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

History of the Belanovica () 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; ([email protected]) 2 University of , Faculty of Mining and Geology, Đušina 7, 11000 Belgrade, Serbia doi: 10.4154/gc.2019.05

Abstract Article history: The petrological and geochemical composition of Neogene lacustrine successions and base- Manuscript received March 13, 2017 ment rocks of the Belanovica basin in Central Serbia, were investigated in three exploration Revised manuscript accepted November 28, 2018 boreholes, drilled in the central part of the former lake. Two boreholes accessed the basement, Available online Fabruary 15, 2019 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- Keywords: Neogene, Belanovica, lake basin, ing by employment of the fission-track low-temperature thermochronometers. Additionally, out- lithofacies, source rocks crop studies and correlation with lake sediments in the - basin is suggested.

1. INTRODUCTION The increasing interest in lacustrine sediments since the early VIĆ et al., 1997; OBRADOVIĆ & VASIĆ, 2007; KRSTIĆ et al., 1970s arose from new proof of their scientific and economic im- 2012; NEUBAUER et al., 2016). portance. Lacustrine successions may preserve details of sedimen- The manner of presentation of the Serbian lakes is also tary processes from the earliest stage of lake genesis to its very highly diverse. Lake basins were presented either according to end (BINFORD & DEEVEY, 1983; ТALBOT & KELTS, 1989; their age and depressions where they have been developed (AN­ ENGSTROM et al., 2000; COHEN, 2003; OBRADOVIĆ & VA- ĐEL­KOVIĆ et al., 1991; OBRADOVIĆ & VASIĆ, 2007) or were SIĆ, 2007). Palaeolimnological data such as shoreline features, classified geographically, such as basins in northern, central and isotopic composition of authigenic carbonates, groundwater influ- eastern Serbia (KRSTIĆ et al., 2003; DOLIĆ, 1986). According ences and changes in sediment grain size, structure and minera- to KRSTIĆ et al. (2003) the lake basins are remnants of a single logy, are useful in the reconstruction of lake-level changes in re- lake (Lake Serbia), whereas other authors recognized many Mio- sponse to regional climate change (DIGERFELDT et al., 1993; cene lakes in mostly endemic and/or geographically isolated en- FRITZ, 1996, 2008; HICKMAN & WHITE, 1989; ALMENDI- vironments (e.g. MAROVIĆ et al., 2007; HARZHAUSER & GER, 1993). The economic importance of former lakes relies on MANDIĆ, 2008). Furthermore, the geochemistry including iso- the significant accumulations of solid and liquid hydrocarbons as tope studies of the Serbian lakes is little known. The present study well as of other valuable resources, such as diatomite and diato- fills that gap by providing geochemical data that support results maceous earth, sedimentary zeolite, clay (particularly bentonite), obtained by classic petrographic techniques. The objective in this magnesite, dolomite, borates, including the recently discovered study was to determine the range of concentrations of selected jadarite (STANLEY et al., 2007; WHITFIELD et al., 2007). elements, which are indicative for the source of material: ultra- Serbian lakes formed during the late Oligocene and Miocene mafic rocks, or acid igneous, and metamorphic rocks. in dominantly NNW–SSE trending depressions along the old re- activated faults (OBRADOVIĆ & VASIĆ, 2007). Sedimentation 2. REGIONAL GEOLOGICAL SETTING occurred in several tectonic, i.e. lake phases, which were related The Belanovica basin is part of the E-W trending Valjevo-Mioni­ to different tectonic events, such as contraction, extension etc. ca-Belanovica graben (MAROVIĆ et al., 2007). This two-part (OBRADOVIĆ & VASIĆ, 2007). graben structure (Belanovica in the east and Valjevo-Mionica The majority of Serbian lakes underwent two (e.g. Valjevo- segment in the west) was one of the major depressions within the Mionica, Slanci, , Čačak-, Pranjane, Mlava basin) Peri-Pannonian Realm. Subsequent movements along the diago- or three (Niš, , Kremna, etc), but rarely only one sedi- nal faults led to the separation of individual basins (ANĐELKOVIĆ mentation cycle (Kosjerić and basins) (OBRADOVIĆ et al., 1991). The more intensive subsidence along the southern- & VASIĆ, 2007; Fig. 1). The alternation of lake sediments with border fault and asymmetrical inversion revealed a markedly those formed in marsh or alluvial systems, sometimes with coal asymmetrical Belanovica basin (MAROVIĆ et al., 2007). The and/or oil shales resulted in highly diverse facies. The alternation northern margin of the Belanovica basin is formed by the Braj­ of lake and marine sedimentation has been identified in the kovac and Bukulja Mountains, composed of ~30–20 Ma old gra­ Valjevo-Mionica coastal area, at the ancient watering place of nitoid rocks (KNEŽEVIĆ et al., 1994; CVETKOVIĆ et al., 2007) Vračević (OBRADOVIĆ & DIMITRIJEVIĆ, 1978; OBRA­DO­ and Devonian to Carboniferous low-grade metamorphic rocks Geologia Croatica Могаvа trough (Niš, Zaplanje, Jelašnica,Leskovac, Popovac, Ražanj, Ваrbeš, Braničevo andMlava basin)and15. The positionofFigure 2isrepresented by therectangle. 7. Kosjeгić basin;8.Dragačevo basin;9.Pranjani basin, 14. basin;10.Kremna basin;11.KopaonikbasinandJarandol basin;12.Aleksinac 13.Senje-Resava Velika basin;2.Valjevo-MionicaLegend: basin;3.Jadar4. 1.Slanci(Slanci-) Takovo-Gomji basin;5.Čačak-Kraljevo Milanovac basin; basin;6. Dobrinje-Ježevac Figure 1:500.000(MAROVIĆ mapofSerbia etal., 1.Neoalpinetectonic 2007)withlocationsbasins(OBRADOVIĆ ofthelacustrine & VASIĆ, 2007). 6 Geologia Croatica 72/1 Geologia Croatica

