Jurkovic.indd 241 � AB STRA CT In Palaeozoic rocks of South-eastern Bosnia (SEB) there are numerous, but very small vein and replacement barite ore deposits containing up to 10% Pb-Zn-Fe-Cu sulphides. Their geochemical characteristics are compared with large barite monosulphide (Hg-tetrahedrite) ore deposits in Mid-Bosnian Schist Mountains (MBSM). The 87Sr/86Sr isotope ratios in the barites of both areas are very similar, (0.710972 and 0.714170 in SEB, 0.711764 and 0.712548 in MBSM), and indicate the epigenetic hydrothermal origin of the barite ore deposits. This conclusion is supported by the elevated Sr content in barites of both areas (0.48 to 2.83% in SEB, 1.44% in MBSM) and the δ13C and δ18O val- ues in calcite and siderite of barite ore deposits which are shifted toward lower values relative to typical values oc- curring in the Devonian host rock. The δ18O values in barites from SEB (+14.2‰ to +15.6‰) are remarkably lower than those from MBSM (+15.8‰ to +22.4‰). This can be explained by the lower temperature and lower salinity of mineralisation fl uids in barite ore deposits of SEB. The δ34S values in barites of SEB are positive (+11.6‰ to 17.7‰), and enriched in heavy sulphur isotopes in comparison with sulphides of SEB (–0.41 to +4.26‰), whereas those in tetrahedrites are negative (–4.95 in SEB, –5.50 to –15.40‰ in MBSM) indicating two remarkably different sulphur sources and times of formation. Barite ore deposits of both areas, SEB and MBSM, have been genetically linked to fl uids that originated during Late Variscan S-type magmatism and metamorphism of Upper Proterozoic and Lower Palaeozoic rock complexes. However, later Post Variscan/Eoalpine heating processes affected signifi cant parts of barite ore deposits in MBSM. They caused fl uidization of sulphides in barite deposits, ascension of subcrustal deep- seated fl uids enriched in H2S and mercury (± fl uorine), which passed through Upper Proterozoic and Caledonian ore deposits amalgamating their Au and Ag content leading to formation of a new mineral, Hg-tetrahedrite rich in Au (10–50 g/t) and Ag (1000 do 3000g/t). Keywords: Palaeozoic complexes of South-eastern Bosnia and Mid-Bosnian Schist Mountains, barite ore de- posits, trace elements, isotopic composition of sulphur, oxygen and strontium in barite, Pb-Zn-Fe-Cu-Sb sul- phides, Hg-tetrahedrite Geochemical 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 � Ivan Jurković1, Vesnica Garašić1 and Hazim Hrvatović2 1Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, Pierottijeva 6, HR-10 000 Zagreb, Croatia; (vesnica.garasic@rgn.hr) 2Federal Geological Institute, Ustanička 11, Ilidža, Sarajevo, Bosnia and Herzegovina doi: 104154/gc.2010.20 Geologia Croatica 63/2 241–258 10 Figs. 7 Tabs. Zagreb 2010 Geologia CroaticaGeologia Croatica Geologia Croatica 63/2Geologia Croatica 242 1. INTRODUCTION The biggest barite ore deposits in the whole Dinarides are located in the Mid-Bosnian Schist Mountains (MBSM). This Palaeozoic complex consists mostly of Lower Palaeozoic (Ordovician(?)–Silurian-Devonian) rocks and subordinately of Lower–Middle Carboniferous and Upper Permian rocks. These deposits are, regarding their mineral paragenesis, uni- que even on a global scale. The main mineral in the mineral paragenesis, in addition to barite and locally siderite, is Hg- Ag-Au-rich antimony tetrahedrite, named schwazite after the Schwaz locality, in Austria. Schneiderhöhn (1942) group ed this type of paragenesis as a separate genetic type. Barite occurrences in the Palaeozoic complex of South- eastern Bosnia (SEB) represent the most South-eastern out- crops of numerous mineable barite deposits in the Dinarides (Fig. 1). Compared to numerous geochemical data of barites from MBSM only a few geochemical analyses of barites from SEB (PEZDIČ et al., 1977/1979; KUBAT et al., 1979/ 1980) have been performed. The aim of this study is to present the more comprehen- sive geochemical data on barite occurrences in SEB and compare them with those in the MBSM area. A model for the origin of the barite has been developed on the basis of trace elements, 87Sr/86Sr ratios, isotope composition of sul- phur and oxygen in barites, carbon and oxygen in neocar- bonates (neocalcite, neodolomite, neosiderite), and sulphur isotope composition in associated Pb, Zn, Cu, Sb and Fe sul- phides. Research history of the barite occurrences in South-eastern Bosnia Initial data concerning the barite occurrences in South-eastern Bosnia were described by JOJIĆ (1947), RA MOVIĆ, M. (1954) and JEREMIĆ (1958). In the barite belt of Reno vica- -Prača-Omrke, which has a general NNE-SSW trend, RAMOVIĆ, M. (1956, 1957) discovered three different par- agenetic types of barite bodies (Fig. 2a). JEREMIĆ (1963) registered 52 barite occurrences in Palaeozoic rocks of SEB (Figs. 2b, 2c, 2d). Most barite veins strike at 340o, dip more than 12o to NE, are very small (100 tons to a few thousand tons), and the total production from 1954–1966 was 24.000 tons of barite (RAMOVIĆ, M. et al., 1976; RAMOVIĆ, M. et al., 1979). KUBAT et al. (1979/1980) produced the fi rst isotopic sulphur analyses for Pb and Fe sulphides, barite, and 1 Pb isotopic analysis for galena (PEZDIČ et al., 1977/1979). RAMOVŠ & KULENOVIĆ (1982) determined the strati- graphic position of mineralisation in sideritised limestones in the areas of Šarulje-Mastilove Stijene, the Kamenička River and Milotina as being primarily Lower Devonian and to a lesser extent Middle Devonian. JANJIĆ & ĐORĐEVIĆ (1985) published results of isotopic analyses in minerals of ore deposits Potkozara (Kratina) and Oglečevski potok (Kor- dići). KULENOVIĆ (1987) produced a brief overview of barite occurrences in SEB, stating that deposits occur in a 15 km long and 3 to 6 km wide belt extending from Fočanska Jabuka in the South-west across Borovac, Klek and Prača to Renovica in the Northeast (Figs. 2e, 2f, 2g, 2h). RAMOVIĆ, E. (1991) published the project investigation of BLEČIĆ (1983) on fl uid inclusions in sphalerite and barite in the Ran- oprge deposit, fl uid inclusions in quartz and δ34S of anti- monite in Kratina and Kordići (Goražđe). Most researchers of SEB consider that barite deposits originated in the Her- cynian metallogenic epoch probably associated with quartz- porphyry being similar that quartz-porphyry in the MBSM (RAMOVIĆ, M., 1957; JEREMIĆ, 1963; ŽIVA NOVIĆ, 1972; RAMOVIĆ, M. et al., 1976; RAMOVIĆ, M. et al., 1979). KULENOVIĆ (1986, 1987) and ČIČIĆ (2002) proposed a hypothesis suggesting the existence of more than one metal- logenic epoch in the Palaeozoic of SEB indicating the prob- able existence of a Caledonian metallogenic epoch (in the Upper Silurian and Lower Devonian). 2. GEOLOGICAL SETTING The Palaeozoic of SEB is elaborated by KATZER (1926), KOSTIĆ–PODGORSKA (1958), ŽIVANOVIĆ (1962), DIMI- TRIJEVIĆ, N.M. & DIMITRIJEVIĆ, D.M. (1972), BU- ZALJKO & PAMIĆ (1982), VUJNOVIĆ (1983), RAMOVŠ & KULENOVIĆ (1982), KULENOVIĆ (1986), KRSTIĆ et al. (1988), ČIČIĆ (2002) & HRVATOVIĆ (2006), and RA- MOVŠ et al. (1984). The most detailed research resulting in many new pal- aeontological data was carried out by KULENOVIĆ (1986), and produced evidence for Upper Silurian (S3), Lower Dev- onian (D1), Middle Devonian (D2), Upper Devonian (D3), Lower Carboniferous (C1) and Upper Permian (P3) deposits (Fig. 3). Upper Silurian (S3) deposits, being <100 m thick, were found near Prača and Ustikolina, but the upper and lower boundaries are uncertain. They consist of silicic, clastic and Fi gu re 1: The location of the Palaeozoic complex of South-eastern Bosnia (SEB) in relation to Palaeozoic complexes of the Mid-Bosnian Schist Moun- tains (MBSM), Eastern Bosnia (EB) and the Una-Sana area in Bosnia and Herzegovina. Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 243 Fi gu re 2: Barite occurrences in Palaeozoic rocks of SEB: a) Lensoid barite bodies in limestone of Kurjača, near Prača (RAMOVIĆ, M. 1957); b) Folded barite vein in schists of Badnjevi, near Prača (JEREMIĆ, 1963); c) Brecciated barite body in limestone of Debeljak, near Prača (JEREMIĆ, 1963); d) Crossed quartz and barite veins in silicifi ed breccia of Ravne Njive, near Prača (JEREMIĆ, 1963); e) Barite bodies in Palaeozoic brecciated chert of Gradina, in SEB (KULENOVIĆ, 1987); f ) Barite bodies in Palaeozoic rocks of Homar Klek, in SEB (KULENOVIĆ, 1987) where 1 = gray metasandstone, 2 = barite bodies, 3 = brecciated bar- ite, 4 = alevrolite, 5 = red sandstone; g) Barite bodies in Palaeozoic gray metasandstone of Rasoha-Jasik, in SEB (KULE NOVIĆ, 1987); h) Barite body in Pal- aeozoic rocks of Šušnjata Glava in SEB (KULENOVIĆ, 1987). a) b) c) d) e) f ) g) h) Geologia Croatica 63/2Geologia Croatica 244 dolomitic limestone rock with conodonts. Sedimentation from the Upper Silurian continued into the Lower Devonian, but transitional deposits (S3–D1) could not be separated. Se- quences are composed of alevrolites, cherts, argilloschists, metasandstones, tuffi tes and marbleized limestone (KULE- NOVIĆ, 1986). The Lower Devonian consists of alevrolites with chert (either independent small masses or intercalations in alevro- lites), layered and bank limestones. This lower part of the Lower Devonian is overlain by sequences composed of cherts, diverse argilloschists, metasandstones and limestones among which very fossiliferous bank limestones occur. Chert brec- cias, metadiabases, schistose spilites, diabases and some red clastites are locally developed. According to KULE NOVIĆ (1986) granitoides occurring in the Odska River and Osanica, intruded between Lower and Upper Devonian or in the Up- per Devonian. The Upper Devonian is composed of limestone schists, cherts, chert breccias, ferrous sandstone and marbleized limestones. Tabular sericite-quartz schists mark the lower part of the Lower Carboniferous. They are overlain by phyllite schists with intercalations or lenses of schistose sandstones containing fossil fl ora of Lower Visean age. Fossiliferous Lower Carboniferous phyllites with black lydite inter ca- lations are the next deposits in the sequence (KULENOVIĆ, 1986). The uppermost, unfossiliferous part of the phyllite schists represents, the transition from the Lower to Middle Carboniferous according to KULENOVIĆ (1986). These are discordantly overlain by deposits of Upper Permian sand- stones, schists, conglomerates and fossil-rich Bellerophone limestones. KRSTIĆ et al. (1988) discovered olistoliths and olistostromes composed of limestones and clastics in the "Culm fl ysch" in the Prača area. They stated that olistostrome formation is associated with very active tectonic zones, which caused the shearing and movement of large blocks such as Vlaška Stijena, Kiseljak, Klek and some others. ČIČIĆ (2002) and HRVATOVIĆ (2006) presented short over views of the stratigraphic development of quartz-por- phyry in SEB. The most widespread rocks of the Mid-Bosnian Schist Mountains (MBSM) are pre–Devonian metamorphic rocks (SOFILJ et al., 1980). MAJER et al. (1991) determined that they were formed by low grade metamorphism at 350°– Fi gu re 3: Geological map of the area between Fočanska Jabuka and Prača (after KULENOVIĆ, 1986). Circles denote the locations of barite samples analyzed here, whereas rectangles represent lo- cations, which are undergoing analysis. T1–2 = Lower-Middle Triassic; P3 = Upper Permian; C1–2 = Lower-Middle Carbonif- erous; D3 = Upper Devonian; D2 = Mid- dle Devonian; D1 = Lower Devonian; S3– D1 = Upper Silurian-Lower Devonian; S3 = Upper Silurian; Γ = Granitoid. Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 245 400°C and a pressure of 3–5 kbars. Their crystallization age, obtained by K–Ar dating is 343 ± 13 Ma (PALINKAŠ et al., 1996). Fossiliferous Devonian carbonate rocks overlie this metamorphic complex (ŽIVANOVIĆ, 1972). The uplift of this area is related to the Hercynian orogeny and extrusions of rhyolites. Upper Permian continental and lagoonal depos- its that unconformably overlie older Palaeozoic rocks, grade into Lower and Middle Triassic sediments. Mineralization in the SEB Palaeozoic complex com- prises small, but numerous barite deposits. They occur as ir- regular metasomatic barite bodies and epigenetic veins in the carbonate rocks, and contain traces or accessory amounts of Pb, Zn, and subordinantly Cu and Fe sulphides (Fig 4). Additionally, they occur as epigenetic barite veins located in metaclastites but enriched in sulphides (up to 10%). All sul- phides have positive δ34S values (0 to +5‰). The rare younger Hg–Ag tetrahedrite is characterized by a negative δ34S value (–4.95‰). The Hg–Ag–Au tetrahedrite deposits in the MBSM rep- resent a peculiar and unique phenomenon in the whole Di- narides (KATZER, 1907; JURKOVIĆ, 1956). The Mačkara vein type is observed in pre–Devonian metamorphic rocks of the Gornji Vakuf area (JURKOVIĆ, 1960; JURKOVIĆ et al., 1994). The Kreševo vein and metasomatic irregular bodies are very widespread in the area composed of Devo- nian dolomites and limestones (JURKOVIĆ, 1996). The Trošnik metasomatic type that occurs in the Fojnica– Bakovići area represents, at present, a unique exception among tetrahedrite-bearing barite deposits in MBSM. Its tet- rahedrite is neither the main nor the unique sulphide mineral rich in mercury, but is subordinate to pyrite and chalcopyrite and characterized by traces of mercury and positive δ34SCDT values (JURKOVIĆ, 1958). 3. ANALYTICAL METHODS Ore samples were collected from seven outcrops in SEB and ten outcrops in MBSM. Barites were hand-picked under bin- ocular microscope and then crushed and powdered for chem- ical analyses in an agate mortar. Trace elements were analysed by inductively coupled plasma (ICP) mass spectrometry in Acme Analytical Labo- ratories (Vancouver) Ltd in Canada. In order to use X-ray powder diffractometry (XRD), barite samples were pow- dered in an agate mortar. Diffractograms were recorded by a Philips diffractometer with counter and Cu-Kα radiation at U =40 kV and I = 20 mA at the Institute of mineralogy, pe- trology and mineral resources at Faculty for Mining, Geology Fi gu re 4: Photographs of white barite occurrences: a) in Permian limestone of Datelji; b) in Carboniferous schists of Pale; c) in Devonian limestone of the Glumac deposit (Kreševo); d) in Devonian limestone of the Dubrave deposit (Kreševo). Note hammer for the scale. a) b) c) d) Geologia Croatica 63/2Geologia Croatica 246 Table 1: Trace element contents of barites from SEB and MBSM. MBSM SEB SEB SEB SEB SEB SEB MBSM SEB Sample K D S DP J P FC range ppm ppm ppm ppm ppm ppm ppm ppm ppm Ba >50000 >50000 >50000 >50000 >50000 >50000 >50000 Be <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 Co 0.3 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 Cs 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Ga <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Hf 0.5 0.4 0.3 0.3 0.3 0.7 0.6 0.5 0.3–0.7 Nb <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Rb 0.4 0.3 0.1 0.2 0.2 0.2 <0.1 0.4 <0.1–0.3 Sn <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 <1.0 Sr 14354 12201 4846 6158 18888 7650 28292 14354 4846–28992 Ta 1.4 0.9 0.8 0.8 0.9 1.7 1.7 1.4 0.8–1.7 Th <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 <0.2 U <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 V 13 10 <8.0 <8.0 <8.0 <8.0 <8.0 13 <8–10 W <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Zr 1.6 0.4 <0.1 <0.1 0.2 0.2 1.4 1.6 <0.1–1.4 Y 1.0 0.7 0.9 0.5 0.6 1.2 1.3 1.0 0.5–1.3 La 2.4 1.6 1.4 1.8 1.7 1.1 3.5 2.4 1.1–3.5 Ce 0.9 0.3 0.2 0.2 0.3 0.2 0.7 0.9 0.2–0.7 Pr 0.10 0.04 0.03 0.04 0.04 0.03 0.06 0.10 0.03–0.06 Nd 0.3 <0.3 <0.3 <0.3 <0.3 <0.3 <0.3 Sm 0.45 0.33 0.35 0.25 0.30 0.58 0.67 0.45 <0.25–0.67 Eu 0.85 <0.02 0.04 0.24 <0.02 1.03 1.00 0.85 <0.02–2.03 Gd 1.02 0.80 0.81 0.70 0.68 1.44 1.62 1.02 0.68–1.62 Tb 0.08 0.06 0.06 0.05 0.05 0.10 0.10 0.08 0.05–0.10 Dy 2.78 2.20 2.09 1.76 1.74 3.80 4.05 2.78 1.74–4.05 Ho <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 Er 0.03 <0.03 <0.03 <0.03 <0.03 <0.03 <0.03 Tm 0.02 0.11 0.01 <0.01 <0.01 0.03 0.03 0.02 0.01–0.11 Yb 0.07 <0.05 0.06 <0.05 <0.05 0.06 0.08 0.07 <0.05–0.08 Lu <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Mo 0.20 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Cu 3.90 1.40 1.60 0.30 2.30 18.10 0.80 3.90 0.3–18.1 Pb 2.40 1.20 4.50 11.20 4.30 0.40 0.50 2.40 0.4–11.2 Zn 6.00 1.00 1.00 <1 2.00 1.00 <1 6.00 <1–2 Ag <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Ni 0.90 0.20 0.30 0.10 0.20 <0.1 <0.1 0.90 <0.01–0.3 As <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Au <0.0005 <0.0005 0.00120 <0.0005 <0.0005 <0.0005 <0.0005 Cd <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Sb 0.30 0.10 0.10 1.20 0.10 0.90 0.20 0.30 0.1–0.2 Bi <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Hg 0.19 0.09 1.66 0.42 0.63 0.22 0.03 0.19 0.03–1.66 Tl <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Se <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Ca 300.00 500.00 1.31 0.01 <0.1 <0.1 <0.1 300.00 <0.01–13100 ΣREE 9.03 5.87 5.41 5.46 5.25 8.73 12.17 LaN/YbN 24.59 22.95 16.74 25.82 24.39 13.15 31.38 Eu/Eu* 19.08 0.46 0.91 5.97 0.45 24.17 23.04 Ce/Ce* 0.47 0.12 0.08 0.08 0.12 0.09 0.24 Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 247 and Petroleum Engineering at the University of Zagreb. Car- bon, sulphur and oxygen isotopes were determined at the Stable Isotope Laboratory of the University of Lausanne us- ing the Finnigan Mat facility. Strontium isotopic ratios were determined by thermal ionisation mass spectrometry (TIMS) in the Activation Laboratory Ltd in Anchaster (Ontario). 4. RESULTS 4.1. Trace element composition of barite samples Trace elements were analysed in six samples of pure barite from the Prača-Foča area in SEB and in one sample of pure barite from the Glumac deposit in the Kreševo area (K) in MBSM. Barite samples in SEB were collected in the Šarulje (Š), Jabukovik (J), Pale (P), Datelji (D), Dragosin Potok (DP) and Fočanska Jabuka (FJ) barite deposits. The trace element contents of the analysed barites are listed in Table 1. They are generally present in very low con- centrations. The values of 15 trace elements (Be, Ga, Nb, Sn, Th, U, W, Ho, Lu, Ag, As, Cd, Bi, Ti, Se) are below the de- tection limits of the analytical method in both areas. Five trace elements (Cs, Co, Nd, Mo, Er) only occur in the Glu- mac deposit (MBSM), whereas Au (1.2 ppm) is only detected in the Šarulje deposit (SEB). Of the 24 trace elements de- tected in the barites of both areas, 16 show similar values in both SEB and MBSM, 6 are slightly higher in MBSM and 2 trace elements (Zn and Ni) are signifi cantly higher in MBSM (Table 1). REEs are present in very low concentra- tions. Maximum total REE contents range from 5.25 to 12.17 ppm. (Table 1). The chondrite normalized (SUN & MC- DONOUGH, 1989) REE patterns of all analysed barites are shown in Fig. 5. The REE patterns are characterized by an enrichment of the LREE against the HREE such as Ho, Er, Tm, Yb and Lu (minimal LaN/YbN = 13.15 to 31.38). The Tm values in all barite deposits excluding Jabukovik and Dra- gosin Potok deposits are an exception to this statement. The REE patterns of all barite samples display a negative Ce anomaly (Ce/Ce* = 0.08 to 0.47). Signifi cant difference in the REE patterns of studied barites is visible only in Eu anomaly. Barites of the Jabukovik, Datelji and Šarulje de- posits are characterised by a negative Eu anomaly (Eu/Eu* = 0.45; 0.46 and 0.91 respectively), whereas those of the Dragosin Potok, Pale, Fočanska Jabuka and Kreševo depos- its show positive anomaly (Eu/Eu* = 5.97; 24.17; 23.04; 19.08 respectively). 4.2. Ca content in barites Minor substitution of Ca for Ba in the crystal lattice of bar- ite is often observed. In the studied barites, the highest Ca content is found in the barite from the Šarulje deposit (1.31 %). The barite from the Datelji deposit contains 0.05 % Ca, in Kreševo area 0.03 % Ca and the barite from Dragosin Po- tok only 0.01 % Ca. Other studied barites are characterized by a Ca content which is below the detection limits of 0.01 % (Table 1). The X-ray analyses of the barites from Šarulje, Datelji and the Kreševo area reveal the presence of calcite as individual phase only in the barite from the Šarulje de- posit (3.24 % CaCO3). The Ca content in other Ca bearing barites is most probably substituted for Ba in the crystal lat- tice. Consequently, the barite from the Datelji deposit con- tains 0.17 % CaSO4, 0.10% in the Kreševo area and the bar- ite from Dragosin Potok has 0.03 % CaSO4 component. 4.3. Sr content in barites In comparison to other foreign elements in the crystal lattice of barite, Sr is evidently enriched in all the studied barite. Its content varies from 0.48 to 2.83 % in the barites of SEB and in the barite from MBSM it is 1.44 % (Table 2). The Sr con- tent of barites in Table 2 is additionally expressed as a SrSO4 component. The obtained Sr value for barite of MBSM is in agreement with Sr values for 22 barite samples already pub- lished by Jurković et al. (1997), which range from 0.48 to 3.15% Sr (average 2.0%). The X-ray analyses of the barites revealed that their Sr content is the lowest in Šarulje deposit, the middle in Kreševo area and the highest in Fočanska Jabuka deposit, and demonstrated that strontianite (SrCO3) as an individual phase does not exist in the barites. Accord- ingly, the presence of Sr in the barites could be explained by its substitution for Ba in the crystal lattice, and expressed as a SrSO4 component. Such a relatively high Sr content is typical for an ascend- ing hydrothermal type of mineralization, whereas a low Sr content characterizes the volcano-sedimentary type of barite deposits. Fi gu re 5: Plot of rare-earth elements normalized to C1 chondrites (SUN & MCDONOUGH, 1989). Legend: Šarulje (S), Jabukovik (J), Pale (P), Datelji (D), Dragosin Potok (DP), Fočanska Jabuka (FJ) and Kreševo (K). Table 2: Content of Sr and SrSO4 in barite. Sample Sr (%) SrSO4 (%) K 1.44 3.03 D 1.22 2.56 S 0.48 1.03 DP 0.62 1.30 J 1.89 3.96 P 0.77 1.60 FC 2.83 5.93 Geologia Croatica 63/2Geologia Croatica 248 4.4. Isotopic composition of sulphur (as sulphate) and oxygen in barites The isotopes are analysed not only in the barites of previ- ously mentioned localities in SEB and Kreševo area, but also in some other barite deposits in MBSM (Table 3). Sulphur isotope data in Table 3 are expressed relative to Canon Diablo troilite and oxygen isotope data relative to Vi- enna Standard Mean Ocean Water. The sulphur