elements have been not detected. The studied weathered Hg-tetrahedrite contains the fol- lowing microconstituents: Ni (70 ppm), Ag (>300 ppm), Co (90 ppm), W (50 ppm), Cd (20 ppm) and Se (70 ppm), whereas Au (9175 ppb) is present in cavities and fi ssures of tetrahedrite. The discovery of selenium in the fresh tetrahe- drite (>100 ppm Se) and also in the weathered tetrahedrite (70 ppm Se) from the Saski Rad ore deposit defi nitely con- fi rms the presence of selenium as a constitutive trace element in the tetrahedrite crystal lattice of the MBSM region. The REE values of the studied sample are very low (9.96 ppm in total), similar to the other Hg-tetrahedrites. Gangue minerals (barite, calcite and dolomite) are pre- sent and account for 0.688 wt.%. 5.3. Analytical results of the barite (S-RAD sample) Analysis of the barite, which occurs in paragenesis with tet- rahedrite in the Rad ore deposit is presented in Table 5. Table 4: Quantitative chemical analysis of the weathered Hg-tetrahedrite sample (SAS-41) from the Saski Rad deposit. Abbrevations: M.a. – mechanical admixtures; Tr-El. – trace elements. weathered tetrahedrite SAS-41 this work Major elements REE Trace elements Admixture wt.% MDL % ppm MDL ppm ppm MDL ppm % Cu 30.380 0.001 La 7.00 0.10 Mo <1.0 0.1 BaSO4 0.141 Fe 11.040 0.010 Ce 0.90 0.10 Tl <0.1 SrSO4 0.020 Zn 0.240 0.010 Pr 0.08 0.02 Be <1.0 1.0 CaCO3 0.225 Mn n.a. Nd <0.30 0.30 Cs <0.1 0.1 MgCO3 0.312 Hg 2.867 0.001 Sm 0.12 0.05 Ga 0.5 0.5 FeCO3 14.082 Ag >0.030 0.002 Eu 0.04 0.02 Hf <0.1 0.1 MnCO3 1.025 Ni 0.007 0.001 Gd 0.28 0.05 Nb <1.0 0.1 PbS 0.440 Co 0.009 0.001 Tb 0.07 0.01 Rb 0.8 0.1 Total 16.245 W 0.005 0.00005 Dy 0.46 0.05 Sn <1.0 1.0 Cd 0.002 0.001 Ho 0.10 0.02 Ta <0.1 0.1 Sb 13.170 0.001 Er 0.42 0.03 Th <0.2 0.2 As 3.770 0.010 Tm 0.07 0.01 U 0.4 0.1 Bi 0.190 0.010 Yb 0.53 0.05 V 15.0 8.0 Te n.a. - Lu 0.09 0.01 Zr 0.6 0.1 S 13.781 0.050 Total 10.16 Y 2.4 0.1 Se 0.007 0.00005 Cr <10.0 10.0 Au* 9175 0.5 ppb Na,K, Al <100.0 LOI 8.666 -5.1 Total 19.7 M.a. 16.245 Tr–El 0.002 REE 0.001 Total 100.413 Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 231 In the fi rst group of trace elements, ranging from Be to Y, 4 elements (Hf, Rb, Ta and Y) were identifi ed accounting for only 12.20 ppm in total. The second group of trace elements (Mo to Se) contains, among others, Cu (68.40 ppm), Sb (21.10 ppm), As (5.40 ppm), Hg (5.25 ppm), Zn (5.0 ppm), Ag (1.0 ppm) and Au (0.6 ppb), which are the major constituents of Hg-tetrahe- drite. Microconstituent elements typical for Hg-tetrahedrite have not been identifi ed in this barite sample. Identical re- sults were recorded in other studied barite samples taken from the various barite deposits throughout the MBSM. The analysed barite sample is characterised by its extremely low content of REE (6.61 ppm in total), which is similar to the other analysed samples of barite from the MBSM and SE Bos- nia. The values for Pr, Nd and Sm were below the MDL. The BaSO4 content of this sample is higher than 90.00 wt.% and its SrSO4 content is 6.24 wt.% (Sr = 29781 ppm). 5.4. Analytical results of siderite The content of the four major components (mol. and wt.%) of the siderite sample, representative of the Maškara-Saski Rad vein system, analysed by JURKOVIĆ et al. (1994), are pre- sented in Table 6. Molar composition refl ects a hydrothermal fl uid system characterised by heightened temperature. 5.5. Analytical results of tetrahedrite and barite from neighbouring ore deposits For the purpose of the comparison, the sulphur and oxygen isotope compositions of Hg-tetrahedrite and barite from the neighbouring Cvrče Village barite deposit (Fig. 1.b) were also determined within the scope of this work. These results, together with isotopic compositions and SrSO4 content of barite from the Djamuš Brdo, Crvče/Zaganj and Borova Ra- van barite deposits determinated by JURKOVIĆ et al. (1994) are presented in Table 7. All analyzed δ34SCDT values in tet- rahedrites are negative (–1,20 to –10,69‰), whereas those in barites are positive (+15,10 to +18,48‰). 