Distribution of Major and Trace Elements in the Kovin Lignite (Serbia)

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Distribution of major and trace elements in the Kovin lignite (Serbia) Dragana Životić1, Olga Cvetković2, Predrag Vulić1, Ivan Gržetić3, Vladimir Simić1, Konstantin Ilijević3, Biljana Dojčinović2, Suzana Erić1, Bogdan Radić4, Sanja Stojadinović2 and Snežana Trifunović3

1 University of Belgrade, Faculty of Mining and Geology, Đušina 7, 11000 Belgrade, Serbia; (corresponding author: [email protected]; tel: +381 11 3219 251; fax: +381 11 3235 537) 2 Center of Chemistry, IChTM, Studentski trg 12–16, 11000 Belgrade, Serbia 3 University of Belgrade, Faculty of Chemistry, Studentski trg 12–16, 11000 Belgrade, Serbia 4 Kovin coal mine, Cara Lazara 85, 26220 Kovin, Serbia doi: 10.4154/gc.2019.06

Abstract Article history: A geochemical and mineralogical study was performed on lignite samples from the Upper Mio- Received June 08, 2018 cene Kovin deposit, hosting three coal seams. The Kovin lignite is characterized by high mois- Revised manuscript accepted December 12, 2018 ture content, medium to high ash yield, medium to high sulphur content and a relatively low gross Available online February 15, 2019 and net calorific value. The mineralogical composition, and major and trace element contents were determined by X-ray diffraction, scanning electron microscopy with energy dispersive X- ray spectroscopy (SEM-EDS) analyses, and inductively coupled plasma optical emission spectrometry (ICP-OES). The most abundant minerals in all lignite samples from the three coal seams are clays (illite/smectite), silicates (quartz, plagioclase), sulphates (gypsum/anhydrite) and carbonate (calcite). The other iron-rich minerals are sulphides, oxides and hydroxides (pyrite, magnetite, haematite, and limonite). In general, mineral matter in the matrix coal consists of illite/ smectite and quartz, while xylite-rich coals, apart from illite/smectite, have a higher content of sulphates and Fe-oxide/hydroxide minerals. The lignite from the Kovin deposit is enriched in As,

Cd, Co, Cr, Cu, Ga, Li, Mn, Mo, Ni, Pb, V, Zn, Gd, Tb, Er and Lu in comparison with the Clarke values for brown coals. The statistical analysis of bulk compositional data shows inorganic af- Keywords: Kovin deposit, lignites, major and trace finity for the majority of the major and trace elements and possible association with pyrite, illite/ elements, mineral composition smectite and calcite.

1. INTRODUCTION The Upper Miocene Kovin lignite deposit is located about Lignites of Upper Miocene age are the most important energy 50 km east of Belgrade (Fig. 1). Together with the Kostolac basin, source in Serbia. Almost all lignite production (90%) from the it is a part of the unique coal basin separated by the Danube River Kolubara and Kostolac basins is used in thermal power plants (MITROVIĆ et al., 2016), which forms the southern boundary of (TPP), (EPS, 2018). Information on the content, distribution and the Kovin deposit. The Kovin deposit is divided into two fields: 2 mode of occurrence of major and trace elements, especially po the western field “A”, and the eastern field “B”, 16.3 km and 23.7 2 tentially toxic and radioactive ones, are of great importance, if km , in areal extent respectively. According to the Geological re coal is used for combustion in a TPP. Many studies of trace ele port of the Kovin deposit, the lignite resources and reserves are ments contained in coal have been carried out in order to under currently estimated at 275 Mt (MITROVIĆ et al., 2016). Subaque stand and evaluate their mode of occurrence, as well as their ous exploitation of lignite (below the Danube river) in the offshore behaviour during combustion (e.g., DAVIDSON, 2000; FINKEL zone of the “A” field, named “Experimental exploitation field” MAN et al., 2018; MEIJ, 1995; SWAINE, 1990; SWAINE & (EEF) began in 1991, and is still active. Since 1991, the Kovin GOODARZI, 1995; WARD, 2016; YUDOVICH, 1978; YUDO- mine has produced about 5 Mt of lignite, with an annual produc VICH et al., 1985; YUDOVICH & KETRIS, 2002, 2005b). The tion of ~ 300,000 t. mode or form of occurrence of trace elements may control po Geological exploration of the wider area of the Kovin de tential hazardous effects to human health (FINKELMAN et al., posit, including the Kostolac coal basin, began in the late 19th 2002) and the environment. Numerous studies performed in SE century. The Upper Miocene (Pontian) age of the coal-bearing Europe on Greek (CHATZIAPOSTOLOU et al., 2006; GENTZIS sediments was confirmed by palaeontological studies (PAVLO et al., 1996, 1997; GEORGAKOPOULOS, 2001; FILIPPIDIS et VIĆ, 1959; SPAJIĆ-MILETIĆ, 1960, 1969; STEVANOVIĆ, al., 1996; FOSCOLOS et al., 1998; KOUKOUZAS et al., 2010), 1951). The distribution of palynomorph assemblages in the lignite Bulgarian (KOSTOVA & ZDRAVKOV, 2007; VASSILEV & from the EEF field (MILIVOJEVIĆ & ŽIVOTIĆ, 2006; ŽIVOTIĆ VASILEVA, 1998, 2009; VASSILEV et al., 2001, 2009; VASSI et al., 2007) suggests that decay-resistant gymnosperm (conife- LEVA & VASSILEV, 2005) and Turkish lignites (GÜRDAL, rous) trees and bushes played an important role in lignite forma 2011; KARAYIGIT & GAYER, 2000; KARAYIGIT et al., 2000; tion. Previous petrographic investigations (ERCEGOVAC et al., 2001; PALMER et al., 2004; SUTCU & KARAYIGIT, 2015; 2006; ŽIVOTIĆ et al., 2005, 2007) performed on samples from VASSILEV et al., 2005) of similar age and rank as the Kovin lig several boreholes from the I and II coal seam, showed that the nite, have focused on the mineral matter and major and trace el lignite from the Kovin deposit is a typical humic coal with vari ements contents. able huminite, liptinite and inertinite contents, and a mean ran Geologia Croatica bia, section L34-127 andL34-115;http://geoliss.mre.gov.rs/OGK/RasterSrbija/bia, section ). Figure 1. power generation. for electric of exploitation case in behaviour their assess to order in deposit Kovin the from coal in elements of trace major and occurrence coal. the in elements trace of major and distribution and content the determine to used were methanotrophic by chemoautotrophic governed alteration diagenetic with seams three all and fields both in composition lithotype and maceral in variation the 2016,al.,2017) confirm et (MITROVIĆ tions investiga geochemical organic and petrographic Recent 2006). (ERCEGOVAC al., 0.30±0.03 et of reflectance huminite dom 52 The aim of this study is to present the content and mode of mode and content the present to is study of this aim The Location of theKovin deposit(a,b)andsimplifiedgeological Ser map (c)oftheKovinafter GeologicMapof Basic deposit withsamplelocations (modified - and heterotrophic bacteria. The same samples samples same The bacteria. heterotrophic and - , , Kovin deposit is formed of Devonian low of Devonian formed is deposit Kovin (Fig. 1). of the sediments basement The Quaternary and tiary Ter of schist, Palaeozoic consists deposit of Kovin the area The SETTINGS GEOLOGICAL 2. is estimated at 1000 m. The Neogene units of the Kovin deposit deposit of Kovin the Neogene units at1000 The m. estimated is of Neogene sediments thickness total The of Serbia. part central the coal with 2013) 2013;al., et filled SZTANÓ (e.g. Pannon Lake as MAGYAR widespread al., et 1999,creasingly in became it Miocene late the During environments. fluvial and plain delta lacustrine, shallow in System Basin Pannonian the in by Neogene sediments. The Kovin deposit together with the Kostolac basin was formed formed was basin Kostolac the with together deposit Kovin The - - grade schist overlain overlain schist grade bearing sediments in in sediments bearing Geologia Croatica 72/1 - Geologia Croatica

- - - 3 – - 53 daf s 0.59 0.20 1.08 3.78 3.71 6.09 5.18 3.75 14.19 25.32 16.38

̅ Calorim X - 3.32 9.07 12.10 36.12 39.39 84.58 – volatile mat – volatile db

̅ X I of the Supplemen the of I - 1.22 1.16 4.55 6.80 30.88 39.53 37.91 23.00 27.38 64.96 22.02 III seam III Seam Min-Max 1.13–4.86 1.64–24.38 5.76–13.96 18.49–61.18 18.61–66.00 74.49–94.87 – arithmetic Min mean value; – minimum; two (without the 28/91 and 31/91 and31/91 28/91 the (without two ̅

- Min-Max 0.21–2.13 0.79–1.51 2.61–6.65 1.90–2.73 – carbon content, dry, ash-free basis, %; H %; basis, ash-free dry, carbon – content, 9.67–46.71 8.66–78.20 11.79–54.13 15.70–26.30 21.79–41.09 55.23–70.45 14.30–25.30 daf – total sulphur content, dry basis wt.%; V dry sulphur content, basis wt.%; – total s

db ̅ X 0.92 0.20 0.75 3.09 2.74 5.00 4.73 3.02 11.17 10.79 18.30 4.84 5.68 7.66 45.57 36.25 89.48 2 (2009) and performed according to ISO 7404 performedISO accordingandto (2009) 2 -

̅ X II seam 1.60 1.05 4.91 6.50 41.33 23.48 36.23 36.26 27.05 64.40 22.42 Polished blocks for maceral blocks for Polished analyses were prepared accord II Seam mples) ash samples, heated was carriedmples) to 450°C using out 91 91 from theS B Table field,1; Kovin Fig. deposit, as2017; described(2016, al. inet MITROVIĆ detail in tary Material). The samples represent different lithotypes and parts coal seams of I, II and III 2 & 3). (Figs. maceral analyses 3.2. Lithotypes and fol 3) & 2 Figs. 1; of ligniteThe identification lithotypes (Table lowed the nomenclature adopted by theand ICCP TAY (1993) et al.LOR (1998). ing to ISO 7404 ISO to ing KEL et al., 2017) and inertinite (ICCP, 2001). and inertinite 2001). KEL 2017) et al., (ICCP, 3.3. Proximate and ultimate analyses The proximate and ultimate analyses lignite of samples were con ducted EL III using a Vario CHNS/O Elemental Analyzer, Ele mentarAnalysensysteme GmbH,according toseveral standards B.H8.390:1987, (SRPS analyticalmoisturedetermination theof for 1987),Ca total 1988). moistureB.H8.317:1988, matter (SRPS volatile and 1997) (SRPS1171, B.H8.338:1986, 1986), ash yield IKA an measurementsperformed on were value lorific (ISO eter adiabatic400,C the following standard procedure (SRPS 1972). B.H8.318:1972, analysis 3.4. X-ray diffraction (XRD) and SEM-EDS Mineralogicalforty analysisof (2009). The identification of macerals followed the nomenclature the followed macerals of identification The (2009). theby developed International Committee Coal and for Organic liptinite 2005), et al., (PIC huminitePetrology for (SYKOROVA sa – oxigen content, dry, ash-free basis, %; X basis, ash-free dry, content, – oxigen daf Min-Max – ash content, dry %; S – ash content, basis, 2.98–7.44

1.99–14.03 2.68–12.54 29.96–72.01 14.43–49.34 81.45–95.03 - db ma - Min-Max 0.22–3.34 0.64–1.39 2.96–6.31 – net calorific value, dry, ash-free basis, MJ/kg; C MJ/kg; basis, ash-free dry, value, – net calorific 2.95–11.70 14.42–52.48 16.90–27.80 12.10–50.26 13.85–68.60 17.06–40.42 52.25–74.02 16.30–26.70 n daf brackish to 79 and KB - -

̅ bearing series X s - 6.32 4.30 7.77 0.99 0.27 0.81 6.33 1.82 6.85 2.60 3.26 3.92 1.82 45.67 35.94 89.38 13.70 I seam

̅ X – analytical moisture content, %; A content, – analytical moisture 2.20 1.19 4.64 9.36 an 44.83 24.29 39.46 31.95 25.90 64.78 23.26 I seam – nitrogen content, dry, ash-free basis; O ash-free dry, content, – nitrogen daf west it splits it west into two coal layers sedimentary faulting, causing ero (Late marly sediments; Miocene) c) - - Min-Max 2.04–7.06 2.03–14.82 3.50–12.86 – arithmetic mean value; mmf – Mineral matter free basis. free mmf – Mineral – arithmetic mean value; matter ̅