------7 Granulometry was determined in epiclastic and sandy-gra- amples were cleaned of weathered surfaces and crushed to <2 cm plication LAS V4.1. Major andMajor trace chemicalplication elementsLAS (includ V4.1. thefrom (76 samples determinedwere 158 contentsin REEs) ing lab SGS thein fromVA-3) 28 and fromVA-2 54 VA-1, borehole oratory in Lakefield(Canada) using ICP-AES analysis (ICP12B ensureanalyticalrepeated toconsistency. samples with package), S before being ground to a <200 μm in an200. agate Accuracy mill RETSCH and PM precision were estimated on the basis of stan dard rock materials and replicate analyses. Contents for 12 ele and detection samples limitsments used in in discussion all 158 manipulating for Procedures Table. Supplementary in given are data and drawing graphs were performed using availa- Sigma ver Plot USA; CA, Jose, San SoftwareInc. SYSTAT from 11.0 sion www.systatsoftware.com. at: ble loose sediments.velly The amount analyses sample for of depends on the grain size, thus g was taken about 100 from the former and - - - - - Geological map of the broader area of the Belanovica basin with borehole locations – detail from the Basic Geological Mapthe Basic Geological Gornji sheet 1:100.000, – detail from Milano locations basin with borehole the Belanovica of area broader of the map Geological According to MAROVIĆ et the al. studied(1999) basin is 3. MATERIALS AND METHODS All sedimentary rock samples were optically analyzed using a petrographic polarized microscope transmitted for light (Leica ap the camera HDover DFC290 connectedLeica a to DMLSP), (TRIVIĆ et al., MAROVIĆ 2010; et al., 2007). Its southern mar Figure 2. Figure software. 2014 using AutoCad M. RADISAVLJEVIĆ, by 1971). Redrawn (FILIPOVIĆ et al., vac gin comprises Jurassic ophiolites dominated by serpentinite,dominated by comprisesophiolitesJurassicgin Cre taceous sedimentsvolcaniclasflysch volcanic and Miocene and tic rocks 2). (Fig. included in the Serbian depositional province, which has been formed as a consequence of the Early Miocene extension and MioceneEarly-MiddlePannonian tothe duebasin of subsidence collapse and core exhumation in the zone and Tiszia (e.g. thePannonian Extensionof basin addi 2015). al., et HORVATH tionally increased theheat transferthat ispresently still observed (MATENCO & RADIVOJEVIC, 2012). Marićet al.: History ofthe Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data Geologia Croatica Figure 3.Lithostratigraphic columns ofboreholes. thesame levels. linesconnect Solid Lithofacies are asinthetext. marked 8 Geologia Croatica 72/1 Geologia Croatica ------), 9 Gy – – – 4 ± 5 2 ± 6 2 ± 1 19 ± 2 13 ± 1 59 ± 9 avg. ± S.D. avg. 4 2 3 tr. tr. tr. 21 13 57 35 (96.5) 2 tr. tr. tr. 15 16 11 16 40 sp.; Fig. 4b). The amount amount The 4b). Fig. sp.; 32 (86.2) 5 2 2 1 tr. tr. 17 14 59 26 (68.8) sands sp., Theodoxus – 1 2 tr. tr. tr. 19 12 66 23 (63.6) – – – 2 tr. tr. 21 13 64 17 (50.6) sp., Planorbarius Unit B in column VA-3 displays an upward decreasein grain- The given unit is typically represented in borehole VA-1 in differentiated weakly are lithofacies aforementioned The – – – 1 1 tr. 18 14 66 5.6–21.3 %). Feldspar occurs in significant amounts(10.6–14.1 % 11 (33.6) as well as muscovite (0.5–15.3%) and chlorite (1.6–15.7 %). Fine- %). (1.6–15.7 chloriteand (0.5–15.3%) muscovite as well as grained clastites of differentshades of brick-red colour, aswell as green silty with clays carbonate nodules within the interval suggest subaerial 3) Fig. exposure. m (see 195–180 size andthickness. Rounded in pebbles gravels were derivedfrom clastitesandaltered rocks, volcanic whilethe finer-grained clas younger et (CVETKOVIĆ al., 2000). Among them, the quartz latites of hypocrystalline porphyritic texture, followed by frag ments lamprophyres, of were the most abundant products origi metalHeavycontentsin nating fromRudnik 4a). mountain (Fig. and theppm underlying(Cr) range from rocks 9.4–10.6 in VA-2 ppm (Ni). 4.4–5.2 Unit A Theunit Neogene oldest is the “Basal coarse-grained clastites” vol the frommaterialderived of consist They 3). Fig. in A (BCC; 268 canic complex and flysch, VA-1; in m fromTriassic limestones or re-depo- 212–162.5 (interval material volcaniclastic sited Volcaniclastic mate and 240–300to m in 258 m in VA-2 VA-3). rial mostly consists of quartzFossil and rock 1). fragments(38.3–86.1%) Table (2.7–4.8%; subordinate is Feldspar %). (7.7–45.0 remains are lacking. Unit B Thetransition from BCC into stone and fine-grainedthe clastites“, marksoverlying the packageof laminated unit (B and in clayey siltstones m Fig. 165 (at depthand above in 254 3), mVA-1, ”Marl wheredepth the in lacustrineVA-2) mollusc fauna occurs for the gastropodsfreshwater (remainsof – succession the first in time sandof and gravel in this unit increases laterally with along the inm VA-2). to 140 inm VA-1 thicknessthe unit of 110 itself (from where three lithofacies are distinguished: fine-grained (1) clas marlstone(compositio- (2) siltstonesprevail); (sandy-clayey tites fine-grained clastitesuniform)nally (3) and sands.Horizon and of laminae by determined 2., and 1. lithofacies in lamination tal different granulometry, colour, composition and thickness is common. Bioturbation occurs locally. Sandsmarlstone.particularly composedof when VA-2, borehole composed well-rounded of grains originating from com volcanic VA-2, sedimentsflysch and occur throughoutof plex column the either as beds or as packages. The most abundant constituents of the sands are quartz and1) Table rock (40.3–66.1%; fragments (1 raulus ------– – 4 1 tr. tr. 18 14 63 5 (13.7) – – – – – 32 ±15 55 ±18 13 ± 10 0.5 ± 0.5 avg. ± S.D. avg. – – – 1 7 tr. tr. 44 48 60 (167.0) – – – 1 9 tr. tr. 45 45 61 (171.3) epiclastite , as a proxy for carbonate content and – – – tr. tr. tr. 30 30 40 3 67 (184.5) – – – 8 6 tr. tr. tr. 86 71 (188.5) Volcanic and Volcanic volcaniclastic rocks (ignimbrites) in borehole Micropalaeontological analyses included 36 samples washed washed samples 36 included analyses Micropalaeontological The content CaCO of etailed mapping coresof from three exploration boreholes (VA-1, biotite calcite rock fragm. rock quartz minerals in % in minerals faunal fragm. chlorite muscovite feldspar heavy min. Modal analyses of redeposited volcaniclastic (epiclastic) rocks and sands from borehole VA-1. Average values and standard deviation were calculated for for calculated were deviation standard and values Average VA-1. borehole from sands and rocks (epiclastic) volcaniclastic redeposited of 1. Modalanalyses Table in brackets. is given of samples in metres depth The types. in both rock each constituent avg. – average; S.D. –Standard deviations; tr. -trace; - not detected. -trace; tr. deviations; –Standard S.D. – average; avg. 4. RESULTS D enabled determinationand VA-3) VA-2 of the basin infill and VA-1 borehole thesediments in Neogene 3). (Fig. rocksbasement overlie Cretaceousm) flyschandvolcanic (212–335 andvolcani Basement fly well-sorted lithified,sandstonesin prevail moderate to Weakly clastic rocksdid The(268–296 m). in not borehole VA-2 VA-3 access the basement. moderately stratified Sandstonesare thin to in VA-1. inclastites sch thick beds and rock consist fragments of that were derived from metamorphic rocks (including serpentinites) and limestones. Fly sch sediments containingin VA-1 serpentinite/ultramafite frag ments have a high heavy metal content, particularly Ni (from 413 Supplementaryppm; Table). 992 to 106 (from Cr and ppm) 1429 to are productsVA-2 of volcanic activity dated to about 23 Ma or up to 50 g from the finer-grained qualitative-quan sediments.the from The g 50 to up titativemineralogical composition was determined four samfor epiclastites of ples using mm the fractions, > 0.063 and in seven sand samples using fractions 0.125–0.25 and 0.25–0.50 mm.highest Thedispersion of data is noted for quartz and rock fragment abundancevaluesandstandard in epiclastites. Average deviation are presented Fractions each for constituent were pre 1. in Table pared by wet-sieving techniques and analyzed afterwards under the binocular microscope (Leica EZ4D) and a polarised light mi croscope (Leica TheDMLSP). latter analysis required thin-sec tions prepared with xilol as the immersion liquid. and sieved under warm water (meshes 0.6–0.125 mm); discrete details fossil of molds required additional cleaning using hy 6% drogen peroxide. SamplesLeica were analyzed (up to 35 x magnification) by binocularOlympus BH2 (magnificationand microscope up 100tobyx). Analysesreflectedwere per light microscopeformed by RUNDIĆ at the Department for Palaeontology of the MiningFaculty of University Belgrade. and of Geology, Marićet al.: History ofthe Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data cimeter. Depending on the intensity the sample of reaction with vial. agate an in ground was sample of g 1 or g 0.5 HCl, diluted Allanalyses wereperformed theat Department Mineralogy, for Crystallography, Petrology and Geochemistry of the Faculty of Mining University Belgrade. and of Geology, precise determination of fine-grainedclastites, was determined in samples69 using a method calcimetryof cal and Scheibler’s Geologia Croatica occur. Intraformational fragments of sandstone, originating from from originating of sandstone, fragments Intraformational occur. of sandstone beds thick moderately to thin part, ally. upper the In occasion occur lamination, or lenticular flaser small-scale loped deve- weakly and (ripple) wavy lamination as such wave-action, of Elements lamination. horizontal and or cross cross trough of sets in organized colour, are and and granulometry ferent (first lacking are of dif are sections biotite deeper the of Table and in 1). samples Sands three chlorite and %) 1 to (up abundant less (18–21.1%) fragments (12.8–14.0 is feldspars %).Muscovite and (63.2–66.1%), of quartz composed are rock Sands 50depth. m to sand conglomerates. by basal marked is unit gravel, “Sand, is 3) Fig. in previous the with (C clastites“.boundary Its fine-grained and unit stone recognized youngest The Unit C i.e. pods. are Accumulated, common (Fig.ostracods gathered 4c). Fresh-water organisms were identified in marlstones: carbonized carbonized ( ostracods marlstones: valves, in shell pyritized scales, and bones identified fish flora, were organisms Fresh-water landslides. syn-sedimentary small – movements horizontal and CaCO m and flaserlamination). Debris of mollusc remains (molds)is com wavy of (lenticular, wave action structures sedimentary display Sands rocks. metamorphic of fragments of composed are tites Figure 4.a.Photomicrograph oflamprophyre; b.Theodoxus sp. 10 Candona on. Fine-grained clastites on. are calcite-clayey Fine-grained siltstones with 10–15% A typical succession occurs within the VA-1, from the surface surface the from VA-1, the within occurs succession typical A 3 (Table 2). Deformational structures resulted from vertical vertical from resulted structures Deformational 2). (Table sp., sp., sp., sp., Amplocypris Hungarocypris ? sp.) and gastro sp.)? and ; c. Accumulated ostracods inmarlstone at 195m(VA-3); d. Clausilia - - - - -

