2019 | 72/1 | 5–18 | 5 Figs. | 2 Tabs. | Suppl. Tab. 1 | www.geologia-croatica.hr Journal of the Croatian Geological Survey and the Croatian Geological Society 1. INTRODUCTION The increasing interest in lacustrine sediments since the early 1970s arose from new proof of their scientific and economic im- portance. Lacustrine successions may preserve details of sedimen- tary processes from the earliest stage of lake genesis to its very end (BINFORD & DEEVEY, 1983; ТALBOT & KELTS, 1989; ENGSTROM et al., 2000; COHEN, 2003; OBRADOVIĆ & VA- SIĆ, 2007). Palaeolimnological data such as shoreline features, isotopic composition of authigenic carbonates, groundwater influ- ences and changes in sediment grain size, structure and minera- logy, are useful in the reconstruction of lake-level changes in re- sponse to regional climate change (DIGERFELDT et al., 1993; FRITZ, 1996, 2008; HICKMAN & WHITE, 1989; ALMENDI- GER, 1993). The economic importance of former lakes relies on the significant accumulations of solid and liquid hydrocarbons as well as of other valuable resources, such as diatomite and diato- maceous earth, sedimentary zeolite, clay (particularly bentonite), magnesite, dolomite, borates, including the recently discovered jadarite (STANLEY et al., 2007; WHITFIELD et al., 2007). Serbian lakes formed during the late Oligocene and Miocene in dominantly NNW–SSE trending depressions along the old re- activated faults (OBRADOVIĆ & VASIĆ, 2007). Sedimentation occurred in several tectonic, i.e. lake phases, which were related to different tectonic events, such as contraction, extension etc. (OBRADOVIĆ & VASIĆ, 2007). The majority of Serbian lakes underwent two (e.g. Valjevo- Mionica, Slanci, Jadar, Čačak-Kraljevo, Pranjane, Mlava basin) or three (Niš, Aleksinac, Kremna, etc), but rarely only one sedi- mentation cycle (Kosjerić and Leskovac basins) (OBRADOVIĆ & VASIĆ, 2007; Fig. 1). The alternation of lake sediments with those formed in marsh or alluvial systems, sometimes with coal and/or oil shales resulted in highly diverse facies. The alternation of lake and marine sedimentation has been identified in the Valjevo-Mionica coastal area, at the ancient watering place of Vračević (OBRADOVIĆ & DIMITRIJEVIĆ, 1978; OBRA DO- History of the Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data Dragana Marić*,1, Danica Srećković-Batoćanin2, Nebojša Vasić2, Marija Radisavljević2 and Tatjana Đekić1 1 University of Niš, Faculty of Natural Sciences, Višegradska 33, 18000 Niš, Serbia; (dragana.maric@gmail.com) 2 University of Belgrade, Faculty of Mining and Geology, Đušina 7, 11000 Belgrade, Serbia doi: 10.4154/gc.2019.05 Abstract The petrological and geochemical composition of Neogene lacustrine successions and base- ment rocks of the Belanovica basin in Central Serbia, were investigated in three exploration boreholes, drilled in the central part of the former lake. Two boreholes accessed the basement, while the third one terminated in the lowermost Neogene interval, composed of coarse-grained clastics. Formation and diversification of the lake basin was influenced by strong syndepositio- nal volcanic activity. The vertical distribution of selected elements from basal clastics (Cr, Ni, and Mg) and from overlying lake sediments (Ba, Sr, Na, K, etc.) indicates both the southern and north- ern margins of the basin, as potential source areas. The elemental concentrations are consistent with petrography. Based on the derived data, a reconstruction of the basin history is presented. The lack of index fossils resulted in a less accurate stratigraphy and the need for further updat- ing by employment of the fission-track low-temperature thermochronometers. Additionally, out- crop studies and correlation with lake sediments in the Valjevo-Mionica basin is suggested. VIĆ et al., 1997; OBRADOVIĆ & VASIĆ, 2007; KRSTIĆ et al., 2012; NEUBAUER et al., 2016). The manner of presentation of the Serbian lakes is also highly diverse. Lake basins were presented either according to their age and depressions where they have been developed (AN- ĐEL KOVIĆ et al., 1991; OBRADOVIĆ & VASIĆ, 2007) or were classified geographically, such as basins in northern, central and eastern Serbia (KRSTIĆ et al., 2003; DOLIĆ, 1986). According to KRSTIĆ et al. (2003) the lake basins are remnants of a single lake (Lake Serbia), whereas other authors recognized many Mio- cene lakes in mostly endemic and/or geographically isolated en- vironments (e.g. MAROVIĆ et al., 2007; HARZHAUSER & MANDIĆ, 2008). Furthermore, the geochemistry including iso- tope studies of the Serbian lakes is little known. The present study fills that gap by providing geochemical data that support results obtained by classic petrographic techniques. The objective in this study was to determine the range of concentrations of selected elements, which are indicative for the source of material: ultra- mafic rocks, or acid igneous, and metamorphic rocks. 2. REGIONAL GEOLOGICAL SETTING The Belanovica basin is part of the E-W trending Valjevo-Mioni- ca-Belanovica graben (MAROVIĆ et al., 2007). This two-part graben structure (Belanovica in the east and Valjevo-Mionica segment in the west) was one of the major depressions within the Peri-Pannonian Realm. Subsequent movements along the diago- nal faults led to the separation of individual basins (ANĐELKOVIĆ et al., 1991). The more intensive subsidence along the southern- border fault and asymmetrical inversion revealed a markedly asymmetrical Belanovica basin (MAROVIĆ et al., 2007). The northern margin of the Belanovica basin is formed by the Braj- kovac and Bukulja Mountains, composed of ~30–20 Ma old gra- nitoid rocks (KNEŽEVIĆ et al., 1994; CVETKOVIĆ et al., 2007) and Devonian to Carboniferous low-grade metamorphic rocks Article history: Manuscript received March 13, 2017 Revised manuscript accepted November 28, 2018 Available online Fabruary 15, 2019 Keywords: Neogene, Belanovica, lake basin, lithofacies, source rocks G eo lo gi a C ro at ic a Geologia Croatica 72/16 Figure 1. Neoalpine tectonic map of Serbia 1:500.000 (MAROVIĆ et al., 2007) with locations of the lacustrine basins (OBRADOVIĆ & VASIĆ, 2007). Legend: 1. Slanci (Slanci-Grocka) basin; 2. Valjevo-Mionica basin; 3. Jadar basin; 4. Takovo-Gomji Milanovac basin; 5. Čačak-Kraljevo basin; 6. Dobrinje-Ježevac basin; 7. Kosjeгić basin; 8. Dragačevo basin; 9. Pranjani basin; 10. Kremna basin; 11. Kopaonik basin and Jarandol basin; 12. Aleksinac basin; 13. Senje-Resava basin, 14. Velika Могаvа trough (Niš, Zaplanje, Jelašnica, Leskovac, Ваrbeš, Ražanj, Popovac, Braničevo and Mlava basin) and 15. The position of Figure 2 is represented by the rectangle. G eologia C roatica Marić et al.: History of the Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data 7 (TRIVIĆ et al., 2010; MAROVIĆ et al., 2007). Its southern mar- gin comprises Jurassic ophiolites dominated by serpentinite, Cre- taceous flysch sediments and Miocene volcanic and volcaniclas- tic rocks (Fig. 2). According to MAROVIĆ et al. (1999) the studied basin is included in the Serbian depositional province, which has been formed as a consequence of the Early Miocene extension and subsidence of the Pannonian basin due to Early-Middle Miocene collapse and core exhumation in the Sava zone and Tiszia (e.g. HORVATH et al., 2015). Extension of the Pannonian basin addi- tionally increased the heat transfer that is presently still observed (MATENCO & RADIVOJEVIC, 2012). 