20.23–65.52 17.19–66.02 81.41–95.05 (Middle shallow brackish Miocene) 603from the A field, and KB - Min-Max 0.82–4.40 0.79–1.89 2.95–6.53 Ib) withIb) a total thickness m. up to15 of 5.84–15.24 34.57–52.90 21.00–28.30 27.95–47.48 12.58–52.90 20.09–33.73 56.48–73.24 20.10–27.20 - – gross calorific value, dry, ash-free basis, MJ/kg; Q MJ/kg; basis, ash-free dry, value, calorific – gross daf g Sarmatian 601 and GD four lignite samples were collected from four bore - - (Late Miocene; RÖGL, 1996) shallow, caspi (Late shallow, 1996) Miocene; RÖGL, Ia and lower - eastern and south part of the A field, it is more or less uni - ) to the northwest. In the central part deposit coal of seams In the Upper Miocene clastic (Pontian) coal Tectonic featuresTectonic the Pontian of sediments are uni relatively o (MJ/kg) (MJ/kg) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%) – moisture content, as received basis, %; W %; basis, as received content, – moisture (wt.%) ar an daf g ar n daf daf daf daf db daf db db INERTINITE Telohuminite Detrohuminite Gelohuminite HUMINITE LIPTINITE V O N Q S Subgroup/group Parameter W W A Q H C Min – minimum; Max – maximum; X rine sediments; Pannonian b) ments, as described in detail in et al. (2016). MITROVIĆ of the Kovin deposit, three coal seams are hosted (MITROVIĆ Seam IIyoungest). and I (the namelyIII oldest), (the 2016) etal., III was found in the eastern part the of Bwith field a total thick metresness from to (including a few 48.7 interbedded waste Coal seam IIrock). through developed the entire Kovin deposit, and in the eastern part is uniform, it towards but the splits it west into seam several thickness coal layers. Total is variable, up to7 m. The youngest, coal seam I has been in explored the southern part of the A 1).field Fig. In(EEF; the Bfield and the eastern, south Pontian fresh water sediments; Pliocene Lower d) fresh water clastic sedi hidrogen content, dry, ash-free basis, %; N basis, ash-free dry, content, hidrogen (upper form, towards but the north Results of proximate and ultimate analyses of the Kovin lignite. of the Kovin analyses and ultimate 2. Results of proximate Table 3. SAMPLES AND METHODS 3.1. Sample collection The forty holes, GD consist of: a) The maceral composition (vol.%, mmf.) after MITROVIĆ et al. (2016). afterMITROVIĆ et al. mmf.) (vol.%, composition maceral 1. The Table Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Max – maximum; s – standard deviation. Note: Values of parameters for individual samples are given in Table S-II of the Supplementary this paper. to material Table in given individual samples are for of parameters Values Note: deviation. Max – maximum; s – standard sion of coal seam I in the centralA and the One B. most of important normal faults is located in part of the depositthe western1). part the(Fig. B field of between fields form an antiform due to post ter, drywt.%; Q basis ter, W form in the part major the deposit; of coal seams angles dip at low (5–7 Geologia Croatica 54 Figure 2.Macropetrographic ofminerals distribution andmajorelements (b) intheAfieldlignite in profiles coal andthe (a)andGD-603 ofboreholes vertical GD-601 Geologia Croatica 72/1 . Geologia Croatica 55 CARVAJAL, 1993) 1993) CARVAJAL, - The mineral composition and distribution some elements of ETVELD (1969). No ETVELDquantification (1969). of the amorphous and sul phide phases was undertaken. in the minerals were investigated in five representative samples FullProf computer program (RODRÍGUEZ program computer FullProf based on the principles for diffractogram profiling set out by RI = 1.54178 1,2 ray diffractograms of 42 samples ray powder diffraction (XRPD). Analysis was performed on a - Macropetrographic profiles of boreholes KB-79 (a) and KB-91 (b) in the B field lignite and vertical and KB-79 coal. (a) and KB-91 in (b) in the B field lignite of boreholes and major elements distributions of minerals profiles 3. Macropetrographic Figure X powder diffractometerPhilips PW 1710 with CuKα Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Å radiation and a 40 kV, 30 mA.XRDThe 30 pattern recordedwas kV, radiation40 Å a and over a 2θ interval of 4–70°, with a stepcounting size of 0.02° and time the fixed of 1 s per step.were subjected to quantitative X- mineralogical analysis usingthe Geologia Croatica with the requirements of the SRPS ISO/IEC 17025:2006 ISO/IEC of SRPS the requirements the (2006). with accordance in parameter, tested for each reproducibility the to accordance in results of test the evaluation and CRM the using provided were results methods analytical the of all the validity for solutions ICP calibration prepare byAlfa GmbH certified Aesar &Co KG,Germany, wereused to Molybdenum, and pure®, 1000µg/ml Spec Titanium, 1000µg/ml, Specpure®, Vanadium, 1000µg/ml; (Silicon, solutions Specpure®, standard plasma single four and 1, 10 Specpure®, µg/ml) Standard Semiquantitative and µg/ml (Multi seam, while xylite while seam, coal inin matrix seamIIthe seam. Stratified predominates whole Mineral seam. the of part central the in (ICCP, 1993)coal predominates were opened, 4 ml of 4ml H opened, were vessels the cooling, After temperature. room to rapidly creased thenandde at thein 220ºC next min, 20remained first min, 10 the in ºC 220 to raised gradually was temperature The min. 30 (65%) H 2ml and Erba, Italy.Erba, Two multi Carlo from purchased reagents grade analytical were reagents as one. the first All program the same under temperature formed of per microwave was phase digestion second the and added tinite is low with liptodetrinite and sporinite as the most abundant abundant most the as sporinite and liptodetrinite low is with tinite lip of 2016; content al., Table 1). et The (MITROVIĆ subgroups maceral abundant most the as detrohuminite and telohuminite up the of part upper the in and (Ia) field bench in A. per B, field in seam the of parts lower xylite while inthe coalin wholeseam I matrix predominates seam, Stratified seam. the of floor the near layers thin in present is coal matrix of mineral A mixture of seam. the lower and parts per xylite while III, of seam lower the part and upper the in nates (Table S previous (MITROVIĆ research et al., 2016). coal matrix Stratified from taken were analyses maceral and of lithotypes results The 4.1. Lithotypesandmaceralcomposition RESULTS 4. energy an with equipped voltage) accelerating kV (30 microscope electron scanning (53/603, 56/603, 3/79, 17/79 and 31/79) using a JEOL JSM- 56 OES). ICP (ICP spectrometry emission – optical ductively coupled plasma by in determined were elements of trace major and contents The spectrometry analysis(ICP-OES) 3.5. Inductivelycoupledplasmaopticalemission EDX examination. for SEM and image electron secondary quality ahigher obtain to lysis, polished blocks were coated with a thin gold filmin order 350INCAEnergy System).Microanalysis the ana After maceral EDS; X nite sample was precisely weighed and mixed with 6 ml HNO 6 ml with mixed and weighed precisely was sample nite ofmg 240–390 lig about rotor. dissolution, For total segmented 1, Italy)(ETHOS a HPR Milestone, using Microwave System Advanced Digestion an on performed was samples of lignite digestion Kingdom). The United bridge, Scientific iCAP 6500Duo ICP (Thermo Fisher Scientific,Cam Huminite is the prevailing maceral group in all seams with with seams all in group maceral prevailing the is Huminite - Element Plasma Standard Solution 4, Specpure®, 1000 Solution 4, Specpure®, Standard Element Plasma - - Max Large Area Analytical Silicon Drift connected with with connected Drift Silicon Analytical Area Large Max - rich coal is present in thin layers near the roof of the the near layers thin in present is coal rich I of the Supplementary material; Figs. 2, 3) predomi - OES measurements were performed using a Thermo aThermo using performed were OES measurements - rich coal is present in thin layers in the upper and and upper the in layers thin in present is coal rich 2 O - rich coal is present in thin layers near the up the near layers thin in present is coal rich 2 (30%), then heated by microwave forenergy - elemental plasma standard solutions standard plasma elemental 3 - PO dispersive X dispersive 4 (85%) (40%) HF 2ml and were - OES measurements. The The OES measurements. - Specpure®, 1000µg/ml) ray spectrometer (SEM- spectrometer ray - 1000/10S high pressure 1000/10S pressure high - rich and and rich 6610LV - rich rich 3 - -

ter heating/burning at450 heating/burning ter af be cannot smectite onpowder identified XRD diffractograms (0.67–10.96%) and calcite (0.01–25.30%). It should be noted that with of variable proportions (4.37–17.13%),haematite plagioclase 52.28%), (3.97–52.61%)quartz (13.10– and (12.05–46.66%)illite/smectite anhydrite of mainly consists material) Supplementary 2, 3; Table S I (Table seam coal the in 3; matter Figs. showmineral ashes that of lignite analyses XRD contents. (>50%) matter high mineral (10–30%) very to medium by characterized is lignite Kovin The 4.3. Mineralogy 0.64% 1.89% from to samples. ranges all in (daf) Ncontent The 27.05% 25.90%, are 27.38%. (daf) and contents O respective the 4.91% respectively, while III, 4.55% and and II I, seams for coal 4.64%, are (Table (daf) respectively Hcontents average I). The III, at 64.78%, and ing II I, 64.96% and 64.40% forseams coal tary material). material). tary sis (V sis has III seam Coal ba dry on volatile matter The field. content. low B to sulphur a medium the in detected been has 37/91) (sample 3.12%at content sulphur total highest The content. high rarely low, to medium from ranges II seam coal Total in content sulphur field. B the in seam the of part bottom the in material) mentary lower and net gross value(Tablecalorific S mineral that obvious and fields. of is lithotypes between detectable Itparameter this is (22.02(22.42 variation slight III MJ/kg). The seam MJ/kg), and II seam to compared MJ/kg) (23.26 value calorific net average net calorific valuearetypical forlignite. Coal seam Ihas a higher respectively. III, and II I, of 27.95–47.48%, 12.10–50.29% 9.67–46.71%, and seams for coal sists of illite/smectite (14.79–73.55%), illite/smectite of sists (8.62–57.19%) quartz and con ash II seam coal in matter mineral The field.B the in nates is more Quartz in abundant the A field, whileillite/smectitedomi 2016). (WARD, 2002, process ashing the during formed be could they because account, into taken carefully should be haematite and of anhydrite content the Also, phases. both always include highest content (4.40% in sample 31/91; Table S Table 31/91; sample in (4.40% content highest (>3%), the content seam with (1–3%)sulphur Coal high medium to 3%. a has I than more of content sulphur higher a contain les samp four basis) whereas (dry content, sulphur a low medium to level ash seams (>50%). high a very contains lignite Most of Kovin the coal for 78.20%, to 8.66 low respectively, (<10%) from average on is which III and II I, to 68.60%, to 13.85 52.90%, to 12.58 basis) from basis). (dry received – as content ranges ash rial The mate sample (moisture of analysed the freshness the on dependant being respectively III, and II I, seams coal for 11.79–54.13%, most samples is 34.57–52.90%,from variable 14.42–52.48% and Table S content relatively and low net and calorific value gross (Table 2; sulphur higher volatile matter, high yield, ash high to medium content, moisture high by its characterized is lignite Kovin The 4.2. Proximateandultimateanalyses abundant. less are minerals other and bonates car pyrite, while minerals, abundant most the Clays are cerals. ma abundant most the being semifusinite and fusinite detrinite, inerto with III, seam in maximum its with II, Iand seam the in low is content 2016).al., Inertinite et (MITROVIĆ macerals The C contents (daf) are similar in all three seams, averag seams, three all in similar are (daf) Ccontents The Based on the dry and ash free basis (daf), values of gross and and of values gross (daf), basis free ash and dry the on Based db - ; Table 2) of the Kovin lignite is typically at a high level atahigh ; Table typically is 2) lignite of Kovin the II of the Supplementary material). The total moisture of moisture total The material). of Supplementary II the - II II ofFigs. material; the Supplementary S1, S2 of the - rich coal has the higher ash content and and content ash higher the has coal rich o C, so in further text illite/smectite will will illite/smectite text further in so C, - II II of the Supplemen Geologia Croatica 72/1 - II of the Supple the of II - - - Geologia Croatica - 57 rich - s 9.66 2.15 4.99 7.17 17.83 23.57 rich layers. - rich chlorite as - ; Fig. 4g) was de 4g) ; Fig. feldspar (Fig. 4). 4). feldspar (Fig. 4 -

̅ X 6.18 2.91 10.85 19.01 18.38 43.36 III Seam hydroxides) in the Kovinhydroxides) - ; Fig. 4f) gypsum possibly ; Fig. as 4 Min-Max 0.13-5.73 0.07-28.38 1.68-17.21 0.59-47.67 6.03-69.30 11.68-30.77 oxide/hydroxides in the Kovin lignite samp - s 5.36 6.70 3.44 17.06 15.64 13.05 feldspar (orthoclase; Fig. 4b). They are detrital 4b). feldspar Fig. (orthoclase; in - rounded grains predominantly of detrital origin (WARD, -

̅ X 4.50 6.82 5.51 The Fe oxides and Thehydroxides (haematite Fe and limonite)are The silicate and aluminosilicate minerals are common con The minerals, clay represented illite/smectite by and chlorite, and 4a) Feldspars are represented Fig. plagioclase by (albite; Detrital epidote, a calcium, aluminium and iron sorosilicate Sulphates, anhydrite (CaSO 22.33 38.92 24.05 II Seam minerals such as pyrite and siderite. A small proportion these of minerals might also detrital be of origin. mixture Limonite (a of goethite, lepidocrocite, and other Fe well, were determinedwell, in high amounts in several samples. In raw lignite, sulphate minerals areauthigenic and/ (mainly epigenetic) or occur as weathering products. Barite (BaSO termined in very amounts. low present in considerable amounts in the Kovin lignites. A large proportion the Fe of the is probably result the weathering of 4h) les (Fig. iron of seam II contain sphalerite, galena, siderite, ankerite dolomite, and monazite, while in coal seam III barite and monazite were found. stituents the inorganic of matter in Kovin lignites and include mainly quartz, illite/smectite, rarely chlorite and plagioclase, and mica and (biotite, K more rarely, muscovite), authigenic but crystals 2002), werealso determined.Epigenetic quartz, with minerals, along clay pyrite, and carbonates, was formedwithin cleats and fractures in the organic matrix, asrea thesult circulation of meteoric of waters. are typical constituents the inorganic of matter, especially in coal seam II. They are a but detrital mostly of origin 2016), (WARD, small part maybe diagenetic, formed as weathering products of feldspar and mica, and usually occurring as layers, lenses and films on the surfaceof macerals. Illite and smectite are present longdispersed finely irregular aggregates of asas rarely size and platy crystals. minerals Clay epigenetic origin, of which precipi tated in fractures, were also observed. subordinate K rite, limonite, minerals. and clay Chlorite (Cr 4d) was found in the Fig. well, I and II seams. The majority the of chlorite in the Kovin lignite detrital is of origin, formed as a weathering product the crystalline of basement rocks. occursmineral 4e), as individual (Fig. crystalsirregular of shapes. origin and are usually associated with Mica (biotite clays. and is represented 4c) platy by muscovite; or irregular Fig. shaped crystals, usually in association with feldspars in clay The mica is predominantly detrital of origin, a small but part might be weathering a product feldspars. of During the processes coal formationof mica is unstable and could transform to chlo Quartz inorganic is a major component the Kovin of lignites, es pecially Some parts in coal 4). seam seams III of I and (Table II veryhave highquartz contents. is recognized It as single angular to semi - Min-Max M M M M M M 0.39-20.33 0.25-19.59 0.49-11.99 3.16-54.64 8.62-57.19 m m m m m m m m 14.79-73.55 III seam rich mine - s 7.47 3.97 3.02 13.07 14.92 11.11 M M M M M M m m m m m m m m m m m m m m m m II seam Content

̅ X M M M M M M m m m m m m m m m m m m m 5.14 8.57 5.39 28.53 26.91 26.51 I seam I seam Min-Max feldspar (albite, orthoclase), and orthoclase), mica,feldspar were (albite, 0.01-25.30 4.37-17.13 0.67-10.96 3.97-52.61 13.10-52.28 12.05-46.66 - EDS examinationEDS revealed that the most abundant - SEM – arithmetic mean value; Min – arithmetic mean value; deviation. – minimum; Max s – standard – maximum; ̅