Melanopsis sidium bivalves ( of freshwater content The tion. lamina horizontal display marlstone and clastites Fine-grained (Table sands 1). exposed underlying the to composition similar having arkose and litharenite sub-litharenite, represent to sidered con are Sandstones calcite. by cemented were sands former the a clastites) basal (B unit that – reflects and marlstone fine-grained BRUSINA, BRUSINA, ( well preserved terrestrial gastropods (e.g. Clausilia gastropods terrestrial well preserved lenticular lamination). Fossil includes material mollusc molds and even or flaser developed weakly and lamination (wavy action wave- reflect structures Their detected. was concretions bonate levels two of with car horizon palaeosol one fraction, sandy less or more with i.e. siltstones clastites, finer-grained In lamination. cross or horizontal either display and grain-size in vary Sands rocks. metamorphic from of fragments presence anotable with gravels) sequences (polymict the unit includes alluvial-lacustrine of part lower The environment. shallow, oxygen-rich relatively on reflect unit overall the through colours grey and yellow red, of shades in Variations gravels. of coarse-grained yellowish-red sequence the marks unit previous the with boundary Their too. Hungarocypris Sand Sand and gravel in VA-2 clastites. with fine-grained alternate Sands and gravels also comprise this unit in the VA-3 column column VA-3 the in unit this comprise also gravels and Sands sp.), gastropods ( sp.), gastropods ex gr. ex Prososthenia sp. and Candona sp. and lyrata Melanopsis NEUMAYR, NEUMAYR, sp., Planorbarius sp., sp.) high. is cf. decollata cf. sp. Gyraulus Mytilopsis Geologia Croatica 72/1 sp.) and ostracods STOLICZKA, STOLICZKA, ex gr. ex sp.; Fig. 4d). Fig. sp.; sp. and Pi sp. and pulici - - - -

Geologia Croatica - 11 rock determination after determination rock (1970) FOLK et al. calcite-clayey siltstone calcite-clayey siltstone marlstone marlstone marlstone marlstone calcite-clayey siltstone marlstone calcite-clayey siltstone marlstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone clayey siltstone clayey calcite-clayey siltstone 3 VA-3 4.2 10.2 20.4 35.7 34.8 37.4 41.6 21.2 39.9 27.2 38.2 31.4 28.0 13.6 11.0 12.7 11.0 % CaCO 98.2 48.9 11.1 241.7 224.5 219.4 211.1 204.3 203.6 195.0 186.5 182.0 181.0 177.6 173.0 168.2 147.5 depth 10 14 17 21 26 29 13I 13J 13E 13F 13B 13K 13C 13A 13G 13D 13H sample 49 50 50 50 50 50 50 50 50 50 50 50 51 52 53 54 55 No. The contents of Cr (9.4–10.6 ppm) and Ni (4.4.–5.2 ppm) inppm) andppm) The Ni (4.4.–5.2 contents of Cr (9.4–10.6 Basement rocks display lithological and geochemical diffe- CC in VA-1 and VA-2 reflect and the CC VA-2 periodicallyin VA-1 high terrigenous Unit A (alluvial phase) A Unit The unit Neogene oldest is basal coarse-grained clastites (BCC). duringbasintheplacelake partlydepositiontook As a developed character of an alluvial system remained, particularly in VA-3. B input into the basin, most probably by torrentialIt is flows. com posed materialof derived from the volcanic complex and flysch, from limestones Triassic or re-deposited volcaniclastic material. 2001). Volcanic and volcaniclastic rocks (ignimbrites) in borehole borehole in(ignimbrites) rocks volcaniclastic and Volcanic 2001). are products volcanismof theVA-2 whichof evolution involves ultrapotassiccalc-alkalinehasandmixing magmas,of which the been very important and led to highly diverse products PRELEVIĆ 2001; al., et CVETKOVIĆ 2007; al., et (CVETKOVIĆ PRELEVIĆ 2004). et al., 2001; et al., VA-2 are notably lower than insedimentaryinwhile%, crustalaverage VA-10.01 (Supplementaryis abundanceNi of Table). The rocks it ranges from 5–90 μg/g (COX, 1995). The borehole VA-3 did access not the basement considering but 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 1971). et al., pa-stratigraphicindicatingandof rences petrologicaldifferences laeorelief at the onset lakeof formation. According to the depth distribution the basement Neogene of the lakebottom was pro- to VA-3. tiltedbably towards the east, from i.e. VA-1 Basin infill (Neogene units) rock determination after determination rock (1970) FOLK et al. calcite-clayey siltstone calcite-clayey siltstone marlstone calcite-clayey siltstone marlstone clayey- sandy siltstone clayey- calcite-clayey siltstone marlstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone marlstone calcite-clayey siltstone calcite-clayey siltstone marlstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone marlstone clayey siltstone clayey marlstone 3 VA-2

------7.6 9.3 22.1 11.9 39.9 25.5 42.5 11.9 54.4 16.1 10.2 11.9 48.4 17.0 30.6 43.3 34.0 28.9 25.5 49.3 42.5 % CaCO 88.2 84.0 79.2 78.5 66.6 48.3 43.0 26.1 concinna 241.3 243.3 222.7 214.8 201.7 195.3 160.4 158.7 140.7 130.2 128.0 127.1 110.5 depth

