GEOLOŠKI ANALI BALKANSKOGA POLUOSTRVA Volume 81 (2), December 2020, 49–61 – https://doi.org/10.2298/GABP201107010S Original scientific paper Оригинални научни рад Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

1 1 ORan TEVanOVić E1LjKO aRinOVić Z RanSiSLaV ETRO,V V ić M & B P Abstract.

Hydrogeological survey of wider Majdanpek mining area in the Carpathian mountain arch of eastern Serbia, including open mine pits, tailings sites, and major karstic springs and caves has been undertaken in order to es - timate environmental conditions in groundwater ibno sdityu (GWB) “Krš–sever”, groundwater quality, and to investigate causes of their earlier indicated poor chemical status. Bearing in mind that Majdanpek copper mine field is directly bordering the karst aquifer and delineated GWB “Krš–sever”, the two karst springs namely Valja Fundata and Kaludjerica were measured and sam - pled in high and low-water periods (spring 2019, late autumn 2019 and spring 2020). Sampling and analysis of groundwater were carried out under the frame of project “Operational Monitoring of Groundwater of the Republic of Serbia”, established by the Ministry of Environmental Protection of Serbia. The field measurements of unstable chemical components and physical properties

as well as laboratory analyses confirme2d+ very2+ poo2r+ and e2– ven hazardous water quality of both surveyed springs Valja Fundata and K4aludjerica. Registered concentrations of some ions, such as Fe , Mn , Ca , SO are high above maxi - mal permitted level for potable water in Serbia. High turbidity rate also con - firms impact of colloidal suspensions from the tailing which is located in karstic blind valley. Leakage of mine water passes through joints, open cavities Key words: and even large cave system Valja Fundata. Results of undertaken survey con - Hazardous substances, firm that low-water period results with worse water quality and much higher karst aquifer, copper, tailing, concentration of hazardous substances than that characterized high-water Majdanpek, Serbia. season when infiltrated rainy water and/or melted snow dilute tailing’s waste - water. Strict application of environmental protection measures and de - sign/construction of the smaller water treatment facility at both surveyed springs should possibly mitigate the impacts of mining activities to karst groundwater and dependant ecosystem. Апстракт.

У циљу оцене стања животне средине и разумевања потен - цијалних узрока још раније евидентираног лошег хемијског статуса водног тела подземних вода „Крш–север“, извршен a je хидрогеолошка проспекција шире околине лежишта бакра Мајданпек, која је укључила истраживање површинског копа, флотационог језера и главних карстних 1University of Belgrade – Faculty of Mininвgр aеnлdа Gиe пoеloћgиyн, аD.e Иpaмrаtmјућenиt уo fв Hиyдdуr oдgаe сoеlo еgкy,с Cпeлnоtаrтeа fцoиr оKнaоrs tп Hољydеr oрgуeдoнloиgкyа , Djušina 7, 11000 Belgrade, Serbia. E-mail: [email protected]

49 Zoran StEVanoVić , V EljKo MarinoVić & B raniSlaV PEtroVić

in situ

бакра Мајданпек директно граничи са карстном издани и водним телом подземних вода „Крш–север“, параметри квалитета подземне воде су анализирани ( и лабораторијски) на два главна карстна врела – Ва - ља Фундата и Калуђерица у периодима високих и ниских вода (пролеће 2019, касна јесен 2019. и пролеће 2020.), у циљу оцене утицаја рударских активности на квалитет подземних вода. Узорковање и анализа под - земних вода извршена је у оквиру пројекта „Оперативни мониторинг подземних вода Републике Србије“, иницираног од стране Министарства заштите животне средине Републике Србије. Теренска мерења нестабил - них хемијских компонентни и физичких карактеристика, као и лаборато -

ријске анализ2е+ пот2в+ рди2л+ е су 2в– еома лош, па чак и опасан квалитет вода оба осматрана карстна врел4а. Регистроване концентрације неких јона, као што су Fe , Mn , Ca , SO далеко су изнад максимално дозвољених концентрација за воду за пиће у Србији. Знатно повећане вредности мутноће указују на продор вода из флотације Ваља Фундата лоциране у дубокој карстној депресији слепе долине истог имена. Процуривање и активна филтрација отпадних вода флотације остварује се преко пукоти - Кључне речи: на, каверни и крупних пећинских канала Ваља Фундате. Резултати спро - Опасне супстанце, ведених истраживања потврђују да периоди ниских вода резултирају карстна издан, бакар, лошијим квалитетом воде и много већом концентрацијом опасних флотацијско језеро , материја, него што је случај у периоду високих вода када долази до Мајданпек, Србија . разблажења услед повећане инфилтрације вода од кише и/или топљења снега. Доследном применом мера заштите животне средине и изград - њом мини постројења за пречишћавање вода на оба осматрана извора, могуће је ублажити утицај рударских активности на подземне карстне воде и низводни еко-систем.