3. MATERIALS AND METHODS All sedimentary rock samples were optically analyzed using a petrographic polarized microscope for transmitted light (Leica DMLSP), connected to a Leica DFC290 HD camera over the ap- plication LAS V4.1. Major and trace chemical elements (includ- ing REEs) contents were determined in 158 samples (76 from the borehole VA-1, 54 from VA-2 and 28 from VA-3) in the SGS lab- oratory in Lakefield (Canada) using ICP-AES analysis (ICP 12B package), with samples repeated to ensure analytical consistency. Samples were cleaned of weathered surfaces and crushed to <2 cm before being ground to a <200 μm in an agate mill RETSCH PM 200. Accuracy and precision were estimated on the basis of stan- dard rock materials and replicate analyses. Contents for 12 ele- ments used in discussion in all 158 samples and detection limits are given in Supplementary Table. Procedures for manipulating data and drawing graphs were performed using Sigma Plot ver- sion 11.0 from SYSTAT Software Inc. San Jose, CA, USA; availa- ble at: www.systatsoftware.com. Granulometry was determined in epiclastic and sandy-gra- velly loose sediments. The amount of sample for analyses depends on the grain size, thus about 100 g was taken from the former and Figure 2. Geological map of the broader area of the Belanovica basin with borehole locations – detail from the Basic Geological Map 1:100.000, sheet Gornji Milano- vac (FILIPOVIĆ et al., 1971). Redrawn by M. RADISAVLJEVIĆ, using AutoCad 2014 software. G eo lo gi a C ro at ic a Geologia Croatica 72/18 Figure 3. Lithostratigraphic columns of boreholes. Lithofacies are marked as in the text. Solid lines connect the same levels. G eologia C roatica Marić et al.: History of the Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data 9 up to 50 g from the finer-grained sediments. The qualitative-quan- titative mineralogical composition was determined for four sam- ples of epiclastites using the > 0.063 mm fractions, and in seven sand samples using fractions 0.125–0.25 and 0.25–0.50 mm. The highest dispersion of data is noted for quartz and rock fragment abundance in epiclastites. Average values and standard deviation are presented for each constituent in Table 1. Fractions were pre- pared by wet-sieving techniques and analyzed afterwards under the binocular microscope (Leica EZ4D) and a polarised light mi- croscope (Leica DMLSP). The latter analysis required thin-sec- tions prepared with xilol as the immersion liquid. Micropalaeontological analyses included 36 samples washed and sieved under warm water (meshes 0.6–0.125 mm); discrete details of fossil molds required additional cleaning using 6% hy- drogen peroxide. Samples were analyzed by binocular microscope Leica (up to 35 x magnification) and by reflected light microscope Olympus BH2 (magnification up to 100 x). Analyses were per- formed by RUNDIĆ at the Department for Palaeontology of the Faculty of Mining and Geology, University of Belgrade. The content of CaCO3, as a proxy for carbonate content and precise determination of fine-grained clastites, was determined in 69 samples using a method of calcimetry and Scheibler’s cal- cimeter. Depending on the intensity of the sample reaction with diluted HCl, 0.5 g or 1 g of sample was ground in an agate vial. All analyses were performed at the Department for Mineralogy, Crystallography, Petrology and Geochemistry of the Faculty of Mining and Geology, University of Belgrade. 4. RESULTS Detailed mapping of cores from three exploration boreholes (VA-1, VA-2 and VA-3) enabled determination of the basin infill and basement rocks (Fig. 3). Neogene sediments in the borehole VA-1 overlie Cretaceous flysch (212–335 m) and volcanic and volcani- clastic rocks in VA-2 (268–296 m). The borehole VA-3 did not access the basement. Basement Weakly lithified, moderate to well-sorted sandstones prevail in fly- sch clastites in VA-1. Sandstones are stratified in thin to moderately thick beds and consist of rock fragments that were derived from metamorphic rocks (including serpentinites) and limestones. Fly- sch sediments in VA-1 containing serpentinite/ultramafite frag- ments have a high heavy metal content, particularly Ni (from 413 to 1429 ppm) and Cr (from 106 to 992 ppm; Supplementary Table). Volcanic and volcaniclastic rocks (ignimbrites) in borehole VA-2 are products of volcanic activity dated to about 23 Ma or younger (CVETKOVIĆ et al., 2000). Among them, the quartz latites of hypocrystalline porphyritic texture, followed by frag- ments of lamprophyres, were the most abundant products origi- nating from Rudnik mountain (Fig. 4a). Heavy metal contents in the underlying rocks in VA-2 range from 9.4–10.6 ppm (Cr) and 4.4–5.2 ppm (Ni). Unit A The oldest Neogene unit is the “Basal coarse-grained clastites” (BCC; A in Fig. 3). They consist of material derived from the vol- canic complex and flysch, from Triassic limestones or re-depo- sited volcaniclastic material (interval 212–162.5 m in VA-1; 268 to 258 m in VA-2 and 240–300 m in VA-3). Volcaniclastic mate- rial mostly consists of quartz (38.3–86.1%) and rock fragments (7.7–45.0 %). Feldspar is subordinate (2.7–4.8%; Table 1). Fossil remains are lacking. Unit B The transition from BCC into the overlying unit (B in Fig. 3), ”Marl- stone and fine-grained clastites“, marks the package of laminated and clayey siltstones (at 165 m depth in VA-1, and above 254 m depth in VA-2) where the lacustrine mollusc fauna occurs for the first time in the succession (remains of freshwater gastropods – Gy- raulus sp., Planorbarius sp., Theodoxus sp.; Fig. 4b). The amount of sand and gravel in this unit increases laterally along with the thickness of the unit itself (from 110 m in VA-1 to 140 m in VA-2). The given unit is typically represented in borehole VA-1 where three lithofacies are distinguished: (1) fine-grained clas- tites (sandy-clayey siltstones prevail); (2) marlstone (compositio- nally uniform) and (3) fine-grained clastites and sands. Horizon- tal lamination in lithofacies 1. and 