Calcite Hematite Plagioclase Quartz Anhydrite Parameter Illite/smectite Sulphides Pyrite Sphalerite Galena Mineral phases Sulphate Gypsum/Anhydrite Barite Oxides and hydroxides Oxides Limonite Hematite Rutile Ilmenite oxides Mn-Fe Mn hydroxides Silicates Quartz Opal/chalcedony Illite Smectite muscovite) Mica (biotite, Chlorite (albite) Plagioclase (orthoclase) K-feldspar Epidote (orhite) Allanite Zircon Carbonates Calcite Siderite Dolomite Ankerite Phosphate Monazite X S-III of the Supplementary this paper. to material Table in given samples are individual for of parameters Values Note: Mineral composition of the Kovin lignite, based on data from SEM-EDS. from data on based lignite, Kovin the of 4. Mineral composition Table minerals in all the studied lignite samples are (illite/smec clays anhydrite (3.16–54.64%) anhydritewith (3.16–54.64%) variable amounts of haematite plagioclaseand (0.25–19.59%), (0.49–11.99%) calcite (0.39– Illite/smectite and20.33%). quartz are almost equally abundant while illite again most inThe the field, prevails A field. B in the abundant mineral matter in coal seam III ash is quartz anhydrite (6.03– while(0.59– illite/smectite69.30%), (11.68–30.77%), and calcite (0.07–28.38%) plagioclase (1.68–17.21%), 47.67%), are less abundant. haematite (0.13–5.73%) tite; Table 4; Fig. 4), silicates (quartz, 4), sulphate (gyp Fig. plagioclase), 4; tite; Table sum/anhydrite) The other and iron carbonate (calcite). XRD analysis of the Kovine lignite ash. lignite Kovine of the 3. XRD analysis Table Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) detected in all coal seams. In addition, in seam I, barite, chlorite, epidote, allanite and zircon were also detected. Samples from rals are sulphides, oxides and hydroxides (pyrite, magnetite, haematite, and limonite) and plagioclase. Minor minerals such as rutile, ilmenite, K M–major mineral (>1 vol.%); m–minor mineral (<1 vol.%) m–minor mineral M–major (>1 vol.%); mineral Geologia Croatica h) Fe oxide/hydroxide. Figure gypsum/anhydrite; g)barite; 4.SEMbackscatter imageswith EDSdata ofminerals; a)albite; b)K-feldspar; c) muscovite; d)Cr-rich chlorite; e)epidote; f) 58 Geologia Croatica 72/1 Geologia Croatica 59 continued; i) rutile in quartz; j) ilmenite; k-m) pyrite; n) sphalerite in quartz; o) Ce, La allanite, p) monazite. p) monazite. in quartz; La allanite, n) sphalerite in quartz; i) rutile pyrite; 4. continued; k-m) o) Ce, j) ilmenite; Figure Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Geologia Croatica Table 6.Trace element content oftheKovin lignite. syn probably most their implies which aggregates spherical and grains angular and rounded individual as occur Carbonates A. field in I oflower(Table seam bench the III in 4), welland as as II ofseams part inthecentral amounts significant in determined was Calcite amounts. small in present are ankerite and dolomite siderite, as such carbonates other the whereas calcite, is lignite seams. all in low in amounts aggregates small as cur Ti Ti and The II. and I seams coal in amounts small in detected also were hydroxides Fe clays. and The siderite including minerals flakesandin usuallyassociationwithappears and haematite other of up built small crusts collomorphous as mainly occurs lignite Table 5.Contents ofthemajorelements intheKovin lignite. 60 As Element Si elements,Major % Element Ni Mo Li Pb Cr Ga Ga Cu Rb Sb Sc Se Ba Al Tl Th Sr Zn V Co Cd Si/Al Fe Ti Ca Mg Na K Mn One of the most abundant carbonate minerals in the Kovin Kovin the in minerals carbonate abundant of most One the 13.70-214.00 35.24-371.41 40.88-173.15 46.04-253.06 11.18-174.79 0.88–11.87 4.00-140.00 6.88-175.67 0.52–5.15 1.67–6.17 0.59–9.01 0.02–0.18 1.14–3.19 0.25–0.67 0.04–0.33 0.04–0.44 0.01–0.15 Min-Max 1.10-11.50 3.82-54.11 2.10-16.30 3.53-72.54 0.39-36.06 1.24-11.24 7.60-76.82 3.40-35.80 1.30-9.00 0.10-3.70 0.58-6.45 Min-Max I seam I seam I seam I seam - Fe oxides (rutile and ilmenite; Fig. ilmenite; 4i,Fe j) and oc (rutile oxides 6.40 2.48 2.66 2.88 0.10 1.88 0.43 0.14 0.16 0.03 111.65 100.78 61.79 23.09 30.86 31.95 68.55 90.41 49.72 41.56 12.95 X <0.5 <0.5 6.00 8.85 9.67 6.01 3.02 1.37 2.04 ̅

X ̅

53.68 14.68 87.50 33.04 21.03 45.63 38.23 54.12 43.24 19.32 2.82 4.38 9.16 3.08 1.96 8.46 1.03 1.39 3.45 1.36 1.16 1.92 0.05 0.52 0.12 0.08 0.11 0.04 s s 47.47 18.47 88.93 21.53 23.38 51.85 83.44 10.94 90.59 37.18 35.89 5.25 7.58 6.40 5.13 2.62 0.92 1.74 X

̅ 5.26 2.11 2.19 2.45 0.09 1.81 0.41 0.12 0.13 0.02 g X

̅ g - Mn oxides and Mn Mn and oxides Mn 10.19-176.12 9.40-206.10 8.38-226.73 4.06-179.87 9.27-170.27 3.95-239.66 6.46-110.76 2.21-85.06 4.30-70.40 3.14-77.21 2.50-34.30 0.90-25.60 0.79-32.97 0.64-15.06 0.70-9.80 0.30-4.90 0.10-2.60 0.20-3.19 Min-Max 0.40–17.33 0.001–0.04 0.20–5.72 2.06–5.12 0.36–5.03 0.01–0.32 0.17–2.15 0.04–0.59 0.01–0.36 0.01–0.31 II seam Min-Max II seam 37.95 71.18 26.68 96.89 39.03 63.82 88.80 13.90 90.24 11.26 69.75 53.03 <0.5 <0.5 5.16 9.99 7.18 2.25 1.32 1.69 7.50 2.90 3.03 2.38 0.13 1.36 0.38 0.11 0.17 0.02 X X ̅ ̅

27.01 50.76 17.89 57.31 23.49 45.08 33.85 41.54 60.79 29.93 2.26 9.63 7.39 8.01 4.34 0.99 0.76 0.72 lena were detected in small amounts in seam II (Fig. II 4n). seam in amounts small in detected were lena ga and Sphalerite determined. were of pyrite epigenetic amounts Very small textinite. and of densinite lumens the within formed were Crystals of debris. plant openings cell and matter organic the within cavities infilling or bands stratified along 2012), situated (CHOU, crystals euhedral and framboidal as occurs pyrite genetic (Fig. m). l, 4k, lignite Kovin Syn the in mineral authigenic typical field in B. II of seam part central the in low in amounts grains angular small as occurs Dolomite origin. bably a syngenetic pro most suggesting matter, organic with associated intimately II and occurs as fine II and occurs seam in amounts small in observed was Siderite origin. genetic 5.31 1.61 1.14 1.11 0.10 0.42 0.13 0.08 0.09 0.01 s s Pyrite is one of the most abundant sulphide minerals and a a and minerals sulphide abundant of one most is the Pyrite 27.50 54.11 11.04 20.17 78.59 30.13 47.18 79.91 77.50 48.58 43.18 4.49 8.56 7.05 5.70 2.00 0.97 1.48 X

̅ g 5.40 2.31 2.88 2.08 0.10 1.25 0.34 0.08 0.14 0.01 X

̅ g 120.71-218.89 11.86-265.33 61.2-239.83 1.75-37.88 9.70-77.50 1.50-25.10 4.50-21.20 3.79-62.41 1.00-16.50 2.84-82.10 0.84-36.25 4.30-62.52 3.31-54.51 1.90-8.90 0.62-8.14 0.90-4.30 1.40-2.90 0.72-2.32 Min-Max 0.34–21.84 III seam 0.26–4.37 1.28–5.34 0.80–3.70 0.01–0.29 0.98–2.10 0.33–0.48 0.11–0.64 0.02–0.55 0.01–0.03 Min-Max III seam - grained lenses, layers and crusts, which are layers lenses, and crusts, grained 123.58 184.17 148.11 9.68 2.39 3.39 1.91 0.14 1.67 0.40 0.34 0.28 0.02 20.38 45.64 13.19 12.76 35.64 43.49 15.76 31.22 33.18 <0.5 <0.5 4.72 8.12 4.98 2.41 2.17 1.40 X ̅ X

11.33 24.78 22.01 97.57 24.31 10.80 30.71 72.86 18.72 15.88 2.08 5.02 8.25 5.53 2.19 1.17 0.56 0.55 7.92 1.33 1.54 1.05 0.09 0.42 0.05 0.22 0.20 0.01 s s 181.58 131.03 Geologia Croatica 72/1 15.17 37.79 25.95 84.04 31.77 11.10 11.59 24.21 26.89 4.32 6.34 9.72 4.20 2.15 2.11 1.30 X 4.88 1.38 2.45 1.56 0.08 1.09 0.24 0.27 0.16 0.01

̅ g X

̅ g Clarke value of valueClarke of Clarke value of valueClarke of brown coal brown coals 0.84±0.09 0.68±0.07 0.24±0.04 1.0±0.15 120±10 150±20 2.2±0.2 5.5±0.3 9.0±0.9 4.2±0.3 6.6±0.4 4.1±0.2 7.6±1.3 3.3±0.2 10±0.9 720±40 10±1 15±1 15±1 18±1 22±2 ppm 100±6 ppm – – – – – – a , a , - Geologia Croatica - - , 61 a ppm 22±1 11±1 10±0.5 3.5±0.3 1.9±0.1 2.6±0.2 8.6±0.4 2.0±0.1 0.5±0.02 1.0±0.05 0.32±0.03 0.50±0.05 0.85±0.08 0.31±0.02 0.19±0.02 Brown coal Brown Clarke value ofClarke value g

X 6.92 6.06 3.96 7.53 0.71 2.89 0.49 1.07 5.59 0.95 0.42 0.88 0.25 0.86 0.43 11.93 15.93 48.87 29.79 environmental factors, - s 6.35 4.02 2.82 1.74 7.45 4.10 0.48 1.33 0.22 1.09 2.43 0.47 0.30 0.34 0.09 0.40 0.29 22.76 14.86 fold geochemical classification,geochemical fold -

̅ X 8.05 6.81 4.36 8.61 0.89 3.30 0.55 1.39 6.40 1.15 0.54 0.98 0.27 0.99 0.52 13.92 17.94 55.26 34.02 VI the Supplementary of material to this - III seam Min-Max 1.40–7.10 0.10–1.60 0.61–4.66 0.15–0.84 0.50–3.10 0.99–8.67 0.11–1.63 0.05–0.93 0.21–1.23 0.08–0.38 0.15–1.38 0.13–0.91 2.70–21.40 1.90–15.21 4.23–26.43 1.70–10.80 2.48–14.57 7.80–55.31 12.64–82.63 g

X 9.59 2.59 4.95 0.88 4.53 3.10 0.47 1.29 6.78 5.58 0.87 0.41 0.93 0.19 1.00 0.52 15.36 42.03 22.79 Thereareseveralgeochemical andeconomicclassifications s 2.7 4.41 1.32 6.14 0.44 2.43 1.31 0.19 1.11 4.07 2.95 0.48 0.21 0.38 0.09 0.45 0.30 16.07 10.70 ments and mineral phases contained in the coal. Chemical, bio logicaland physical factors in mire systems provide specific en vironments in which minerals could be deposited or formed which control the enrichment or depletion of the differentele 5. DISCUSSION The mineral matter in coal seams and deposits depends on the combination of specificplant constituents influenced by water regional depositionallevel, and paleo pecially enriched in As (4.30–70.40 mg/kg), Cr (8.38–226.73 mg/ (8.38–226.73 Cr mg/kg), (4.30–70.40 Asenriched inpecially mg/kg), (4.06– Pb mg/kg), (9.40–206.10 Ni (2.21–85.06 Li kg), mg/ mg/kg) and Zn (3.95–239.66 mg/kg), V (6.36–110.76 179.87 Coalkg). from seam III mg/kg), is enriched in Ba (61.23–239.83 mg/kg). mg/kg) and (120.71–218.89 Sr (11.86–265.33 Cr rareof earth elementsand yttrium SE SEREDIN, (REY; 2010; threeThe 2012). DAI, REDIN & which divides REY into light (LREY – La, Nd, Ce, and Pr, Sm), medium (MREY – Eu, Gd, and Y), Tb, and Dy, heavy (HREY groups Yb, and Tm, according Lu) Er, – Ho, to SEREDIN & DAI is the more convenient for description REY of distribution(2012) in coals and conventional REY ores. The content LREY, of MREY and HREY in the Kovin lignite is generally in all low S Table 7; seams (Table paper) withpaper) a predominance LREY of in all three seams. The ave rage LREY contents in lignite mg/kg, are 31.15 mg/kg 25.71 and mg/kg34.02 seamsfor I, II and III The respectively. Gd, Tb, Er andcontents Lu are higher than the Clarke brown values for coals (KETRIS & YUDOVICH, based on calculation 2009), ave of rage individual lanthanides and Y. – geometric mean value. g

̅ X 2.97 1.02 5.23 5.70 3.46 0.52 1.72 8.05 6.43 1.02 0.49 1.03 0.22 1.13 0.61 10.79 17.27 46.45 25.71 V of the of V - II seam Min-Max 0.40–5.40 0.10–1.70 0.80–9.90 0.46–5.95 0.08–0.83 0.10–4.50 6.0–69.96 0.13–1.94 0.06–0.80 0.14–1.92 0.03–0.36 0.14–2.00 0.09–1.19 1.70–17.80 1.73–24.13 0.81–10.77 3.81–43.60 0.76–15.70 0.76–13.47 g

X richandmixture ma of 3.19 0.86 5.71 3.42 0.55 0.82 6.66 1.06 6.93 0.39 6.69 1.05 0.24 1.07 0.61 11.89 16.37 28.64 48.72 - s 6.34 1.31 0.61 2.35 7.97 2.31 0.35 0.53 3.00 0.75 2.57 0.34 4.74 0.67 0.13 0.72 0.59 12.55 21.91 – arithmetic mean value; s – standard deviation; X deviation; s – standard – arithmetic mean value; ̅