13 14 17 18 19 20 25 26 28 33 35 38 40 41 43 30B 36B 30C 36C 30A 36A sample 32 33 34 35 36 37 38 39 40 41 41 41 42 43 44 44 44 45 46 47 48 No. sandy-clayey siltstone sandy-clayey rock determination after determination rock (1970)FOLK et al. marlstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone calcite-clayey siltstone marlstone marlstone calcite-clayey siltstone marlstone marlstone marlstone marlstone marlstone marlstone marlstone marlstone marlstone marlstone marlstone calcite-clayey siltstone limestone calcite-clayey siltstone marlstone calcite-clayey siltstone 3 VA-1 7.6 44.2 10.2 10.2 12.7 13.6 16.1 13.6 17.0 12.7 14.4 17.0 50.1 48.4 27.2 56.9 39.9 39.9 51.8 59.5 51.0 42.5 51.0 39.9 52.7 20.4 81.5 16.1 50.1 12.7 46.7. % content in samples (for the long core samples, several powdered samples were made for analyses. Such samples have the same number but Such samples have analyses. made for samples were powdered several samples, the long core in samples (for % content % CaCO 3 45.3 52.2 54.0 55.6 59.1 67.7 70.8 75.4 79.9 88.2 99.5 11.4 103.4 105.7 108.8 113.7 117.5 121.3 123.8 128.2 129.8 131.5 134.5 136.8 138.8 146.2 151.5 153.2 157.8 159.0 161.9 depth 15 18 19 20 21 25 27 29 30 33 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 52 53 54 56 57 58 sample 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 No. are signed by uppercase letters, e.g. 13 A, 13 B, etc.). 13 A, 13 B, e.g. letters, uppercase by signed are The CaCO 2. The Table Basement rocks contains Flysch rock infragments VA-1 that were derived from metamorphic rocks (including serpentinites) and limestones. Their high Ni (413–1429 ppm) and Cr (106–992 ppm; Supplemen cesses/environment (MOURA & KROONENBERG, 1990; HAKSTEGE et HUISMANal., 1993; & KIDEN, 1997). Sedi mentary rocks derived near sources may inherit the source rock signatures, particularly the fine-grained ones due to theirless comparisonsandstones(CULLERS,within composition variable 2000). These signatures may be later modifiedby weathering, hydraulic sorting and diagenesis (CULLERS et al, The 1987). allobtained the rocks data exposed support geochemical for the results from the common petrographic techniques and indicate the source rocks. studied the of part southwestern the reflect contents Table) tary area with serpentinite as the predominant source material. In terms correspondsflysch sedimentology, of to the distal partsof the fan in the bottom of the basin. around Considering the (e.g. flysch sedi Belanovica of km west 15 about outcrop that ments Albian-Cenomaniananmay age Slavkovica) of mass volcanic the be inferred. The presence the brachiopod of Kingena 5. DISCUSSION The natural concentration elements in of sediments is a function the mineralogyof the source, of the grain size and diagenetic pro Marićet al.: History ofthe Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data OWEN OWEN in the coarse-grained clastites with serpentinite frag ments suggests a Middle Cenomanian age, whereas the limestonethewhereas Cenomanian age, Middle a suggestsments fragmentsoriginate Cenomafrom Lower AlbianUpperandthe nian carbonates (RABRENOVIĆ et al., 2002; et VASIĆ al., Geologia Croatica nesium nesium (Mg) in VA-3 (up to 2.16%) the suggests margin southern plex and flyschtogetherwith thesediments, high content ofmag volcanic com the from pebbles originating well-rounded sands, of Constituents facies. alluvial-lacustrine the represents interval this of sedimentology terms In sediments. i.e. clastic-carbonate facies, lake and of intrabasinal formation allowed calcite the line microcrystal with together and deposited, were clayey particles DINOVIĆ al., et 2017). dicated the northern Bukulja pluton as the source area (STOJA- in morphologies euhedral some with combined Basin, lanovica Be the from sample clastic coarse the for (Serravalian) Ma 0.8 tracks) (zircon fissionagenorth). ZFT provenance The of 14.8± (only the of basin from the sourcing uni-directional almost to led area source growing gradually 2017). al., This et (ANDRIĆ area source a of extension during exhumation coeval and increasing by the caused is pattern upward thickening and coarsening The distributed. have gravel been and sand which through of channels shape the resembled bodies sand The flows. turbidity muddy, by brought was material that boreholes indicate three all in bodies sands. and clastites fine-grained (3) deltaic and marlstone, lacustrine (2)clastites, lithofacies: (1)fine-grained three alluvial-lacustrine conditions.subaerial periodic VA-2),the in 195–180m reflecting (interval quences se alluvial in concretions carbonate clays with silty green and position ofin clastites shadesthe offine-grained brick-red colour BERG, of the period 1990).de during Such occurred a situation (REN precipitation role the velopment of atmospheric along with theearly soil by de supported additionally is acidification Lake lake water had to be acidic due to influence of volcanicactivity. the as shell, carbonate a calcium with organisms lacking monly com are Serbia in (2012) al. basins et lake KRSTIĆ to cording Ac covered. be would area broader much a otherwise lahars; as of tuff (~ 232 min VA-2)occurrences suggest thatarrived material Localized pyroclastic Fig.(see 3). tuffs vitroclastic of level first the revealing basin the into brought synchronously was material volcaniclastic Finer-grained margin. basin the of proximity the VA-1 boreholes VA-2, ofto and due area the into brought were material such of amounts higher Slightly facies. marginal-lake and alluvial-lake the forming margins close the to ticles retained par Coarser drilled). were boreholes (where the lake ofthe part central the in particularly decreased, material terrigenous grained coarse- and of medium- input the and place took transgression deposition After of the BCC the lake was completely formed. The Unit B(lacustrinephase) al., et 1971). (FILIPOVIĆ Milanovac Gornji al., et (SANT Popovac Lake 2017) the in and to according e.g. data from the Basic Geological Map, sheet basins, other in succession lithological similar to according supposed be may age Miocene Althoughthefilling. arefossil theirremains earlylacking, Middle in lake as such processes, authigenic than rapid more was BCC tion (alluvial flows orlahars). deposition Subsidence during of the ference of and lake toreflectsmargins adifferent way ofcontribu the lithologicalof dif Sedimentology BCC confirms additionally facies. alluvial to corresponds BCC the sedimentology, of terms In basin. the into brought suddenly being as lahars, likely cally flow, lo debris of elements displays latter The rocks. caniclastic vol re-deposited is part upper the and completelydifferentiated) (not system alluvial an to VA-1 in corresponds unit lower The 12 In the middle part of the basin the finest-grained, silty and and silty finest-grained, the basin the of part middle the In (1) The upward of decrease and dimension ofgrain-size sand ( unit This marlstone and fine-grained clastites) fine-grained and marlstone includes includes ------and prodelta and it was intermittently flooded by a lake (construc lake a by flooded phase). destructive tive and intermittently was it and prodelta and front delta plain, a delta well-evolved comprised with Delta delta. facies i.e. model of a deltaic alluvial-lake deposition, resembling basin the into sand) and (gravel compounds terrigenous grained coarser- of amounts enormous brought South the from tems sys Alluvial margins. both from material received unit this of rocks and flysch clastites. flysch and clastites. rocks felsic from of fragments abundance variable the to due correlate not do VA-21994). values In (CULLERS, these processes dary secon- by notseverely is affected distribution its as composition rock source for inferring REE useful most the be to sidered 1994). (CULLERS, element Sc)nites (togetheris with This con mi- accessory certain of (e.g.nerals monazite) zircon, rocks, source in i.e.high-silica gra- concentration the to due be could Table) 2011). al., et (KRSTIĆ Village Jelovik in interbeds coaly in uranium of concentrations the in increase anoted was there basin onica (Fig. 5c).granites It should be the in Valjevo-Mithat mentioned and Bukulja the from derived of material contribution increased the with VA-1 VA-3agreement in Na+K of and in is abundance an and conditions reduced Fig. (recall the 4c). matter of organic periodically suggests flora) The presence of andsulfide (i.e.carbonized mineralization pyrite 1978). (WEDEPOHL, pH higher at Ba2+ adsorb which matter, presence of hydrous Mn and Fe oxides, clay and minerals organic VA-1 in the with VA-2marlstones Na+Kand in agreement in is of contents uniform almost the to respect in Ba+Srof increase (volcanic margin rocks; Fig. the southern from 5b).material The of presence the of K+ to due Ba2+ by substitution the by plained VA-2 Na+Kin (0.6–1.1to marlstones respect in ex %)be could inter least at thewas in ppm) basin Ba+Sr (500–2000 of the Contents stratified. facies, mittently intrabasinal truly first the was and fine-grained clastites fine-grained and termed is unit recognized youngest The Unit C(alluvial-lacustrinephase) exclusive origin from the northern margin, exclusive i.e. margin, from origin the from metamorphic northern and gravels sands ofin VA-1 dominating and VA-2 imply almost Constituents unit. same the from internally mobilized probably tites) shows that the former sands were cemented by calcite, most clas fine-grained and (marlstone B unit from originating stone, phyric and granitoid magmas (PRELEVIĆ et al., et 2004). (PRELEVIĆ magmas granitoid and phyric lampro between interaction mentioned already the with sistent con is interpretation an Such1997). al., et 1986; THOMPSON mantle lithospheric (JAQUESsubcontinental tion-enriched et al., asubduc in Ti-bear by magmas formed have to been and thought is mica ing Ba moderate to low A 1996). PENCZAK, & SHAW 1982; (e.g. HENDERSON, least at biotite Ba-bearing with rocks volcanic or lamprophyres from of fragments amount creasing in an VA-2 suggest in Ba+Srcan of increase slight 1994). The of higher concentrations Ba than the low-silica rocks (CULLERS, contain to tend that rocks involvement more or of Ca2+ granitic substitutes Ba2+ where calcite i.e. siltstones, calcite-clayey of Table).ppm; Supplementary This reflects either different Sr-809.63 amount ppm, Ba-115.20 average unit VA-1 given in (in highest the is clastites fine-grained in strontium and barium of contents 5a). (Fig.The included were Table).VA-1 margins In tary both VA-2 in wellas as area, (up 8.43%; source to the as Supplemen (3) The final lithofacies ( lithofacies final (3) The of (3–16.7Th concentrations high The ppm; Supplementary increase the with of Th+U increase progressive but slight A (2) During deposition of the the of deposition (2)During . Intraformational fragments of sand fragments . Intraformational fine-grained clastites and sands and clastites fine-grained marlstone marlstone sand, gravel, sandstone sandstone gravel, sand, Geologia Croatica 72/1 lithofacies, which which lithofacies, - - ) ------

Geologia Croatica - - 13 The highest boron contents usually occur insedimentary of yellowish-red coarse-grainedof gravels. The colour-variations throughout the unit reflect aoxygen-rich shallow, environment and the gradual closure the basin. of The presence a palaeosol of finer-grainedcarbonateconcretionsin of levels twohorizon with clastites indicates periodic subaerial conditions and supports the previous part The conclusion. lower the unit of includes alluvial- lacustrineintervals presencewithnotablethe (polymict gravels) fragmentsof frommetamorphic rocks. beds associated with activity, volcanic as in the volcaniclastic rocks (unit B, in interval VA-1 ppm; values 170–199m; 87–172 In contrast,Supplementary the Table). tuffaceous VA-2 rocks in display similar behaviour– uniform as B and slight sedimentary increased Li (Fig. 5 Most d, the of e). bo rocks inron sands content of and sandstones VA-1 can and be attributed to the pres VA-3 - - - - Sands and gravels comprise this unit intoo. column VA-3, Figure 5. Distribution of selected in distinguished lithofacies. elements Figure jkovac massifs exposedto erosion. torelative other minerals suggests that all the analyzed sand The high percentagestones are ofmost likely quartzfirst cycle sediments,i.e. productsof 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 sedimentology of these sediments are considered to repre sent alluvial-lacustrine facies. Local occurrences lenticular of bodies sand of or gravel on a metre to decametre scale resemble the channel forms which particles by were distributed. Their boundary with the previous unit is marked by a sequence andgranitoid rocks. This couldsouth be and uplift the northern of a consequence area leaving the Bukulja and Bra of tilting to the Marićet al.: History ofthe Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data Geologia Croatica the age of the studied lacustrine sediments. lacustrine age of studied the the (SANT al., et 2017). Paratethys of Central the to Stage the Early which Badenian corresponds in the Langhian, the development of the around 14.5 Serbian lakes started Ma ago, that Popovacreflect Lake for obtained data new The water. rine when the Sarmatian Valjevo-Mionica basin was by ingressed ma Badenian/ Late before the ceased deposition that suggests sin et al., 2016). Belanovica the ba in sediments lack ofThe marine liest record of it dates back in the late Early Miocene (NEUBAUER water water of fresh presence but the sediments lake Belanovica the in ing (MAROVIĆ east) et al.,the 2007). basins Valjevo-Mionica the into divided (west)later (toBelanovica and but Ottnangian-Karpatian the during formed graben lanovica Valjevo-Mionica-Be The Badenian. Middle to Early sidered were age sediments generally con the lacustrine nian/Sarmatian tentatively correlated tentatively with correlated the Middle Miocene. Tuffaceous rocks margins. basin at the rocks of source the signatures inherited sediments Lake consideration. into taken be also should activity volcanic of influence The flows. alluvial of intensity and rate, erosion basement, of pre-Neogene by the palaeorelief controlled was data, petrographic and chemical integrated from (VA-3) area eastern laeosol development. The basin. the of to rise giving conditions pa- exposed to was subaerial frequently closure gradual the indicate t from flows The acidity. lake-water the increasing for sponsible re was itself which infilling, basin to volcanism synchronous the than more contributed margins both from flows alluvial The facies. open-lacustrine intrabasinal the to there contributing basin of the part deepest and central the in arrived clayeyand particles closetained to the silty whereas basin the margin, finest-grained, re facies marginal-lacustrine and alluvial-lacustrine The ditions. con subaerial to them exposing and sediments lake of the parts of deposition. onset for the responsible were South the from coming flows torrential occasionally and Alluvial South. the Slavkovicaof to mass volcanic Neogene the and ultramafics Jurassic flysch, byAlbian-Cenomanian covered area broad a and North, the to rocks) metamorphic low-grade and (granitoid Mountains Bukulja and Brajkovac the between area the Neogene in the developed during Lake Belanovica The CONCLUSIONS 6. below it. concordantly lie they as Badenian, Middle marine the olderare than sediments Lake Serbian local The in publications. presented oronly scarce been recently age have until their ding regar- Serbia, in sediments of on lacustrine availability The data Age environment. fresh-water or lacustrine a reflects B uniform 1970).and Na low The involved(HARDER, rock of type the on primarily depends sediment in content its as ments, (saline) of environ indicator marine or geochemical fresh-water Boron, fractions. togetherfinest with issodium considered a good the in found are values highest the thus size, grain versely with in varies concentration its sediments finer-grained 1970). In (HARDER, clayof proportions higher to or tourmaline of ence 14 he single northern margin into the western area (VA-1VA-2) area and western the into margin northern single he The The analysis fission-track is useful potentially forunraveling The whole succession, lacking age-diagnostic fossils, was was fossils, age-diagnostic lacking wholeThe succession, inferred evolution basin, of Belanovica the three-stage The The lake bottom dipped southeast periodically revealing revealing periodically southeast dipped bottom lake The Bade Late of deposits marine by overlain also are they As Melanopsis support their Middle Miocene age, as the ear the as age, Miocene Middle their support