isotopes (δ34S) in the barites from SEB span a narrow range, from +11.6‰ to +17.7‰ (mean +14.4‰). The only available δ34S analysis of the barite from the Šarulje deposit (PEZDIČ et al., 1977/1979; KUBAT et al., 1979, 1980) has a value of 12.4‰ and fi ts very well into the range determined here. Barites from MBSM also display a narrow range of δ34S values, varying between +10.1‰ and +16.8‰ (mean value = +11.8‰). This data is in accordance with the earlier published δ34S values from 22 barite samples from MBSM (JURKOVIĆ et al., 1997), which vary from +8.05‰ to +18.48‰ (mean value = +11.5‰). Regarding only the mean values, the barites from MBSM are characterized by a slight enrichment of the light sulphur isotope compared to the barites from SEB. The oxygen isotope values (δ18O) shown in Table 3 rep- resent the fi rst δ18O data for selected barites in the Dinarides. The barites from SEB have δ18O values within a narrow range, from +14.2‰ to +15.6‰ (mean +14.7‰). The barite samples from MBSM reveal remarkably higher δ18O values ranging from +15.8‰ to +22.4‰ (mean +18.47‰). The sul- phur and the oxygen isotope data of the barites investigated in this study are summarized in Fig. 6. 4.5. Isotopic composition of carbon and oxygen in neominerals from SEB The carbon (δ13C) and oxygen (δ18O) isotope ratios in the neominerals of the barite deposits from SEB are represented in Table 4. The δ13C values are expressed relative to the Vienna Peedee Belemnite Standard (VPDB) and the δ18O values rel- ative to both the Vienna Peedee Belemnite Standard (VPDB) and the Vienna Standard Mean Ocean Water (SMOW). The values of δ13C measured in the microcrystalline siderite from Šarulje deposit and in the "red spar" siderite from Ljaljice (Fočanska Jabuka) deposit are –7.60‰ and –3.22‰ respectively. The coarse crystallised calcite from the Dragosin potok deposit has a positive δ13C value (+0.19‰). The δ18OVPDB values are negative for all examined minerals and range from –6.5‰ to –9.90‰ (Table 4). The data are in agreement with previously published δ13C and δ18O values for neominerals occurring in the Devo- nian host rock of other deposits in Bosnia. For the purpose of comparison, data published by JANJIĆ & ĐORĐEVIĆ (1985) and JURKOVIĆ et al. (1997) are listed in Table 4. 4.6. Strontium isotope ratios in the barites and the metarhyolite The strontium isotope ratios (87Sr/86Sr) in the barites are listed in Table 5. The 87Sr/86Sr values in the barites of SEB are 0.710972 and 0.714170 and are very similar to those in the barites from MBSM (0.711764 and 0.712548). Such Sr ratios in the barites from both areas are more radiogenic, when compared to the values between 0.70680 and 0.70925, which characterize coeval seawater, rocks and fossils from Lower Cambrian to Upper Permian (GRADSTEIN et al., 2006). The 87Sr/86Sr value of the metarhyolite from the Vranica Mountain in MBSM is extremely high (0.776995). Table 3: Sulphur and oxygen isotope data in the barites from SEB and MBSM. Sample δ34SCDT δ34Sstd δ18OVSMOW δ18Ostd Locality Sign SEB Datelji D 13.1 0.0 14.8 0.1 Ljaljice Lj-1 17.6 0.2 15.6 <0.5 Jabukovik J 16.7 0.2 15.3 0.3 Fočanska J. FC 17.7 0.2 15.1 0.1 Šarulje S 14.4 0.5 14.4 0.2 Dragosin P. DP 11.6 0.0 15.3 0.2 Pale P 12.2 0.3 14.2 0.0 Šarulje, Glav.* 12.4 MBSM Mačkara 1 MC-1 11.6 <0.3 17.6 <0.5 Kreševo K 10.8 0.2 19.7 0.2 Rijetka Kosa RIK 11.4 <0.3 21.7 <0.5 Otunjski Vis OTV 10.1 <0.3 16.3 <0.5 Sabiljine P. SBP 11.2 0.15 15.8 <0.5 Vrelo-1 VRL-1 11.7 <0.3 18.0 <0.5 Selakova K. SEK 16.8 0.18 16.1 <0.5 Medenik-1 MED-1 10.8 <0.3 22.4 <0.5 Medenik 2 MED-2 12.1 <0.3 21.2 <0.5 Mačkara-2 MAC 11.7 <0.3 16.1 <0.5 Šarulje, Glav.*= δ34S analyse made by PEZDIČ et al. (1977/1979) Fi gu re 6: Comparison of sulphur and oxygen isotope data in the barites from SEB and MBSM. Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 249 5. DISCUSSION The discussion is focused on conclusions of the newly ob- tained geochemical data on barite and those previously pub- lished by numerous authors (PALINKAŠ & JURKOVIĆ, 1994; JUR KOVIĆ et al., 1997; STRMIĆ et al., 2000; PA- LIN KAŠ et al., 2001; JURKOVIĆ & PALINKAŠ, 2002; PA LINKAŠ et al., 2008). Typical Devonian barite deposits with Pb, Zn, and Fe sul- phides in the Palaeozoic area of Graz (Austria) belong to the synsedimentary volcanogenic type of barite deposit and were used here as geochemical parameter to distinguish syngenetic from hydrothermal-epigenetic type of barite deposits. Additionally, the comparison is related to the geochem- ical investigations of the Brixlegg ore deposit, Tyrol, Austria (SCHULZ, 1972; GSTREIN, 1979; SCHROLL & PAK, 1980; FRIMMEL & PAPESCH, 1990; EBNER et al., 1999), and the Rudnany ore deposit, Gemericum unit, Slovakia (CAMBELL et al., 1985; ŽAK et al., 1991; RADVANEC et. al., 2004). Besides the Bosnian tetrahedrite occurrences, these represent the most important European Hg-Ag-Sb tet- rahedrite ore deposits, and are included into the discussion. 5.1. REE The low total REE concentrations, light REE enriched chon- drite normalized REE patterns and negative Ce anomaly de- termined in the barites are usually interpreted as an indica- tion of a hydrothermally infl uenced seawater fl uid component in the barite origin (GUICHARD et al., 1979; MURRAY et al., 1990). The most signifi cant difference in the shape of REE pat- terns is expressed in the Eu-anomaly that is positive for bar- ites from Dragosin Potok, Pale, Fočanska Jabuka and Kreševo area, and negative for the barites from the Šarulje, Datelji and Jabukovik deposits. This indicates the presence of two different sources of hydrothermal fl uids. Spatially large (up to 1 km long) but poor barite ore de- posits associated with siderite and Fe-, Cu-, Pb-, Zn- and Sb- sulphides in the area of Šarulje, Mastilove Stijene, Kamenička River and Milotina, are especially interesting from the ge- netic point of view. According to KULENOVIĆ (1987), these are stratabound types of deposits. The 87Sr/86Sr ratio of barite from Šarulje (Table 5) indicates an epigenetic type of formation. The investigation will try to resolve the ambigu- ity based on more precious REE analyses and 87Sr/86Sr ratios in barite and host rock (Devonian dolomite). 5.2. 87Sr/86Sr ratio The Rb/Sr ratios in the investigated barites from both the, SEB and MBSM, are very low (Table 1). Accordingly, the initial 87Sr/86Sr ratios of the barites have not signifi cantly in- creased since the time of crystallization and refl ect the com- position of the host fl uids. The signifi cantly higher 87Sr/86Sr ratios of the barites from SEB and MBSM (0.710972 to 0.714170) relative to those of contemporaneous seawater, rocks and fossils from Lower Cambrian to Upper Permian (0.70680 and 0.70925, after GRADSTEIN et al., 2006), suggest hydrothermal fl u- ids and an epigenetic origin of Bosnian barites. The higher recorded 87Sr/86Sr ratios of the rocks through which hydro- thermal fl uids have circulated suggest an evolved crustal source for Ba, Sr and Rb. An extremly high 87Sr/86Sr ratio of metarhyolite (0.776995) indicates a crustal source for the rhyolite magma (S-type of granitoid magma). Table 4: Isotopic composition of carbon and oxygen in the neominerals from SEB and their comparation with already published analyses of the same type in SEB and MBSM. Sample Type of Mineral/ δ13CVPDB δ13Cstd δ18OVPDB δ18OVSMOW δ18Ostd Locality Sign deposit rock ‰ ‰ ‰ SEB Dragosin P. DP barite calcite +0.19 0.06 –6.50 +24.2 0.12 Šarulje S barite siderite –7.60 0.04 –6.83 +23.9 