2., determined by laminae of different granulometry, colour, composition and thickness is common. Bioturbation occurs locally. The aforementioned lithofacies are weakly differentiated in borehole VA-2, particularly when composed of marlstone. Sands composed of well-rounded grains originating from volcanic com- plex and flysch sediments occur throughout the column of VA-2, either as beds or as packages. The most abundant constituents of the sands are quartz (40.3–66.1%; Table 1) and rock fragments (15.6–21.3 %). Feldspar occurs in significant amounts (10.6–14.1 %), as well as muscovite (0.5–15.3%) and chlorite (1.6–15.7 %). Fine- grained clastites of different shades of brick-red colour, as well as green silty clays with carbonate nodules within the interval 195–180 m (see Fig. 3) suggest subaerial exposure. Unit B in column VA-3 displays an upward decrease in grain- size and thickness. Rounded pebbles in gravels were derived from clastites and altered volcanic rocks, while the finer-grained clas- Table 1. Modal analyses of redeposited volcaniclastic (epiclastic) rocks and sands from borehole VA-1. Average values and standard deviation were calculated for each constituent in both rock types. The depth of samples in metres is given in brackets. minerals in % epiclastite sands 71 (188.5) 67 (184.5) 61 (171.3) 60 (167.0) avg. ± S.D. 5 (13.7) 11 (33.6) 17 (50.6) 23 (63.6) 26 (68.8) 32 (86.2) 35 (96.5) avg. ± S.D. quartz 86 40 45 48 55 ±18 63 66 64 66 59 40 57 59 ± 9 feldspar 6 30 9 7 13 ± 10 14 14 13 12 14 11 13 13 ± 1 rock fragm. 8 30 45 44 32 ±15 18 18 21 19 17 16 21 19 ± 2 calcite tr. tr. tr. tr. – 4 1 2 2 2 2 3 2 ± 1 muscovite – – – – – 1 1 – 1 5 15 4 4 ± 5 biotite – – 1 1 0.5 ± 0.5 – – tr. tr. tr. tr. tr. – chlorite tr. – – – – – – – – 2 16 2 2 ± 6 faunal fragm. tr. tr. – tr. – tr. – – tr. 1 tr. tr. – heavy min. – tr. tr. – – tr. tr. tr. tr. tr. tr. tr. – avg. – average; S.D. –Standard deviations; tr. -trace; - not detected. G eo lo gi a C ro at ic a Geologia Croatica 72/110 tites are composed of fragments of metamorphic rocks. Sands display sedimentary structures of wave action (lenticular, wavy and flaser lamination). Debris of mollusc remains (molds) is com- mon. Fine-grained clastites are calcite-clayey siltstones with 10–15% CaCO3 (Table 2). Deformational structures resulted from vertical and horizontal movements – small syn-sedimentary landslides. Fresh-water organisms were identified in marlstones: carbonized flora, fish bones and scales, pyritized shell valves, ostracods (Candona sp., Amplocypris sp., Hungarocypris? sp.) and gastro- pods. Accumulated, i.e. gathered ostracods are common (Fig. 4c). Unit C The youngest recognized unit (C in Fig. 3) is “Sand, gravel, sand- stone and fine-grained clastites“. Its boundary with the previous unit is marked by basal conglomerates. A typical succession occurs within the VA-1, from the surface to 50 m depth. Sands are composed of quartz (63.2–66.1%), rock fragments (18–21.1%) and feldspars (12.8–14.0 %). Muscovite is less abundant (up to 1 %) and chlorite and biotite are lacking (first three samples of Table 1). Sands in the deeper sections are of dif- ferent granulometry and colour, and are organized in sets of trough cross or cross and horizontal lamination. Elements of wave-action, such as wavy (ripple) lamination and weakly deve- loped small-scale flaser or lenticular lamination, occur occasion- ally. In the upper part, thin to moderately thick beds of sandstone occur. Intraformational fragments of sandstone, originating from a basal unit (B – marlstone and fine-grained clastites) reflects that the former sands were cemented by calcite. Sandstones are con- sidered to represent sub-litharenite, litharenite and arkose having similar composition to the underlying exposed sands (Table 1). Sand and gravel in VA-2 alternate with fine-grained clastites. Fine-grained clastites and marlstone display horizontal lamina- tion. The content of freshwater bivalves (Mytilopsis sp. and Pi- sidium sp.), gastropods (Melanopsis cf. decollata STOLICZKA, Melanopsis ex gr. lyrata NEUMAYR, Gyraulus ex gr. pulici BRUSINA, Prososthenia sp., Planorbarius sp.) and ostracods (Hungarocypris sp. and Candona sp.) is high. Sands and gravels also comprise this unit in the VA-3 column too. Their boundary with the previous unit marks the sequence of yellowish-red coarse-grained gravels. Variations in shades of red, yellow and grey colours through the overall unit reflect on relatively shallow, oxygen-rich environment. The lower part of the unit includes alluvial-lacustrine sequences (polymict gravels) with a notable presence of fragments from metamorphic rocks. Sands vary in grain-size and display either horizontal or cross lamination. In finer-grained clastites, i.e. siltstones with more or less sandy fraction, one palaeosol horizon with two levels of car- bonate concretions was detected. Their structures reflect wave- action (wavy lamination and weakly developed flaser or even lenticular lamination). Fossil material includes mollusc molds and well preserved terrestrial gastropods (e.g. Clausilia sp.; Fig. 4d). Figure 4. a.Photomicrograph of lamprophyre; b. Theodoxus sp.; c. Accumulated ostracods in marlstone at 195 m (VA-3); d. Clausilia sp. G eologia C roatica Marić et al.: History of the Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data 11 5. DISCUSSION The natural concentration of elements in sediments is a function of the mineralogy of the source, the grain size and diagenetic pro- cesses/environment (MOURA & KROONENBERG, 1990; HAKSTEGE et al., 1993; HUISMAN & KIDEN, 1997). Sedi- mentary rocks derived near sources may inherit the source rock signatures, particularly the fine-grained ones due to their less variable composition in comparison with sandstones (CULLERS, 2000). These signatures may be later modified by weathering, hydraulic sorting and diagenesis (CULLERS et al, 1987). The obtained geochemical data for all the exposed rocks support the results from the common petrographic techniques and indicate the source rocks. Basement rocks Flysch in VA-1 contains rock fragments that were derived from metamorphic rocks (including serpentinites) and limestones. Their high Ni (413–1429 ppm) and Cr (106–992 ppm; Supplemen- tary Table) contents reflect the southwestern part of the studied area with serpentinite as the predominant source material. In terms of sedimentology, flysch corresponds to the distal parts of the fan in the bottom of the basin. Considering the flysch sedi- ments that outcrop about 15 km west of Belanovica (e.g. around the volcanic mass of Slavkovica) an Albian-Cenomanian age may be inferred. The presence of the brachiopod Kingena concinna OWEN in the coarse-grained clastites with serpentinite frag- ments suggests a Middle Cenomanian age, whereas the limestone fragments originate from the Upper Albian and Lower Cenoma- nian carbonates (RABRENOVIĆ et al., 2002; VASIĆ et al., 2001). Volcanic and volcaniclastic rocks (ignimbrites) in borehole VA-2 are products of volcanism the evolution of which involves the mixing of ultrapotassic and calc-alkaline magmas, which has been very important and led to highly diverse products (CVETKOVIĆ et al., 2007; CVETKOVIĆ et al., 2001; PRELEVIĆ et al., 2001; PRELEVIĆ et al., 2004). The contents of Cr (9.4–10.6 ppm) and Ni (4.4.