6. DISCUSSION 6.1. The problem of microconstituents in the tetrahedrite According to RAMDOHR (1986) 1/4 of copper places in tetrahedrite must be replaced by Fe, Zn, Co, Ni, Ag and Hg; arsenic and antimony by Bi, Sn, W, Ge and Te, and sulphur by selenium. DUDA & REJL (1987) defi ned only Ni, Co, W, Cd and Se as trace elements in tetrahedrite. JOHNSON et al. (1988) and FOTT & HUGHES (2004) consider that copper can be replaced by Fe, Zn, Mn, Hg, Cd, and Ag; ar- senic and antimony by Bi and Te; and sulphur by Se. They consider that the structure of tetrahedrite must be analo guous to the structure of the mineral sodalite. The microconstituent elements can be inserted in tetra- hedrite: (a) as micro-scale inclusions occupying defects in the structure; (b) as myrmekitic intergrowths of various fi ne- ness, some of which originate through decomposition and (c) as exsolution textures. Table 5: Trace element and REE contents of the barite sample (S-RAD) from the Saski Rad deposit. barite S-RAD this work REE Trace elements Trace elements ppm MDL ppm ppm MDL ppm ppm MDL ppm La 1.40 0.10 Be <1.00 1.00 Mo 0.20 0.10 Ce 0.10 0.10 Co <0.20 0.20 Cu 68.40 0.10 Pr <0.02 0.02 Cs <0.10 0.10 Pb 1.40 0.10 Nd <0.30 0.30 Ga <0.50 0.50 Zn 5.00 1.00 Sm <0.05 0.05 Hf 3.10 0.10 Ni 0.20 0.10 Eu 1.65 0.02 Nb <0.10 0.10 As 5.40 0.50 Gd 2.04 0.05 Rb 0.30 0.10 Cd <0.10 0.10 Tb 0.12 0.01 Sn <1.00 1.00 Sb 21.10 0.10 Dy 0.61 0.05 Ta 7.50 0.10 Bi <0.10 0.10 Ho 0.18 0.02 Th <0.20 0.20 Ag 1.00 0.10 Er 0.32 0.03 U <0.10 0.10 Au* (ppb) 0.6 0.50 Tm 0.03 0.01 V <8.00 8.00 Hg 5.25 0.01 Yb 0.15 0.05 W <0.50 0.50 Tl <0.10 0.10 Lu 0.01 0.01 Zr <0.10 0.10 Se <0.50 0.50 Total 6.61 Y 1.30 0.10 Total 107.95 BaSO4 > 93.00 % Total 12.20 Sr 29781 SrSO4 6.24 % Table 6: The content of the four major components of the siderite sample from the Saski Rad deposit (JURKOVIĆ et al., 1994). components wt % mol % FeCO3 81.23 74.39 CaCO3 9.52 10.18 MgCO3 6.59 12.22 MnCO3 2.66 2.47 Total 100.00 99.26 Table 7: Sulphur and oxygen isotope compositions of Hg-tetrahedrites and barites and SrSO4 content of barites from some barite deposits of the Boro- va Ravan area. Captions: 1 – JURKOVIĆ et al., 1994; 2 – this paper. Ore deposit Tetrahe- drite Barite δ34SCDT ‰ δ34SCDT ‰ δ18OSMOW ‰ SrSO4 wt.% Djamuš Brdo1 –10.69 18.48 n.a. 2.70 Cvrče / Zaganj1 –9.68 17.11 n.a. 2.20 Borova Ravan1 n.a. 15.89 n.a. 2.50 Cvrče Village2 –1.20 15.10 18.10 n.a Geologia Croatica 64/3Geologia Croatica 232 According to RAMDOHR (1986) exsolutions in tetra- hedrite are exceptionally rare (only bismuthinite and ques- tioned “goldfi eldite”). The needles of bismuthinite (bi) ori- ented paralell to (111) (Fig. 3) and discs and needles of bis muthinite (Fig. 4) as exsolutions in tetrahedrite crystals (t) from the Trošnik, Fojnica deposit (MBSM) have been found by the fi rst author of this work during his postdoctoral study (1957) at the Geological Department of Heidelberg University. These results have been confi rmed by professor Ramdohr and published by JURKOVIĆ (1958). Myrmekitic intergrowths of tetrahedrite (t) with one sul- phide or sulphosalt (sl), the most probably Ag-mineral ac- cording to optical properties, have been also documented by JURKOVIĆ (1958) and are shown in Fig. 5. This texture most likely originated by decomposition of one rich silver- bearing tetrahedrite containing 0.20 and 0.34 wt. % Ag (JURKOVIĆ et al., 1997). According to our opinion, very often gold occurs me- chanically inserted as micro-scale inclusions in tetrahedrite occuppying defect places in its structure. JURKOVIĆ (1958) took photomicrographs of gold also occurring as irregular masses of microscopic dimension (Fig. 6). 6.2. Distribution of the most important tetrahe- drite microconstituents as trace elements in the ore deposits located in the MBSM and SE Bosnian areas The distribution of Co, Ni, Sn, W, Ag, Au, Hg, Bi and Se in the seven main genetic types of ore deposits (Chapter 3) is presented in the Table 8. Cobalt is the most abundant element in the oldest phase (Mačje Jame, 78 ppm) and in the youngest phase of miner- alisation (Maškara-Saski Rad veins, 113 ppm). One uninden- tifi ed mineral with optical characteristics very similar to a Figure 4: The photomicrograph of the needles of bismuthinite (bi) orient- ed paralell to (111) as exsolutions in tetrahedrite crystals (t) from the Trošnik, Fojnica deposit. Magnifi cation: 300x. Figure 5: The photomicrograph of the discs and needles of bismuthinite (bi) as exsolutions in tetrahedrite crystals (t) from the Trošnik, Fojnica de- posit. Magnifi cation: 450x. Figure 6: The photomicrograph of myrmekitic intergrowths of tetrahedrite (t) with one sulphide or sulphosalt (sl) from the Trošnik, Fojnica deposit. Magnifi cation: 300x. Figure 7: The photomicrograph of gold (Au) occurring as small, irregular masses in tetrahedrite (t) from the Maškara-Saski Rad gold-bearing tetra- hedrite. Magnifi cation: 300x. Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 233 Co-Ni-arsenide was discovered using a polarised micro- scope, but only from the Mačje Jame deposit. Nickel is most abundant in the Mačje Jame deposit (105 ppm) then in the Vrtlasce deposit (78 ppm) and in the Maš- kara-Saski Rad tetrahedrite veins (71 ppm). Tin has been found optically as cassiterite and stannite minerals by JURKOVIĆ (1956, 1958a) in the Vrtlasce de- posit (average 429 ppm Sn; maximal 900 ppm) and in the Mačje Jame (115 ppm Sn). JURKOVIĆ & HRVATOVIĆ (manuscript) found tin in the Vranjska Rijeka deposit. These three ore deposits are characterized by a well developed pneumatolytic phase. In the hydrothermal phase (Hg-tetra- hedrite) tin is very rare and hardly measurable. Tungsten as the mineral ferberite (Fe,Mn)WO4 was dis- covered by RAMOVIĆ (1956), in the silver-bearing sphaler- ite-antimonite quartz vein named “Main vein” and “NW Čemernica” veins (W = >100 ppm). Small contents of W we found in the Mačje Jame deposit (26 ppm) and in the Maš- kara-Saski Rad Hg-tetrahedrite veins (20 ppm). The major- ity of tungsten was consumed earlier by formation of mineral wolframite. Bismuth and selenium are closely genetically related. Their presence was fi rst observed in the Mačje Jame deposit (Bi = 15 and Se = 14 ppm), but they are most abundant in the Vranjska Rijeka deposit (230 ppm Bi and 20 ppm Se), as the minerals cosalite and elemental bismuth (JURKOVIĆ & HRVATOVIĆ, in press). The Vranjska Rijeka deposit con- tains 0.33 g/t of gold, the Vrtlasce deposit contains 0.07 g/t and there is less in the Mačje Jame deposit at 0.01 g/t. The occurrence of Bi and Se simultaneously with gold in these three deposits indicates their clear positive correlation. The best positive correlation between Bi, Se and Au has been established in the Hg-tetrahedrite deposits, Maškara- Saski Rad and Kreševo types. The element Bi, having usu- ally microelement status, becomes a very important major element (0.20–0.25 wt.%; max. 0.58 wt.%), whereas the abundance of Se exceedes 100 ppm. Tetrahedrites with such contents of Bi and Se, contain 8 to 62 g/t of Au and between 300 ppm and 0.34 wt.% of Ag (JURKOVIĆ et al., 1997). In Hg-tetrahedrite, gold is in pronounced positive cor- relation with mercury which in the Hg-tetrahedrite also be- comes a major element (on average 3.0 wt.%) for the fi rst time. In the earlier mineralization phases, mercury was only a trace element. The occurrence of scarce cinnabar in the Čemernica deposit is an exception, but in our opinion, this phenomenon is only a younger overprint. Silver is characterized by a positive correlation with Pb–Sb sulphides and sulphosalts in the Vrtlasce and Čemer- nica deposits. In the Middle Ages, these two groups of silver- bearing deposits were rich suppliers of silver ore for the Saxon miners. The second bearers of silver are small, but numerous polymetallic barite ± siderite ± calcite ± quartz veins and re- placement bodies, and are best developed in SE Bosnia. They are rare in the MBSM. Ag is linked with Fe, Cu, Zn, Pb, and Sb sulphides and sulphosalts, particularly with PbS and Pb- antimonides. The silver content is moderate (some tenths of a gram/t) and gold only occurs as a trace element. The third, youngest silver mineralization phase is ge- netically related to the occurrences of Hg-Bi-tetrahedrite in the monosulphide barite-siderite Maškara-Saski Rad veins, and in the barite ± fl uorite replacement bodies of the Kreševo type. These deposits contain Hg-tetrahedrite, in which the Ag content ranges between 300 ppm and 3400 g/t, whereas its Au content varies from 8 to 62 g/t. The Bakovići deposit also has a high content of gold (21 g/t) but only 13 g/t Ag. Cadmium isomorphically supstitutes zinc in the crystal lattice of sphalerite and zinc in the Hg-tetrahedrite. Tellurium in the Hg-tetrahedrite from the MBSM has not, so far, been investigated by chemical analyses. Optical investigations of polished sections of Maškara Hg-tetrahe- drites under polarized microscope revealed some minute minerals, with optical characteristics very similar to Au-tel- luride (JURKOVIĆ, 1960). This suggests that there should be a positive correlation between gold and tellurium. Thalium with an increased content of 91.9 ppm has been only been discovered in one out of more than fi fty analysed samples. Comparison of the