0.05 Ljajice LJ barite siderite –3.22 0.10 –9.90 +20.7 0.12 SEB* Kratina stibnite dolosparite –1.10 to –2.02 Kordići microsparite –0.66 to –1.53 –11.60 to –12.73 MBSM** Gornji V. Zec Mountain barite/ tetrahedrite calcite –2.62 to +1.20 –8.32 to –6.66 Deževica Kreševo siderite –5.55 to +1.01 –8.82 to –10.33 * analyses published by JANJIĆ & ĐORĐEVIĆ, 1985. **analyses published by JURKOVIĆ et al., 1997. Table 5: Strontium isotope analyses in the barites from SEB and MBSM and metarhyolite. Sample Mineral/rock 87Sr/86Sr Locality Sign Value +/– 2s SEB Šarulje Š barite 0.710972 6 Ljajice LJ-1 barite 0.714170 5 MBSM Kreševo K barite 0.712548 8 Mačkara MAC barite 0.711764 4 Vranica D1 metarhyolite 0.776995 5 Geologia Croatica 63/2Geologia Croatica 250 The comparison of 87Sr/86Sr ratio in barites from SEB and MBSM and those from the Brixlegg, Graz and Rudnany deposits are shown in Fig. 7a. 5.3. SrSO4 content in barite The relationhips between the SrSO4 content in barites of Bosnia and some other worldwide known barite deposits are shown in Fig. 7b. The SrSO4 content in barites depends sig- nifi cantly on the genetic type of barite deposit. For instance, the Palaeozoic barites from Graz (Austria) belong to the synsedimentary volcanogenic type of barite deposit and have low SrSO4 contents (0.6 to 1.6 wt%). Devonian barites of the same genetic type in Meggen and Rammelsberg depos- its, also have low SrSO4 contents (0.23–0.59 wt%). In con- trast, barites of Bosnia and also those of the Brixlegg (BX) deposit in Austria and the Rudnany (RD) deposit in Slovakia are characterized by considerably higher SrSO4 contents (0.9 to 5.01 wt% and 0.8 to 3.2 wt%, respectively), which are typical for hydrothermal epigenetic deposits. Extended rang es of SrSO4 contents could be the result of partial remobiliza- tion processes during the Hercynian and Alpine orogeny. 5.4. δ13C and δ18OVPDB of the main host-rock and neominerals The δ13C and δ18OVPDB values determined in neominerals of Devonian rocks hosting different barite deposits in Bosnia, have been compared with those being typical for primary Devonian dolomite, and are shown in Figs. 8a and 8b. In pri- mary Devonian dolomite the typical δ13C values range from +0.5‰ to +3‰ and the δ18OVPDB values between –3.5‰ and –7.0‰ (GRADSTEIN et al., 2006). Carbon and oxygen iso- tope values of all neominerals in the Devonian dolomites are shifted relative to these typical values toward lower values as clearly demonstrated in Fig. 8. This indicates a change in the isotopic characteristics of Devonian host rocks during mineralization and points to the epigenetic origin of barite deposits. The isotopic data of carbon and oxygen of previ- ous investigators, (presented in Table 4), also suggests the same conclusion. The comparison of δ13C and δ18OSMOW ratio in siderites from SEB and MBSM and those from the Brix- legg, Graz and Rudnany deposits are shown in Figs. 9a and 9b. Fi gu re 7: Comparison of 87Sr/86Sr ratio, SrSO4 %, δ34S and δ18O values in bar- ites from SEB and MBSM and those from Brixlegg (BX), Graz (GZ) and Rud- nany deposits (RD): a) besides 87Sr/86Sr ratio in barites, typical values of 87Sr/86Sr ratio in Devonian dolomite (D) and in strontianite (SrCO3) and in celestine (SrSO4) of Rudnany deposit are shown too; b) the SrSO4 content in barites; c) measured δ34S values in barites where HT = hydrothermal bar- ite; S = sedimentary barite, VS = volcanogenic-sedimentary barite; d) meas- ured δ18O values in barite. Fi gu re 8: Comparison of δ13C (a) and δ18OVPDB (b) values of neominerals in Devonian rocks hosting diff erent barite deposits in Bosnia and those being typical for primary Devonian dolomite. a) b) c) d) a) b) Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 251 5.5. δ34S in barites and sulphides Most barite deposits in MBSM contain tetrahedrite as the sole ore mineral. Measured δ34S values in 18 samples of Hg tetra- hedrite in MBSM range from –5.50‰ to –15.40‰ (mean val- ues −10.49‰). The δ34S values in 3 pyrite samples from the same deposits are –0.7‰, –4.6‰ and –9.86‰ (ŠIFTAR, 1988, 1990). Distinctively, the tetrahedrite from the Trošnik (Foj nica) deposit, which has a minimal content of Hg, gave positive δ34S values (+3.28‰ and +3.73‰), as did another sulphide mineral in this deposit (KUBAT et al., 1979/1980). The measurements of δ34S values in antimonite in the Čemer- nica deposit gave +3.48‰, +2.12‰ and +2.21‰ and in sphalerite +3.71‰ (KUBAT et al., 1979/1980). Obviously, two different sulphur sources were included in the genesis of sulphide minerals in MBSM. The δ34S values in barites are characterized relative to these sulphides by a signifi cant en- richment of the heavy sulphur isotope (+10.1‰ to +16.8‰). Hg-tetrahedrite also occurs in the barite deposits in SEB, but as a minor component. Its δ34S values are also negative (–4.95%, Fočanska Jabuka). The main ore minerals are ga- lena, sphalerite and pyrite, and chalcopyrite is subordinate. According to KUBAT et al. (1979/1980) the δ34S values of these sulphides range from –0.5 to +4.5‰ (Table 6). Com- pared to these data, the δ34S values in barites are enriched by heavy sulphur isotope (as in the barite deposits in MBSM). Two isotopically different types of sulphide also occur in the Rudnany deposit. The main ore minerals are Hg-tet- rahedrite and chalcopyrite, which have markedly negative δ34S values (Fig. 10). In contrast, pyrite and cinnabar have positive δ34S values (CAMBELL et al., 1985). According to ŽAK et al. (1991) and GRECULA et al. (1991) negative δ34S values in tetrahedrite and chalcopyrite are consequences of isotope fractionation between H2S, (derived from deep- seated fl uids) and SO4 2–, (derived from the Permian sea wa- ter). In Palaeozoic strata of Graz, galena, sphalerite and py- rite occur, and they exhibit relatively high positive δ34S val- ues ranging from +2.5‰ to +13.2‰ (PAK et al., 1980). Data are not available for the Brixlegg deposit where Hg-tetrahe- drite is the sole ore mineral and other sulphides only occur as accessory minerals δ34S. Analysis of tetrahedrite from Schwaz, Tyrol (obtained from Professor PROHASKA (Leo- ben) revealed a negative δ34S value (–1.60‰). Comparison of the sulphur isotopic composition in sul- phide minerals from different barite deposits in SEB, MBSM, Graz and Rudnany is shown in Figs. 10a and 10b. Positive δ34S values in sulphides of both barite deposits from SEB (Table 6) and polymetallic sulphide deposits from MBSM (KUBAT et al., 1979/1980), and also positive δ34S values in barites from barite deposits in SEB and MBSM indicate that one of the sources of the sulphur in these deposits could be older Lower Palaeozoic stratiform volcano-sedimentary sul- phide deposits. Studies of such a type of sulphide deposit were undertaken on the Lower Palaeozoic series of Gemeri- cum in Slovakia. They revealed δ34S values ranging between +2‰ to +15‰ (KANTOR & RYBAY, 1970; RADVANEC et al., 1992). There are still no measurements of δ34S values in Lower Palaeozoic stratiform volcano-sedimentary sul- phide deposits in the Dinarides. Variscan metamorphism caused the circulation of hy- drothermal fl uids that remobilized sulphur from the Lower Palaeozoic and older stratiform volcano-sedimentary sul- phide deposits and led to the formation of the younger sul- phide deposits. The obvious enrichment of heavy sulphur isotopes in barites compared with those in sulphides in the barite deposits of both, SEB and MBSM, indicates retrograde Variscan metamorphism and infl