–5.2 ppm) in VA-2 are notably lower than in VA-1 (Supplementary Table). The average crustal abundance of Ni is 0.01 %, while in sedimentary rocks it ranges from 5–90 μg/g (COX, 1995). The borehole VA-3 did not access the basement but considering the data from the Basic Geological Map corresponds to flysch sediments at the southern and to Devonian-Carboniferous metamorphic rocks at its northern margin (FILIPOVIĆ et al., 1971). Basement rocks display lithological and geochemical diffe- rences indicating petrological and stratigraphic differences of pa- laeorelief at the onset of lake formation. According to the depth distribution of the Neogene basement the lake bottom was pro- bably tilted towards the east, i.e. from VA-1 to VA-3. Basin infill (Neogene units) Unit A (alluvial phase) The oldest Neogene unit is basal coarse-grained clastites (BCC). As deposition took place during a partly developed lake basin the character of an alluvial system remained, particularly in VA-3. BCC in VA-1 and VA-2 reflect the periodically high terrigenous input into the basin, most probably by torrential flows. It is com- posed of material derived from the volcanic complex and flysch, from Triassic limestones or re-deposited volcaniclastic material. Table 2. The CaCO3 % content in samples (for the long core samples, several powdered samples were made for analyses. Such samples have the same number but are signed by uppercase letters, e.g. 13 A, 13 B, etc.). VA-1 VA-2 VA-3 No. sample depth % CaCO3 rock determination after FOLK et al. (1970) No. sample depth % CaCO3 rock determination after FOLK et al. (1970) No. sample depth % CaCO3 rock determination after FOLK et al. (1970) 1 15 45.3 7.6 sandy-clayey siltstone 32 13 241.3 22.1 calcite-clayey siltstone 49 10 241.7 10.2 calcite-clayey siltstone 2 18 52.2 44.2 marlstone 33 14 243.3 11.9 calcite-clayey siltstone 50 13A 224.5 20.4 calcite-clayey siltstone 3 19 54.0 10.2 calcite-clayey siltstone 34 17 222.7 39.9 marlstone 50 13B 219.4 35.7 marlstone 4 20 55.6 10.2 calcite-clayey siltstone 35 18 214.8 25.5 calcite-clayey siltstone 50 13C 211.1 34.8 marlstone 5 21 59.1 12.7 calcite-clayey siltstone 36 19 201.7 42.5 marlstone 50 13D 204.3 37.4 marlstone 6 25 67.7 13.6 calcite-clayey siltstone 37 20 195.3 7.6 clayey- sandy siltstone 50 13E 203.6 41.6 marlstone 7 27 70.8 16.1 calcite-clayey siltstone 38 25 160.4 11.9 calcite-clayey siltstone 50 13F 195.0 21.2 calcite-clayey siltstone 8 29 75.4 13.6 calcite-clayey siltstone 39 26 158.7 54.4 marlstone 50 13G 186.5 39.9 marlstone 9 30 79.9 17.0 calcite-clayey siltstone 40 28 140.7 16.1 calcite-clayey siltstone 50 13I 182.0 27.2 calcite-clayey siltstone 10 33 88.2 12.7 calcite-clayey siltstone 41 30C 130.2 10.2 calcite-clayey siltstone 50 13H 181.0 38.2 marlstone 11 36 99.5 14.4 calcite-clayey siltstone 41 30B 128.0 11.9 calcite-clayey siltstone 50 13J 177.6 31.4 calcite-clayey siltstone 12 37 103.4 17.0 calcite-clayey siltstone 41 30A 127.1 48.4 marlstone 50 13K 173.0 28.0 calcite-clayey siltstone 13 38 105.7 50.1 marlstone 42 33 110.5 17.0 calcite-clayey siltstone 51 14 168.2 13.6 calcite-clayey siltstone 14 39 108.8 48.4 marlstone 43 35 88.2 30.6 calcite-clayey siltstone 52 17 147.5 11.0 calcite-clayey siltstone 15 40 11.4 27.2 calcite-clayey siltstone 44 36C 84.0 43.3 marlstone 53 21 98.2 12.7 calcite-clayey siltstone 16 41 113.7 56.9 marlstone 44 36B 79.2 34.0 calcite-clayey siltstone 54 26 48.9 4.2 clayey siltstone 17 42 117.5 39.9 marlstone 44 36A 78.5 28.9 calcite-clayey siltstone 55 29 11.1 11.0 calcite-clayey siltstone 18 43 121.3 46.7. marlstone 45 38 66.6 25.5 calcite-clayey siltstone 19 44 123.8 39.9 marlstone 46 40 48.3 49.3 marlstone 20 45 128.2 51.8 marlstone 47 41 43.0 9.3 clayey siltstone 21 46 129.8 59.5 marlstone 48 43 26.1 42.5 marlstone 22 47 131.5 51.0 marlstone 23 48 134.5 42.5 marlstone 24 49 136.8 51.0 marlstone 25 50 138.8 39.9 marlstone 26 52 146.2 52.7 marlstone 27 53 151.5 20.4 calcite-clayey siltstone 28 54 153.2 81.5 limestone 29 56 157.8 16.1 calcite-clayey siltstone 30 57 159.0 50.1 marlstone 31 58 161.9 12.7 calcite-clayey siltstone G eo lo gi a C ro at ic a Geologia Croatica 72/112 The lower unit in VA-1 corresponds to an alluvial system (not completely differentiated) and the upper part is re-deposited vol- caniclastic rocks. The latter displays elements of debris flow, lo- cally likely lahars, as being suddenly brought into the basin. In terms of sedimentology, the BCC corresponds to alluvial facies. Sedimentology of BCC additionally confirms the lithological dif- ference of lake margins and reflects to a different way of contribu- tion (alluvial flows or lahars). Subsidence during deposition of the BCC was more rapid than authigenic processes, such as lake in- filling. Although the fossil remains are lacking, their early Middle Miocene age may be supposed according to similar lithological succession in other basins, e.g. in the Lake Popovac (SANT et al., 2017) and according to data from the Basic Geological Map, sheet Gornji Milanovac (FILIPOVIĆ et al., 1971). Unit B (lacustrine phase) After deposition of the BCC the lake was completely formed. The transgression took place and the input of medium- and coarse- grained terrigenous material decreased, particularly in the central part of the lake (where the boreholes were drilled). Coarser par- ticles retained close to the margins forming the alluvial-lake and marginal-lake facies. Slightly higher amounts of such material were brought into the area of boreholes VA-1 and VA-2, due to the proximity of the basin margin. Finer-grained volcaniclastic material was synchronously brought into the basin revealing the first level of vitroclastic tuffs (see Fig. 3). Localized occurrences of tuff (~ 232 m in VA-2) suggest that pyroclastic material arrived as lahars; otherwise a much broader area would be covered. Ac- cording to KRSTIĆ et al. (2012) lake basins in Serbia are com- monly lacking organisms with a calcium carbonate shell, as the lake water had to be acidic due to influence of volcanic activity. Lake acidification is additionally supported by the early soil de- velopment along with the role of