Introduction

Pre-Cambrian to Early Paleozoic age are locally in - truded by granites (Hercynian orogeny). The big Mining has a very long history in eastern Serbia. transgression, which started in Middle jurassic, re - Тraces of extraction of copper minerals, malachite sulted in thick carbonate dneTpOonisjiEtVsi ć of mostly upper and azurite and early metallurgy at the archaeolog - jurassic–Tithonian age ( a , 1979). During ical site Rudna Glava date back to five millennia B.C. the period between Turonian and Paleogene, a vol - although exploitation of copper minerals continuedth canogenic-sedimentary series called Timok Mag - during the Roman and Ottoman Empires, the period matic Complex (TMC) were formed in the eastern Mine at River Pek that lasted from the middle to the end of the 19 part, in a tectonic trough. Thea TnMjEšCE Visić about 85 km century was marked by the opening of new and long, and up to 25km wide ( B , 2010), with modern copper mines. One of them, Majdanpek the Majdanpek area in its northernmost part. an - (meaning: ) is still in active opera - desites, pyroclastics and tuffa rocks, followed by rich tion with two open pit mines and a flotation tailing porphyry-type copper deposits, prevail in this acnoKm O - lake. The main ore resource is copper, and, to a Vpilć ex which iasR maMoarTea than 2,000 mEeLtErensK OtVhiić ck ( jOžELj - lesser extent, silver and gold. , 1990; K et al., 1994; j & K , The geological setting of the Majdanpek ore field 2002).There were several phases (at least two) of (Fig. 1) is complex. The area belongs to the Carpa - volcanism, and the volcanic processes were sub - thian-Balkanides, a geologically heterogeneous and aerial to submarine eruptive, waintjhE šhEyVpić abyssal intru - morphologically vEeTrKyO Vdiić ssected orRougBeinć ic belt of the sion and rarely explosive ( B , 2010). The 5a0 lpine system ( P , 1935; G , 1974). The regional tectonic pattGeeronl. ains. Bcaolkm. ppolouossi.,t 2e0.2 L0,o 8n1 (g2 ),r 4e9g–6i1 - oldest metamorphic rocks, gneisses and schists of onal faults elongate in the direction of nnW–SSE, in Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

Fig. 1. Location and hydrogeological maps of the studied Majdanpek mining area.

parallel to the main geological structure (longitudi - jurassic (Tithonian) is rich in groundwater, and is nal) and are intersected by a group of perpendicular recharged mainly by rainfall and by sinking flows (transversal) faults that are younger and shorter that gravitate from higher altitudes and imperme - (Fig. 1). able Paleozoic rocksT tEoVwanarOdV ilć ower-positioned Meso - The karstification process in the Carpathian zoic limestones ( S , 1991). The springs karst was intensive and, in the Majdanpek area, it issuing from the three above-mentioned caves and resulted in specific landscapes (sinkholes, blind val - a few others (Kaludjerica, Baščao, štameta; Fig. 1) leys, ponors, stone bridges)a ZaanRdE Vloić ng caves (Rajkova, are the main drainage points of the karst aquifer GPeaosl.k aon.v Baa,l kV. apoljluao Fs.,u 2n02d0a, 8t1a )(2 (), L49–61 , 1976). The karst anidLi POaVrieć used for local potable water supp5ly1 aquifer formed in the carbonate rocks of upper (F et al., 1975). Zoran StEVanoVić , V EljKo MarinoVić & B raniSlaV PEtroVić