uence of the sulphate de- rived sulphur from the Permian sea. 5.6. δ18OVPDB, SMOW in barites and fl uid inclusions The δ18O values in barites in SEB (+14.2‰ to +15.6‰) are very similar to those in the Brixlegg and Rudnany barite de- Fi gu re 9: Comparison of δ13C (a) and δ18OSMOW (b) values in siderites from SEB and MBSM and those from the Brixlegg, Graz and Rudnany deposits where CP = Typical Carboniferous-Permian values. Table 6: Sulphur isotope data for sulphides in barite deposits of SEB (KU- BAT et al.,1979/80) Locality Mineral δ34S (‰) Ranoprge galena +3.04 chalcopyrite +2.49 pyrite +2.80 Kurjača galena +0.34 Šarulje galena +0.53 Kopilovo galena –0.41 pyrite +1.44 Goražde stibnite +1.21 stibnite +2.29 stibnite +4.26 a) b) Geologia Croatica 63/2Geologia Croatica 252 posits (Fig. 7). Remarkably higher δ18O values occur in bar- ite samples from MBSM (+15.8‰ to +22.4‰ ). According to RAMOVIĆ E. (1991) the only fl uid inclusion study in barite deposits in SEB was that of BLEČIĆ (1983), who dis- covered primary fl uid inclusions in the barite in the Pb-Zn deposit in Ranoprge (Fočanska Jabuka) and determined Th between +110ºC and +140ºC and a salinity of 10 wt% NaCl equ. In the last 15 years, numerous fl uid inclusion studies were carried out in ore deposits (mostly barite deposits) of Palaeo- zoic complexes in MBSM (PALINKAŠ & JURKOVIĆ, 1994; JURKOVIĆ & PALINKAŠ, 1999; STRMIĆ et al., 2000; PALINKAŠ et al., 2001; JURKOVIĆ & PALINKAŠ, 2002; PALINKAŠ et al., 2008). The results of all these studies dem- onstrated higher salinity 24.2 do 26.3 wt% NaCl equ. in Kreševo and 32.6 to 32.9 wt% NaCl equ. in Raštelica. Analy- ses of fl uid inclusions of these authors in barites of barite de- posits in MBSM revealed higher homogenisation temperatures (+210ºC to +310ºC in Kreševo area, +230ºC to 270ºC and 320º to +350ºC in the Raštelica deposit. There is a clear cor- relation between lower δ18O values and lower Th of fl uid in- clusions in barite deposits from SEB relative to higher δ18O values and higher Th of fl uid inclusions in barite deposits from the MBSM. This is in agreement with the statement of HOEFS (1997) who stated that mineralisation fl uids of higher temper- ature are characterized by higher salinity and higher δ18O val- ues. The process of barite mineralisation in the Brixlegg de- posit took place at temperatures ranging from +70ºC to 130ºC (FRIMMEL, 1991). In Rudnany, (a vein ore deposit consist- ing of siderite, barite, tetrahedrite and chalcopyrite), the study of fl uid inclusions determined Th varying between +150ºC and +300ºC (RADVANEC et al., 2004). 5.7. Origin of the barium-strontium bearing hydrothermal fl uids The 87Sr/86Sr ratios determined in the barites (0.710972 to 0.714170) from both SEB and MBSM are high. The high Ba content and high 87Sr/86Sr ratio in the mineralisation fl uid could be achieved by hydrothermal leaching of Rb-rich al- tered felsic rock. According to FRIMMEL & PAPESCH (1990) the high 87Sr/86Sr ratios are typical for fl uids being connected to S-type magmatism and/or being crustal contaminated by circulation through Rb-rich clastites and extrusive magmatic rocks. Until 1969 or 1972 respectively it was believed that the carbonate sequences of Jezero (Jajce) and Vranica Mountain were of Upper Carboniferous to Lower Permian age (KATZ ER, 1926). Rhyolitic magmatism occurred in the Middle and Up- per Permian and partly in the Triassic (KATZER, 1926). JURKOVIĆ & MAJER (1954) found signs of contact meta- morphism at the contact between the rhyolite and these car- bonate rocks on the Vranica Mountain and Sinjakovo, con- cluding that the rhyolite is of Upper Carboniferous to Middle Permian age. MUDRENOVIĆ et al. (1969) however, found Silurian-Devonian conodonts in limestones in the Jezero area (Jajce). Based on Devonian fossils on the Vranica Mountain, however, the age boundary of rhyolite to Middle-Upper Car- boniferous-Lower Permian has been revised (ŽIVANOVIĆ, 1972). According to HRVA TOVIĆ (1996, 2006) rhyolites are the product of two stage volcanic activity. Most of them are synsedimentary with metasediments of presumed Silu- rian age. Some hypabyssal rhyolites intruded into Late Silu- rian and Early Devonian limestones, which also occur as xenoliths within the volcanic bodies. HRVATOVIĆ marked the Upper Permian as the upper boundary of rhyolite age, while he observed a large quantity of quartz-porphyry peb- bles in basal breccias and conglomerates of discordant Up- per Permian Formation of Kruščica Mt. The basal discordant breccias, with quartz-porphyry fragments, were previously observed by JEREMIĆ (1963). Petrological studies of the rhyolites of Sinjakovo and Vranica Mt. were undertaken by JURKOVIĆ & MAJER (1954) and MAJER & GARAŠIĆ (2001). JURKOVIĆ & MAJER (1954) determined the leu- cogranite or albite granitic character of the rhyolite magma. MAJER & GARAŠIĆ (2001) identifi ed the peraluminous character of the rhyolite of Vranica Mountain (PI = 1.9–4.1). The low content of compatible trace elements and high con- tents of incompatible trace elements indicate a crustal mag- matic origin. Additionally, the authors concluded that rela- tionships between Rb, Y and Nb suggest a syncollisional origin of the rhyolite magma. In the same sample of metarhyolite being studied by MAJER & GARAŠIĆ (2001) we determined an extremely high 87Sr/86Sr ratio (0.776995 ±2s), confi rming the hypoth- esis of a crustal origin of the rhyolite magma. In Slavonian S-granites (Psunj, Papuk and Krndija Mountain), LAN- PHERE & PAMIĆ (1992) discovered that the 87Sr/86Sr ratio corresponds to a value of 0.72539±17, while in the Mosla- vačka Mountain it is 0.74302±5. An unusual spectrum of paragenetic types of ore deposits (JURKOVIĆ, 1956) sup- Fi gu re 10: Comparison of δ34S values in tetrahedrites and other sulphides from SEB, MBSM and those from the Brixlegg, Graz and Rudnany deposits where T = tetrahedrite, Ch = chalcopyrite, Py = pyrite, SS = sedimentary sulphides, HS = hydrothermal sulphides, VSS = volcanogenic-sedimentary sulphides. a) b) Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 253 ports the presence of an S-type granite in MBSM. Ore de- posits of Ba and subordinately of Fe (barite, siderite, anker- ite, pyrite and stibnite) dominate. All other ore deposits of Cu, Pb, Zn and As are very small and their minerals are sub- ordinate to barite and siderite ore deposits. Metals, typical for I-type magma (Sn, W, Mo, F, B, Li) occur very rarely, only as occurrences of mineralogical importance. 