Index fossils are lack fossils are Index

------

FILIPOVIĆ, I., PAVLOVIĆ, Z., MARKOVIĆ, B., RODIN, V., MARKOVIĆ, O., V.,MARKOVIĆ, RODIN, B., PAVLOVIĆ,MARKOVIĆ, I., Z., FILIPOVIĆ, (2000): S. JUGGINS, & J.E. ALMENDINGER, S.C., FRITZ, D.R., ENGSTROM, DOLIĆ, D. (1986): Neki aktuelni problemi daljeg istraživanja tercijarnih naslaga SR Sr of Reconstruction (1993): S. BJORCK, & DIGERFELDT,J.E. G., ALMENDINGER, CVETKOVIĆ, V., POLI, G. & PRELEVIĆ, D. (2001): Eruptive history and low-pressure PÉCSKAY,KORONEOS, A., G., CHRISTOFIDES, V., Z., G., CVETKOVIĆ, POLI, CVETKOVIĆ, V., PRELEVIĆ, D. & PÉCSKAY, Z. (2000): Lamprophyric rocks of the CULLERS, R.L. & PODKOVYROV, V.N. (2002): The source and origin of terrigenous CULLERS, R.L., BARRETT, T., CARLSON, R. & ROBINSON, B. (1987): Rare earth CULLERS, R.L. (2000): The geochemistry of shales, siltstones and sandstones of Penn- of fractions size in rocks source of signature chemical The (1994): R.L. CULLERS, COX, P.A. (1995): The ElementsonEarth.–OxfordUniversityPress,287p. COHEN, A.S. (2003). Palaeolimnology: the history and evolution of lake systems.– Ox- BINFORD, M.W. & DEEVEY, E.S. (1983): Palaeolimnology: an historical perspective PAVLOVIĆ,M., EREMIJA, M., ANĐELKOVIĆ, MITRO- M., & J. ANĐELKOVIĆ, SANT,N., ANDRIĊ, MATENCO,K., O., MANDIĆ, L., TOMLJENOVIĆ, PAVE-B., ALMENDINGER, J.E. (1993): A groundwater model to explain past lake levels at Park- REFERENCES analysis. palaeontological for(Belgrade) providing RUNDIĆ Ljupko to indebted Weare acknowledged. gratefully viewer for revision ofcareful their effortTheir is the manuscript. re unknown an and (Vienna) Oleg MANDIĆ reviewers journal the thank to like Wewould results. research their of part a lish d.o.o.” Balkans pub to for “Ultra permission company the from No176019. Project ence, colleagues to indebted are authors The This research has by been ofsupported the Serbian Sci Ministry ACKNOWLEDGMENT nology. as diments, well thermochro as the low-temperature fission-track se- lake age of the these for unraveling hold potential could the 000, GornjiMilanovac sheet].–Saveznigeološki zavod, Beograd. [Basic GeologicMap of SFRY 1:100 L34-137 Milanovac Gornji list 1:100.000, GAGIĆ, N., ATIN, B.&MILIĆEVIĆ, M.(1971):OsnovnageološkakartaSFRJ rain.– Nature,408,161–166.doi:10.1038/35041500 ter deglaciated recently in evolution lake during trends biological and Chemical XI KongresgeologaJugoslavije,2,61–68, . bije [Some actual problems forfurther studies of Tertiary deposits in SRSerbia ].– ecology, 94,99–118. doi:10.1016/0031-0182(92)90115-L sandplain, west-central Minnesota.– Palaeogeography, Palaeoclimatology, Palaeo- past lake levels and their relation to groundwater hydrology in the Parkers Prairic kan Peninsula, Acta Vulcanologica, 13/(1/2),127–143. & VASELLI,H. DOWNES, (eds.): TertiaryBal- O. Dinarides the in magmatism In: Serbia).– (Central complex eruptive Borač Miocene Early the of evolution doi: 10.1127/0935-1221/2007/0019-1736 matism in the northern Dinarides.– European Journal of Mineralogy, 19, 513–532. Bukulja (central Serbia): evidence for Pannonian extension-related granitoid mag- Mt. of rocks granitoid Miocene V.ERIĆ, The (2007): & K. RESIMIĆ-ŠARIĆ, garica, 43/1,25–41.ISSN0236-5278 Yugoslavia).–Serbia, Hun (central Geologica complex Acta eruptive Miocene brian Research,117, 157–183.doi:10.1016/S0301-9268(02)00079-7 Precam- Russia.– southern group, UI Mesoproterozoic the in rocks sedimentary 10.1016/0009-2541(87)90167-7 doi: 275–297. 63, Geol., Chem. USA.– Colorado, WetMountains, the in study case a sediment: stream and soil Holocene in changes mineralogic and element morphic studies.–Lithos,51,181–203.doi:10.1016/S0024-4937(99)00063-8 meta- and provenance for Implications USA: Colorado, age, sylvanian-Permian 2541(94)90074-4 10.1016/0009- doi: Geology,327–343. 113,Chemical USA.– Colorado, region, Holocene stream sediment derived from metamorphic rocks in the Wet Mountains ford UniversityPress,New York. nurev.es.14.110183.001351 on lacustrine ecosystems.– Ann. Rev. Ecol. Syst., 14/1, 255–286. doi: 10.1146/an- Serbia, Tertiary –inSerbian](ed.M. Anđelković), 237p.,Beograd. VIĆ-PETROVIĆ, J. (1991): Paleogeografija Srbije, Tercijar [Palaeogeography of doi: 10.1016/j.marpetgeo.2017.02.024 study of the Sarajevo-Zenica Basin.– Marine and Petroleum Geology, 83, 305–332. the from Inferences basins: extensional asymmetric in sedimentation and tonics LIĆ, D, HRVATOVIĆ, H., DEMIR, V. & OOMS, J. (2017): The link between tec- 10.1177/ doi: 105–115. 3, Holocene, 095968369300300202 USA. Minnesota, Prairie, ers Geologia Croatica 72/1 ------Geologia Croatica