The fissure aquifer of TMC is not rich in ground - selected sites are visited in both high-water and water. The groundwater flow pattern is linked to low-water periods, in order to assess the differences joint and fissure systems as well as main faults. Pa - in water discharge, groundwater table position and leozoic formations, magmatic and metamorphic physical-chemical composition. Two springs – Valja in situ rocks mostly represent aquitards or aquifuges and Fundata and Kaludjerica – were visited in an at - in imLiPoOsVti ć cases act as a barrier to groundwater flow tempt to assess the impact of mining activities on (FMethodeotl aol.g, y1975). the quality of groundwater of GWB “Krš–sever”. The water quality of these springs was measured and sampled for laboratory analyses. Groundwater samples were collected on three occasions: in the spring of 2019, in late autumn of The ongoing process of the Republic of Serbia’s 2019 and in the spring of 2020. The low-water sea - (RS) European union (Eu) accession requires many son (smallest discharge at the springs) correspond - steps toward improving environmental conditions, ed with the late autumn period of 2019. Standard primarily in the water sector. adaptation to the procedures for sampling, transport and storage of Water Framework Directive ( WFD , 2000) and Eu groundwater samples were applied. standards, especially in the area of environmental Field parameters such as turbidity, water tem - regulations, has thus become one of the priorities. perature, electrical conductivity (Ec), pH, oxidation- The project of the Ministry of Environmental Pro - reduction potential (Eh) and dissolved oxygen (DO) tection of Serbia – “Operational Monitoring of were measured by use of WTW measuring instru - Groundwater of the Republic of Serbia”, which aims ments 355 Turb iR and 340i SET (pH/Conductiv - to create new bases, expand the groundwater mon - ity/Oxi), while the total hardness and total alka2l+ inity itoring network and imprToEvVean tOhVei ć protection of wa- of wat-er were measured using the instrument called ter resources in the RS ( S et al., 2020), has Exac3t Micro 20 (iTS inc.). Concentration of Ca and been completed (2017–2020). HCO was measured using the MColortest (Merck The Serbian Environmental Protection agency Millipore). Groundwater samples were collected (SEPa) is in charge of systematic monitoring of the when the measured field parameters of fresh quality of groundwater in the RS, while monitoring groundwater at the karst springs were stable. the quantity of groundwater falls within the compe - Groundwater samples were taken in PVC bottles for tence of the Republic Hydrometeorological Service the purpose of conducting the analyses of relevant of Serbia (RHSS). However, the monitoring situation major ions and pesticides, and in gl3ass bottles pre - is far from satisfactory. Only about 30 delineated served with acid (2 ml of conc. HnO ) for metal ions groundwater bodies (GWB), or 20% of the total, are analyses. subjected to systematic observation. Moreover, Major ions, metal ions and pesticides were anal - there is a noticeable disproportion in the spatial dis - ysed in the accredited laboratory of the institute of tribution of relatively dense piezometers located in Public Health in Kragujevac (aTC 01-169 SRPS alluviums or large rivers and the Vojvodina provin - iSO/iEC 17025:2006; iQ nET Certified Management ce, and karst aquifers and artesian aquifers in neo - System; iSO 9001: Q-1644-iVR). Volumetric titrime - gene sedimentary basins, which are both largely try was used to determine the concentration of chlo - unobserved. rides and to quantitatively determine the total The undertaken project of operational monitor - oxidisable organic material. The concentration of ni - ing has increased the number of observed ground - trites was determined using the molecular absorp - in water bodies, comprising – in the last stage - 50 tion spectrometric method. The spectrophotometric situ additional groundwater bodies, including the one method was used to determine the amount of ni - located in the Majdanpek area (GWB “Krš-sever“). trates and ammonia. Sulphate was determined 52 Operational monitoring consists of field visits, using the method of liGqeuoil.d a nc. hBarlok.m poalutoosg., r2a02p0h, 8y1. (D2),e 4t9e–r61- measurements and laboratory analyses. all the mination of elements, by inductively coupled Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