atmospheric precipitation (REN- BERG, 1990). Such a situation occurred during the period of de- position of the fine-grained clastites in shades of brick-red colour and green silty clays with carbonate concretions in alluvial se- quences (interval 195–180 m in VA-2), reflecting the periodic subaerial conditions. This unit (marlstone and fine-grained clastites) includes three lithofacies: (1) alluvial-lacustrine fine-grained clastites, (2) lacustrine marlstone, and (3) deltaic fine-grained clastites and sands. (1) The upward decrease of grain-size and dimension of sand bodies in all three boreholes indicate that material was brought by muddy, turbidity flows. The sand bodies resembled the shape of channels through which sand and gravel have been distributed. The coarsening and thickening upward pattern is caused by the increasing and coeval exhumation during extension of a source area (ANDRIĆ et al., 2017). This gradually growing source area led to almost uni-directional sourcing of the basin (only from the north). The provenance ZFT (zircon fission tracks) age of 14.8 ± 0.8 Ma (Serravalian) for the coarse clastic sample from the Be- lanovica Basin, combined with some euhedral morphologies in- dicated the northern Bukulja pluton as the source area (STOJA- DINOVIĆ et al., 2017). In the middle part of the basin the finest-grained, silty and clayey particles were deposited, and together with microcrystal- line calcite allowed the formation of intrabasinal and lake facies, i.e. clastic-carbonate sediments. In terms of sedimentology this interval represents the alluvial-lacustrine facies. Constituents of sands, well-rounded pebbles originating from the volcanic com- plex and flysch sediments, together with the high content of mag- nesium (Mg) in VA-3 (up to 2.16%) suggests the southern margin as the source area, as well as in VA-2 (up to 8.43%; Supplemen- tary Table). In VA-1 both margins were included (Fig. 5a). The contents of barium and strontium in fine-grained clastites is the highest in VA-1 (in given unit average Ba-115.20 ppm, Sr-809.63 ppm; Supplementary Table). This reflects either different amount of calcite-clayey siltstones, i.e. calcite where Ba2+ substitutes Ca2+ or more involvement of granitic rocks that tend to contain higher concentrations of Ba than the low-silica rocks (CULLERS, 1994). The slight increase of Ba+Sr in VA-2 can suggest an in- creasing amount of fragments from lamprophyres or volcanic rocks with Ba-bearing biotite at least (e.g. HENDERSON, 1982; SHAW & PENCZAK, 1996). A low to moderate Ba and Ti-bear- ing mica is thought to have been formed by magmas in a subduc- tion-enriched subcontinental lithospheric mantle (JAQUES et al., 1986; THOMPSON et al., 1997). Such an interpretation is con- sistent with the already mentioned interaction between lampro- phyric and granitoid magmas (PRELEVIĆ et al., 2004). (2) During deposition of the marlstone lithofacies, which was the first truly intrabasinal facies, the basin was at least inter- mittently stratified. Contents of Ba+Sr (500–2000 ppm) in the marlstones in VA-2 in respect to Na+K (0.6–1.1 %) could be ex- plained by the substitution of K+ by Ba2+ due to the presence of material from the southern margin (volcanic rocks; Fig. 5b). The increase of Ba+Sr in respect to the almost uniform contents of Na+K in marlstones in VA-1 and VA-2 is in agreement with the presence of hydrous Mn and Fe oxides, clay minerals and organic matter, which adsorb Ba2+ at higher pH (WEDEPOHL, 1978). The presence of sulfide (i.e. pyrite mineralization and carbonized flora) suggests periodically reduced conditions and an abundance of organic matter (recall the Fig. 4c). A slight but progressive increase of Th+U with the increase of Na+K in VA-1 and VA-3 is in agreement with the increased contribution of material derived from the Bukulja and Brajkovac granites (Fig. 5c). It should be mentioned that in the Valjevo-Mi- onica basin there was a noted increase in the concentrations of uranium in coaly interbeds in Jelovik Village (KRSTIĆ et al., 2011). The high concentrations of Th (3–16.7 ppm; Supplementary Table) could be due to the concentration of certain accessory mi- nerals (e.g. zircon, monazite) in high-silica source rocks, i.e. gra- nites (CULLERS, 1994). This element is (together with Sc) con- sidered to be the most useful REE for inferring source rock composition as its distribution is not severely affected by secon- dary processes (CULLERS, 1994). In VA-2 these values do not correlate due to the variable abundance of fragments from felsic rocks and flysch clastites. (3) The final lithofacies (fine-grained clastites and sands) of this unit received material from both margins. Alluvial sys- tems from the South brought enormous amounts of coarser- grained terrigenous compounds (gravel and sand) into the basin resembling a deltaic model of deposition, i.e. alluvial-lake facies with well-evolved delta. Delta comprised a delta plain, delta front and prodelta and it was intermittently flooded by a lake (construc- tive and destructive phase). Unit C (alluvial-lacustrine phase) The youngest recognized unit is termed sand, gravel, sandstone and fine-grained clastites. Intraformational fragments of sand- stone, originating from unit B (marlstone and fine-grained clas- tites) shows that the former sands were cemented by calcite, most probably mobilized internally from the same unit. Constituents of dominating sands and gravels in VA-1 and VA-2 imply almost exclusive origin from the northern margin, i.e. from metamorphic G eologia C roatica Marić et al.: History of the Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data 13 and granitoid rocks. This could be a consequence of tilting to the south and uplift of the northern area leaving the Bukulja and Bra- jkovac massifs exposed to erosion. The high percentage of quartz relative to other minerals suggests that all the analyzed sand- stones are most likely first cycle sediments, i.e. products of in- tense chemical weathering (CULLERS & PODKOVYROV, 2002). Such an inference is additionally supported by the good correlation of boron (B) and lithium (Li), particularly in VA-2, where the lake depositional environment lasted the longest. In terms of sedimentology these sediments are considered to repre- sent alluvial-lacustrine facies. Local occurrences of lenticular bodies of sand or gravel on a metre to decametre scale resemble the channel forms by which particles were distributed. Sands and gravels comprise this unit in column VA-3, too. Their boundary with the previous unit is marked by a sequence of yellowish-red coarse-grained gravels. The colour-variations throughout the unit reflect a shallow, oxygen-rich environment and the gradual