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Oceanography, Limnology and 10.1007/s10933-007-9134-x doi: 39, 5–16. Springer. laeolimnology, of Holocene clays of the Rhine and Mouse rivers in the central-eastern Nether HICKMAN, M. & WHITE, J.M. (1989): Late Quaternary palaeoenvironment of Spring of palaeoenvironment Quaternary Late (1989): J.M. WHITE, & M. HICKMAN, A.L., LEWIS, JAQUES, C.D. & SMITH, C.B. (1986): The kimberlites and lamproites Kontinentalno-jezersko (1992): N. ZUPANČIČ, & D. GRGUROVIĆ, O., JOVANOVIĆ, granitic (1994): S. Tertiary rocks & CVETKOVIĆ, V. KARAMATA, KNEŽEVIĆ, V., KRSTIĆ, N., N., DUMURDŽANOV, OLUJIĆ, J., VUJNOVIĆ, L. & JANKOVIĆ- lakes Miocene Lower (2003): E. BODOR, & G. JOVANOVIĆ, L., SAVIĆ, N., KRSTIĆ, Balkan the on lakes Neogene The (2012): G. JOVANOVIĆ, & L. SAVIĆ, N., KRSTIĆ, (1999): M. PETROVIĆ, & V. CVETKOVIĆ, S., STANIĆ, N., KRSTIĆ, M., MAROVIĆ, MAROVIĆ, M., TOLJIĆ, M., RUNDIĆ, LJ. & MILIVOJEVIĆ, J. (2007): Neoalpine L. & MATENCO, RADIVOJEVIC, D. (2012): On the formation and evolution of the fluvial Quaternary of Geochemistry (1990): S.B. KROONENBERG, & M.L. MOURA, lacus- Phytogenic (1997): N. VASIĆ, & J. DJURDJEVIĆ-COLSON, J., OBRADOVIĆ, HUISMAN, D.J. & KIDEN, P. (1997): The geochemical record of Upper Cenozoic sed- Cenozoic Upper of record geochemical The (1997): P. KIDEN, & D.J. HUISMAN, HARZHAUSER, HARZHAUSER, M. & MANDIĆ, O. (2008): Neogene lake systems of Central and Sedimen analysis.– facies in tool a as sediments of content Boron (1970): H. HARDER, HENDE Marićet al.: History ofthe Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data - clas rock sedimentary Detrital (1970): D.W. LEWIS, & P.B. ANDREWS, R.L., FOLK, America.– North in change climatic of records Palaeolimnological (1996): C.S. FRITZ, of Pa- history from lake sediments.– Journal Deciphering climatic FRITZ, C.S. (2008): Geochemistry (1993): H. WIJCK, VAN & S.B. KROONENBERG, A.L., HAKSTEGE, Geologia Croatica Contents of indicative chemical elements in the Belanovica basin lake deposits in ppm or in %, (as indicated), including detection rocks. volcaniclastic detection considers area (A, C). text Band Shaded the including limit(s). in as marked indicated), Lithofacies(as are %, in or ppm in deposits lake basin Belanovica the in elements chemical indicative of Contents TableSupplementary 16 VA-1 A Volc. B from –to (inm): Interval limit(s) 207.33 206.33 205.33 204.33 203.33 163.00 202.33 162.00 201.33 158.93 200.33 153.04 199.33 147.20 198.33 146.20 197.33 141.98 196.33 139.70 195.33 138.70 194.33 127.80 193.33 125.30 192.33 121.20 191.33 117.30 190.33 112.70 189.33 103.70 188.33 216.00 187.33 215.00 186.33 212.23 185.33 211.33 184.33 210.33 181.10 209.33 171.10 208.33 99.50 94.70 90.20 85.70 81.30 78.00 69.85 65.40 208.33 207.33 206.33 205.33 204.33 203.33 163.00 202.33 159.93 201.33 154.04 200.33 148.20 199.33 147.20 198.33 142.98 197.33 140.70 196.33 139.70 195.33 129.80 194.33 126.30 193.33 122.20 192.33 118.30 191.33 113.70 190.33 104.70 189.33 100.50 217.00 188.33 216.00 187.33 213.13 186.33 212.23 185.33 211.33 182.10 210.33 172.10 209.33 164.00 95.70 91.20 86.70 82.30 79.00 70.85 66.40 779.00 713.00 936.00 532.00 903.00 615.00 153.00 851.00 826.00 357.00 149.00 349.00 357.00 135.00 351.00 492.00 450.00 580.00 686.00 565.00 275.00 106.00 658.00 791.00 700.00 747.00 742.00 663.00 760.00 1ppm- (ppm) 95.50 59.70 89.90 92.50 94.10 33.40 69.40 34.70 91.00 52.60 44.60 55.10 46.40 40.20 29.00 63.50 40.30 88.10 29.60 49.30 50.80 27.90 55.20 57.10 49.00 59.90 41.50 1% Cr

1046.00 1042.00 1056.00 1245.00 1429.00 1185.00 1004.00 969.00 745.00 983.00 211.00 945.00 138.00 843.00 529.00 177.00 509.00 107.00 425.00 163.00 520.00 140.00 583.00 146.00 568.00 704.00 760.00 566.00 131.00 302.00 223.00 139.00 913.00 988.00 939.00 1ppm- (ppm) 84.80 57.90 95.40 75.90 96.40 77.40 67.30 75.30 51.30 40.20 78.70 63.60 41.10 96.60 78.80 36.00 93.30 86.20 82.20 80.80 65.30 1% Ni

0.01%- 15% 5.38 5.79 6.23 7.82 5.96 7.33 1.68 5.29 1.50 5.56 1.77 5.12 4.61 6.49 3.64 8.05 1.61 6.00 1.67 3.70 1.37 4.23 0.86 6.14 1.21 5.88 0.84 5.29 1.39 3.23 1.21 2.20 1.06 0.80 1.01 7.94 0.93 0.64 7.57 0.90 0.97 6.71 1.74 0.66 6.08 1.15 1.18 5.76 0.70 1.30 6.26 0.84 1.28 5.65 1.10 1.14 Mg (%)

5ppm- 108.40 119.80 107.80 108.20 106.20 216.80 103.20 159.20 121.40 151.40 137.80 178.20 228.20 141.20 173.00 207.20 179.80 282.80 122.60 121.40 120.60 150.60 128.80 141.60 120.60 113.00 115.80 113.40 108.40 100.80 124.80 115.40 135.60 147.60 150.60 112.20 (ppm) 99.60 85.80 91.40 42.60 50.60 55.80 50.20 48.80 45.40 78.20 82.40 77.40 88.80 89.20 97.60 89.80 81.20 90.40 98.20 99.80 1% Ba

1648.00 1213.00 1885.00 1914.00 1140.00 1379.00 1017.00 1666.00 0.5ppm- 542.00 583.00 493.00 552.00 379.00 436.00 203.00 412.00 365.00 222.00 447.00 305.00 996.00 317.00 713.00 277.00 135.00 156.00 691.00 268.00 272.00 246.00 237.00 261.00 466.00 187.00 356.00 321.00 261.00 176.00 306.00 141.00 229.00 336.00 256.00 129.00 501.00 296.00 358.00 592.00 170.00 451.00 721.00 208.00 515.00 583.00 252.00 220.00 (ppm) 0.1% Sr

0.1ppm- (ppm) 30.00 13.60 17.80 11.30 18.10 19.70 21.00 1000 2.90 3.50 2.50 1.90 2.40 2.90 7.60 3.30 6.00 3.20 4.10 2.50 6.80 2.30 5.20 6.20 2.80 5.60 3.30 6.20 2.80 4.90 2.50 5.60 2.80 4.50 4.90 6.20 6.80 5.50 9.20 6.00 5.70 2.50 8.90 3.90 4.00 5.30 2.80 9.90 4.70 2.10 6.20 2.30 8.60 2.50 8.30 2.40 6.80 Th

0.5ppm- 0.5ppm- 12.30 10.90 (ppm) 13.10 11.90 10.00 10.30 10.90 10.10 11.60 13.10 11.20 12.20 11.70 10.20 11.60 8.20 9.60 5.40 4.00 2.60 4.40 6.50 3.20 6.80 3.90 6.00 3.30 6.60 3.40 7.00 3.00 8.10 3.50 2.60 7.70 4.30 6.30 3.80 5.50 5.90 4.40 5.90 3.70 4.00 7.30 6.00 6.30 5.00 4.00 7.30 3.70 8.70 4.40 8.10 5.00 7.20 1% Sc

Th/Sc 0.32 0.19 0.23 0.20 0.30 1.40 0.33 1.50 0.31 1.57 0.29 1.50 0.35 1.57 0.44 1.54 0.46 1.75 0.50 1.82 0.40 1.63 0.31 1.60 0.27 1.73 0.63 1.44 1.08 1.44 1.67 1.01 3.09 0.96 0.21 2.41 0.97 0.30 2.43 0.88 0.25 1.57 0.94 0.17 2.82 0.85 0.19 4.90 0.99 0.24 4.47 1.02 0.21 4.20 0.94 0.23

0.05ppm- (ppm) 0.21 0.58 0.47 0.24 0.27 2.39 0.26 2.04 0.36 0.79 2.95 2.25 3.45 1.92 0.31 1.23 0.30 2.35 0.62 2.55 0.65 1.15 0.32 1.85 0.24 2.22 0.32 1.86 0.54 2.56 1.62 1.12 0.57 1.20 0.29 0.51 0.82 0.25 3.32 1.01 0.57 0.86 0.83 2.27 4.51 1.32 0.50 1.92 1.61 0.27 3.25 1.77 0.26 2.19 1.27 0.23 1% U

0.01%- 15% 0.24 0.28 0.19 0.24 0.23 0.10 0.24 0.14 0.22 0.08 0.09 0.11 0.10 0.11 0.11 0.09 0.09 0.10 0.09 0.11 0.09 0.07 0.15 0.07 0.17 0.07 0.14 0.07 0.18 0.06 0.17 0.04 0.26 0.03 0.64 0.35 0.03 0.65 0.19 0.03 0.43 0.20 0.04 0.32 0.15 0.03 0.33 0.20 0.02 0.25 0.21 0.03 0.24 0.25 0.02 0.26 (%) Na