rich phosphates, of monazite 4o) (Fig. ̅ X - 3.42 1.08 6.15 4.01 0.63 0.97 7.25 1.27 7.39 0.51 7.96 1.22 0.27 1.26 0.75 13.24 18.09 31.15 53.25 SEREDIN & DAI, 2012; LREY = La+Ce + Pr + Nd + Sm; MREY = Eu + Gd + Tb + Dy + Y; HREY = Ho + Er + Tm + Yb + Lu; Yb + Tm HREY = Ho + Er + Y; + DyTb + + Gd + + Nd + Sm; MREY = Eu + Pr 2012; LREY = La+Ce SEREDIN & DAI, b rich high coal have contents the aforemen of V of the Supplementary of V material to this paper; IV theSupplementary of material tothis paper; - - - I seam Min-Max 1.80–5.90 0.15–2.20 1.16–9.45 0.23–1.59 0.20–2.10 0.33–2.68 0.04–1.35 0.40–2.45 0.12–0.52 0.31–2.71 0.14–2.65 5.00–28.70 2.90–10.20 3.56–12.86 6.46–33.22 3.53–11.18 2.09–17.54 14.01–51.15 22.17–87.75 b Rare grains REY of The lignite from the Kovin deposit is enriched in As, Cd, Co, b b KETRIS & YUDOVICH, 2009; KETRIS & Pr Ce Sm Nd HREY Eu Tb La Element ΣREY MREY Dy Gd Ho Y Er Tm Yb Lu LREY Note: Values of parameters for individual samples are given in Table S-III for major elements, S-IV for trace elements and S-V for Rare earth for and S-V yttrium and elements elements of the trace S-IV for major elements, S-III for Table in given individual samples are for of parameters Values Note: Supplementary paper. this to material 4.4. Geochemistry the Al, andVariations Si, of K contents Ti in the studied samples are obvious in each seamand mostlydepend on coal lithotypes S Table 5; (Table lanite aluminium, (calcium, iron sorosilicate mineral; 4p), Fig. detrital of probably origin, occur as individual small crystals of irregular shapes in coal seam I. irregular shape were detected in coal seams II and III. Ce, La al a Rare earth element content in the Kovin lignite. lignite. 7. Rare in the Kovin earth content element Table Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Min – minimum; Max – maximum; X trix and mineral dry (9.01%, Fe ratio dry (6.17), phur Si/Al content (4.40%, basis), dry content has basis) the highest and Mn contentbasis) (0.15%, S all mentioned of elements and Pb except Zn (Table Supplementary material to this The coal paper). in seam II is es Figs. Figs. 5, 6). The bottom part of seam I in 31/91) field(sample B dry6) and the withhighest Fig. basis; high totalash (52.56%, sul Figs. 2, 3). It is obvious thatobviousthemineral is It 2,3). Figs. tioned elements. major The contents average Si in the Kovin lig coal for seams I, II andnites and 9.68% III, are 6.40%, 7.50% while therespectively, respective Al contents are 2.48%, 2.90% implies 5) three(Table seamsall in ratio Si/Al high A 2.39%. and high contents quartz, of illite/smectite and plagioclase. Zn, Gd, Cu, Tb, Er and Ga,Cr, in Lu V, com Mn, Li, Pb, Ni, Mo, parisonwith Clarkebrown values for coals (KETRIS YUDO& TheVICH, lignite 2009). in seam I is particularly enriched in As (4.00–140.00 mg/kg), mg/kg), mg/kg) and Zn (11.18–174.79 Cr (35.24–371.41mg/kg), (6.88–175.76 Pb mg/kg), Ni (13.70–214.00S Table 6; (Table Geologia Croatica High inorganic affinity (r affinity inorganic High associations 5.1. Affinity oftheelementsandgeochemical (VASSILEV formation coal &VASSILEVA,and 1996, 1998). peatification during conditions environment the of construction re partial for the indicator an as used be It can changes. facies and deposits, seams, characterize may coal in distribution and abundance their al., 2012). occurrences, of modes mineral The al., et 2002; DAI elements et al., et 1998;(CHRISTANIS in KALAITZIDIS variation the influence also may factors genetic (GLUSKOTER, 1975; TAYLOR al., et 1998; WARD, 2016). Epi 62 Yb in coal seam I with strong positive correlations with ash yield, yield, ash with positive correlations strong Iwith seam coal in Yb Cr, Pb, Ba, Rb,Ti, Sc, V, Ga, K, Ho, and Gd, Eu, Sm, Nd, Ce, La, 2010; KORTENSKI &SOTIROV, Si, for Al, 2002) observed is some trace elements incoal. A Figure 5.Macropetrographic ofash, distributions (b)intheAfieldlignite totalsulphur content profiles andthe (a)andGD-603 ofboreholes and vertical GD-601 ash db – ash content, dry basis, –ashcontent, %;S dry =0.7–1.0; Table al., et 8; ESKANAZY db –total basis, sulphurcontent, wt.%. dry

Co, Cu, Mo, Pb, Rb, Se, in seam III, have mixed affinities with with affinities mixed have III, seam in Se, Rb, Pb, Mo, Cu, Co, Mg, II; seam in I; Mo, Zn, seam Pb, in and Zn Cu, As, Mg, Mn, V, as such Some elements, III). Pr, Dy, Nd, seam La, the Y (in Li, and II) seam the Lu Ho, (in Eu, Sm, Yb, I); Fe, Pb, Na, Th, K, Dy, Tb, Co, Li, Mo, Y, Ni, Cd, Se,Th, Na, Er, Tm, seam the Lu (in Na (Table Table 8, S Kand Si, yield Al, and ash between correlation strong The III. seam Lu in Ho, and Tb, Er, Gd, Yb Eu, Sm, Ce, Zn, Ni, Sc, Th, Cr, Cd, Ga, Ba, Si, for Ti, Al, and Fe, Mn, Na, II, K, seam in Tb Li, Sc, Se,V, In, Si, for well Cr, Ga, Ti, as Al, as Ba, Cu, and Gd tively high inorganic affinity (r affinity inorganic high tively rela but still aless with Elements seams. three all yield in ash with correlation shows astrong analyses maceral from matter ral of content mine the expected, As seams. (Fig. three 4)rals all in mine silicate and of aluminosilicate predominance per) the imply - V of the Supplementary material to this pa this to material V of Supplementary the ash =0.5–0.69; =0.5–0.69; Table 8) include: Fe, Geologia Croatica 72/1 - - Geologia Croatica 63 EDS dataEDS most trace - According to the geochemical and SEM silicate minerals (quartz, plagioclase, orthoclase, albite, biotite, elements have good correlation coefficients with Al and Si (Table (Table Si and Al with correlationcoefficients good have elements indicating6), their connection close with silicate and alumino and Ca db – total sulphur content, dry sulphur content, basis wt.%. – total db – ash content, dry %; S – ash content, basis, db = –0.35 – –1.00; Table 8). 8). Table – –1.00; = –0.35 ash Macropetrographic profiles of boreholes KB-79 (a) and KB-91 (b) in the B field lignite and the vertical and some and the KB-79 content (a) and KB-91 total sulphur (b) in the B field lignite of boreholes distributions of ash, profiles 6. Macropetrographic Figure A in coal. elements trace correlation coefficients varying from 0.35 to0.49 between ash andyield the aforementioned elements. in Sr seam S I; Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) in seam II, and Ca, As and Sr in seam III show organic affinity (r Geologia Croatica between Fe, As and Cd and all of them with S with of all them Fe, and Cd and As between (Fig. correlation As 4). in strong Avery enriched particularly neral mi The m). l, (Fig. 4k, data correlation the confirms mination of SEM result The pyrite. with ply aclose connection im III, seam Sr in and II seam Mo Co, I, Cr, in and seam Mo, in tot (r content sulphur between positive correlation Astrong lignite. Kovin the in mineral sulphide abundant most the is Pyrite cene. pa the in Mio Upper the input in seams of coal all formation during clastic laeomire the confirms result This seams. coal all in chlorite and Fig. muscovite; and illite/smectite 4) with well as as sulphur content, SiandAl. Table 8.Element affinitiesdeduced from calculation of Pearson’s correlation coefficients between the concentration ofeachelement inthe coalandashyield, total 64 Note: Values ofthecorrelation coefficients forindividualelements are given in material tothispaper. Table S-VI oftheSupplementary well as a good correlation between sulphur content (r content sulphur between correlation agood well as S position of the lignite in both fields. Also, the relatively high con high relatively the Also, hae fields. and pyrite high the to related be can oftent lignite Fe both the in in lignite the of position com mineralogical the with compatible are they Ti Kand and Al, Si, in rich are minerals determined The coalfields. both for rals mine common the are (albite),clase pyrite and calcite haematite, plagio gypsum/anhydrite, illite/smectite, quartz, and similar, quite are lignites of Kovin the compositions mineralogical The and traceelementsincoal 5.2. Comparisonbetweencoalpetrologyandmajor (calcite). minerals carbonate the with associated Sr is I shows that seam Sr of in and Ca Fig. correlation chlorite; tite, strong 4d). The (illite/smec minerals aluminosilicate with probable connection (Table Al Si and with 8) show amost Zn correlation good and and 2012). 2005a; 1994; &KETRIS, MAN, YUDOVICH Cr, Ni, Pb (DAI et al., pyrite 2003;tion with et al.,DIEHL 2012; FINKEL aclose connec and elements of these origin same the indicates r Al affinity r r r Positive correlation withtotal sulphurcontent r Positive correlation withashyield r r Negative correlation withash yield r Si affinity r r r Si Si Al Al Stot Stot ash ash ash ash ash db = 0.7–1.0 = 0.7–1.0 >0.7; as II, seam Table in As I, seam 8) Se,in Fe, Cd, and As, = 0.5–0.69 = 0.5–0.69 –total basiswt.%; sulphurcontent, dry = -1.0–-0.35 = -0.34–0.34 =0.35–0.49 =0.50–0.69 =0.7–1.0 =0.5–0.69 =0.7–1.0 - rich lignite in the bottom part of seam I of field B is B field of I seam of part bottom the in lignite rich Mn, Co,Mn, Cr, Mo. Fe, As, Cd, Se. Cu, Li,Sc, Ga, Th, V, Gd, Tb. Si, Ti, I seam Sm, Gd, Ho, LREY, MREY. Sc, Th, V, La,Ce, Nd, Ba, Cr, Li,Pb, Ga, Rb, K, Al, Ti, As, Cu, Zn,Pr. Ba, Pb, Rb, Sm,MREY. Mg, K, Sr. Sr. Ca. S Cd, Co, Li,Mo, Se, Ni, Th, Tb, Dy, Y, Er, Tm, Lu. Fe, Na, Ho, Yb, LREY, MREY, HREY. Ba, Cr, Pb, Ga, Rb, Sc, V, La,Ce, Nd, Sm,Eu, Gd, Al, Si, Ti, K, Co, Pr, Ni, Eu, Tb, Dy, Y, Er, Tm, Yb, Lu, HREY. Fe, Na, db , Mg, Mn, , Mg, Mn,

db in seam I, clearly I, seam in Stot =0.5–0.69) =0.5–0.69) - EDS exa Mo. Mo. As. Tb, Ho, Tb, Ba, Cr, Cu, Li,Pb, Ga, Sc, Th, V, Sm,Eu, Gd, K, Si, Ti, II seam Ba, Cr, Cu, Li,Sc, Se,V, Ga, Gd, Tb, Ho. Ti, Na, Mo, Zn. Mo, Se,Er, Yb, Lu, HREY. Fe, Na, S Er, Tm, LREY, MREY. As, Cd, Co, Rb, Ni, Sr, La,Ce, Pr, Nd, Dy, Y, Mg, Mn, Pb, Th, Sm,Eu, Ho, Yb, Lu, HREY. Fe, Na, K, Ba, Cr, Cu, Li,Sc, Se,V, Ga, Gd, Tb. Si, Ti, Al, Pb, Th, Sm,Eu, Yb, Lu, HREY. K, Fe, db , Ca. S

- - -

mire resulting in deposition of siliciclastics. deposition in resulting mire of precursor the inundations frequent more may indicate 6) 5 and (Figs. content ash Increased accumulation. peat during changed level water the that 2016) al., indicate et (MITROVIĆ contents forrespectively.and B, fields A Figs. 6 in 5and presented Cr, are Ni, Pb, Se) lignite Kovin the in (As, elements Cd, trace important of most the variation vertical A field(Fig. 2),andthe B field (Fig. the Profiles3). representing and matrix and matrix and mineral rich coals with two thin xy thin two with coals rich mineral and matrix and matrix and plagioclase. and of illite/smectite amounts variable with quartz as such of minerals position siliciclastic in content of Na de imply Kand contents Al higher well as as samples, most and Si high The 2016). al., et (MITROVIĆ conifers from contribution asmall with species aquatic along with shrubs and herbs from originates (OM) mainly matter Organic mire. the level water of of ahigher environment afreshwater veloped in de accumulation 14/79–21/79;peat (samples that 3) Fig.imply III seam of coal the part bottom the in contents ash higher and content relatively low sulphfur of detrohuminite, a predominance with coals rich mineral and of matrix mixtures and rich Mineral 5.2.1. CoalseamIII jor element proportions (Si, Fe, Mg, Ti, Al, K Ca, jor element proportions were in variation mineralogy placed alongside profiles ofthe ma vertical the representing profiles geochemistry, and mineralogy contents. calcite and gypsum/anhydrite high with connected be could content Ca high the while content, matite The variations in lithotypes, maceral composition and ash ash and composition maceral lithotypes, in variations The The central part of the seam consists of mixtures of xylite of mixtures consists of seam the part central The To further evaluate the relationships between lithotypes, lithotypes, between relationships the evaluate To further

Sr. Sr. Lu, LREY, MREY, HREY. Zn, Ce, Pr, Nd, Sm,Eu, Gd, Tb, Dy, Y, Ho, Er, Yb, Si, Ti, Fe, Ba,Cd, Na,Mn, Cr, K, Sc, Li,Ni, Ga, Th, V, Ca, As, Sr. III seam Tb, Ho, Er, Yb, Lu, MREY, HREY. Ba,Cd,Na, Mn, Cr, Sc, Ni, Ga, Th, Ce, Sm,Eu, Gd, Ti, Fe, K, Mg, Co, Cu, Mo, Pb, Rb, Se. Mg, Co, Cu, Mo, Pb, Se, La. Tm. Tm. Li, V, La,Pr, Nd, Dy, Y. MREY, HREY. Zn, Ce, Sm,Eu, Gd, Tb, Ho, Er, Yb, Lu, LREY, Al, Si, Ti, Fe Ba,Cd, Na,Mn, Cr, ,K, Sc, Ni, Ga, Th, Li, V, La,Pr, Nd, Dy, Y, LREY.

Geologia Croatica 72/1 , Na, Mn) in the the Mn) Na, in Geologia Croatica - - - 65 rich rich - - ), as ), well db rich samples - rich and matrix coals with - 79 (sample 2/79) may suggest a slight 2/79) (sample 79 40/91, 8/79; Fig. 3). Lignite is characte 3). Fig. 8/79; 40/91, - - oxide/hydroxides (Fig. 4h). An outstandingoxide/hydroxides 4h). (Fig. - oxide/hydroxides and sulphates. The central part - rich and mixtures xylite of - ratio is still high, as as well the amounts sug Ca and of Fe, The content of As, Cr, Ni, Pb, V and Zn Pb, The Ni, in As,content seam Cr, of II coal is Xylite 91 (samples 33/91, 34/91) indicate 34/91) a higher(samples 91 33/91, contribution of - per part seam of II. Higher contents and Si Al of in borehole oal with moderate contents ash and of sulphur built up the oal (54/603), with moderate amounts of ash and sulphur. The c negative correlationnegative between Ca and sulphur content (S c part of seam II in field The coal is(samples characterisedA 2). Fig. moderate by to very high ash 48/601, 49/601, 55/603, 56/603; toand moderate a low sulphur content. The high Al, Si, K, and contentsNa suggest a high contribution from siliciclastic sedi xylite of consists A field inIIseam partupper Thements.of Si/Al gesting a greater contribution siliciclastic sediments of with vari amountsable Fe of KB siliciclastic sediments, while the higher contents Ca and of total sulphur in KB borehole predominance sulphateof minerals andchanges in water level and the paleoenvironment. severaltimes higher in comparison with the Clarke values for brown coal (KETRIS & YUDOVICH, Arsenic 2009). could be FINKEL 2012; al., et DIEHL 2003; al., et pyrite (DAI inpresent YUDOVICH & KETRIS, KOLKER, 2012 MAN, 1994; 2005a, and references therein) also but as the arsenate in or ion clays Organicphosphate mineralsbound 1990). arsenic (SWAINE, is also common, with higher contents organisms, in lower algae and 2003). al., (LIU et moss and ferns, plants, than in seed herbages Three dominant forms As in of coal (YUDOVICH & KETRIS, are pyritic,2005a, b) organic and arsenate. Recent research on As rich coals from the Xishanyao formation, China (ZHANG et al., 2018) confirms sulphfideand adsorption arsenic. of solution The same authorsbound, conclude residual form,that the origins geological leading toorganic the enrichment arsenic of bound in coal are: hydrothermaltonic fracturing solution the region, of sources terrigenous of detrital ma activities controlledterial controlled regional by settings geological with the distribu by the tec elementstion and of type plants in of the paleomire. The results the chemicalof and mineralogical investigation the Kovin of lig nitesamples indicate pyritic a Asform in of seam II. strongA correlation with in Cr Al, and of seam Si, Fe Ti II, suggests that themainly Cr occurs inaluminosilicate minerals. could Nickel be present in coal in organic and inorganic form. can It be asso ciated with (kaolinite, clays illite, and smectite) sulphides (pyrite, millerite, YUDOVICH bravoite; & KETRIS, Organically 2005b). Nickel bound is also Ni common 1996). et al., in coal (RUPPERT up rised moderate by ash to and high low sulphur contents with vari higher by and contents,Si Ca Al and able followed Fe suggesting a higher contribution siliciclasticsediments of with variable amounts Fe of as with ash content (Table 8) suggests the organic affinity of Ca of affinity organic the suggests 8) (Table content ash with as et LI al., and According S. to 2012; previous research (CHOU, in neutral to alkaline 2016) WARD, groundwater Ca 2010; 2007, and S could be taken peat by forming plants in thepalaeomire and bound with organic matter. prevalence telohuminite of occur in the bottom part coal seam of (samples39 II in B field suggest a 37/79) higher (4/79, contribution of sulphates and Fe oxide/hydroxides formed in a neutral to alkaline and probably environment.oxic Matrix and mixtures matrix of and xylite of seamof II is characterised moderate by to high ash and low/ a moderate to high sulphur content with variable major contentof elements. The higher contents Ca and Fe in xylite