microconstituents of studied Hg-te- trahedrite from the Saski Rad vein deposit, with those of the Hg-tetrahedrite samples taken from the Duboki Vagan de- Table 8: The distribution of Co, Ni, Sn, W, Ag, Au, Hg, Bi and Se in the seven main genetic types of ore deposits. Ore types Co ppm Ni ppm Sn ppm W ppm Ag ppm Au ppb Hg ppm Bi ppm Se ppm Rhy-KREŠEVO 8.0 8.0 3.0 3.00 <0.1 n.a. 0.04 0.1 <0.5 Rhy-BUSOVAČA 6.0 <20.0 2.0 n.a. <0.5 n.a. n.a. n.a. n.a. MAČJE JAME 77.7 104.7 114.7 25.80 1.3 n.a. 0.32 15.4 13.5 VRANJSKA RIJ. 25.3 7.7 44.1 1.10 10.3 0.33 2.02 >229.4 20.0 VRTLASCE 13.8 77.7 428.7 0.50 >52.9 0.07 28.00 >36.1 29.9 ČEMERNICA 1.0 n.a. 4.00 >100.00 153.2 0.01 436.8 10.0 n.a. BAKOVIĆI 1.0 3.0 4.00 n.a. 13.0 21.00 n.a. 10.0 n.a. SEB–A 4.6 29.7 <1.0 0.70 20 - 50 tr. 0.7 0.3 <0.5 SEB–B 1.0 16.4 <1.0 0.08 0.04 0.30 0.46 <0.1 <0.5 SASKI RAD 113.1 71.3 <1.0 20.00 >300.0 11.00 3.81% 0.25% >100.0 Geologia Croatica 64/3Geologia Croatica 234 posit (Kreševo, MBSM) and the Brixlegg deposit (Tyrol, Austria) is presented in Table 8. There is an interesting cor- respondence in the content of Se between Saski Rad and Brixlegg deposits. The Au content in the Saski Rad and Duboki Vagan tetrahedrites is several times higher than that of Brixlegg tetrahedrite. Furthermore, the Saski Rad and Duboki Vagan tetrahedrite have higher Ni and Bi content compared to the Brixlegg tetrahedrite. However, the Brix- legg tetrahedrite contains more Co and Cd than the Saski Rad tetrahedrite. 6.3. Problem of lanthanides (REE) Table 10 compares the total REE content, and values of the three dominant lanthanides (La, Ce, and Nd), in the (meta)- rhyolite and keratophyre of the Kreševo (KRE) and Busovača (BUS) regions, with the REE contents of some important ore deposits in the MBSM and SE Bosnia. This arose from the suspicion that the oldest Mačje Jame and Vranjska Rijeka iron deposits may have a direct genetic connection with metamorphogenic fl uids generated during progressive and retrograde Variscan (Hercynian) metamorphism. The total REE and the contents of the dominant lanthanides (La,Ce,Nd) in rhyolite, keratophyre and the oldest iron deposits of Mačje Jame and Vranjska Rijeka is very high and almost the same, indicating a direct genetic link. Rash reduction of total REE content during the subse- quent phase of mineralization (Vrtlasce deposit) is the result of crystallization of some lanthanide minerals in the earlier phase. These were most probably minerals of the bastnaesite group, as described by RADVANEC et al. (2004) in the sim- ilar Slovakian ore deposit. Only partial analytical data is available for the Čemernica type deposit and the later Bakovići ore type mineralisation phase, and therefore they could not be included in Table 10. Numerous analytical values have been obtained from the fi fth phase of mineralization. The highest content of total REE characterizes the siderite from SE Bosnia (33.0 ppm). Lower contents have been found in siderite from the Trošnik ore deposit (15.6 ppm), in the Hg-tetrahedrite from the Maš- kara-Saski Rad deposit (9.2 ppm) and in barite from the Maškara-Saski Rad deposit (8.4 ppm), whereas barite from the SE Bosnia contains only 5.1 ppm of total REE. Fluorite from the Dubrava (Kreševo) ore deposit is the mineral con- taining the least REE. Its two analyses contain 0.427 and 0.406 ppm of total REE. These fl uorites belong to the latest phase of mineralisation in the MBSM. Analyses of fl uorites were performed by INAA facilities in the Institute for Petrol- ogy and Geochemistry, Karlsruhe University (PALINKAŠ & JURKOVIĆ, 1994). The evidence suggests a successive decrease of total REE contents, not only because of the formation of new REE minerals, but also due to insertion of REE in the vacant de- fect places of the crystal lattices of other minerals, especially siderite, ankerite, barite and tetrahedrite. Evidence suggests that mixed hydrothermal fl uids played a specifi c role in this process during the last mineralization phase. The develop- ment of REE from the oldest to the youngest ore deposits indicates gradual reestablishment of a uniform and unique hydrothermal system in the MBSM area. 6.4. Composition of FeCO3, CaCO3, MgCO3 and MnCO3 isomorphic components of siderite in the diff erent genetic and paragenetic types of ore deposits in the MBSM and SE Bosnia Table 11 shows six siderite chemical analyses belonging to the six most important genetic and paragenetic ore types