5.8. Genetic model for the formation of the barite- sulphide deposits in the Palaeozoic complexes of MBSM and SEB On the basis of geological and geochemical data comprising former investigations and data determined in this study, it can be concluded that barite ore deposits in SEB and MBSM had been formed by hydrothermal fl uids,linked to magmatic and metamorphic processes and infl uenced by Permian sea- water. The following phases of hydrothermal mineralisation have been recognized in the SEB and MBSM area: a) Early Variscan phase which is not the subject of this study; b) Late Variscan phase which is responsible for the origin of barite ore deposits containing Fe-, Cu-, Zn-, Pb- and Sb- (As) sul- phides with positive δ34SCDT values; c) Post-Variscan (Early Eoalpine) phase which affected the existing Late Variscan barite ± siderite ore deposits with mercury-bearing fl uids as- sociated with the processes of degassing of the Upper man- tle, and leading to formation of Hg-, Ag- and Au-rich tetra- hedrites showing negative δ34SCDT values. Degassing pro cesses were linked to the early phase of the Permo-Triassic inter- continental rifting. Late Variscan phase. In the whole of the Dinarides, barite ore deposits were formed in the late stage of the Var- iscan cycle and are located in the Upper Silurian, Devonian, Carboniferous and Permian rocks. Ore mineralisation in the clastites is usually present in the form of veins or impregna- tions, whereas in carbonate rocks it occurs as irregular bod- ies or replacement nests. Barite is the dominant mineral, quartz is subordinate and siderite and calcite occur only lo- cally. Sulphides of Fe, Cu, Zn, Pb, Sb and As occur in very variable mutual relationships, ranging from trace amounts up to 10 %, but all have positive δ34S values. The form of occurrence and geochemical data of the studied barite ore deposits indicate their epigenetic nature and origin, caused by circulation of hydrothermal fl uids which were related to late stage Variscan metamorphism and magmatism and in- fl uenced by Permian seawater. The bulk of the Late Variscan barite ore deposits were formed most likely in Lower Per- mian time. Most of the barite ore deposits in MBSM experienced processes of regeneration and remobilisation in the Post- Variscan stage. Only rare barite deposits have been partly or completely preserved. The Trošnik deposit is a very good example of a preserved type of barite ore deposit, located near Fojnica in the NE part of MBSM. It occurs in a pre- Devonian complex of rocks. The paragenesis of the deposits contain pyrite and chalcopyrite as the main minerals, whereas siderite and quartz occur as gangue minerals. Sb- and Fe-rich tetrahedrite occurs too, but contains only traces of Hg and has positive δ34S values (+3.23‰ to +3.73‰, KUBAT et al., 1979/1980). A very similar result (+4.0‰) was produced in the current analysis of this tetrahedrite. Barite ore deposits in SEB, however, have been almost completely preserved in their primary state. They are small but numerous, characterized by Fe-, Cu-, Zn-, Pb- and Sb- sulphides, but do not contain Au, only small amounts of Ag. A post-Variscan overprint characterized by the formation of Au-, Hg-tetrahedrite having negative δ34S values (–4.95‰) is only locally present (Fočanska Jabuka, Šarulje). Geochemical differences between barite ore deposits in MBSM and SEB are summarized in Table 7. Monosulphide Hg-tetrahedrite barite ore deposits in MBSM differ from polysulphide barite ore deposits in SEB in having: a) more positive δ18O values in barites, b) lower δ34S values in bar- ites, c) pronouncedly negative δ34S values in Hg-tetrahedrite, d) signifi cantly higher homogenisation temperature and higher salinity in fl uid inclusions of barites, quartzes and fl uorites. Regarding the connection of other ore deposits in Dinar- ides with the Late Variscan phase, it should be emphasized that at the end of the Lower Permian, continental or shallow marine clastic sediments of the Grödener Formation were formed under a warm arid climate. These sediments are widespread in the Dinarides and are according to JURKOVIĆ & PALINKAŠ (1996) bearers of uranium (Žirovski Vrh, Slovenia), copper (Cerkno-Sava Fold, Slovenia; Vitez- Ustiprača, Monte Negro) and low manganese haematite ore deposits (Mokronog-Hrastno, Slovenia; Rude, Croatia; Bu- kovica, Croatia). These deposits are described by DROV- ENIK et al. (1980), ŠINKOVEC (1971), ČOP et al. (1998), and KULENOVIĆ (1987). The Middle Permian sediments grade upwards into the Upper Permian shallow marine evap- orite and carbonate sediments, (the Bellerophon Formation), or locally into the Sabkha transition zone or continental red beds. An early diagenetic Sabkha type deposit is described by PALINKAŠ et al. (1993). Most of the Upper Permian evaporites occur on tectonic lines along the Una, Sana, Vr- bas and Bosna rivers, and in the Mostar, Sinj, Knin and Drniš areas. Upper Permian evaporites are characterized by a mean δ34S value of + 11‰ (JURKOVIĆ & ŠIFTAR, 1995). The post-Variscan/ Eoalpine phase. Strong magmatic activity (rhyolites, keratophyres, diabases) took place during the Permian period, especially in the Asslian-Sakmarian stages. PAMIĆ et al. (2004) using K-Ar method determined the age of metadiabase (287.8 ± 11.1 Ma) and ortho-green- schist (268.7 ± 10.2 Ma) at Bradine (Ivan Mt., MBSM) and connected their results to post-Variscan magmatism. Using the same method on the same rock types, the authors deter- mined a cooling phase which lasted until the Triassic (247.0 ± 9.5 Ma; 238.4 ± 9.2 Ma). The results support the heating event during Upper Permian time in the MBSM. Heating of some parts of the crust in the Dinarides dur- ing the Middle/Upper Permian enabled lateral (extensional) movements of the continental crust and the rise of upper mantle fl uids. The optimum geotectonic environments in the Geologia Croatica 63/2Geologia Croatica 254 Dinarides developed along a Permo-Triassic intracontinental rift. Contemporaneously, former Late Palaeozoic faults, the western Voljevac fault and eastern Busovača fault, as well as a dense framework of faults of lower order between them, had been reactivated. The geotectonic conditions facilitated penetration of mercury (± fl uorine)-bearing fl uids from deep levels of the Upper mantle to higher levels of the crust. KA- RAMATA et al. (1995) emphasized that the highest concen- tration of mercury in former Yugoslavia occurred in the Tri- assic mineralization of the Dinarides (mercury deposits Idrija, Tršće, Spič, Draževići, Kovač Mt). Independently of this statement, JURKOVIĆ & PALINKAŠ (1996) wrote ”Fluorine and mercury bounded to the Hg-tetrahedrite in the MBSM were probably derived at least partially from the up- permost zone of the mantle”. On their way to upper levels fl uids passed through Upper Proterozoic and Caledonian Au- and Ag- bearing ore deposits, and Hg being present in fl uids amalgamated with the Au and Ag. At still higher levels, these fl uids reached barite ore deposits being formed in the Late Variscan phase. There, most of the primary sulphides have been fl uidized, and a new mineral, Hg- tetrahedrite, rich in Au (10–50 g/t) and Ag (1000 do 3000g/t) was formed. Results of 183 mercury-bearing minerals analysed from the ore deposits of the Dinarides suggested the conclusion that isomorphic substitution of mercury into the host miner- als decreased in the following order: sphalerite → tetrahe- drite → gold/silver → pyrite → galena → realgar → anti- monite (KARAMATA et al., 1995). This is in agreement with the situation in the MBSM. Strongly negative δ34S values of Hg-tetrahedrite in MBSM ore deposits were explained by remobilization of isotopically light sulphur of biogenic origin from the Mid- dle/Upper Permian stratiform U-Cu (±Fe) ore deposits in the Dinarides and/or from older similar genetic types of ore de- posits. The role of isotope fractionation between ascending deep-seated H2S and descending SO4 2– from Permian sea- water is not excluded. The early phase of intracontinental rifting: Contro- versial opinions exist concerning the beginning of the Alpine cycle. CASSINIS et al. (1975) and WOPFNER (1984) con- sidered that the hiatus between the Lower and Middle Per- mian sedimentary cycles separates the Variscan cycle from the overlying Alpine cycle. KRAINER (1993) considers the rifting processes during the Middle Triassic as indicating the beginning of the Alpine cycle. The contemporaneous nature of