plasma optical emission spectrometry (iCP-OES), open pits. The former method has in the meantime has been used for selected ions: iron, manganese, been completely abandoned. The two open pits – cadmium, nickel, zinc, copper, mercury and arsenic. “northern” and “Southern” – were caused by long Gas chromatography-mass spectrometry (GC-MS) and intensive exploitation at great depth. The bot - was the analytical method that was used to deter - tom of the latter is more than 200m deeper than the mine organochlorine pesticides (OCPs) in ground - surrounding terrain and the riverbed of the nearby water samples. stream Mali Pek, which in natural conditions and Several earlier studies were collected and evalu - prior to the deepening of the open mine used to rep - ated for t he purpose of assessing the environmental resent the erosional base. The flotation tailing is lo - conditions. Some available information on previous cated above the “Southern” pit, in the hill with an pollution accidents were studied as well. altitude of approximately 500 m a.s.l. The site was This analysis and the assessment of pressure on chosen in the late 1960s, to be closer to the under - the quality of water in GWB “Krš-sever” required an ground mine works and the then newly opened pit. important step in the form of hydrogeological con - Deep and blind valley Valja Fundata, formed in ceptualisation. Therefore, hydrogeological explo - jurassic karstified limestone, was found to be a suit - ration of the wider Majdanpek area was undertaken, able place for the deposition and flotation of ex - including a survey of open mine pits and tailings, tracted ore material and rocks (Fig. 2). On the while visits to major karstic springs and caves were southern side of the Valja Fundata valley lies the val - , steps that were necessary for the creation of the ley of the perennial stream Valja Mastaka (Fig. 1). conceptual model and the assessment of the envi - Some 25 m above the valley there is a large orifice rRoensmuelntts al conditions and groundwater status. of the Valja Fundata cave (FiigL.i P3OaV)i,ć which is passable for a few dozen of metres ( F et al. 1975). This Conditions on Site cave also functions as a permanent spring which is most probably connected with the blind valley of Valja Fundata (Fig. 2). aware of this fact, to prevent leakage from the tailing, the mining engineers of the Majdanpek Mine have constructed a form of a bar - in the previous period, very thick TMC deposits rage gate inside the cave, in its last accessible part. required a combination of underground mining initially, some registered larger faults, fissures and works and removal of rocks and minerals in the ponors in the blind valley were also plugged with

Fig. 2. Hydrogeological cross-section of the Valja Fundata tailing and cave. 1, Karst aquifer; 2, Fissured aquifer; 3. Intergranular aquifer; 4, Tailing’s water table; 5, Jurassic limestones; 6, Andesites; 7, Ore and crushed – fragmented rocks and clays; 8, Fault (according to FILIPOVIć et al., 1975).

Geol. an. Balk. poluos., 2020, 81 (2), 49–61 53 Zoran StEVanoVić , V EljKo MarinoVić & B raniSlaV PEtroVić

clays or cement. Further deposited excavated an - the contamination of karst groundwater draining at desite material in tailing today is more than 100 m the speleological site of Valja Fundata. Discharged thick and is fully saturated. The floatation tailing from the cave, the tailing’s fluid entered the Valja Valja Fundata is a mixture of crushed fragments and Mastaka stream, reaching the river Veliki Pek near particles with copper and magnetite minerals and Debeli Lug (Fig. 1). Rapid waste water outflow killed fluid mass. The solid phase of the tailing has a fine the entire river’s fauna for several tens of kilome - grain distribution, wRaitGhiš dić iameters ranging between treTsE,V anllO tVhić e waRya tGoiš ićts confluence with the Danube 0.002 to 0.6 mm ( D , 1992). (S & D , 1995). information about this

Due to the 2p– rese2+ nce o2f+ sulphide mineralisation, accident was published in OoRnD e of tihLLei amMSost-cited groundwater4 is often acidic (low pH), with a high books on karst, written by F & W (2007). content of SO , Fe , Mn ions and several metallic another accident took place in 1996. after the micro-constituents. Mine waters, pumped out di - Valja Fundata accident, the management of Majdan - rectly to riverbeds, polluteR atGhieši ć surface wTatnearCsK OaVnićd pek decided to create a new tailing, smaller in size, dependent eco-systems ( D , 1992; a , in the head watershed of the šaška River. This area 2018). nicely coloured water (light green to azure- is away from the karstic rocks, and not very far from blue), such as that of the Valja Fundata tailing, is the the open pit, which made ore transportation feasi 3- result of oxidation of pyrite minerals and sulfidation ble. However, after a long and heavy rain on 8 and 9 (Fig. 3b). May 1996, the flotation dam broke and 100,000 m

Fig. 3. a, Valja Fundata a large cave orifice; b, Valja Fundata tailing dump site (springtime 2019).