from the MBSM deposits: Mačje Jame, Vranjska Rijeka, Vrtlasce, Trošnik, Maškara-Saski Rad and Bakovići-Čemer- Table 10: The contents of the total REE and the values of the three dominant lanthanides (La, Ce, and Nd) in the (meta)-rhyolite and keratophyre of the Kreševo (KRE) and Busovača (BUS) regions compared with those of some important ore deposits in the MBSM and SE Bosnia. Rhyolite-keratophyre Ore occurrences and deposits in the MBSM and SE Bosnia Localities Kreševo Fojnica Busovača Vitez Mačje Jame Vranjska Rijeka Vrtlasce Fojnica SEB–A sd–ba Trošnik Fojnica Saski R. tetrah. Saski R. barite SEB–B barite Kreševo fl uorite ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm ΣREE 183.1 159.5 216.5 158.8 59.5 33.0 15.6 9.15 8.4 5.14 0.416 La 38.0 29.4 33.1 36.8 9.8 5.9 2.9 8.19 1.8 1.30 0.026 Ce 76.8 64.8 74.6 60.1 23.7 4.9 5.5 0.64 0.3 0.24 100.0 72.0 >100.0 Au 38.96 11.0 9.0 2.3 Σ REE 15.03 10.16 9.96 17.43 Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 235 nica. The paragenesis and some PT conditions of these de- posits are described in Chapter 3. Table 11 demonstrates the clear interdependence of the composition of Fe-carbonates and PT conditions during their genesis. 7. CONCLUSIONS a) Both fresh and weathered Hg-tetrahedrite samples from the Saski Rad deposit have been examined concerning their microconstituents. W (20 ppm) and Se (>100 ppm) have been detected for the fi rst time in the MBSM Hg-tetrahedrite. There is an interesting correlation of the Se content between the Saski Rad and Brixlegg deposits. The Au content of the Saski Rad Hg-tetrahedrite is relatively high (11 ppm), four times lower than in the Duboki Vagan tetrahedrite, but four times higher than in the Brixlegg Hg-tetrahedrite. b) The low content of total REE (10 ppm) and strong negative δ34SCDT values (average: –10.09‰) in the Hg-tetra- hedrite samples of the Saski Rad vein deposit are in accord- ance with 18 other previously analysed Hg-tetrahedrite sam- ples from the whole of the Mid-Bosnian Schist Mts. c) The quantitative relationship of the main constituents in the studied tetrahedrite is very similar to that in the tetra- hedrite of the Maškara deposit, confi rming the earlier as- sumption that the Saski Rad vein deposit represents the bro- ken part of the Maškara ore vein. d) The Co, Ni, Sn, W, Ag, Au, Hg, Bi and Se distribu- tion in the seven most important paragenetic types of the MBSM and SE Bosnia ore deposits is signifi cant in several ways. Optical studies suggest that Co and Ni, are most prob- ably present as Co-Ni arsenides in the oldest iron deposits (Mačje Jame and Vranjska Rijeka), and also occur as micro- constituents in Hg-tetrahedrite. Sn is completely consumed in the pneumatolytic-hydrothermal Pb, Zn and Cu sulphide deposits as cassiterite and stannite. The fi rst Sn occurrence is detected in the Mačje Jame deposit. W, as the mineral fer- berite, was found in the silver-bearing Čemernica sphalerite- antimonite deposit. Bi with 230 ppm and Se with 20 ppm drew attention to the fi rst gold (0.33 ppm) presence in the Vranjska Rijeka copper (0.7 % Cu) deposit. The second very strong occurrence of Bi (with 0.25–0.58 wt.%) and Se (with >100 ppm) is observed in the last hydrothermal Hg-tetrahe- drite-bearing barite ± siderite phase. Hg (average 3.07 wt.%), occurs in association with Bi and Se as a major constituent, whereas in all other deposits it is absent or present only as a trace element. There is a positive correlation between Bi, Se, Hg and Au, Ag presence in studied ore deposits. e) A review of numerous previous scientifi c investiga- tions of parageneses, isotope composition (C, O, S, Sr, Pb), fl uid inclusion, trace elements, and REE data analysis, sug- gests that the seven main paragenetic and genetic types of the MBSM and SE Bosnia ore deposits are generated domi- nantly from metamorphogenic fl uids. The important masses of (meta)-rhyolites and keratophyres are formed by anatexis, as evidenced by Sr isotope data. Palaeozoic protoliths, met- amorphosed by several stages of Variscan progressive and retrograde metamorphism, are the sources of hydrothermal fl uids. A similar opinion concerning the genesis of siderite ± barite deposits of Rudnány (Slovakia) was published by GRECULA et al. (1989); ŽAK et al. (1950) and RADVAN EC et al. (2004). The most convincing evidence of the metamorphogenic origin of the hydrothermal fl uid is the strong similarity of to- tal REE and