closure of the basin. The presence of a palaeosol horizon with two levels of carbonate concretions in finer-grained clastites indicates periodic subaerial conditions and supports the previous conclusion. The lower part of the unit includes alluvial- lacustrine intervals (polymict gravels) with the notable presence of fragments from metamorphic rocks. The highest boron contents usually occur in sedimentary beds associated with volcanic activity, as in the volcaniclastic rocks in VA-1 (unit B, interval 170–199m; values 87–172 ppm; Supplementary Table). In contrast, the tuffaceous rocks in VA-2 display similar behaviour as sedimentary rocks in VA-1 and VA-3 – uniform B and slight increased Li (Fig. 5 d, e). Most of the bo- ron content of sands and sandstones can be attributed to the pres- Figure 5. Distribution of selected elements in distinguished lithofacies. G eo lo gi a C ro at ic a Geologia Croatica 72/114 ence of tourmaline or to higher proportions of clay (HARDER, 1970). In finer-grained sediments its concentration varies in- versely with grain size, thus the highest values are found in the finest fractions. Boron, together with sodium is considered a good geochemical indicator of marine (saline) or fresh-water environ- ments, as its content in sediment depends primarily on the type of rock involved (HARDER, 1970). The low Na and uniform B reflects a lacustrine or fresh-water environment. Age The availability of data on lacustrine sediments in Serbia, regar- ding their age have until recently been scarce or only presented in local publications. The Serbian Lake sediments are older than the marine Middle Badenian, as they lie concordantly below it. As they are also overlain by marine deposits of Late Bade- nian/Sarmatian age the lacustrine sediments were generally con- sidered Early to Middle Badenian. The Valjevo-Mionica-Be- lanovica graben formed during the Ottnangian-Karpatian but later divided into the Valjevo-Mionica (west) and Belanovica (to the east) basins (MAROVIĆ et al., 2007). Index fossils are lack- ing in the Belanovica lake sediments but the presence of fresh- water Melanopsis support their Middle Miocene age, as the ear- liest record of it dates back in the late Early Miocene (NEUBAUER et al., 2016). The lack of marine sediments in the Belanovica ba- sin suggests that deposition ceased before the Late Badenian/ Sarmatian when the Valjevo-Mionica basin was ingressed by ma- rine water. The new data obtained for Lake Popovac reflect that the development of the Serbian lakes started around 14.5 Ma ago, in the Langhian, which corresponds to the Early Badenian Stage of the Central Paratethys (SANT et al., 2017). The fission-track analysis is potentially useful for unraveling the age of the studied lacustrine sediments. 6. CONCLUSIONS The Belanovica Lake developed during the Neogene in the area between the Brajkovac and Bukulja Mountains (granitoid and low-grade metamorphic rocks) to the North, and a broad area covered by Albian-Cenomanian flysch, Jurassic ultramafics and the Neogene volcanic mass of Slavkovica to the South. Alluvial and occasionally torrential flows coming from the South were responsible for the onset of deposition. The lake bottom dipped southeast periodically revealing parts of the lake sediments and exposing them to subaerial con- ditions. The alluvial-lacustrine and marginal-lacustrine facies re- tained close to the basin margin, whereas the finest-grained, silty and clayey particles arrived in the central and deepest part of the basin contributing there to the intrabasinal open-lacustrine facies. The alluvial flows from both margins contributed more than the synchronous volcanism to basin infilling, which itself was re- sponsible for increasing the lake-water acidity. The flows from the single northern margin into the western area (VA-1 and VA-2) indicate the gradual closure of the basin. The eastern area (VA-3) was frequently exposed to subaerial conditions giving rise to pa- laeosol development. The three-stage evolution of the Belanovica basin, inferred from integrated chemical and petrographic data, was controlled by palaeorelief of the pre-Neogene basement, erosion rate, and intensity of alluvial flows. The influence of volcanic activity should also be taken into consideration. Lake sediments inherited signatures of the source rocks at the basin margins. The whole succession, lacking age-diagnostic fossils, was tentatively correlated with the Middle Miocene. Tuffaceous rocks could hold the potential for unraveling the age of these lake se- diments, as well as the fission-track low-temperature thermochro- nology. ACKNOWLEDGMENT This research has been supported by the Serbian Ministry of Sci- ence, Project No 176019. The authors are indebted to colleagues from the company “Ultra Balkans d.o.o.” for permission to pub- lish a part of their research results. 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(2007): LiNaSiB3O7(OH) – novel structure of the new borosilicate mineral jadarite deter- mined from laboratory powder diffraction data.– Acta Crystallographica, B63, 396–401. doi: 10.1107/50108768107010130 G eo lo gi a C ro at ic a Geologia Croatica 72/116 Cr (ppm) Ni (ppm) Mg (%) Ba (ppm) Sr (ppm) Th (ppm) Sc (ppm) Th/Sc U (ppm) Na (%) K (%) B (ppm) Li (ppm) limit(s) 1ppm- 1% 1ppm- 1% 0.01%- 15% 5ppm- 1% 0.5ppm- 0.1% 0.1ppm- 1000 0.5ppm- 1% 0.05ppm- 1% 0.01%- 15% 0.01%- 15% 10ppm-1% 1ppm- 1% Interval (in m): from – to VA -1 B 65.40 66.40 41.50 65.30 1.14 112.20 220.00 6.80 7.20 0.94 1.27 0.02 0.33 20.00 49.80 69.85 70.85 49.00 82.20 1.28 147.60 515.00 8.30 8.10 1.02 1.77 0.03 0.37 20.00 57.80 78.00 79.00 55.20 93.30 1.30 115.40 451.00 8.60 8.70 0.99 1.61 0.02 0.34 15.00 53.30 81.30 82.30 50.80 78.80 1.18 108.40 358.00 6.20 7.30 0.85 1.32 0.03 0.34 13.00 49.50 85.70 86.70 29.60 41.10 0.66 115.80 129.00 4.70 5.00 0.94 0.83 0.04 0.24 11.00 28.30 90.20 91.20 40.30 63.60 0.97 81.20 229.00 5.30 6.00 0.88 1.01 0.03 0.27 12.00 41.10 94.70 95.70 29.00 40.20 0.64 89.80 176.00 3.90 4.00 0.97 0.82 0.03 0.16 11.00 23.00 99.50 100.50 46.40 75.30 1.01 97.60 356.00 5.70 5.90 0.96 1.20 0.03 0.23 13.00 43.60 103.70 104.70 44.60 77.40 1.06 122.60 466.00 6.00 5.90 1.01 1.12 0.04 0.28 18.00 46.00 112.70 113.70 52.60 96.40 1.21 282.80 1666.00 5.50 3.80 1.44 2.56 0.06 0.22 25.00 50.80 117.30 118.30 91.00 131.00 1.39 179.80 1017.00 6.20 4.30 1.44 1.86 0.07 0.23 16.00 45.20 121.20 122.20 34.70 75.90 0.84 207.20 1379.00 4.50 2.60 1.73 2.22 0.07 0.16 13.00 27.20 125.30 126.30 69.40 95.40 1.21 173.00 1140.00 5.60 3.50 1.60 1.85 0.07 0.18 12.00 37.70 127.80 129.80 33.40 57.90 0.86 141.20 691.00 4.90 3.00 1.63 1.15 0.07 0.18 10.00 31.80 138.70 139.70 94.10 146.00 1.37 228.20 1914.00 6.20 3.40 1.82 2.55 0.11 0.26 20.00 