the early phase of the intracontinental rifting and the beginning of the Alpine cycle in the Dinarides is emphasised here, because the Permian/ Triassic boundary (251 Ma) has a well documented suite of Table 7: Summarized geochemical data from barite ore deposits in SEB and MBSM. Geochemical data Ore area n Late Variscan n Post Variscan/Eoalpine Authors Th (homogenisation temperature) SEB +110ºC to +140ºC BLEČIĆ (1983) MBSM +190ºC to +140ºC (Kreševo) +210ºC to +250ºC ; +320ºC to +350ºC (Raštelica) PALINKAŠ & JURKOVIĆ (1994) STRMIĆ et al. (2000) salinity wt% NaCl equ. SEB ~ 10 wt% BLEČIĆ (1983) MBSM 24.2 to 32.9 wt% PALINKAŠ & JURKOVIĆ (1994) STRMIĆ et al. (2000) % SrSO4 in barites SEB 6 1.03 to 5.93 (2.73)% this work MBSM 1 23 3.03 % 1.60 to 6.60 (4.22)% this work JURKOVIĆ et al. (1997) δ34SCDT in barites SEB 7 +11.6 to +17.7 (+14.61) ‰ this work MBSM 10 +10.1 to +16.8 (+11.80) ‰ this work δ18OVSMOW in barites SEB 7 +14.2 to 15.6 (+14.7) ‰ this work MBSM 10 +15.8 to +22.4 (+18.50) ‰ this work δ34SCDT in tetrahedrites SEB 1 –4.95 ‰ KUBAT et al. (1979/80) MBSM 18 –5.5 to –15.4 (–10.49) ‰ JURKOVIĆ et al. (1997) δ34SCDT in Fe-Cu-Zn-Pb-Sb sulphides SEB 10 –0.41 to +4.26 ‰ KUBAT et al. (1979/80) MBSM –4.55 ‰ JURKOVIĆ et al. (1997) δ13CVPDB in neocarbonates SEB 3 –7.60 to +0.19‰ this work MBSM +1.20 to –5.50 (–2.12) ‰ JURKOVIĆ et al. (1997) δ18OSMOW in neocarbonates SEB 3 +20.7 to +24.2 ‰ this work MBSM +23.7 to +29.1 ‰ JURKOVIĆ et al. (1997) 87Sr/86Sr ratio SEB 2 0.710972 and 0.714170 this work MBSM 2 0.711764 and 0.712548 this work Jurković et al.: Geochemical characteristics of barite occurrences in the Paleozoic complex of South-eastern Bosnia... Geologia Croatica 255 chemical evidence supported by global correlation (GRAD- STEIN et al., 2006). The most important are as follows: a) an extraordinarily fast rise in the δ34S of sea water sul- phate, ranging from +8 up to +12‰ to +20 up to +29‰ be- tween the Middle and Upper Lower Triassic (245 Ma) termed the “Roet event” (NIELSEN, 1965; RICK, 1990); b) global cooling and the beginning of mass extinction coin- cide with the remarkable increase in 87Sr/86Sr values from 0.7068 to 0.7080 from the end of the Capitanian (260Ma) to the Upper Permian-Lower Triassic boundary (251 Ma) (MARTIN & MACDOUGALL, 1995). KORTE et al. (2003) consider that this event may be a response to increased continental weather- ing following glacial climates of the early Permian. c) The end-Permian mass extinction coincides with an abrupt negative shift of 4% in values of carbon isotopes in marine and terrestrial settings, probably caused by decreased marine production and an infl ux of light carbon from vol- canic, soil-carbon or a methanogenic source (SEPHTONE et al, 2002). The Triassic period begins just after this carbon minimum (ERWIN, 1995) d) large scale global shifts to higher δ18O values in carbon- ates indicate a general progressive change from the Late Per- mian through the Triassic and are interpreted as the result of cooler sea water or a glacial episode suggesting a total cool- ing of 4°C in tropical seas (WALLMAN, 2001). 6. CONCLUSION Geochemical investigations of barites revealed: (1) Trace element compositions in barites from both area (SEB and MBSM) are very similar indicating a unique ore bearing area with the infl uence of seawater on hydrothermal barite origin. (2) Barites of both areas show elevated Sr content (0.48 to 2.83% in barites from SEB, 1.44% in barite from MBSM), typical for epigenetic hydrothermal barite ore deposits. The Sr substitues for Ba in the crystal lattice. (3) The 87Sr/86Sr isotope ratios in the barites of both areas are similar (0.710972 and 0.714170 in barites from SEB, 0.711764 and 0.712548 in barites from MBSM) and are more radiogenic in comparison with values which character- ize coeval seawater, rocks and fossils from Lower Cambrian to Upper Permian (0.70680 to 0.70925). This also indicates an epigenetic hydrothermal origin of barite ore deposits. (4) Very high 87Sr/86Sr isotope ratio (0.776995) determined in a rhyolite sample from Vranica Mt. (MBSM) confi rms the origin of rhyolite magma by crustal anatexis. (5) The δ13C and δ18O values in calcite, dolomite and sider- ite of barite ore deposits are shifted toward lower values rel- ative to typical values occurring in Devonian host rock, also indicating an epigenetic origin of barite ore deposits. (6) The δ18O values in barites in SEB (+14.2‰ to +15.6‰) are remarkably lower than δ18O values of barite samples from the MBSM (+15.8‰ to +22.4‰). This can be explained by a lower temperature and lower salinity of mineralisation fl u- ids in barite ore deposits of SEB (HOEFS, 1997). (7) The barite ore deposits of SEB are characterized by δ34S values which are positive (+11.6‰ to +17.7‰) and enriched in heavy sulphur isotope in barites in comparison with sulphides (–0.41 to +4.26‰), and negative in tetrahedrite (–4.95‰). This indicates three different sulphur sources for barite ore deposits in SEB. The same is true for δ34S values in barite ore deposits of MBSM (+10.1 to +16.8‰ in barites, –9.86 to –0.71‰ in pyrites, –5.50 to –15.40‰ in tetrahedrites). The source of heavy sulphur isotope in Fe, Cu, Zn, Pb, Sb sul- phides and in barites is deep seated, linked to Caledonian, Neoproterozoic and Early Palaeozoic sulphide deposits. The δ34S values of barites of the Late Variscan deposits have been infl uenced by Permian sea-water sulphate. This infl uence was stronger in the barites of the post-Variscan phase. In contrast the very light sulphur isotope in Hg-tetrahedrites is probably of biogenic origin and/or a consequence of isotope fractiona- tion between H2S derived from deeper seated upper mantle fl uids and SO4 2–, derived from the Permian evaporites. (8) In both ore areas of Bosnia, SEB and MBSM, two par- agenetic types of barite ore deposits were determined. The older type originated in the Late Variscan phase (Lower Per- mian) and the younger one in the Post Variscan/Early Eoalpine phase. The older type of barite ore deposit contains more than 90% barite, small amounts of quartz, locally sider- ite and calcite, and polysulphides (Fe-, Cu-, Pb-, Zn- and Sb(As)–sulphides), the amount of which depends on the host rock (5–10% in clastites, 1–2% in carbonate rocks). This type dominates in SEB, and very rarely shows signs of the Post-Variscan overpint. In the MBSM area, it only occurs in the Trošnik deposit and partly altered in the Jezero area (Jajce). All other barite ore deposits in MBSM (Kreševo, Kiseljak, Zec and Pogorelica Mt., Gornji Vakuf, Medenik) were overprinted during the Post-Variscan phase and have the genetic characteristics of a younger regenerated type of barite ore deposit. The younger type of barite ore deposit is characterized by monosulphide (Au-, Ag- and Hg-rich tetrahe- drite). Other sulphides, mainly Cu-sulphosalts, only occur in trace amo unts. This tetrahedrite has been formed by regenera- tion and fl uidization of sulphides of older types of barite ore deposit with a supply of Hg, Au, Ag and F from the mantle and/ or amalgamation of Au and Ag from Caledonian and older ore deposits. The younger type of barite ore deposit occurs only sporadically in SEB (Fočanska Jabuka) and then as younger barite veins and nests with Hg tetrahedrite having negative δ34S (–4.95‰). ACKNOWLEDGEMENT We would like to thank Ladislav PALINKAŠ and Vladimir BERMANEC who critically reviewed an earlier version of this manuscript. 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