the dominant La, Ce and Nd elements in the me- ta-rhyolite and their pellitic and psammitic metamorphosed protoliths on one hand and the oldest Mačje Jame and Vran- ska Rijeka iron ore deposits on the other (Table 10). f) Previous investigations of the MBSM and SE Bosnia ore deposits established unexpected contrasting parageneses that indicate several different hydrothermal fl uids and PT conditions. The best example is Čemernica, an important rich silver-bearing deposit containing >150 g/t Ag, only traces of Au and >100 ppm W, in relation to the richest gold- bearing pyrite deposit Bakovići having 11 g/t Au and only 13 g/t Ag, but without W. Deposits differ in salinity and in homogenization tem- perature (Th). SEB-A and SEB-B barite-siderite deposits as- sociated with polymetallic sulphides (the SE Bosnia type) are characterized by lower salinity (<10 wt.% NaCl) and low Th = 100–150°C. Polymetallic monomineral barite-siderite ± octahedral fl uorite ore deposits, Hg-tetrahedrite-bearing Maškara-Saski Rad and Kreševo types are characterized by high salinity (15–25 wt.% NaCl) and high Th = 230–330°C. g) The composition of FeCO3, CaCO3, MgCO3 and MnCO3 isomorphic components of sideritic gangue in the MBSM and SE Bosnia ore deposits are dependent upon PT conditions and the hydrothermal fl uid system. REFERENCES BARTALSKÝ, B. (1991): Results of the study of vein mineralization in the Rožňava ore fi eld – evidence for the metamorphic-hydrothermal genetic model.– Unpublished CSc Thesis. Geological Survey of Slovak Republic, Spišská Nová Ves (in Slovak). BLEČIĆ, A. (1983): Ispitivanje izotopa sumpora, kisika i ugljika u anti- monskim ležištima Potkozara i Kordići [Examination of sulphur, oxygen and carbon isotope in antimony deposits of Potkozara and Kordići – in Croatian].– In: RAMOVIĆ, E. (1991): Metalogenija Bosne i Hercegovine [Metallogeny of Bosnia and Herzegovina – in Croatian].– Unpubl. PhD Thesis, Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, 239 p. Table 11: Interdependence between the composition of siderite and its genetic ore type (PT conditions). Mačje jame Vranjska rijeka Vrtlasce Fojnica Trošnik Fojnica Maškara Saski Rad Bakovići Čemernica wt. % wt. % wt. % wt. % wt. % wt. % FeCO3 62.53 70.13 71.75 74.39 81.23 86.66 CaCO3 8.78 3.55 15.75 12.89 9.52 1.43 MgCO3 19.30 24.13 10.30 10.03 6.59 2.50 MnCO3 9.40 2.20 2.02 2.69 2.66 10.10 ∑ 100.01 100.00 99.82 100.00 100.00 100.69 Geologia Croatica 64/3Geologia Croatica 236 CAMBEL, B. & JARKOVSKY, J. (1985): Rudnianske rudne pole-geo- chemicko-metalogeneticka charakterstika [The Rudnany ore fi eld- geochemical-metallogenetic characteristics – in Slovakian].– Slov- enska akademia vied, Bratislava, 363 p. DUDA, R. & REJL, L. (1987): La grande encyclopedie des minéraux.– Published by GRÜND, Paris, 520 p. FOIT JR., F. F. & HUGHES, M. J. (2004): Structural variations in mer- curian tetrahedrite.– American Mineralogist, 89, 159–163. FRIMMEL, H.E. & PAPESH, W. (1990): Sr, O, and C Isotope Study of the brixlegg Barite Deposit, Tyrol (Austria).– Econ. Geology, 85, 1162–1171. GRECULA, P., RADVANEC, M. & ŽÁK, K. (1989): Metamorphic ori- gin of hydrothermal ore fl uids of vein mineralization in the gemeri- cum belt, Western Carpathians. 28th International Geological Con- gress, Washington, USA. Abstract Volume, 584–585. GSTREIN, P. (1983): Ueber mögliche Umlagerungen fon Fahlerzen im devonischen Schwazer Dolomit wie auch in der angrenzenden Schwazer Trias. Oester. Akad. D. Wissench., 6.– In “Ore Mobiliza- tion in the Alps and in SE-Europe”, Leoben-Wien, 65–74. HRVATOVIĆ, H. (1996): Strukturno-facijalna analiza sjeverozapadnog škriljavog gorja [Structural and facies analysis of the Mid-Bosnian Schist Mts. – in Bosnian].– Unpubl. PhD Thesis, University of Tu- zla, 112 p. JEREMIĆ, M. (1963): Metalogenija paleozojskih ležišta barita Bosne [Metallogeny of barite deposits in Paleozoic of Bosnia].– Arhiv za tehnologiju, I, 1–2, Tuzla, 1–59. JOHNSON, N.E., CRAIG, J.R. & RIMSTIDT, J.D. (1988): Crystal che- mistry of tetrahedrite.– American Mineralogist, 73, 389–397. JURKOVIĆ, I. (1951): Prethodni izvještaj o planini Vranici i njoj sus- jednih planina [Preliminary report from Vranica and adjacent mountains – in Croatian].– Arhiv Inst. za geol. istraž., Sarajevo. JURKOVIĆ, I. (1956): Mineralne parageneze Srednjobosanskog Rudog- orja s osobitim osvrtom na tetraedrite [Mineral parageneses of the Mid-Bosnian Ore Mountains with particular respect on tetrahe- drites – in Croatian].