- - - - - ) db IV the of - rich freshwa organic com - - rich lithotypeswith - ) and Ca content sug rank coals. - db bearing spinels (HUGGINS et al., - VI the Supplementary of material to this rich chlorite (Fig. 4d). The ultramafic - - detrohuminite maceral association an allochthonous - The top of coal seam III (sample 11/79) consists mixtures of The coal top seam of 11/79) III (sample Coal from seam III is enriched 6). in Ba, and Cr (Table Sr rich layers indicating an unstable water table from higher to rich coal samples (14/79 and 16/79) with a predominance and of 16/79) rich coal samples (14/79 - - nces between fields A and B. Organic B. lignites matterthe of and A betweenncesfrom fields lower water level in water the level mirelower and conditions. lesswet A predomi nance detrohuminite of with ash content lower confirms decline in water the level of mire. High amounts inertinite of in these samples canbe attributed in part tooxidation, regarding but the inertinite O’KEEFE et al., 1998; et al., origin (TAYLOR is more probable A slight increase in 2013). the sulphur (S telohuminite suggest that deposition the started OM of in a topo genous fresh water mire, which was transformed into a time lim ited forest swamp. wet The high content carbonate of and sulphate minerals with high relatively Ca and total sulphur content (S gests input of mineral matter by inflowing sulphate re 5.2.2. Coal seam II diffesome Thecoalseam geochemical II shows composition of lite Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) dominance detrohuminite of telohuminite over built the bottom both coalfields Matrix was derived from 2016). herbs al., and shrubs et with (MITROVIĆ variable vegetation woody of amounts andmixtures matrix of and mineral rich coals with slighta pre 2000; RUPPERT et al., 1996). In the studied 1996). et al., coals,2000; a strong RUPPERT cor of matrixof and mineral rich coalswith the dominance detro of huminite. The high ash content as as well the Al, Si, K and Na contents, S associated (Table with ratio 5.00 an of Si/Al tion and in illite. could Cr be also present in oxide/carbonate/ monosulphide Coals group, and in silicates 1999). et (DALE al., ultramafictousually situatednearare ppm) (≥~100 Cr enrichedin rocks that contain chrome with Cr relation of ash content in and Al, K and Si, seam Ti, Fe III suggests that the mainly Cr occurs in aluminosilicate mine rals, most probably Cr rockswhich outcrop in the southeastern part the study of area can be the source in Cr of the studied lignite. Furthermore, a high and Ni other Cr, content elements detected of in lignite from the Drmno field1; (Fig. ŽIVOTIĆ et al., suggests2015) asimilar source. The strong correlation with Ba of ash content suggests an inorganic form while as probably indicates barite Sr 4g), (Fig. an The results the 8). organic chemical of form and mineralo (Table gical investigation the Kovin of lignite samples indicate an or ganic form As in of seam III. Supplementarymaterial to this indicates paper) higher a water in thelevel mire with deposition siliciclastic minerals of such as quartz and subordinate minerals clay and plagioclase. The high content Cr wasdetected in mineral high Chromium ash 6). content (Fig. could be present in coal as both organic and inorganic forms (KETRIS & YUDOVICH, In most bituminous2009). coals from two formsmajor the USA are present (HUGGINS & HUFFMAN, organic 2004): associa indicate the influence of neutral to alkalineFurther neutral to groundwater. influenceof theindicate ash and Ca between correlationcoefficient negative good a more, S Table 8; content (Table ter with the formation sulphate of minerals (gypsum/anhydrite; 4f)Fig. confirmedby mineralogicalexamination. Two thin xy lite pounds (SAXBY, 2000) especially inpounds low (SAXBY, paper) indicatespaper) that Ca may also be bound with organic matter as ions in exchangeable carboxylic acids and or hydroxyl phenolic Also, its occurrence 2016). WARD, 2010; groups(LI 2007, et al., is in possible metalloporphyrins and other metal Geologia Croatica (r=0.96), Co (r=0.79), Cr (r=0.79), Ni (r=0.81), Se (r=0.93) (r=0.93) Se (r=0.81), Ni (r=0.79), Cr (r=0.79), Co (r=0.96), (r=0.82), Cr (r=0.91), Ni (r=0.87), Se(r=0.91), Cd with As and of (r=0.94), Fe As (r=0.97), correlation with Cd Co strong very The palaeomire. the in conditions anaerobic and neutral sumably Co, I(Table Cr, seam Mo, Sein 8; Fig. pre m) l, in 4k, formed of Cd, As, form apyritic indicate samples lignite of Kovin the pyrite. in rences strong correlation of Se with S of Se with correlation strong U, with Fe, 2006), Mo, V, & KETRIS, Pb. and (YUDOVICH The zones oxidation bed the in enriched Seis PbSe). coals, oxidized In (clausthalite, forms selenitic some and (pyrite) minerals sulphide in concentrated Se is coals, sulphur high In 2006). 2005b, RIS, &KET (YUDOVICH form inorganic and organic in present be could I. Selenium seam in pyrite of with Cd close connection the correlation As–S correlation Cr, strong Serespectively. Cd, Ni, for Pb and As, Avery higher 18, are values 2009) 27, these YUDOVICH, 25, 9times 24 and & (KETRIS coal for value Clarke brown the with comparison In (9.0 Se mg/kg). (371.4(214.0 and NiCr kg), mg/kg), mg/kg) of value (140.0 As highest the Sewith and (6.5 Cd mg/kg), mg/ Cr, Cd, Ni, Pb As, in enriched especially Iis of seam part That mixture of matrix and xylite and of matrix mixture 44/601(samples layer Ib of the lower (Ia) lower The part layers. upper the (Ib) and tween Lig 5.2.3. CoalseamI claythe minerals. of Pb in presence the indicate seams all Ti K in Si, and Al, with of Pb 2009). positive correlations The &YUDOVICH, (KETRIS coals for value Clarke brown the than content higher times ral (DALE silicates in seve is that aPb content has present II al.,et 1999). seam in be lignite Kovin also could It 2003). ROBERTSON, (HOWER & 1994), coals in selenide well lead as as KELMAN, (FIN minerals sulphide with (galena) orassociated sulphide as occurs mainly Lead associations. mineral and organic both cating indi affinity, specific no shows deposit Kovin the of II seam in 66 correlation of Cd–S correlation al., et 1985). strong possible (YUDOVICH very also is Cd The of form 1999).”organic” al., However, an et DALE (e.g. pyrite; sulphides 2002), other in well (ZnS; as as GOODARZI, sphalerite in mostly Zn with associated predominantly is I. Cadmium seam 26/91 sediments. of siliciclastic contribution ahigher with Si/Al compatible is which ratio, higher Fe of a and Ca with amounts variable and contents sulphur and ash by moderate (Ia) layer characterised upper is the while tents, con sulphur and ash high to by moderate layer characterised is Ib and 52/603, followed by a Si/Alhigher ratio. The from the lignite 45/601 samples in Fe of Mn Ca, and contents high with Al, Si and sists of siliciclastic sediments, while xylite while of sediments, sists siliciclastic pyrite as the main source of both elements (Fe, S elements of both source main the as pyrite with (Table Fe and contents sulphur 8)tween commensurate is Fe in be (Fig. 7b). correlation enriched good also is which The (31/79;sample rich 4b), Fig. mineral S lowermost, the in Table identified (4.40%; sulphur highest are contents ash paper) and this to The material of Supplementary the flooding. frequent with ble ta water unstable an indicating contents sulphur and ash high to by moderate characterised is lignite The contents. Fe Mn Ca, and nite from seam I seam nite from the A from field shows be some differences The results of the chemical and mineralogical investigation investigation mineralogical and of chemical the results The The characteristics of lignite in seam I of the B field (samples (samples field B the of I seam in lignite of characteristics The - 31/91) con coal matrix the in matter mineral revealed that db (Table 6) indicates a pyritic form of As in coal coal of in As form (Table apyritic indicates 6) db (Table 8), clearly (r=0.97) indicates Cd–Fe - 46/601 and 51/603 46/601and - rich coal, has variable amounts of amounts variable has coal, rich db (r=0.76) supports their occur their (r=0.76) supports - rich coal has higher higher has coal rich - 53/603), a of made db ) in seam I. seam ) in con - II II - not show specific affinity in all coal seams. seams. coal all in affinity not show specific does Zn concentrations, high the Despite II. seam coal element in this for observed is affinity specific no whereas III, seam coal in aluminosilicates I, seam coal in sulphides with Ni associated is seams. coal three all in minerals aluminosilicate in Seoccur and Cr, Pb III. seam in form organic an and I, seam in Cd of and As bound. ically organ and inorganically both are II seam of in elements A group affinity. organic outstanding an have also Sr) S, Ca, (As, them of butaffinity, some inorganic a strong elements demonstrate these of all Almost coals. for values brown Clarke the with parison Mo, Ni, Pb, Li, Mn, com V, Lu in Cr, Ga, and Er Tb, Cu, Gd, Zn, seams. coal all of Kin Na and Si, Al, carriers main the are chlorite and illite/smectite with muscovite) and biotite, together thoclase, albite, or plagioclase, (quartz, minerals aluminosilicate and cate face Sur minerals. of aluminosilicate concentrations high in resulted inputs clastic in increases with level apalaeomire water in higher A accumulation. peat during by conditions mably controlled presu of was elements enrichment and distribution The pyrite. the closefirms ofinterrelation the aforementioned with elements structure (KOLKER, 2012). (KOLKER, structure pyrite the Sin with substituted Sb be may Se,and As, as ments, ele some in enriched pyrite of syngenetic formation the in sulted have may re palaeomire, the in environment areducing with along rocks, of basement the leaching and weathering the from Co, Cr, Cd, Ni, As, Se, derived as such elements in rich ment, while barite and monazite were found in coal seam III. seam coal in found were monazite and barite while II, seam coal in identified were monazite and ankerite lomite, do siderite, galena, I. Sphalerite, seam coal in detected also were zircon and allanite epidote, chlorite, barite, addition, In seams. (calcite). carbonate iron and other The (gypsum/anhydrite) clays (illite/smectite), silicates (quartz, plagioclase), sulphate are seams coal all from samples lignite studied the all in minerals dant. abun less are minerals other and carbonates pyrite, while dant, abun most the are Clays %. 37 vol. and 3 between varies matter of content mineral The abundant. much less are inertinite and nite Lipti of gelohuminite. amounts variable with detrohuminite and telohuminite are subgroups maceral abundant most The seams. I(from and lowest highest). II to III, seams, lignite three layers), clay gravel clay, and with thin carbonaceous silt with shallow, caspi of consists sequence sedimentary Kovin Miocene Upper The CONCLUSION 6. and comments greatly benefited this paper. this benefited greatly comments and suggestions helpful whose reviewers anonymous the to grateful also Weare acknowledged. OI172035),gratefully and is which No. OI176006, of of Republic (Projects ence the Serbia OI176016 Sci and Education of Ministry the by financed was work This ACKNOWLEDGEMENT K ilmenite, rutile, as such minerals limonite). Minor and haematite, magnetite, (pyrite, hydroxides and oxides sulphides, are minerals - feldspar (albite, orthoclase), and mica, were detected in all coal coal all in detected (albite, were feldspar mica, and orthoclase), and groundwater from the surrounding palaeo surrounding the from groundwater - and The results of the correlation analysis indicate a pyritic form form apyritic indicate analysis of correlation the results The Co, Cd, As, in enriched is deposit Kovin the from lignite The According to the mineralogical and geochemical data, sili data, geochemical and mineralogical the to According SEM coal three the in group maceral prevailing the is Huminite - EDS examination revealed that the most abundant abundant most the that revealed EDS examination - brackish to fresh water clastic sediments (sand and sediments clastic water fresh to brackish Geologia Croatica 72/1 - environ - rich rich - - - Geologia Croatica

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International - 5162(02) - Geologia Croatica 69 XC XC XC XC XC XC XC XC XC XC XC MC MC MC MC MC MC MC MC MC MiC MXC MXC MXC MXC MXC MXC MXC MXC MXC MXC MXC MXC MXC MMiC MMiC MMiC MMiC MMiC MMiC MMiC MMiC MMiC MMiC Lithology Depth 35.35–36.00 45.00–45.60 45.60–46.05 47.05–48.35 48.60–49.30 49.30–49.50 50.60–50.90 51.60–52.85 65.15–65.35 65.60–65.70 65.70–66.65 73.70–75.50 75.50–76.00 76.00–76.40 67.90–69.30 24.60–25.00 25.50–25.75 25.75–26.35 26.35–27.65 27.65–28.15 22.50–24.25 43.10–43.50 88.00–88.12 88.40–88.60 88.60–88.80 95.30–95.80 96.40–97.00 97.00–97.50 36.80–37.60 38.00–38.20 38.50–39.00 39.00–39.10 40.15–40.65 39.00–39.55 42.65–43.10 247.65–248.05 115.45–116.00 116.05–116.30 116.30–116.60 114.10–114.25 114.45–114.75 114.75–114.85 115.00–115.30 115.30–115.45 2/79 3/79 4/79 5/79 6/79 8/79 33/91 34/91 36/91 37/91 38/91 39/91 40/91 24/79 19/79 20/79 21/79 11/79 14/79 15/79 16/79 17/79 18/79 27/91 28/91 29/91 30/91 31/91 26/91 51/603 52/603 53/603 44/601 45/601 46/601 43/601 54/603 55/603 56/603 47/601 48/601 49/601 50/603 42/601 Sample ID I I I I I I II II II II II II II II II II II II II II II II II II II III III III III III III III III III I (Ia) I (Ia) I (Ia) I (Ib) I (Ib) I (Ib) I (Ib) I (Ib) I (Ib) Coal Seam Coal B B A A Field KB–79 KB–91 GD-603 GD-601 Borehole ID Borehole 1 43 44 40 41 42 37 38 39 34 35 36 30 31 32 33 27 28 29 24 25 26 21 22 23 18 19 20 15 16 17 12 13 14 9 10 11 5 6 7 8 2 3 4 No SUPPLEMENTARY MATERIAL SUPPLEMENTARY Kovin the of lithology and seam coal S–I.field, depth, with samples of List Table 2016, 2017). (after MITROVIĆ et al., lignite Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) MC – Stratified matrix coal (weakly gelified); XC – Xylite-rich coal; MXC – Xylite-rich Mixture of XC – coal; coal (weakly matrix gelified); MC – Stratified matrix and xylite-rich and Mixture coal of xylite-rich MMiC and matrix coal; – Mixture 1998). et al., MiC coal; of matrix and mineral-rich – Mineral-rich (TAYLOR coal Geologia Croatica Table ofproximate Results S-II. andultimate analyses MITROVIĆetal., ofindividualsamples(after 2017adopted). 70 matter, basiswt.%;Q dry H W 2/79 Sample ID 55/603 3/79 56/603 4/79 5/79 6/79 8/79 11/79 14/79 15/79 16/79 17/79 18/79 19/79 20/79 21/79 24/79 26/91 27/91 28/91 29/91 30/91 31/91 33/91 34/91 36/91 37/91 38/91 39/91 40/91 42/601 43/601 44/601 45/601 46/601 47/601 48/601 49/601 50/603 51/603 52/603 53/603 54/603 daf ar –moisture content, asreceived basis, %; W –hidrogen content, dry, ash-free basis, %;N II Coal Seam II II II II II II II III III III III III III III III III I I I I I I II II II II II II II I (Ia) I (Ia) I (Ib) I (Ib) I (Ib) II II II I (Ia) I (Ib) I (Ib) I (Ib) II g daf