0.01%- 15% 0.33 0.43 0.34 0.36 0.32 0.44 0.35 0.31 0.59 0.20 0.33 0.30 0.35 0.24 0.33 0.22 0.31 0.21 0.59 0.26 0.57 0.18 0.28 0.18 0.27 0.16 0.25 0.23 0.50 0.22 0.39 0.28 0.42 0.23 0.20 0.41 0.16 0.19 0.60 0.27 0.31 0.58 0.24 0.29 0.72 0.34 0.27 0.42 0.34 0.36 0.52 0.37 0.32 0.65 0.33 0.37 (%) K

Geologia Croatica 72/1 10ppm-1% 21.00 28.00 (ppm) 23.00 26.00 30.00 36.00 43.00 59.00 67.00 58.00 87.00 90.00 28.00 85.00 33.00 12.00 14.00 18.00 26.00 20.00 24.00 10.00 11.00 12.00 13.00 14.00 16.00 36.00 25.00 34.00 18.00 43.00 13.00 17.00 43.00 11.00 15.00 40.00 12.00 30.00 38.00 11.00 28.00 62.00 13.00 23.00 38.00 15.00 25.00 38.00 20.00 26.00 64.00 20.00 27.00 5.00 B

201.00 203.00 161.00 148.00 126.00 1ppm- 68.10 80.20 (ppm) 55.20 79.90 65.70 53.50 45.70 48.60 38.90 34.60 39.90 68.60 32.90 51.80 16.60 51.50 28.70 55.20 24.00 53.10 17.80 31.80 21.00 37.70 17.70 27.20 19.80 45.20 21.20 50.80 35.90 46.00 18.10 43.60 22.30 23.00 25.50 41.10 46.00 28.30 23.10 49.50 13.00 53.30 83.40 18.70 57.80 80.90 35.80 49.80 76.90 1% Li

Geologia Croatica

17

Li 1% 85.10 96.30 84.80 65.70 60.50 85.80 79.10 57.50 61.70 93.80 48.30 63.20 73.60 53.00 84.20 67.50 76.70 39.40 90.00 78.70 75.10 73.50 64.70 47.40 86.30 41.10 45.40 50.10 72.80 81.30 86.30 64.00 66.50 41.80 64.40 49.50 15.70 35.90 43.50 39.50 47.50 26.30 81.00 35.60 34.40 36.40 46.10 (ppm) 1ppm- 100.00 142.00 114.00 103.00 127.00 112.00 152.00 175.00 177.00 143.00 131.00 130.00

B 51.00 64.00 73.00 60.00 57.00 26.00 29.00 31.00 25.00 21.00 32.00 57.00 44.00 39.00 75.00 50.00 22.00 15.00 14.00 15.00 36.00 70.00 56.00 18.00 31.00 31.00 37.00 56.00 14.00 14.00 15.00 20.00 15.00 34.00 20.00 15.00 27.00 16.00 26.00 23.00 27.00 22.00 28.00 24.00 26.00 41.00 33.00 88.00 81.00 76.00 62.00 79.00 62.00 56.00 56.00 71.00 (ppm) 100.00 172.00 117.00 10ppm-1%

K 0.46 0.66 0.84 0.66 0.50 0.43 0.40 0.37 0.42 0.35 0.53 0.67 1.06 0.39 (%) 0.37 1.30 0.68 0.16 0.13 0.15 0.13 0.40 0.74 0.71 0.47 0.42 0.47 0.30 0.74 0.41 0.31 0.17 0.27 0.30 0.21 0.24 0.21 0.22 0.16 0.21 0.22 0.16 0.20 0.17 0.25 0.11 0.25 0.10 0.07 0.11 0.09 0.11 0.11 0.11 0.10 0.10 0.09 0.09 0.12 15% 0.01%-

0.2 0.5 Na 0.43 0.43 0.22 0.28 0.33 0.24 0.29 0.22 0.27 0.23 0.34 0.22 0.25 0.17 0.20 0.21 0.22 0.34 0.38 0.27 0.35 (%) 0.18 0.22 0.20 0.56 0.17 0.57 0.23 0.02 0.06 0.51 0.05 0.07 0.59 0.08 0.07 0.59 0.10 0.15 0.42 0.12 0.41 0.14 0.52 0.13 0.55 0.47 0.65 0.47 0.64 0.62 0.65 0.38 0.53 0.48 0.49 0.63 15% 0.01%-

U 39.6 19.8 10.5 4.81 7.48 1.11 1.64 4.54 7.42 1.86 3.52 2.94 8.16 5.43 13.3 3.33 6.31 1% 12.1 1.74 1.16 0.81 7.19 3.40 2.82 2.03 1.95 3.25 0.87 22.4 1.54 0.97 0.29 1.59 1.46 0.32 2.96 2.23 0.29 0.99 0.30 1.06 0.22 0.79 0.32 1.35 3.54 1.26 2.05 0.12 0.17 0.20 0.16 0.20 0.15 0.21 0.14 0.15 0.15 0.14 (ppm) 0.05ppm-

2.40 1.68 1.60 0.97 1.03 0.90 0.57 0.93 0.95 0.18 1.67 1.42 1.38 1.27 1.06 1.37 1.36 1.86 1.30 1.34 1.35 0.91 0.97 0.92 2.69 1.14 1.83 0.57 2.46 1.02 1.14 0.16 1.33 1.30 0.26 1.36 0.09 0.26 0.53 0.22 0.56 0.20 0.52 0.22 0.67 0.19 0.65 0.18 0.14 0.20 0.16 0.17 0.78 0.30 0.16 0.15 0.15 0.15 0.15 Th/Sc

11 10 9.7 8.2 8.1 6.8 4.5 5.2 3.6 6.3 8.9 8.5 8.3 6.7 Sc 4.20 3.00 3.50 4.30 8.20 6.60 8.20 6.20 9.60 5.00 6.20 4.00 5.80 8.90 6.40 3.00 2.30 2.80 2.80 5.30 3.10 3.40 1% 10.50 11.40 10.00 10.10 12.50 12.20 14.80 12.40 11.10 10.20 12.10 14.60 12.50 12.50 13.80 13.20 13.50 12.30 12.00 12.50 12.60 11.50 14.00 (ppm) 0.5ppm-

Th 7.70 7.40 5.90 6.90 8.00 6.40 7.40 6.00 5.80 9.40 7.10 8.60 5.10 6.20 8.70 5.60 3.00 3.80 3.80 4.80 9.80 9.00 5.10 9.40 8.90 6.30 8.30 7.80 2.00 5.60 6.80 3.20 4.90 6.80 3.90 4.80 2.80 5.60 2.20 4.50 2.30 5.60 2.40 4.40 2.60 1.80 2.50 2.20 2.30 2.40 1.80 3.60 2.00 1.90 1.80 2.20 1000 10.90 16.70 12.20 (ppm) 0.1ppm-

Sr 0.1% 917.00 717.00 384.00 576.00 317.00 419.00 641.00 868.00 781.00 588.00 850.00 516.00 175.00 208.00 218.00 800.00 361.00 267.00 149.00 358.00 283.00 353.00 (ppm) 214.00 416.00 363.00 852.00 284.00 607.00 296.00 335.00 426.00 405.00 263.00 330.00 283.00 456.00 264.00 917.00 195.00 281.00 281.00 146.00 243.00 195.00 279.00 184.00 202.00 174.00 208.00 249.00 1240.00 1888.00 1820.00 1214.00 1564.00 1760.00 1111.00 0.5ppm- 1203.00 1787.00

Ba 92.80 64.60 62.60 36.60 26.20 58.00 52.60 62.20 91.80 1% 94.20 54.20 82.80 49.80 68.40 66.20 75.20 34.60 47.60 80.00 85.00 81.20 78.00 81.60 82.80 75.20 53.20 67.00 65.40 64.00 60.40 873.00 147.40 352.80 173.00 141.80 226.00 246.80 315.20 445.00 122.80 248.40 120.00 328.20 321.00 227.40 (ppm) 102.00 197.80 225.20 114.20 272.20 124.60 121.20 117.00 117.80 114.80 133.60 424.00 109.00 5ppm- 2891.40

2.14 3.26 5.74 3.07 4.92 6.39 2.71 5.68 8.29 4.13 3.52 2.51 4.71 5.09 7.09 7.64 5.36 7.36 1.31 0.78 0.98 1.09 8.43 5.24 3.49 1.13 3.59 1.67 6.07 (%) Mg 1.23 3.12 6.94 1.20 1.74 7.54 1.17 3.32 7.88 4.95 7.42 6.08 7.56 4.84 7.87 4.47 9.02 3.43 9.74 7.94 9.14 8.15 9.18 9.40 7.90 9.95 8.40 8.20 8.30 9.08 15% 0.01%-

Ni 8.80 1% 70.70 83.20 88.70 49.20 26.40 52.70 46.10 18.60 46.40 94.40 (ppm) 1ppm- 102.00 325.00 271.00 295.00 502.00 241.00 482.00 405.00 269.00 142.00 221.00 131.00 209.00 274.00 178.00 149.00 446.00 445.00 321.00 633.00 306.00 990.00 129.00 112.00 337.00 533.00 667.00 985.00 510.00 923.00 460.00 361.00 652.00 1162.00 1216.00 1051.00 1050.00 1215.00 1266.00 1128.00 1231.00 1068.00 1116.00 1200.00 1083.00 1205.00 1036.00 1135.00