53.10 139.70 140.70 92.50 140.00 1.67 178.20 1885.00 5.60 3.30 1.75 2.35 0.10 0.21 18.00 55.20 141.98 142.98 135.00 163.00 1.61 137.80 713.00 6.20 3.90 1.54 1.23 0.09 0.22 12.00 51.50 146.20 147.20 89.90 107.00 3.64 151.40 996.00 5.20 3.20 1.57 1.92 0.11 0.24 85.00 51.80 147.20 148.20 149.00 177.00 4.61 121.40 447.00 6.80 4.40 1.50 2.25 0.11 0.30 90.00 68.60 153.04 154.04 59.70 84.80 1.77 159.20 1213.00 4.10 2.60 1.57 0.79 0.08 0.20 58.00 34.60 158.93 159.93 95.50 138.00 1.50 216.80 1648.00 6.00 4.00 1.50 2.04 0.14 0.31 59.00 48.60 162.00 163.00 153.00 211.00 1.68 91.40 203.00 7.60 5.40 1.40 2.39 0.10 0.44 36.00 53.50 163.00 164.00 59.90 80.80 1.10 150.60 252.00 21.00 5.00 4.20 2.19 0.25 0.65 64.00 35.80 Volc. 171.10 172.10 57.10 86.20 0.84 135.60 208.00 19.70 4.40 4.47 3.25 0.21 0.52 38.00 18.70 181.10 182.10 27.90 36.00 0.70 124.80 170.00 18.10 3.70 4.90 1.92 0.20 0.42 38.00 13.00 184.33 185.33 49.30 96.60 1.15 113.40 296.00 11.30 4.00 2.82 4.51 0.15 0.72 62.00 23.10 185.33 186.33 88.10 139.00 1.74 113.00 256.00 9.90 6.30 1.57 0.86 0.20 0.58 38.00 46.00 A 186.33 187.33 63.50 78.70 0.90 141.60 141.00 17.80 7.30 2.43 3.32 0.19 0.60 40.00 25.50 187.33 188.33 40.20 51.30 0.93 150.60 261.00 8.90 3.70 2.41 0.51 0.35 0.41 43.00 22.30 188.33 189.33 55.10 67.30 0.80 121.40 187.00 13.60 4.40 3.09 0.57 0.26 0.42 43.00 18.10 189.33 190.33 106.00 223.00 2.20 89.20 261.00 9.20 5.50 1.67 1.62 0.17 0.39 34.00 35.90 190.33 191.33 275.00 302.00 3.23 88.80 237.00 6.80 6.30 1.08 0.54 0.18 0.50 36.00 21.20 191.33 192.33 565.00 566.00 5.29 77.40 246.00 4.90 7.70 0.63 0.32 0.14 0.25 14.00 19.80 192.33 193.33 686.00 760.00 5.88 82.40 272.00 2.80 10.10 0.27 0.24 0.17 0.27 5.00 17.70 193.33 194.33 580.00 704.00 6.14 78.20 268.00 2.50 8.10 0.31 0.32 0.15 0.28 11.00 21.00 194.33 195.33 450.00 568.00 4.23 45.40 156.00 2.80 7.00 0.40 0.65 0.09 0.57 24.00 17.80 195.33 196.33 492.00 583.00 3.70 48.80 135.00 3.30 6.60 0.50 0.62 0.09 0.59 26.00 24.00 196.33 197.33 351.00 520.00 6.00 50.20 277.00 2.80 6.00 0.46 0.30 0.09 0.31 14.00 28.70 197.33 198.33 357.00 425.00 8.05 55.80 317.00 30.00 6.80 0.44 0.31 0.11 0.33 33.00 16.60 198.33 199.33 349.00 509.00 6.49 50.60 305.00 2.30 6.50 0.35 3.45 0.10 0.35 28.00 32.90 199.33 200.33 357.00 529.00 5.12 42.60 222.00 2.50 10.90 0.29 2.95 0.09 0.33 87.00 39.90 200.33 201.33 826.00 843.00 5.56 103.20 365.00 3.20 10.30 0.31 0.36 0.22 0.59 67.00 38.90 201.33 202.33 851.00 945.00 5.29 106.20 412.00 3.30 10.00 0.33 0.26 0.24 0.35 43.00 45.70 202.33 203.33 615.00 983.00 7.33 108.20 436.00 2.90 9.60 0.30 0.27 0.23 0.32 30.00 65.70 203.33 204.33 903.00 1056.00 5.96 107.80 379.00 2.40 11.90 0.20 0.24 0.24 0.36 26.00 79.90 204.33 205.33 532.00 745.00 7.82 85.80 552.00 1.90 8.20 0.23 0.47 0.19 0.34 23.00 55.20 205.33 206.33 936.00 1042.00 6.23 119.80 493.00 2.50 13.10 0.19 0.58 0.28 0.43 28.00 80.20 206.33 207.33 713.00 969.00 5.79 99.60 583.00 3.50 10.90 0.32 0.21 0.24 0.33 21.00 68.10 207.33 208.33 779.00 1046.00 5.38 108.40 542.00 2.90 12.30 0.23 0.23 0.26 0.37 27.00 76.90 208.33 209.33 760.00 1004.00 5.65 99.80 583.00 2.40 11.60 0.21 0.26 0.24 0.32 26.00 80.90 209.33 210.33 663.00 939.00 6.26 98.20 721.00 2.50 10.20 0.24 0.27 0.25 0.36 25.00 83.40 210.33 211.33 742.00 988.00 5.76 100.80 592.00 2.30 11.70 0.19 0.50 0.33 0.27 23.00 126.00 211.33 212.23 747.00 913.00 6.08 90.40 501.00 2.10 12.20 0.17 2.27 0.32 0.29 28.00 148.00 212.23 213.13 700.00 1185.00 6.71 120.60 336.00 2.80 11.20 0.25 0.57 0.43 0.31 30.00 161.00 215.00 216.00 791.00 1429.00 7.57 128.80 306.00 4.00 13.10 0.30 0.25 0.65 0.19 15.00 203.00 216.00 217.00 658.00 1245.00 7.94 120.60 321.00 2.50 11.60 0.21 0.29 0.64 0.20 17.00 201.00 Supplementary Table Contents of indicative chemical elements in the Belanovica basin lake deposits in ppm or in %, (as indicated), including detection limit(s). Lithofacies are marked as in the text (A, B and C). Shaded area considers volcaniclastic rocks. G eologia C roatica Marić et al.: History of the Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data 17 Cr (ppm) Ni (ppm) Mg (%) Ba (ppm) Sr (ppm) Th (ppm) Sc (ppm) Th/Sc U (ppm) Na (%) K (%) B (ppm) Li (ppm) limit(s) 1ppm- 1% 1ppm- 1% 0.01%- 15% 5ppm- 1% 0.5ppm- 0.1% 0.1ppm- 1000 0.5ppm- 1% 0.05ppm- 1% 0.01%- 15% 0.01%- 15% 10ppm-1% 1ppm- 1% Interval (in m): from – to 217.00 218.00 929.00 990.00 6.94 102.00 363.00 2.00 12.50 0.16 0.29 0.51 0.17 15.00 152.00 218.00 219.00 749.00 1162.00 7.54 114.20 284.00 3.20 12.20 0.26 0.32 0.59 0.21 34.00 175.00 219.00 220.00 908.00 1216.00 7.88 124.60 296.00 3.90 14.80 0.26 0.29 0.59 0.22 27.00 177.00 220.00 221.00 707.00 1051.00 7.42 121.20 426.00 2.80 12.40 0.22 0.30 0.5 0.21 26.00 143.00 221.00 222.00 731.00 985.00 7.56 117.00 263.00 2.20 11.10 0.20 0.22 0.42 0.16 27.00 131.00 222.00 223.00 597.00 923.00 7.87 117.80 283.00 2.30 10.20 0.22 0.32 0.41 0.17 28.00 130.00 232.00 233.20 766.00 1050.00 9.02 85.00 264.00 2.40 12.10 0.19 3.54 0.52 0.11 26.00 41.80 242.00 243.00 992.00 1215.00 9.74 81.20 195.00 2.60 14.60 0.18 2.05 0.55 0.10 33.00 49.50 250.50 251.50 816.00 1266.00 7.94 424.00 281.00 1.80 12.50 0.14 0.12 0.47 0.07 172.00 15.70 256.00 257.00 740.00 1128.00 9.14 109.00 281.00 2.50 12.50 0.20 0.17 0.65 0.11 117.00 35.90 267.20 268.30 934.00 1231.00 8.15 78.00 146.00 2.20 13.80 0.16 0.20 0.47 0.09 88.00 43.50 278.00 279.00 775.00 1068.00 9.18 81.60 243.00 2.30 13.20 0.17 0.16 0.64 0.11 81.00 39.50 290.20 291.20 838.00 1116.00 9.40 82.80 195.00 2.40 13.50 0.78 0.20 0.62 0.11 76.00 47.50 300.00 301.20 845.00 1200.00 7.90 75.20 279.00 1.80 12.30 0.30 0.15 0.65 0.11 62.00 26.30 309.50 310.50 406.00 652.00 9.95 53.20 184.00 3.60 12.00 0.16 0.21 0.38 0.10 79.00 81.00 322.00 323.00 786.00 1083.00 8.40 67.00 202.00 2.00 12.50 0.15 0.14 0.53 0.10 62.00 35.60 327.00 328.00 867.00 1205.00 8.20 65.40 174.00 1.90 12.60 0.15 0.15 0.48 0.09 56.00 34.40 328.00 329.00 763.00 1036.00 8.30 64.00 208.00 1.80 11.50 0.15 0.15 0.49 0.09 56.00 36.40 332.00 333.00 900.00 1135.00 9.08 60.40 249.00 2.20 14.00 0.15 0.14 0.63 0.12 71.00 46.10 VA -2 C 51.00 52.00 37.00 46.40 1.23 68.40 214.00 8.30 8.1 1.02 1.54 0.02 0.41 14.00 47.40 65.15 66.10 75.80 94.40 1.20 197.80 1203.00 5.60 4.5 1.33 1.59 0.05 0.27 20.00 41.10 71.00 72.00 82.70 112.00 1.17 272.20 1787.00 4.90 3.6 1.36 2.96 0.08 0.24 20.00 50.10 76.15 76.80 415.00 306.00 3.12 66.20 416.00 7.80 6.8 1.14 0.97 0.06 0.31 14.00 86.30 77.50 78.50 118.00 129.00 1.74 225.20 852.00 6.80 5.2 1.30 1.46 0.07 0.30 15.00 45.40 84.50 85.50 435.00 337.00 3.32 75.20 607.00 6.80 6.3 0.09 2.23 0.07 0.21 15.00 72.80 95.00 96.00 766.00 533.00 4.95 34.60 335.00 4.80 8.9 0.53 0.99 0.10 0.16 16.00 81.30 102.00 103.00 920.00 667.00 6.08 47.60 405.00 5.60 10 0.56 1.06 0.15 0.22 23.00 86.30 108.50 109.50 746.00 510.00 4.84 80.00 330.00 