– gross calorific value, dry, ash-free basis, MJ/kg;Q W ar 50.68 23.67 30.36 14.42 50.07 47.11 27.81 48.08 13.78 52.89 49.31 54.13 32.55 47.28 48.15 31.34 11.79 47.84 40.08 51.08 35.75 50.28 41.18 34.76 43.54 49.65 32.66 51.59 51.62 43.01 42.59 45.65 44.35 47.21 43.79 48.60 49.92 31.66 44.40 50.79 51.45 52.90 34.57 52.48

(wt.%) an daf –analyticalmoisture content, %;A –nitrogen content, dry, ash-free basis;O W an 10.68 10.38 11.09 12.73 11.08 11.08 11.70 11.60 10.05 10.02 12.02 12.38 15.24 6.52 4.14 5.99 8.53 3.80 2.95 5.60 5.38 4.10 4.78 4.23 7.49 4.48 1.90 6.78 9.75 7.85 9.82 6.75 4.26 4.02 7.16 6.76 9.03 6.66 4.77 4.91 4.77 5.84 9.89 7.24 (wt.%) daf n A

– net calorific – netcalorific value, dry, ash-free basis, MJ/kg;C db 13.85 19.00 54.98 59.84 68.60 20.63 28.02 63.83 25.70 78.20 12.62 22.62 56.29 27.62 25.51 58.27 65.96 26.26 42.91 17.90 50.85 20.08 40.76 52.56 35.95 21.74 56.11 16.47 16.38 37.05 37.92 31.36 34.23 27.78 35.43 24.40 21.03 57.75 34.11 18.69 16.86 12.58 52.90 8.66

(wt.%) db – ash content, dry basis, –ashcontent, %;S dry daf –oxigen content, dry, ash-free basis. Proximate analyses S db 1.67 1.88 1.07 1.67 0.22 2.87 0.78 0.51 3.34 0.21 1.53 1.24 1.33 0.82 1.45 1.70 2.13 0.56 1.83 1.80 1.98 1.73 1.41 3.33 4.40 1.46 1.65 1.35 3.12 0.80 1.00 0.92 2.28 2.85 3.96 1.86 1.69 2.26 2.94 0.97 1.67 0.82 1.68 1.63 (wt.%) db –total basiswt.%; sulphurcontent, dry V V db 50.26 46.29 19.29 26.57 12.10 42.29 38.98 23.13 42.85 11.38 46.71 41.47 43.11 23.45 37.81 41.15 23.18 39.13 35.44 46.97 27.95 47.48 33.81 29.88 37.97 45.34 28.08 48.33 46.09 36.69 35.49 40.78 37.73 45.02 38.44 42.75 44.50 25.88 38.30 45.47 46.88 44.02 29.26 9.67 (wt.%) daf – carbon content, –carbon dry, ash-free basis, %; Q g daf 27.8 25.9 21.7 18.9 16.9 26.1 24.8 17.9 25.1 15.7 26.3 25.9 25.6 23.5 24.2 25.8 21.3 18.7 26.3 23.3 25.1 23.0 25.3 22.8 21.0 24.3 25.9 21.2 25.6 25.5 24.4 23.9 24.2 24.3 25.1 23.8 23.4 25.8 20.2 24.2 26.0 28.3 26.4 22.3 (MJ/kg) Geologia Croatica 72/1 Q n

daf db 26.7 24.8 20.9 17.8 16.3 25.1 23.7 17.0 23.9 14.3 25.3 24.9 24.6 22.5 23.3 24.8 20.3 18.2 25.4 22.1 24.1 21.7 24.2 22.1 20.1 23.3 24.8 19.9 24.6 24.4 23.3 22.6 23.2 23.3 24.2 22.7 22.5 24.7 19.1 23.1 24.9 27.2 25.5 21.1 (MJ/kg) –volatile Geologia Croatica - 0 0 0 0 71 2.6 2.5 2.9 0.3 2.4 1.5 1.9 1.7 1.1 2.6 4.6 3.3 3.3 0.4 1.9 3.1 3.9 0.9 2.6 4.3 2.8 n.a 0.1 n.a 2.3 3.0 0.4 2.8 1.2 1.2 4.0 1.8 8.5 25.3 14.9 0.01 20.3 28.4 11.4 16.3 Calcite 0 0 0 0.8 1.7 9.5 4.4 5.7 9.8 0.5 9.1 4.7 8.1 7.0 7.0 1.7 0.3 3.4 6.1 3.5 9.8 7.9 6.0 n.a 3.6 0.6 1.6 n.a 5.4 1.4 2.5 4.6 4.5 5.7 0.1 0.3 3.1 8.4 tite 11.3 17.1 19.6 15.2 18.2 18.6 Hema- 3.9 8.8 0.7 5.9 4.7 6.6 6.9 3.4 5.5 2.0 8.9 7.9 8.7 8.3 0.8 4.1 2.6 4.3 3.4 4.2 2.5 4.7 n.a n.a 6.3 1.7 6.6 0.5 2.5 4.5 4.0 7.1 2.6 11.9 10.0 11.0 12.0 17.4 13.3 12.9 11.2 17.2 13.1 15.4 clase Plagio- 0 3.2 6.2 9.9 9.4 9.3 n.a 1.6 5.6 n.a 4.7 0.6 9.6 54.6 17.4 52.3 16.7 38.6 10.3 15.0 34.2 13.1 24.9 45.0 18.9 24.4 12.1 50.7 24.6 12.4 28.4 30.9 45.6 14.8 13.5 29.7 16.8 47.7 15.9 42.8 36.1 42.6 14.8 47.0 drite Anhy- 4.0 8.6 n.a n.a 6.0 45.1 57.2 14.3 22.6 37.4 24.5 37.6 23.6 14.6 52.6 20.2 12.0 51.7 37.8 15.1 37.2 30.4 27.5 15.9 28.3 28.6 19.2 10.1 29.4 50.7 69.3 67.2 25.5 37.1 61.5 45.4 15.8 62.4 11.0 19.9 19.1 13.3 27.9 10.5 Quartz n.a n.a 36.5 22.4 14.8 46.7 12.1 25.1 20.0 43.5 43.4 34.8 17.5 38.8 23.9 13.6 18.3 63.2 40.2 25.0 19.9 53.8 47.8 47.7 28.9 35.3 22.3 42.3 14.8 15.1 12.7 30.8 30.6 13.9 11.7 18.4 17.6 20.4 33.0 73.6 50.3 21.5 45.3 23.0 Illite/ smectite II II II I (Ib) I (Ib) I (Ib) I (Ia) II II II I (Ib) I (Ib) I (Ib) I (Ia) I (Ia) II II II II II II II I I I I I I III III III III III III III III III II II II II II II Coal Coal Seam

56/603 55/603 54/603 53/603 52/603 51/603 50/603 49/601 48/601 47/601 46/601 45/601 44/601 43/601 42/601 40/91 39/91 38/91 37/91 36/91 34/91 33/91 31/91 30/91 29/91 28/91 27/91 26/91 24/79 21/79 20/79 19/79 18/79 17/79 16/79 15/79 14/79 11/79 8/79 6/79 5/79 4/79 3/79 2/79 Sample ID n.a – Not analysed. Quantitative mineralogical composition of the Kovine lignite ashes lignite of the Kovine composition mineralogical S-III. Quantitative Table of individual sam basis) matter-free (450°C) (wt.%; on organic analysis XRPD by ples. (wt.%) 24.48 29.56 24.85 27.19 40.42 25.15 33.12 26.05 26.37 26.88 23.95 23.88 21.79 23.25 41.09 29.45 28.90 25.30 26.73 28.96 33.73 22.85 25.23 27.66 26.31 20.77 26.70 28.16 17.06 26.41 24.30 22.53 26.39 25.32 26.19 28.31 27.59 25.86 20.09 23.30 27.77 22.70 29.87 35.71 daf O (wt.%) 1.20 1.39 1.01 1.21 1.35 0.81 1.51 1.05 1.09 1.08 1.21 1.22 1.17 1.32 0.79 0.68 0.79 1.11 1.89 0.93 1.22 1.37 1.22 0.97 0.89 1.04 1.08 0.97 1.34 1.02 1.31 1.15 1.10 1.22 0.99 1.11 0.90 0.96 0.90 1.43 1.38 0.87 0.64 0.89 daf N Ultimate analyses Ultimate (wt.%) 5.25 5.18 4.51 5.18 4.56 5.20 6.65 4.82 5.05 3.92 4.37 4.23 4.31 4.96 2.61 4.03 5.27 4.35 6.53 4.79 2.95 4.28 4.34 5.12 6.31 4.44 4.76 4.65 6.11 4.66 4.56 4.03 4.99 4.17 5.17 5.33 5.43 5.02 4.78 3.80 5.41 5.01 3.84 2.96 daf H (wt.%) 66.75 59.71 66.01 65.34 52.25 64.35 57.43 66.33 65.90 66.67 68.59 68.68 70.45 65.37 55.23 63.36 61.88 66.83 61.32 63.56 56.48 62.23 66.93 64.13 63.41 70.09 66.50 64.62 74.02 64.58 65.50 66.81 64.64 67.06 64.80 58.30 64.61 66.12 73.24 69.55 61.97 69.47 62.08 60.16 daf C Sample ID 2/79 3/79 4/79 5/79 6/79 8/79 11/79 14/79 15/79 16/79 17/79 18/79 19/79 20/79 21/79 24/79 26/91 27/91 28/91 29/91 30/91 31/91 33/91 34/91 36/91 37/91 38/91 39/91 40/91 42/601 43/601 44/601 45/601 46/601 47/601 48/601 49/601 50/603 51/603 52/603 53/603 54/603 55/603 56/603 Table S-II. Continued. Table Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Geologia Croatica Table S-IV. Content ofmajorelements (%)ofindividualsamples. 72 Sample ID 46/601 2/79 47/601 3/79 48/601 4/79 49/601 5/79 50/603 6/79 51/603 8/79 52/603 11/79 53/603 14/79 54/603 15/79 55/603 16/79 56/603 17/79 18/79 19/79 20/79 21/79 24/79 26/91 27/91 28/91 29/91 30/91 31/91 33/91 34/91 36/91 37/91 38/91 39/91 40/91 42/601 43/601 44/601 45/601 Coal Seam I (Ib) II II II II II II II I (Ia) II I (Ib) II I (Ib) III I (Ib) III II III II III II III III III III III I I I I I I II II II II II II II I (Ia) I (Ia) I (Ib) I (Ib) 12.68 12.00 13.46 21.84 11.69 16.84 17.33 14.53 13.35 19.79 11.87 12.75 7.83 2.55 3.88 3.10 7.43 0.40 3.07 2.32 4.36 0.88 1.50 1.97 4.48 0.34 6.46 4.83 6.85 9.01 2.30 3.84 8.19 9.77 7.60 3.92 2.32 2.68 8.80 8.38 6.08 7.60 4.86 6.68 Si 2.08 1.19 1.89 5.72 3.87 1.53 3.17 0.20 1.17 4.49 0.95 2.72 0.52 4.37 5.15 0.66 0.88 1.79 5.07 0.26 3.38 3.08 2.28 2.56 2.84 3.70 1.57 4.68 1.38 3.46 2.18 4.06 1.58 3.65 1.80 5.02 1.44 1.34 3.76 3.99 2.26 2.35 2.52 2.91 Al Si/Al 3.76 2.15 2.06 2.22 3.10 2.03 2.35 2.03 2.61 3.00 2.44 1.61 1.72 5.00 2.27 2.26 2.24 2.50 3.33 1.28 5.12 4.72 2.84 1.89 4.71 5.34 4.36 1.93 1.67 3.43 1.76 2.02 6.17 2.08 2.18 2.54 1.61 2.00 2.34 2.10 2.69 3.23 1.93 2.30 2.67 2.46 1.51 2.39 3.45 5.03 2.80 1.75 0.36 1.86 2.51 0.59 3.25 1.48 3.70 4.00 1.00 1.30 1.02 2.29 0.80 3.73 1.79 1.59 1.31 2.95 3.00 1.73 2.61 1.99 2.48 1.49 3.71 9.01 2.60 1.83 3.52 2.43 0.78 1.84 1.89 2.60 2.73 3.55 Fe 0.11 0.09 0.04 0.06 0.25 0.22 0.08 0.11 0.01 0.05 0.31 0.04 0.09 0.02 0.25 0.18 0.03 0.04 0.09 0.21 0.01 0.32 0.20 0.10 0.12 0.15 0.29 0.10 0.16 0.05 0.16 0.08 0.15 0.09 0.13 0.06 0.24 0.05 0.04 0.15 0.14 0.14 0.16 0.09 Ti 3.19 2.05 2.15 1.53 1.12 1.18 1.33 1.52 0.17 1.91 0.95 1.54 1.22 2.68 1.05 1.44 1.92 1.57 1.55 1.73 2.10 1.06 1.83 1.99 2.04 1.56 0.98 0.94 1.14 1.88 1.76 1.38 1.64 1.44 1.68 1.56 1.00 1.55 1.88 1.33 1.32 1.96 1.96 2.14 Ca 0.58 0.45 0.42 0.43 0.41 0.29 0.35 0.56 0.04 0.39 0.18 0.25 0.38 0.42 0.44 0.67 0.36 0.23 0.37 0.50 0.33 0.26 0.48 0.42 0.44 0.41 0.36 0.27 0.36 0.32 0.51 0.30 0.42 0.28 0.59 0.42 0.34 0.35 0.41 0.47 0.49 0.41 0.54 0.54 Mg 0.11 0.17 0.08 0.08 0.13 0.11 0.05 0.14 0.01 0.10 0.09 0.12 0.04 0.15 0.49 0.12 0.13 0.09 0.18 0.36 0.11 0.28 0.61 0.25 0.16 0.50 0.64 0.45 0.09 0.04 0.29 0.05 0.10 0.33 0.06 0.05 0.09 0.04 0.08 0.15 0.09 0.15 0.18 0.09 Na Geologia Croatica 72/1 0.12 0.17 0.09 0.12 0.18 0.20 0.09 0.31 0.01 0.09 0.19 0.08 0.15 0.04 0.55 0.44 0.04 0.06 0.16 0.31 0.02 0.20 0.52 0.24 0.12 0.38 0.46 0.25 0.13 0.05 0.33 0.08 0.16 0.26 0.25 0.17 0.14 0.07 0.09 0.26 0.25 0.17 0.15 0.14 K 0.027 0.031 0.038 0.014 0.013 0.017 0.011 0.014 0.001 0.015 0.010 0.017 0.008 0.016 0.034 0.014 0.008 0.016 0.009 0.026 0.011 0.019 0.021 0.014 0.009 0.015 0.016 0.013 0.015 0.016 0.030 0.014 0.018 0.154 0.021 0.016 0.014 0.015 0.019 0.014 0.013 0.017 0.018 0.018 Mn Geologia Croatica 73