Earlier Accidents

of waste fluid came out, polluting šaška River down - stream, and later Porečka reRkaG aišllić the way to its con - The first big accident happened in 1974, after fluence with the Danube ( D et al., 1997). The several years of the tailing’s operation, when the ac - water intake used for the downstream tourist town tivation of some of Valja Fundata ponors at the bot - Donji Milanovac and several villages in the Majdan - 5to4 m (or banks?) of the tailing provided a path for the pek municipality was Gaeboal. nand. oBanlke. dpo aluso sa., 2d0i2r0e, c81t (c2o), n49s–e 61- flow of the tailing’s dense fluid, which resulted in quence of polluted alluviums. The šaška tailing site Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

has not been in use since this accident, and only riod, reaching the value of 12 nTu (MPL = 1 nTu), Valja Fundata is used now for the flotation process. which is very rare for karst springs and their often in the meantime, the volume and surface of the lake dynamic regimes. expanded; in Fig. 1, is possible to see the contour of The low-water period results in worse water qual - the lake in its earlier stage (mid 1970s) and how it ity than the high-water period, as evidenced by the Groundwater Quality of the Two Observed looks today. concentration of several other chemical consti tuents. Springs – For 3instance, the concentr–ation of ammonium ion

(nH ) is a2b– ove MPL durin2g the periods of low-water (0.71 mg/4l), similar as nO 0.036 mg/l. The content of the SO ion, which is dominant in anion compo - sition, is regularly high above MPL (250 mg/l), reach - Field measurements of unstable chemical com - ing its maximum value of 1152 mg/l again during the ponents and physical properties, as well as labora - low-w2+ ater seas2o+n (Fig. 4a). Water of the Valja Fun - tory analyses, confirmed very poor and even data spring is characterised by a high concentration hazardous water quality of the two surveyed karst of Fe and Mn ions throughout the year, b2+u t the springs – Valja Fundata and Kaludjerica. highest value is noted once again during the low-

Registered concentrations of some ions are high water season, w2h+ en the concentration of Fe is six above the maximum permitted level (MPL) for times higher than permitted (1870 μg/l vs. 300 μg/l), potable water in Serbia (SL. GLaSniK RS, 1999, while that of Mn is even ten times higher than per - 2019). Electrical conductivity in all the samples mitted (504 μg/l vs. 50 μg/l) (Fig. 4b). (3+3 of each spring) was above 1000 μS/cm. Table in high-water periods, water samples from the Table 1. Chemical composition of spring water of Valja Fundata and Kaludjerica. 1 shows only components with concentrations Kaludjerica spring had turbidity values of 25.99 and above MPL. 122.2 nTu in 2019 and 2020, respectively. However,

Examined during periods of high-water, turbidity as in case of Valja Fundata, the water’s turbidity is of water of the Valja Fundata spring has values of the highest during the low-water season, reaching 2.31 and 5.54 nephelometric Turbidity units (nTu) all of 694.8 nTu (Fig. 5). Gineo 2l. 0an1. 9Ba alkn. pdo l2uo0s2., 200,2 r0e, 8s1p (2e)c, 4t9iv–6e1 ly. it is interesting that During low-water periods, four chemical compo55- turbidity is even higher during the low-water pe - nents of the Kaludjerica water are above MPL. They Zoran StEVanoVić , V EljKo MarinoVić & B raniSlaV PEtroVić

Fig. 4. a, Concentration of major ions (HCO 3, Ca, SO 4) in water of karst springs Valja Fundata (VF) and Kaludjerica (K); b, Concentration of Fe, Mn, Zn, Cu ions in water of karst springs Valja Fundata (VF) and Kaludjerica (K ).

2+ 2+

concentration of 2F+e and Mn ions in the Kaludjerica

spring water is enormo2u+ s, especially during the low- water season: Fe is 200 times higher than permitted (53462 μg/l), while Mn is 80 times higher than per - mitted (4175 μg/l) (Fig. 4b). The heavily polluted water of these two karst springs pollutes the streams Valja Mastaka and Veliki Pek. The impact of the poor quality of river water can be observed far downstream. For instance, in the al -

luvial groundw2– ater of the latter river, which is tapped to supply wa4ter to the town of Kučevo, the concen - tration of SO during the low-water period is about two times higher than permitted (363 mg/l). This could be the result of old accidental pollution, but it could also mean that new waves are “refreshing” the pollution of this alluvial aquifer. in contrast, other examined karst springs, which belongs to other karstified blocks such as those is - suing from Rajkova and Paskova caves (Fig. 1) char - acterized by very good water quality and are Fig . 5 . Muddy, heavily polluted water of the Kaludjerica spring utilized for potable water supply. no treatment pro - during low water season (December 1 2019). cess except chlorination is applied. The dislocation ST from mining activity and pure catchments are main fDacistocrus sosf isounch water quality.