– Unpubl. PhD theses, University of Zagreb. 306 p. JURKOVIĆ, I. (1958): Kasiterit, stanin i molibdenit u rudnoj pojavi Vrt- lasce kod Klisca [Cassiterite, stannite and molybdenite from the ore occurrence Vrtlasce at Klisac – in Croatian].– Geol. glasnik, 4, Sarajevo, 1958, 309–320. JURKOVIĆ, I. (1960): Quecksilberfahlerz vom Mačkara Gang bei Gornji Vakuf in Bosnien.– Neues Jh.d.Mineral., Abh. 94, Stuttgart, 539–558. JURKOVIĆ, I. (1962): Parageneze rudnih pojava u oblasti Čemernice kod Fojnice [Parageneses of ore occurrences in the area of Čemer- nica near Fojnica – in Croatian].– Geol. glasnik, 6, Sarajevo 1962, 141–156. JURKOVIĆ, I. (1986): Quantitative Chemical and Optical Investigations of the Tetrahedrite from Barite-bearing Deposit Vidici on the North- ern Slopes of the Mountain Međuvršje, South of the Town of Kre- ševo, Bosnia.– Geološki vjesnik, 39, 187–224. JURKOVIĆ, I. (1987): Barite Deposits on Mount Međuvršje South and South-East of the Town of Kreševo, Bosnia.– Geol. vjesnik, 40, 313–336. JURKOVIĆ, I. (1995): Bakovići, the biggest gold deposit of Bosnia and Herzegovina.– Rud. geol. naftni zbornik, 7, 1–15. JURKOVIĆ, I. & MAJER, V. (1954): Rioliti (kremeni porfi ri) Vranice planine i albitski riolit Sinjakova u Srednjobosanskom Rudogorju [Rhyolites-quartzporphyries – of the Vranica Mountain and albite rhyolite of Sinjakovo in the Mid-Bosnian Ore Mountains – in Cro- atian].– Vjesnik Zavoda za geološka i geofi zička istraživanja NR Srbije, XI, Beograd, 207–233. JURKOVIĆ, I. & PALINKAŠ, L. (1996): Late Variscan, Middle-Upper- Permian, post-Variscan and Triassic rifting related ore de posits in the Northwestern and central Dinarides.– Proceeding of the Annu- al Meeting, UNESCO Project No. 356, Plate Tectonic Aspects of the Alpine Metallogeny in the Carpatho-Balkan Region, Sofi a, 1, 19–27. JURKOVIĆ, I. & MIKO, S. (1997): Tetrahedrite from the Dubrave- Dugi Dol Barite Deposit, Kreševo, Bosnia and Herzegovina.– Rudarsko-geološko-naftni zbornik, 9, 11–16. JURKOVIĆ, I. & PALINKAŠ, L. (1999): Sulphur isotope and fl uid inclu- sion data of barites from the Dinarides.– Sixth Biennal Meeting of SGA and IAGOD.– Mineral Deposits, Processes to Processing, Lon- don, 1999. Proceedings, Balkema, pub., Rotterdam, 1999, 45–49. JURKOVIĆ, I. & PALINKAŠ, L. (2002): Discrimination criteria for as- signig ore deposits located in the Dinaridic Palaeozoic-Triassic for- mations to Variscan or Alpidic metallogeny.– In: BLUNDELL, D.J, NEUBAUER, F. & VON QUADE, A. (eds.): The Timming and Location of Major Ore Deposits in an orogen. Geological Society, London, Special Publications, 204, 229–245. JURKOVIĆ, I. & HRVATOVIĆ, H. (in press): Geology, petrology and geochemistry of the Mačje Jame and Vranjska Rijeka iron ore de- posits, Mid-Bosnian Schist Mountains. JURKOVIĆ, I., ŠIFTAR, D. & PEZDIČ, J. (1994): Geology and geo- chemistry of the mineralization from the Gornji Vakuf, Bosnia.– Rudarsko-geološko-naftni zbornik, 6, 19–37. JURKOVIĆ, I., RAMOVIĆ, M. & ZEC, F. (1999): Chemical and geo- chemical characteristics of the Čemernica antimonite deposit in the Mid-Bosnian Schist Mountains.– Rud.-geol.-nafnti zbornik, 11, 1–16. JURKOVIĆ, I., GARAŠIĆ, V. & HRVATOVIĆ, H. (2010): Geochemi- cal characteristics of barite occurrences in the Palaeozoic complex of South-eastern Bosnia and their relationship to the barite deposits of the Mid-Bosnian Schist Mountains.– Geol. Croat., 63/2, 241– 258. JURKOVIĆ, I.B., GARAŠIĆ, V. & JURKOVIĆ, I.M. (2011): Geochem- ical characteristics of mercurian tetrahedrite, barite and fl uorite from the Duboki Vagan, Glumac and Dubrave-Dugi Dol barite deposits, south of Kreševo, Mid-Bosnian Schist Mts.– Geol. Croat., 64/1, 49–59. JURKOVIĆ, I., TONČIĆ-GREGL, R., STRMIĆ, S. & ŠIFTAR, D. (2002): Geology and geochemistry of the Raštelica barite deposits southwest of Sarajevo, Bosnia and Herzegovina.– Rud.-geo.-naftni zbornik, 14, 37–46. JURKOVIĆ, I., PALINKAŠ, L, ŠIFTAR, D., MIKO, S., JAKŠIĆ, M. & PEZDIČ, J. (1997): Gechemical characteristics of mercurian tetra- hedrites from the Mid-Bosnien Schist Mts.– The 4th SGA Meeting, Finland. Published by Balkema, Rotterdam, 829–833. KATZER, F. (1907): Die Fahlerz– und Quecksilbererzlagerstätten Bos- niens und der Hercegovina.– Berg-und Hüttenmännisches Jahr- buch der k. k. montanist. Hochschulen zu Leoben und Pribram. LV 2, 121 p. KATZER, F. (1926): Geologie Bosniens und der Herzegovina.