18 Zn ±1 4.0 4.3 9.1 38.0 18.0 66.0 26.0 31.0 11.2 98.2 59.4 26.5 47.5 54.4 62.5 16.5 35.6 27.2 39.2 43.6 43.0 25.6 49.6 15.4 31.1 16.6 82.6 56.1 44.4 41.6 57.9 11.0 23.9 65.8 56.4 68.1 42.8 31.9 23.4 239.7 155.5 144.8 174.8 157.9

V 22 ±2 7.6 6.4 3.3 67.2 42.0 31.0 17.8 15.0 49.8 76.8 89.4 13.3 78.7 49.9 49.7 88.1 16.3 34.0 30.9 35.4 54.5 31.5 43.0 29.6 47.6 25.4 59.0 33.1 48.1 54.0 61.1 38.1 23.1 17.5 50.1 55.1 47.8 46.8 52.8 30.7 60.9 35.8 110.8 100.3 Tl < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5

Th 1.7 3.3 1.7 0.7 0.2 2.1 0.2 1.0 0.1 3.7 0.9 0.1 1.9 2.4 2.8 1.9 1.4 2.5 1.9 1.9 1.8 2.9 1.1 1.2 0.1 2.5 0.7 2.4 0.6 2.6 1.7 1.6 0.4 0.3 1.6 1.4 2.0 1.3 1.7 1.1 1.5 0.9 ±0.2 < 0.1 < 0.1 < 0.1

Sr 120 ±10 82.5 69.1 79.8 10.2 94.9 58.0 73.9 46.0 65.9 53.7 68.3 77.1 94.8 81.5 58.6 78.7 98.8 82.5 77.4 65.4 61.4 97.4 99.6 105.1 116.7 128.8 177.7 253.1 176.1 100.7 120.7 136.4 201.7 183.9 210.3 204.4 175.7 218.9 186.7 155.3 221.6 113.8 108.5 106.7

Se 2.3 1.0 1.8 1.7 1.7 3.0 1.3 2.3 1.6 0.3 2.8 2.5 1.4 2.0 3.3 1.9 4.9 1.2 1.9 0.9 3.6 1.8 4.3 2.6 3.5 1.4 1.9 1.5 2.4 1.7 4.4 9.0 2.7 1.6 3.5 1.8 1.6 1.4 2.0 4.6 3.6 2.7 3.5 2.7 2.6 ±0.15

Sc 4.1 6.1 2.8 3.0 2.1 5.0 1.2 0.6 2.1 8.1 6.1 8.1 3.2 4.7 0.6 5.1 5.0 6.2 4.7 7.1 3.0 8.7 2.8 6.7 4.0 8.3 5.8 8.2 4.5 3.1 3.1 7.9 8.3 7.6 7.0 4.8 5.8 4.5 14.5 11.2 15.1 12.9 12.8 11.1 10.8 ±0.2 Sb 4.3 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5

10 Rb 7.0 5.5 4.2 5.4 6.2 0.4 0.8 3.7 7.8 0.8 9.3 3.0 2.4 5.2 7.6 1.2 6.2 7.9 7.3 9.9 5.3 6.2 8.0 2.7 33.0 36.1 15.7 18.2 14.2 11.7 36.3 18.0 24.9 10.9 14.9 21.1 18.0 15.7 18.8 10.5 10.5 13.6 ±0.9 < 0.5 < 0.5 Coal Seam Coal II II I (Ia) II I (Ib) II I (Ib) II I (Ib) II II II II III II III III III III III III III III I I I I I I II II II II II II II I (Ia) I (Ia) I (Ib) I (Ib) I (Ib) II II a Sample ID 49/601 2/79 50/603 3/79 51/603 4/79 52/603 5/79 53/603 6/79 54/603 8/79 55/603 11/79 56/603 14/79 Clarke value ofClarke value coal brown 15/79 16/79 17/79 18/79 19/79 20/79 21/79 24/79 26/91 27/91 28/91 29/91 30/91 31/91 33/91 34/91 36/91 37/91 38/91 39/91 40/91 42/601 43/601 44/601 45/601 46/601 47/601 48/601 Table S-IV. Continued. S-IV. Table Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Geologia Croatica Table S-V. Content oftrace elements (mg/kg)ofindividualsamples. 74 a 42/601 40/91 39/91 38/91 37/91 36/91 34/91 33/91 31/91 30/91 29/91 28/91 27/91 26/91 24/79 21/79 brown coal valueClarke of 20/79 56/603 19/79 55/603 18/79 54/603 17/79 53/603 16/79 52/603 15/79 51/603 14/79 50/603 11/79 49/601 8/79 48/601 6/79 47/601 5/79 46/601 4/79 45/601 3/79 44/601 2/79 43/601 Sample ID KETRIS & KETRIS YUDOVICH (2009) a I (Ia) II II II II II II II I I I I I I III III II III II III II III I (Ib) III I (Ib) III I (Ib) III I (Ia) III II II II II II II I (Ib) II I (Ib) II I (Ib) II I (Ia) Coal Seam 140.0 < 0.5 < 0.5 < 0.5 < 0.5 36.7 10.5 ±1.3 31.8 28.7 35.0 22.8 56.7 16.1 19.8 10.5 39.0 21.2 12.7 18.2 24.9 31.1 13.0 17.7 11.4 11.6 28.1 15.8 55.1 39.1 70.4 15.8 33.6 21.5 30.3 34.9 29.5 24.3 4.6 4.4 5.7 9.4 4.5 4.0 4.3 7.6 As

122.1 100.3 108.2 142.3 123.8 138.7 190.4 232.4 181.7 138.7 111.4 156.5 122.6 226.3 173.1 239.8 100.1 170.3 122.7 90.7 99.2 72.2 62.3 80.9 72.0 74.8 91.1 34.9 62.7 77.8 94.8 40.9 61.2 47.5 94.6 78.0 48.1 96.7 72.6 63.4 58.4 43.5 65.0 ±20 150 9.3 Ba

±0.04 0.24 2.4 1.1 1.3 0.5 1.5 2.3 1.8 1.7 6.5 3.1 1.2 1.9 1.1 1.4 2.0 2.0 1.6 1.7 1.4 2.2 1.3 1.2 1.6 2.4 0.7 0.9 0.8 0.6 0.8 1.6 2.3 1.4 2.4 2.6 1.4 3.2 0.2 1.7 1.5 1.8 2.4 2.1 1.5 2.0 Cd

24.5 ±0.3 23.2 11.1 14.6 35.8 11.9 15.3 21.8 13.5 11.5 33.7 11.0 11.3 13.9 24.8 16.7 25.1 15.2 34.3 11.9 21.9 26.3 16.9 10.5 20.1 7.0 7.3 2.5 8.6 7.6 7.8 7.6 6.6 1.5 8.8 3.4 2.3 6.5 7.7 9.4 3.4 9.8 8.0 6.4 4.2 Co

106.1 126.1 113.9 371.4 108.8 184.0 265.3 139.5 216.8 226.7 214.5 191.0 251.7 150.9 127.8 149.6 125.3 101.4 76.9 96.0 29.8 47.5 82.9 43.0 41.9 74.1 94.6 63.8 75.9 39.8 11.9 35.2 58.4 36.6 31.2 59.5 84.4 83.7 86.2 65.6 78.7 52.2 93.3 8.4 ±1 15 Cr

45.3 41.1 46.6 11.6 11.0 65.1 34.4 58.0 62.6 28.1 28.9 21.0 45.8 59.9 57.3 77.2 62.4 71.3 38.3 28.7 72.5 40.6 15.2 23.5 29.1 29.7 30.7 68.9 39.9 24.5 24.6 38.7 69.0 54.3 21.7 27.4 3.6 5.2 8.6 3.8 3.5 8.0 6.3 3.1 Cu ±1 15

10.1 11.9 11.2 ±0.3 19.4 11.7 13.4 13.6 10.4 14.3 14.6 10.0 22.9 16.2 16.3 16.5 20.0 25.6 19.8 3.4 5.7 5.8 6.2 4.7 5.4 7.8 6.7 3.2 8.0 1.0 2.3 5.5 2.1 3.0 4.3 9.8 9.7 6.7 0.9 7.4 7.0 8.9 9.3 3.2 9.5 5.5 Ga

34.7 47.2 42.8 14.6 16.7 82.8 16.9 39.7 35.8 17.2 29.8 45.4 21.9 18.2 46.5 29.4 43.0 24.0 23.3 54.1 22.6 11.0 37.9 33.6 33.0 85.1 75.1 21.7 17.4 17.3 21.1 84.8 26.2 23.5 9.5 8.0 9.9 8.6 1.7 3.8 8.8 4.3 2.2 9.5 ±1 10 Li

11.5 ±0.2 Mo 4.9 4.8 1.4 4.2 7.4 6.7 4.6 8.7 8.9 3.9 4.1 4.4 5.2 3.7 5.3 6.6 5.6 8.9 4.3 4.4 2.5 3.8 8.9 1.9 2.8 4.1 1.1 2.7 4.3 4.8 4.3 8.3 9.8 4.9 6.8 0.7 5.0 5.4 5.4 7.4 8.1 4.0 7.7 2.2 Geologia Croatica 72/1 110.6 131.7 135.1 214.0 148.5 110.0 206.1 25.2 31.2 ±0.9 13.2 34.8 47.7 64.2 46.7 24.0 31.6 33.2 55.0 61.4 45.4 44.3 74.5 77.5 26.9 43.5 19.5 26.3 13.7 15.8 35.7 77.3 50.6 92.9 33.2 43.0 73.4 63.3 83.2 47.3 65.1 36.2 91.5 9.7 9.4 9.0 Ni

115.2 113.9 179.9 110.0 111.4 175.7 107.0 116.3 ±0.4 21.6 20.0 49.2 76.8 38.8 55.2 19.5 60.2 80.9 40.4 40.1 70.4 50.3 52.9 82.1 14.5 58.3 51.5 16.9 10.4 26.2 55.4 46.2 74.8 56.2 40.7 31.8 82.4 80.2 54.2 24.3 91.4 96.4 2.8 6.9 4.1 6.6 Pb

Geologia Croatica 75

Y 8.6 5.11 7.62 6.64 9.56 6.79 4.74 5.94 5.87 0.76 5.70 2.39 4.37 2.09 7.11 5.27 3.03 4.77 7.57 0.99 4.94 8.61 7.60 7.72 8.67 6.85 5.64 4.62 3.30 9.17 3.60 5.11 9.47 9.55 5.03 5.34 5.03 8.61 7.36 ±0.4 13.47 14.94 12.79 12.34 17.54 11.12

Dy 2.0 0.87 1.32 1.34 1.26 1.09 0.54 1.00 0.93 0.13 0.81 0.29 0.81 1.94 0.33 1.40 2.05 0.75 0.49 1.06 1.27 0.11 0.84 1.63 1.37 1.41 1.41 1.21 0.91 0.75 0.51 1.64 0.54 0.71 2.54 1.60 1.78 0.72 0.76 0.83 1.33 1.17 1.80 2.68 1.63 ±0.1

Tb 1.30 0.32 0.75 1.10 2.60 2.50 1.40 0.60 4.50 0.50 3.00 1.40 0.70 0.10 1.90 0.50 2.00 0.50 0.60 1.20 1.50 3.10 2.10 0.40 1.10 0.90 1.60 0.80 2.25 0.70 0.50 1.70 2.00 0.20 0.90 0.80 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 < 0.1 ±0.03

Gd 2.6 8.46 7.11 4.76 4.96 5.92 7.23 0.76 4.63 3.53 7.19 3.80 3.49 3.54 6.40 2.48 7.94 8.14 9.79 6.17 8.54 4.37 9.92 5.22 8.66 7.12 8.69 5.97 4.54 3.95 8.77 8.32 9.58 7.76 ±0.2 13.02 11.38 14.38 12.92 11.05 11.93 15.70 11.74 14.57 11.89 11.18

Eu 0.5 0.51 0.59 0.48 0.51 0.59 0.71 0.59 0.46 0.08 0.41 0.31 0.23 0.83 0.25 0.84 0.94 0.28 0.25 0.40 0.59 0.15 0.65 0.70 0.57 0.54 0.78 0.70 0.45 0.48 0.35 0.71 0.31 0.62 1.59 0.71 0.71 0.54 0.48 0.27 0.54 0.50 0.73 0.92 0.80 ±0.02

1.9 Sm 0.80 0.90 0.70 1.00 1.50 1.60 1.00 0.80 0.10 0.60 1.30 0.20 1.70 0.15 1.50 1.90 0.50 0.40 0.50 1.00 0.10 1.40 0.80 0.90 1.00 1.10 1.60 0.50 1.20 0.60 1.10 0.50 1.40 2.20 1.10 0.90 1.50 0.60 0.40 1.20 1.20 1.30 1.70 1.60 ±0.1

11 ±1 Nd 6.50 6.80 6.20 5.00 4.00 4.15 5.90 6.30 0.80 4.70 1.50 2.90 8.30 3.00 7.70 3.40 2.60 6.50 7.70 1.70 4.70 8.00 8.30 9.00 5.90 5.65 3.90 3.70 9.00 4.20 5.40 7.60 9.00 9.90 2.85 4.90 4.00 6.40 5.20 7.90 8.50 8.00 10.20 10.80

Pr 3.5 4.05 3.60 2.90 2.10 2.15 3.10 3.80 0.40 3.10 0.90 2.30 4.00 2.00 5.40 5.90 2.20 1.80 4.20 4.50 1.40 2.30 7.10 4.70 5.10 5.40 3.70 4.20 2.10 2.00 5.30 2.80 2.80 1.80 5.20 5.40 2.10 2.60 2.60 3.90 3.00 4.30 4.60 4.40 3.90 ±0.3

22 Ce ±1 9.70 1.70 9.30 3.80 5.00 5.85 5.80 5.40 2.70 8.50 7.50 8.00 9.00 6.00 9.60 13.95 10.10 10.30 13.50 13.00 12.10 15.40 20.15 21.20 12.10 15.90 12.50 21.40 14.50 13.80 19.40 15.40 12.65 18.40 13.80 28.70 17.80 17.60 10.30 11.40 14.60 14.70 16.10 13.00