2+ – –

- 2– 3 2 are3: Ca and all three nitrogen i4ons nH , nO and 5n6 O (Table 1). The content of SO is regularly above The Majdanpek copGpeoelr. a mn. Binalek.f pieoludo si.s, 2 d02ir0,e 8c1t (l2y), b49o–r61- MPL, varying from 419.3 to 1084.3 mg/l (Fig. 4a). The dering the karst aquifer and the delineated GWB of Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

“Krš-sever”. Waste consisting of crushed and defrag - favour of good water quality. This was confirmed at mented rocks mixed with pre-processed low-copper numerous sources, where local waterworks apply ore, disposed in the Valja Fundata tailing, are in the only chloTrEinVaantOioVnić for water distributed to con - catchment area of the Valja Fundata cave and spring sumers ( S , 1995). in contrast, groundwater and the Kaludjerica karst spring. The distance is in the zone of oxidation of copper deposits depends ., very short, a2s the total catchment area of this tec - primarily on geologic and hydrogeologic conditions, tonically relatively isolated limestone block is only chemical-mineralogic composition ofR athGieš idć eposits about 3 km . Such conditions enable direct hydr - anRdaG tišhieć existing climatic factors ( D , 1992; aulic communication of the waste mine and tailing’s D et al 1994). Complex physical-chemical waters with karst groundwater. an attempt to close processes take place during the interaction between this communication by a barrage gate inside the water and sulphide ore bodies. They are reflected in cave or by plugging some ponors on the tailing side the change of anion-cation composition, the decrease would be “a mission (that is almost) impossible” in of pH values, and the increase of the values of miner - the case of the karst aquifer in question. Due to per - alisation (electricalD cOoRnO ductiviTitiKya) and enricChHmuLeTZnE t of meability of karst, developed large cavities, limited microelements ( n & W , 2007; S et , attenuation capacity and a high gradient, remedial al., 2011). measures to prevent leakage can only partly amor - Rock wastes in Majdanpek consist of fragments tize and slow this undesired flow from the tailing. and blocks of mineralised hydrothermRaallGyiš aić ltered The natural chemistry of karst groundwater in volcanic rocks and crystalline schists ( D et al. the Carpathian karst is of high quality. Within open 1994). Degradation of sulphide minerals in waste karst structures groundwater is just slightly miner - rocks provides groundwater with specific physical alised, with intensive water exchange and rapid fil - and chemical properties. in parts with waste dumps, tration. The developed channels and caverns of the mine water directly percolates into karstified lime - karst system provide a short contact between water stones, mixing with original karst aquifer’s waters and rock, and the geogenic factors are therefore in of the GWB “Krš-sever” (Fig. 6a). Tailing fluid con -

Fig. 6. a, Position of main objects in Majdanpek area on satellite image (Source Google Earth); b, Conceptual model of mixture of fresh groundwater and tailing water in Majdanpek area.

Geol. an. Balk. poluos., 2020, 81 (2), 49–61 57 Zoran StEVanoVić , V EljKo MarinoVić & B raniSlaV PEtroVić