4.50 8.5 0.52 0.79 0.12 0.20 22.00 64.00 112.00 113.00 602.00 460.00 4.47 114.80 456.00 5.60 8.3 0.67 1.35 0.14 0.25 24.00 66.50 117.00 118.00 454.00 361.00 3.43 133.60 917.00 4.40 6.7 0.65 1.26 0.13 0.25 41.00 64.40 B 120.10 121.27 822.00 633.00 6.07 49.80 353.00 6.30 11 0.57 0.87 0.2 0.30 37.00 112.00 128.00 129.00 367.00 321.00 3.59 82.80 358.00 9.40 8.2 1.14 1.95 0.17 0.42 31.00 73.50 130.60 131.50 507.00 445.00 3.49 328.20 267.00 9.00 9.7 0.92 2.82 0.20 0.71 56.00 78.70 136.90 137.90 537.00 446.00 5.24 120.00 361.00 9.80 10.10 0.97 3.40 0.22 0.74 70.00 90.00 146.00 147.00 121.00 149.00 8.43 248.40 800.00 4.80 5.30 0.91 7.19 0.18 0.40 36.00 39.40 149.50 150.50 33.60 46.10 1.09 54.20 218.00 3.80 2.80 1.35 0.81 0.35 0.13 15.00 76.70 150.50 151.50 42.50 52.70 0.98 122.80 208.00 3.80 2.80 1.34 1.16 0.27 0.15 14.00 67.50 151.50 152.50 21.60 26.40 0.78 94.20 175.00 3.00 2.30 1.30 1.74 0.38 0.13 15.00 84.20 152.50 153.10 35.40 49.20 1.31 445.00 516.00 5.60 3.00 1.86 12.1 0.34 0.16 22.00 103.00 158.30 159.10 179.00 178.00 7.36 315.20 850.00 8.70 6.40 1.36 6.31 0.22 0.68 50.00 53.00 162.00 163.00 315.00 274.00 5.36 246.80 588.00 12.20 8.90 1.37 3.33 0.21 1.30 75.00 73.60 163.90 164.60 199.00 209.00 7.64 226.00 781.00 6.20 5.80 1.06 13.3 0.20 0.37 39.00 63.20 168.75 169.65 109.00 131.00 7.09 141.80 868.00 5.10 4.00 1.27 5.43 0.17 0.39 44.00 48.30 178.50 179.70 217.00 221.00 5.09 91.80 1111.00 8.60 6.20 1.38 8.16 0.25 1.06 100.00 93.80 182.70 183.70 129.00 142.00 4.71 62.20 1760.00 7.10 5.00 1.42 2.94 0.22 0.67 57.00 61.70 191.00 192.00 303.00 269.00 2.51 173.00 641.00 16.70 10.00 1.67 3.52 0.34 0.53 32.00 57.50 193.20 194.20 527.00 405.00 3.52 52.60 419.00 9.40 9.60 0.18 1.86 0.23 0.35 21.00 79.10 195.00 196.00 600.00 482.00 4.13 58.00 317.00 10.90 11.40 0.95 7.42 0.27 0.42 25.00 85.80 201.70 202.50 296.00 241.00 8.29 2891.40 1564.00 5.80 6.20 0.93 4.54 0.22 0.37 31.00 60.50 202.50 204.00 649.00 502.00 5.68 26.20 576.00 6.00 10.50 0.57 1.64 0.29 0.40 29.00 114.00 209.50 210.50 369.00 295.00 2.71 36.60 384.00 7.40 8.20 0.90 1.11 0.24 0.43 26.00 65.70 214.10 215.10 333.00 271.00 6.39 352.80 1214.00 6.40 6.60 1.03 7.48 0.33 0.50 57.00 142.00 218.30 219.40 418.00 325.00 4.92 62.60 717.00 8.00 8.20 0.97 4.81 0.28 0.66 60.00 100.00 221.50 222.40 70.70 88.70 3.07 64.60 917.00 6.90 4.30 1.60 10.5 0.22 0.84 73.00 84.80 222.40 223.30 82.90 83.20 5.74 147.40 1820.00 5.90 3.50 1.68 19.8 0.43 0.66 64.00 96.30 223.30 224.20 67.50 70.70 3.26 873.00 1888.00 7.40 3.00 2.40 39.6 0.43 0.46 51.00 85.10 224.20 225.10 69.10 102.00 2.14 92.80 1240.00 7.70 4.20 2.46 22.4 0.23 0.74 56.00 64.70 229.05 230.20 16.70 18.60 1.67 227.40 283.00 8.90 3.40 1.83 3.25 0.57 0.47 31.00 127.00 230.20 231.00 11.20 8.80 1.13 321.00 149.00 5.10 3.10 2.69 2.03 0.56 0.47 18.00 75.10 G eo lo gi a C ro at ic a Geologia Croatica 72/118 Cr (ppm) Ni (ppm) Mg (%) Ba (ppm) Sr (ppm) Th (ppm) Sc (ppm) Th/Sc U (ppm) Na (%) K (%) B (ppm) Li (ppm) limit(s) 1ppm- 1% 1ppm- 1% 0.01%- 15% 5ppm- 1% 0.5ppm- 0.1% 0.1ppm- 1000 0.5ppm- 1% 0.05ppm- 1% 0.01%- 15% 0.01%- 15% 10ppm-1% 1ppm- 1% Interval (in m): from – to 231.00 231.80 8.50 5.60 1.48 360.20 274.00 8.80 3.20 1.64 3.02 0.64 0.49 24.00 108.00 231.80 232.45 13.80 15.40 2.30 453.60 592.00 14.70 5.00 2.75 6.21 0.73 0.49 30.00 152.00 240.00 241.00 213.00 199.00 2.01 42.40 292.00 11.50 6.40 2.67 2.24 0.19 0.58 45.00 54.90 247.30 248.50 357.00 294.00 2.42 37.00 303.00 11.00 9.50 1.79 1.61 0.26 0.44 29.00 60.70 252.00 253.20 111.00 128.00 1.40 48.80 299.00 12.70 5.80 2.19 2.55 0.26 0.55 36.00 34.60 A 258.20 259.20 79.10 117.00 1.13 63.20 270.00 16.00 6.00 2.66 7.14 0.28 0.63 47.00 30.90 259.20 260.20 64.80 105.00 1.10 52.80 185.00 14.00 6.10 2.29 1.36 0.27 0.62 34.00 31.40 270.50 271.50 247.00 79.00 0.98 178.60 267.00 17.80 14.00 1.27 4.54 0.40 0.45 43.00 19.80 273.50 274.50 75.30 34.50 0.97 114.80 206.00 24.30 8.90 2.73 5.13 0.33 0.61 37.00 17.20 277.60 278.60 10.60 5.20 0.54 82.20 65.50 29.80 7.50 4.01 3.24 0.17 0.44 14.00 6.60 287.00 288.00 9.80 4.40 0.58 115.20 58.00 28.90 7.20 4.19 2.75 0.18 0.48 5.00 13.10 293.00 294.00 9.40 4.40 0.55 100.20 56.00 28.50 6.80 0.95 3.99 0.21 0.55 5.00 13.50 VA -3 C 84.50 85.50 32.40 43.90 0.93 96.40 140.00 6.80 7.1 1.04 3.21 0.02 0.34 18.00 36.30 87.50 88.50 19.00 21.80 0.47 80.00 101.00 4.70 3.5 0.95 1.06 0.03 0.16 12.00 18.50 89.50 90.50 51.60 79.10 1.14 119.20 297.00 9.50 8.2 1.34 1.73 0.03 0.36 18.00 47.80 93.20 94.20 39.20 50.00 1.12 92.60 174.00 8.80 8.4 1.15 1.54 0.02 0.4 14.00 55.30 96.20 97.20 36.20 49.30 1.04 86.80 196.00 9.10 7.9 1.04 1.81 0.02 0.35 12.00 48.10 105.20 106.20 32.90 47.40 1.10 81.60 167.00 8.20 7.3 1.15 1.46 0.02 0.34 10.00 48.00 109.70 110.70 23.80 32.90 0.76 120.00 134.00 6.00 5.4 1.12 1.12 0.03 0.27 5.00 33.00 118.70 119.70 15.30 24.80 0.32 30.00 35.50 2.50 1.50 1.11 1.84 0.02 0.10 18.00 8.00 B 128.20 129.20 22.00 32.40 0.66 68.80 93.80 5.70 4.40 1.29 0.90 0.02 0.22 18.00 21.10 136.70 137.70 24.90 37.90 0.82 64.40 108.00 6.30 5.30 1.18 1.12 0.02 0.27 18.00 29.30 154.70 155.70 35.40 54.20 1.00 62.80 133.00 6.90 6.50 1.06 0.98 0.02 0.35 15.00 43.00 161.20 162.20 18.60 25.10 0.38 39.80 86.40 4.00 2.50 1.60 0.83 0.03 0.13 14.00 12.50 168.20 169.20 39.10 77.50 1.16 72.00 298.00 9.60 8.70 1.10 1.67 0.03 0.39 42.00 48.60 173.20 174.20 68.80 126.00 1.39 192.40 601.00 5.70 5.10 1.11 1.90 0.04 0.25 33.00 37.30 180.50 181.50 49.50 90.00 0.94 246.60 1716.00 4.40 3.70 1.19 2.44 0.06 0.22 32.00 27.60 186.78 187.28 28.10 51.60 0.71 594.00 333.00 13.70 3.00 4.53 4.53 0.03 0.23 16.00 40.00 190.70 191.70 52.50 97.20 1.25 123.00 901.00 6.40 4.50 1.42 1.86 0.07 0.26 20.00 39.50 194.00 195.00 47.20 84.80 1.04 76.00 444.00 7.30 5.50 1.32 2.08 0.08 0.28 21.00 31.20 199.30 200.30 71.70 120.00 1.49 117.00 958.00 4.80 3.80 1.26 1.39 0.06 0.21 17.00 35.90 202.70 203.70 53.10 79.90 1.28 72.40 295.00 7.50 5.40 1.38 2.47 0.07 0.42 18.00 56.60 209.50 210.50 107.00 131.00 1.54 192.20 1569.00 5.60 4.10 1.36 2.04 0.09 0.23 26.00 51.60 219.00 220.00 101.00 146.00 1.48 125.40 1010.00 4.50 3.80 1.18 1.59 0.08 0.19 23.00 38.10 225.90 226.90 156.00 197.00 2.16 110.00 869.00 5.10 4.60 1.10 1.42 0.10 0.21 20.00 46.60 229.40 230.40 160.00 220.00 2.03 56.00 331.00 8.40 5.90 1.42 1.43 0.11 0.34 21.00 57.40 A 231.30 232.30 218.00 215.00 3.67 69.00 605.00 6.70 6.20 1.08 1.50 0.11 0.33 25.00 66.30 257.30 258.30 400.00 338.00 3.68 40.60 314.00 10.30 9.70 1.06 1.27 0.16 0.46 23.00 66.90 272.00 273.00 428.00 391.00 2.95 103.80 260.00 9.90 11.70 0.84 0.97 0.18 0.42 20.00 78.10 84.50 85.50 32.40 43.90 0.93 96.40 140.00 6.80 7.10 0.95 3.21 0.02 0.34 18.00 36.30 87.50 88.50 19.00 21.80 0.47 80.00 101.00 4.70 3.50 1.34 1.06 0.03 0.16 12.00 18.50 89.50 90.50 51.60 79.10 1.14 119.20 297.00 9.50 8.20 1.16 1.73 0.03 0.36 18.00 47.80