La 10 8.73 5.78 5.00 4.39 4.47 6.37 8.33 0.81 5.26 2.11 3.61 7.61 3.56 8.24 3.19 3.03 7.44 1.90 6.12 9.28 8.78 6.80 8.03 3.70 4.16 5.10 6.53 9.94 9.80 3.33 4.86 4.01 6.35 4.89 8.46 8.29 8.33 8.31 ±0.5 11.95 10.77 15.21 11.59 12.86 10.24 Coal Seam Coal I (Ib) II II II II II II II I (Ia) II I (Ib) II I (Ib) III I (Ib) III II III II III II III III III III III I I I I I I II II II II II II II I (Ia) I (Ia) I (Ib) I (Ib) a

Sample ID 46/601 2/79 47/601 3/79 48/601 4/79 49/601 5/79 50/603 6/79 51/603 8/79 52/603 11/79 53/603 14/79 54/603 15/79 55/603 16/79 56/603 17/79 of brown coal of brown Clarke value 18/79 19/79 20/79 21/79 24/79 26/91 27/91 28/91 29/91 30/91 31/91 33/91 34/91 36/91 37/91 38/91 39/91 40/91 42/601 43/601 44/601 45/601 Content of Rare earth elements and yttrium (REY, mg/kg) of individual samples. mg/kg) of Rare earth and yttrium Content (REY, elements S-VI. Table Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) LREY = La+Ce + Pr + Nd + Sm; MREY = Eu + Gd + Tb + Dy + Y; HREY = Ho + Er + Tm + Yb + Lu; (SEREDIN & DAI, 2012). (SEREDIN & DAI, + Lu; Yb + Tm Ho + Er + HREY = Y; + DyTb + + Gd + + Nd + Sm; MREY = Eu + Pr LREY = La+Ce Geologia Croatica a Table S-VI. Continued. 76 2/79 Sample ID 49/601 3/79 50/603 4/79 51/603 5/79 52/603 6/79 53/603 8/79 54/603 11/79 55/603 14/79 56/603 15/79 brown coal valueClarke of 16/79 17/79 18/79 19/79 20/79 21/79 24/79 26/91 27/91 28/91 29/91 30/91 31/91 33/91 34/91 36/91 37/91 38/91 39/91 40/91 42/601 43/601 44/601 45/601 46/601 47/601 48/601 KETRIS & KETRIS YUDOVICH (2009); a II Coal Seam II II I (Ia) II I (Ib) II I (Ib) II I (Ib) II II III II III II III III III III III III III I I I I I I II II II II II II II I (Ia) I (Ia) I (Ib) I (Ib) I (Ib) II II b SEREDIN&DAI (2012) ±0.05 0.60 0.50 0.32 0.44 0.69 0.23 0.49 0.18 0.06 0.04 0.54 0.79 0.80 0.10 0.87 0.77 0.27 0.79 0.32 0.05 0.85 0.44 0.48 0.63 0.93 0.34 0.42 0.18 0.71 0.26 0.51 1.35 0.60 0.52 0.58 0.27 0.22 0.49 0.49 0.69 0.86 0.62 0.34 0.50 0.45 Ho

±0.08 1.22 0.85 0.89 0.82 1.41 0.77 1.10 0.49 0.14 0.40 0.79 1.87 1.92 0.52 1.23 1.03 0.76 1.10 0.80 0.21 1.13 1.08 1.14 1.22 1.22 0.72 0.95 0.58 1.29 0.64 1.05 2.45 1.25 1.20 1.17 0.76 0.63 1.16 1.11 1.87 2.38 1.52 0.83 1.17 1.29 Er

±0.02 0.16 0.31 0.26 0.26 0.20 0.25 0.23 0.19 0.03 0.13 0.09 0.52 0.34 0.13 0.30 0.31 0.26 0.17 0.28 0.08 0.36 0.33 0.38 0.25 0.20 0.21 0.12 0.13 0.39 0.14 0.18 0.29 0.36 0.34 0.17 0.23 0.12 0.21 0.18 0.38 0.52 0.31 0.25 0.31 0.32 Tm

±0.05 1.41 0.81 0.90 1.70 0.74 1.13 0.50 0.14 0.31 1.14 2.02 2.00 0.45 1.36 1.26 0.64 1.53 0.80 0.15 1.13 1.08 1.19 1.22 1.38 0.75 1.02 0.60 1.42 0.63 1.13 2.71 1.44 1.18 1.48 0.79 0.56 1.21 1.13 1.71 2.45 1.53 0.87 1.20 1.21 1.0 Yb ±0.02 0.19 1.19 0.35 0.46 0.90 0.40 0.67 0.14 0.09 0.28 0.61 1.03 0.89 0.26 0.91 0.64 0.24 1.15 0.27 0.13 0.67 0.44 0.37 0.78 0.85 0.47 0.64 0.43 0.75 0.33 0.92 2.65 0.70 0.49 0.84 0.54 0.19 0.49 0.51 0.75 0.90 0.88 0.60 0.62 0.59 Lu

LREY 25.87 26.38 31.33 22.29 22.96 29.37 14.01 14.56 51.15 37.01 13.23 42.99 39.87 15.09 27.02 30.74 55.31 37.38 36.98 46.49 33.40 31.03 19.40 17.96 46.66 20.60 29.93 50.24 43.34 43.60 18.78 23.26 17.01 29.25 23.89 36.56 37.79 38.43 32.51 34.43 23.60 3.81 9.61 7.80 b MREY 20.75 14.54 16.23 25.00 12.15 13.86 22.86 30.38 24.30 25.26 23.67 10.49 24.88 12.63 23.18 18.08 19.01 22.15 26.43 13.16 16.49 22.54 10.57 16.70 24.04 21.66 18.20 21.39 11.94 10.71 21.61 20.05 24.65 33.22 22.11 16.25 17.38 16.78 9.44 1.75 6.46 7.56 4.23 8.93 b HREY Geologia Croatica 72/1 4.58 2.62 2.89 4.90 2.40 3.61 1.50 0.46 1.16 3.17 6.22 5.95 1.46 4.66 4.01 2.17 4.75 2.47 0.61 4.14 3.37 3.56 4.10 4.58 2.47 3.15 1.91 4.56 2.00 3.79 9.45 4.35 3.73 4.23 2.59 1.72 3.56 3.42 5.40 7.11 4.86 2.89 3.80 3.85 b 51.19 43.54 50.45 52.19 37.51 46.84 24.95 22.17 35.64 87.75 67.26 22.25 72.91 67.55 27.75 56.65 45.84 12.64 82.63 58.83 59.54 72.74 64.41 46.66 39.04 28.80 73.76 33.17 50.42 83.73 69.35 65.53 44.39 37.79 29.44 54.42 47.36 66.61 78.12 ΣREY 65.40 51.66 55.61 44.23 6.02 Geologia Croatica

Sr (0.69). (0.38). As Mg (0.49), Co (0.43), Cu (0.39), Mo (0.41), (0.32), Pb (0.43), Cu Mg (0.49), Co Rb (0.47), Se (0.42). III seam Ca (-0.81), As (-0.52), Sr (-0.72). (-0.81), As Ca Al (0.93), Si (0.99), Ti (0.94), Fe (0.95),K (0.97), Fe (0.94), Ti Al (0.93), Si (0.99), Na (0.92), Mn (0.98), (0.83), Si/Al (0.96), Ba (0.64), Nd (0.59), V (0.58), La (0.57), Pr Li (0.66), Cd (0.94), Cr (0.96), Ga (0.94), NiCd (0.72), Sc (0.77), (0.93), (0.85), Sm (0.86), Eu (0.82), Zn (0.90), Ce Th (0.82),Yb (0.77), Ho (0.94), Er (0.76), Tb Gd (0.94), (0.99), LREY (0.74), MREY (0.91), HREY (0.89). Lu Y (0.63). Dy (0.66), (0.22). Tm Ti (0.97), Fe (0.94), K (0.96), Na (0.92), Mn (0.83), (0.97), Fe Ti (0.95), Cr (0.98), Ga Ni (0.95), Ba (0.98), Cd (0.71), (0.90), Eu (0.81), Sm (0.88), (0.90), Ce Th Sc (0.79), (0.81),Yb (0.81), Ho (0.95), Er (0.74), Tb Gd (0.95), HREY (0.88). (0.98), MREY (0.90), Lu V (0.82), Zn (0.95), Ce (0.90), Pr (0.74), Nd (0.71), (0.90), Pr V (0.82), Zn (0.95), Ce (0.75), DyTb (0.81), (0.95), Gd (0.96), Sm (0.93), Eu Si (0.93), Ti (0.95), Fe (0.87), K (0.91), Na (0.81), Fe (0.95), Ti Si (0.93), Mn (0.96), Cr (0.90), (0.77), Si/Al (0.85), Ba (0.93), Cd (0.92),Th Ga (0.96), Li (0.87), Ni (0.82), Sc (0.93), (0.93), (0.95), Lu Yb Y (0.74), Ho (0.94), Er (0.88), LREY (0.81), MREY (0.96), HREY (0.95). III seam Mg (0.62), Co (0.54), Cu (0.56), Mo (0.63), (0.53), Pb Cu (0.54), Mg (0.62), Co Se (0.58), La (0.63). Li (0.66), V (0.58), La (0.51), Pr (0.59), Nd (0.53), V (0.58), La (0.51), Pr Li (0.66), Y (0.59), LREY (0.68). Dy (0.62),

(-0.40), Ca (-0.41). (-0.40), Ca db As (0.76).As Mo (0.50). (0.48), Ni (0.42). (0.39), Cd Fe Mo (0.42), Zn (0.45). II seam S Al (0.84), Si (0.95), Ti (0.97), Ba (0.80), Cr (0.83), (0.97), Ti Al (0.84), Si (0.95), (0.58),Th (0.54), K (0.55), Na (0.59), Pb (0.63), Fe (0.28), (0.32), Co Mg (-0.11), Mn (-0.13), Cd As (-0.05), Ni (0.07), (-0.02), Rb (-0.01), Sr (-0.18), La (-0.04), Ce Cu (0.84), Ga Li (0.86), Sc (0.95), Cu (0.88), Se (0.70), (0.82). Tb V (0.80), Gd (0.93), (0.68), Lu (0.53), Yb (0.66), Ho (0.66), Sm (0.66), Eu HREY (0.50). Y (-0.19), Er (0.23), (-0.22), Nd (-0.22), Dy (-0.23), Pr Tm (-0.22), LREY (-0. 03), MREY (0.01). Tm II seam Yb (0.70), Lu (0.63), HREY (0.65). (0.70), Lu Yb Fe (0.60), Na (0.53), Mo (0.53), Se (0.63), Er (0.50), Fe Eu (0.67), Yb (0.59), Lu (0.69), HREY (0.57). (0.59), Lu Yb (0.67), Eu Fe (0.61), K (0.69), Pb (0.56), Th (0.67), Sm (0.67),Th (0.56), (0.61), K (0.69), Pb Fe Ti (0.95), Na (0.77), Ba (0.89), Cr (0.93), Cu (0.90), (0.95), Na (0.77), Ba (0.89), Cr (0.93), Cu Ti (0.72), Ho (0.75). Tb Gd (0.96), Ga (0.93), Li (0.71), Sc (0.82), Se (0.80), V (0.76), Ga (0.93), Li (0.71), Sc (0.82), Se (0.80), Si (0.88), Ti (0.84), K (0.74), Ba (0.86), Cr (0.75), (0.84), Ti Si (0.88), Ga (0.86), (0.74), Sc (0.86), Li (0.90), Pb (0.86),Cu Th (0.76), V (0.84), Sm (0.77), Eu (0.77), Gd (0.88),V (0.84), Sm (0.77), Eu (0.76), Th (0.73), Ho (0.75). Tb

(0.41), Mg (0.40), Mn (0.45), (0.45), As db Fe (0.79), As (0.79), Cd (0.78), Se (0.76). (0.79), Cd (0.79), As Fe Mn (0.65), Cr (0.58), Mo (0.66). (0.60), Co V (0.37). Na (0.35), Ga (0.47), Ni (0.49), Sc (0,35), Cu (0.48), Zn (0.44), Pr (0.42). (0.48), Zn (0.44), Pr Cu I seam Sr (-0.45). Cr (0.75), Ga Rb (0.71), (0.92), Pb (0.73), Sc (0.73), (0.81), Nd (0.70), Sm (0.81), V (0.79), La (0.74), Ce (0.72),Yb (0.74), Gd (0.78), Ho (0.79), Eu (0.74). LREY (0.80), MREY (0.72), HREY (0.62), Li (0.68), (0.65), Co Na (0.56), Cd (0.68), Fe (0.69),Tb (0.67), Th Mo (0.56), Ni Se (0.65), (0.59), (0.69). (0.51), Lu Tm Y (0.57), Er (0.66), Dy (0.62), S (-0.33). Ca Al (0.75), Si (0.95), Ti (0.80), K (0.85), Ba (0.81), (0.80), Ti Al (0.75), Si (0.95), Si (0.78), Ti (0.87), Cu (0.85), Ga (0.86), Li (0.94), Cu (0.87), Ti Si (0.78), (0.85). Tb V (0.73), Gd (0.76), (0.81), Th Sc (0.79), I seam Mg (0.54), K (0.64), Ba (0.61), Pb (0.60), RbMg (0.54), K (0.64), Ba (0.61), Pb (0.55), Sm (0.54), MREY (0.52). Fe (0.55), Na (0.55), Co (0.53), Ni (0.54), Pr (0.55), (0.53), Ni (0.54), Pr (0.55), Na (0.55), Co Fe Y (0.59), Er (0.64), (0.63), DyTb (0.62), (0.67), Eu (0.57), HREY (0.69). (0.69), Lu Yb (0.59), Tm Al (0.78), Ti (0.85), K (0.87), Ba (0.80), Cr (0.71), Ti Al (0.78), MREY (0.75). Ga (0.78), Rb (0.88), Li (0.71), Pb (0.74), Sc (0.78), (0.76), Nd (0.75), V (0.88), La (0.80), Ce (0.75), Th Sm (0.75), Gd (0.83), Ho (0.74), LREY (0.81), =0.35–0.49 =0.7–1.0 =0.5–0.69 =−1.0– -0.35 =−0.34–0.34 =0.35–0.49 =0.50–0.69 =0.7–1.0 – total sulphur content, dry sulphur content, basis wt.% – total = 0.5–0.69 = 0.7–1.0 = 0.5–0.69 = 0.7–1.0 db Si Si Al Al Stot ash Stot Stot ash ash ash ash r r r r Correlation with ash yield Correlation r Al affinity r Correlation with total sulphur content sulphur with total Correlation r r r r Si affinity r r S Table S-VII. Continuied. S-VII. Table Element affinities deduced from calculation of Pearson’s correlation coefficients between the concentration of each element in the coal and ash yield, ash yield, coal and in the element of each concentration the between coefficients correlation Pearson’s of calculation from affinities deduced Element S-VII. Table sulphur content. Si, Al and total Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia) Geologia Croatica Figure S1. X-ray patterns oflignite diffraction ash(450 78 o C) of individual samples of boreholes GD-601 (a) and GD-603 (b)intheAfield. (a)andGD-603 ofindividualsamplesboreholes GD-601 C) Geologia Croatica 72/1 Geologia Croatica 79 C) KB-79 (a) and KB-91 (b) in the B field. of individual samples of boreholes o X-ray diffraction patterns of lignite ash (450 diffraction of lignite patterns S2. X-ray Figure Životić et al.: Distribution of major and trace elements in the Kovin lignite(Serbia)