– Erster Band, I. u II. Hälfte, Sarajevo. KUBAT, I., RAMOVIĆ, E., TOMIČEVIĆ, D., PEZDIČ, J. & DOLE- N EC, T. (1979/80): Results of the investigations of isotopic com- positions of sulphur, oxygen, carbon and lead in some ore deposits and ore occurrences from Bosnia and Herzegovina (in Bosnian).– Geol. glasnik, 24–25, 61–84. KULENOVIĆ, E. (1987): Mineralizacije u paleozoiku Jugoistočne Bosne [Mineralisation in Palaeozoic of South-eastern Bosnia – in Serbian].– Geol. glasnik, 31/31, 106–143. LUKAS, W. (1971): Tektonisch-genetische Untersuchung der fahlerz – Lagerstätte am Falkenstein bei Schwaz (Tirol).– N. Jb. Geol. Palä- ont. Mh, 47–63. Jurković I.B. et al.: Cobalt, nickel, tungsten, cadmium, selenium, silver and gold-bearing mercurian tetrahedrite from the Saski Rad... Geologia Croatica 237 MAJER, V. & GARAŠIĆ, V (2001): Metarioliti Vranice planine u pale- ozoiku središnje Bosne [Metarhyolites of Vranica Mountain in Paleozoic of Middle Bosnia – in Croatian].– Rudarsko-geološko- naftni zbornik, 13, 9–14. MAJER, V., LUGOVIĆ, B. & TRUBELJA, F. (1991): Metamorphism of the Midd-Bosnian Schist Mountains – a preliminary investiga- tion (in Croatian).– Radovi ANUBiH, Sarajevo, 87/13, 141–158. PALINKAŠ, L. & JURKOVIĆ, I. (1994): Lanthanide Geochemistry and Fluid Inclusion Peculiarities of the Fluorite from the Barite Depos- its South of Kreševo (Bosnia and Herzegovina).– Geol. Croat., 47/1, 103–115. POECH, F. (1900): L’industrie minérale de Bosnie-Herzègovine, Wienne. RADUSINOVIĆ, D. (1960): Mineralni sastav koncentrata tečnih nano- sa nekih bosanskih reka [Mineral composition of some fl uvial plac- ers in Bosnia – in Serbian].– Unpubl. report, Beograd, 31 p. RADVANEC, M., GRECULA, P. & ŽAK, K. (2004): Siderite miner- alization of the Gemericum superunit (Western Carpathians, Slova- kia): review and a revised genetic model.– Ore Geology Reviews, 24 (2004), Elsevier B. V., 267–298. RAMDOHR, P. (1986): The ore minerals and their intergrowths.– 2nd edition, vol. 2., Pergamont press, International Series in Earth Sci- ences volume 35, Oxford. RAMOVIĆ, M. (1956): Volframit iz Čemernice kod Fojnice, NR BiH [Wolframite from Čemernica near Fojnica, Bosnia and Herzegowi- na – in Serbian].– Tehnika, 11, 1651–1652 (Rudarstvo i metalurg- ija 7 RM Beograd) 243–244. RAMOVIĆ, M. (1957): Pregled nalazišta minerala olova i cinka u Bos- ni i Hercegovini. [Overview of mineral deposits of zinc and lead in Bosnia and Herzegovina – in Serbian].– Geol. glasnik, 3, Sarajevo, 3–121. RAMOVIĆ, M. (1976): Barit. Mineralne sirovine Bosne i Hercegovine Knjiga II. Ležišta nemetala [Barite. Mineral resources in Bosnia and Herzegovina. Nemetallic ore deposits – in Serbian].– Geoin ž- enjering, Sarajevo, 358– 379. RUECKER, A. (1896): Einiges über die Goldvorkommen in Bosnien.– Monographische Skizze, Wien, 1–101. SOFILJ, J. & ŽIVANOVIĆ, M. (1979): Osnovna geološka karta M 1:100000 list Prozor [Geological map 1:100 000, sheet Prozor].– Savezni geološki zavod, Beograd. SOFILJ, J., ŽIVANOVIĆ, M. & PAMIĆ, J. (1980): Tumač osnovne geološke karte list Prozor [Geological map 1:100000, Geology of the Prozor sheet – in Croatian].– Savezni geološki zavod, Beo grad. ŠIFTAR, D. (1988): The chemical characteristics of barite from some Bosnian deposits.– Rudarsko–metalurški zbornik, Ljubljana, 35, 75–89. ŠIFTAR, D. (1990): Usporedba kemizma barita iz područja Raštelice i Kreševa u srednjobosanskom Rudogorju [Comparison of barite chemistry fom Raštelica area and Kreševo in Mid–Bosnian Ore Mountrains – in Croatian].– Geol. vjesnik, 43, 109–112. VASILJEVIĆ, R. (1972): Geologija i metalogenija paleozoika u području Jezera i Sinjakova kod Jajca [Geology and metalogeny of Palaeo- zoic in Jezero and Sinjakovo area near Jajce – in Serbian].– Un- publ. PhD Thesis, University of Zagreb, 128 p. VESELY, V. (1921): Tetraedrit iz Maškare u Bosni [Tetrahedrite from Maškara in Bosnia – in Serbian].– Glasnik Hrvatskog prirodoslov- nog društva, Zagreb, 99 p. ŽAK, K., RADVANEC, M., GRECULA, P. & BARTALSKÝ, B. (1991): S, C, O, Sr isotopes and a metamorphic-hydrothermal model of vein mineralization, Gemeric unit, Western Carpathians.– Mineralia Slo- vaca, 23, 95–108 (in Slovak with English abstract). ŽIVANOVIĆ, M. (1972): Geological structure and tectonic framework of the Vranica Mountain in Central Bosnia (in Serbian).– Unpubl. PhD Thesis, University of Beograd. Manuscript received November 24, 2010 Revised manuscript accepted July 22, 2011 Available online October 26, 2011