Cr 1% 69.10 67.50 82.90 70.70 35.40 21.60 42.50 33.60 11.20 16.70 37.00 75.80 82.70 (ppm) 1ppm- 418.00 333.00 369.00 649.00 296.00 600.00 527.00 303.00 129.00 217.00 109.00 199.00 315.00 179.00 121.00 537.00 507.00 367.00 822.00 415.00 929.00 118.00 749.00 435.00 908.00 766.00 707.00 920.00 731.00 746.00 597.00 602.00 766.00 454.00 992.00 816.00 740.00 934.00 775.00 838.00 845.00 406.00 786.00 867.00 763.00 900.00 52.00 76.80 66.10 78.50 72.00 85.50 96.00 225.10 224.20 223.30 222.40 219.40 215.10 210.50 204.00 202.50 196.00 194.20 192.00 183.70 179.70 169.65 164.60 163.00 159.10 153.10 152.50 151.50 150.50 147.00 137.90 131.50 231.00 129.00 230.20 121.27 218.00 219.00 220.00 221.00 103.00 222.00 109.50 223.00 113.00 233.20 118.00 243.00 251.50 257.00 268.30 279.00 291.20 301.20 310.50 323.00 328.00 329.00 333.00 51.00 65.15 77.50 71.00 84.50 76.15 95.00 224.20 223.30 222.40 221.50 218.30 214.10 209.50 202.50 201.70 195.00 193.20 191.00 182.70 178.50 168.75 163.90 162.00 158.30 152.50 151.50 150.50 149.50 146.00 136.90 130.60 230.20 128.00 229.05 120.10 217.00 218.00 219.00 220.00 102.00 221.00 108.50 222.00 112.00 232.00 117.00 242.00 250.50 256.00 267.20 278.00 290.20 300.00 309.50 322.00 327.00 328.00 332.00 limit(s) Interval (in m): – to from

C B VA-2 Marićet al.: History ofthe Belanovica (Serbia) Neogene lake basin inferred from petrological and geochemical data Geologia Croatica 18 VA-3 A B C A from –to (inm): Interval limit(s) 272.00 257.30 231.30 229.40 225.90 219.00 209.50 202.70 199.30 194.00 190.70 186.78 180.50 173.20 168.20 161.20 154.70 136.70 128.20 118.70 109.70 105.20 231.00 231.80 240.00 247.30 252.00 258.20 259.20 270.50 273.50 277.60 287.00 293.00 96.20 93.20 89.50 89.50 87.50 87.50 84.50 84.50 273.00 258.30 232.30 230.40 226.90 220.00 210.50 203.70 200.30 195.00 191.70 187.28 181.50 174.20 169.20 162.20 155.70 137.70 129.20 119.70 110.70 106.20 231.80 232.45 241.00 248.50 253.20 259.20 260.20 271.50 274.50 278.60 288.00 294.00 97.20 94.20 90.50 90.50 88.50 88.50 85.50 85.50 428.00 400.00 218.00 160.00 156.00 101.00 107.00 213.00 357.00 111.00 247.00 1ppm- 53.10 71.70 47.20 52.50 28.10 49.50 68.80 39.10 18.60 35.40 24.90 22.00 15.30 23.80 32.90 36.20 39.20 51.60 51.60 19.00 19.00 32.40 32.40 (ppm) 13.80 79.10 64.80 75.30 10.60 8.50 9.80 9.40 1% Cr

391.00 338.00 215.00 220.00 197.00 146.00 131.00 120.00 126.00 199.00 294.00 128.00 117.00 105.00 1ppm- 79.90 84.80 97.20 51.60 90.00 77.50 25.10 54.20 37.90 32.40 24.80 32.90 47.40 49.30 50.00 79.10 79.10 21.80 21.80 43.90 43.90 (ppm) 15.40 79.00 34.50 5.60 5.20 4.40 4.40 1% Ni

0.01%- 15% 2.95 3.68 3.67 2.03 2.16 1.48 1.54 1.28 1.49 1.04 1.25 0.71 0.94 1.39 1.16 0.38 1.00 0.82 0.66 0.32 0.76 1.10 1.04 1.12 1.14 1.14 0.47 0.47 0.93 0.93 1.48 2.30 2.01 2.42 1.40 1.13 1.10 0.98 0.97 Mg 0.54 0.58 0.55 (%)

5ppm- 103.80 110.00 125.40 192.20 117.00 123.00 594.00 246.60 192.40 120.00 119.20 119.20 360.20 453.60 178.60 114.80 115.20 100.20 (ppm) 40.60 69.00 56.00 72.40 76.00 72.00 39.80 62.80 64.40 68.80 30.00 81.60 86.80 92.60 80.00 80.00 96.40 96.40 42.40 37.00 48.80 63.20 52.80 82.20 1% Ba

1010.00 1569.00 1716.00 0.5ppm- 314.00 605.00 331.00 869.00 295.00 958.00 444.00 901.00 333.00 601.00 298.00 133.00 108.00 134.00 167.00 196.00 174.00 297.00 297.00 101.00 101.00 140.00 140.00 260.00 274.00 592.00 292.00 303.00 299.00 270.00 185.00 267.00 206.00 (ppm) 0.1% 86.40 93.80 35.50 65.50 58.00 56.00 Sr

0.1ppm- 10.30 13.70 (ppm) 14.70 11.50 11.00 12.70 16.00 14.00 17.80 24.30 29.80 28.90 28.50 1000 6.70 8.40 5.10 4.50 5.60 7.50 4.80 7.30 6.40 4.40 5.70 9.60 4.00 6.90 6.30 5.70 2.50 6.00 8.20 9.10 8.80 9.50 9.50 4.70 4.70 6.80 6.80 9.90 8.80 Th

0.5ppm- 0.5ppm- (ppm) 11.70 14.00 9.70 6.20 5.90 4.60 3.80 4.10 5.40 3.80 5.50 4.50 3.00 3.70 5.10 8.70 2.50 6.50 5.30 4.40 1.50 8.20 3.50 7.10 3.20 5.00 6.40 9.50 5.80 6.00 6.10 8.90 7.50 7.20 6.80 1% Sc 5.4 7.3 7.9 8.4 8.2 3.5 7.1

Th/Sc 1.06 1.08 1.42 1.10 1.18 1.36 1.38 1.26 1.32 1.42 4.53 1.19 1.11 1.10 1.60 1.06 1.18 1.29 1.11 1.12 1.15 1.04 1.15 1.16 1.34 1.34 0.95 0.95 1.04 0.84 1.64 2.75 2.67 1.79 2.19 2.66 2.29 1.27 2.73 4.01 4.19 0.95

0.05ppm- (ppm) 1.27 1.50 1.43 1.42 1.59 2.04 2.47 1.39 2.08 1.86 4.53 2.44 1.90 1.67 0.83 0.98 1.12 0.90 1.84 1.12 1.46 1.81 1.54 1.73 1.73 1.06 1.06 3.21 3.21 0.97 3.02 6.21 2.24 1.61 2.55 7.14 1.36 4.54 5.13 3.24 2.75 3.99 1% U

0.01%- 15% 0.16 0.11 0.11 0.10 0.08 0.09 0.07 0.06 0.08 0.07 0.03 0.06 0.04 0.03 0.03 0.02 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.03 0.03 0.03 0.03 0.02 0.02 0.18 0.64 0.73 0.19 0.26 0.26 0.28 0.27 0.40 0.33 0.17 0.18 0.21 (%) Na

0.01%- 15% 0.46 0.33 0.34 0.21 0.19 0.23 0.42 0.21 0.28 0.26 0.23 0.22 0.25 0.39 0.13 0.35 0.27 0.22 0.10 0.27 0.34 0.35 0.36 0.36 0.16 0.16 0.34 0.34 0.42 0.49 0.49 0.58 0.44 0.55 0.63 0.62 0.45 0.61 0.44 0.48 0.55 (%) K 0.4

Geologia Croatica 72/1 10ppm-1% 23.00 25.00 21.00 20.00 23.00 26.00 18.00 17.00 21.00 20.00 16.00 (ppm) 32.00 33.00 42.00 14.00 15.00 18.00 18.00 18.00 10.00 12.00 14.00 18.00 18.00 12.00 12.00 18.00 18.00 20.00 24.00 30.00 45.00 29.00 36.00 47.00 34.00 43.00 37.00 14.00 5.00 5.00 5.00 B

108.00 152.00 1ppm- 66.90 66.30 57.40 46.60 38.10 51.60 56.60 35.90 31.20 (ppm) 39.50 40.00 27.60 37.30 48.60 12.50 43.00 29.30 21.10 33.00 48.00 48.10 55.30 47.80 47.80 18.50 18.50 36.30 36.30 78.10 54.90 60.70 34.60 30.90 31.40 19.80 17.20 13.10 13.50 8.00 6.60 1% Li