taminates fresh groundwater to a certain extent, en - staff involved in similar projects and environmental dangering the local habitat and biocenose. The con - Cimopnacctl uassieosnsms ent studies related to mining. ceptual model of this mixing mechanism is shown in Figure 6b. Earlier accidents confirmed that the higher the pressure in the aquifer system, the higher the risk of pollution. For instance, high-water level in the in Serbia and former Yugoslavia, the period after tailing, plus intensive rainfall which fully saturates the World War ii was marked by intensive develop - the aquifer and increases the water table, are defi - ment of the industrial and mining sectors. Many nitely factors that could initiate a new wave of pol - new mines were opened, and ore extraction and lution. However, intensive rainfall dilutes hazardous metal production were stressed. The Majdanpek substances and reduces their concentration. Further mine functioned with two open pits, a waste dump survey and monitoring should be focused on estab - and a flotation lake – the Valja Fundata tailing. Many lishing more precisely the ratio/equilibrium be - decisions taken during that period of fast industri - tween these two aquifer recharge components. alisation aimed to increase employment and sup - Results of the undertaken survey confirmed that port the economic development of the then socialist low-water periods are more problematic, resulting country. not only in Majdanpek and Bor mining cen - in lesser quality water and a much higher concen - tres in eastern Serbia, but all across ex-Yugoslavia, tration of hazardous substances than that which not much attention was being paid to the environ - characterises the high-water season. Moreover, the ment and the consequences of intensive mining on main threats to the dependent and sensitive riverine natural resources and local eco-systems. Today, eco-system are the low flow in the downstream when the approach involving sustainability and en - rivers (Valja Mastaka, Veliki Pek) and the higher pol - vironmentally safe activities is dominant in the en - lution rate. tire Europe, locating a mine tailing directly on karst although there are not too many topographically and in a deep depression with a blind valley on the suitable locations surrounding the mine works in bottom would not be considered justifiable under Majdanpek, the decision to choose a blind valley in any circumstances. a karstic terrain that is not completely fossilised Great damage suffered by the water, environ - (still with temporary flows) for a dumping site is ab - ment and local biocenose as a result of two major solutely unfeasible and dangerous from the environ - accidents in 1974 and 1996 in the Valja Fundata and mental point of view. This was confirmed in the šaška tailings was never completely remedied. years that followed. unfortunately, remediation and Groundwater stored in alluviums of upper water - rehabilitation of the existing tailing, even if a new sheds of Veliki Pek and Porečka reka and their trib - location is found, is not only very expensive but also utaries Valja Mastaka and šaška is not usable, or is difficult to implement. For instance, drying the lake - used just for individual water supply (dug wells) and installing an impervious cover with new soil and with caution. Permanent seepage from the tail - layers and forestation may be possible in certain sit - ing to the adjacent karst aquifer and springs Valja uations, but not in the case of Valja Fundata, because Fundata and Kaludjerica, evidenced during the sur - of its dimensions. However, mitigation is possible at vey campaigns in 2019/2020, requires special at - two water outlets of the flotation lake - sources Valja tention and systematic monitoring beyond the Fundata and Kaludjerica. a small treatment plant, project “Operational Monitoring of Groundwater of including a retention pit, a filtration chamber and the Republic of Serbia”. an aeration facility, could improve the quality of if Eu WFD is fully transposed in Serbian legisla - water or at least prevent pollution peaks during pe - tion, with strictly applied one of its main principles riod of low-water. – “the polluter pays”, many industrial and mining 58 This example of “poor practice” is, however, a les - factories will be obligGeedol . taon. Bpaalky. pmoluoors.e, 2 a02t0t,e 8n1 t(2i)o, 4n9 –t6o 1 son learned and should be conveyed to technical their technological processes, and to construct their Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

Karst hydrogeology and geo - morphology facilities in line with environmentally friendly re - RGF , Spec . ed ., vol. 2, The Faculty of Mining and Geology, quirements. as for the Majdanpek Mine, it should be ORBD eograd, 1iL0L8ia pMpS . (in Serbian ). mandatory to have a water treatment facility de - F , D. & W , P. 2007. signed and installed at the two surveyed springs – RuBić . j. Wiley & sons, Chichester. VAacljkan Founwdlaetad ganmd eKnaltus djerica. G , a. 1974 . Eastern Serbia in light of new global tec - tonics and reflection of such model to explanation of tectonics of northern branch of alpides. in: janković S. (Ed.). Mineral material complex of Serbia and Monte - negro at the cOrroes sdienpgo soift sn otwf Soe mrbiila lenniums. MaRGO - The research was carried out using the funds provided aRT, Belgrade, 368–378. (in Serbian with a Summary by the Ministry of Environmental Protection of Serbia and anKiOnV Ei ćnglish). the Ministry of Education, Science and Technology Devel - j , S.1990. . Fond za geološka opment of Serbia through the Oi 176022 project, for istraživanja i zajednica nauke. Beograd, 760 pp. (in Proceedings of the Intern. Symp. “Geology and wRheifceh rtheen acueths ors express their gratitude. ELESneKrObVićan). OžELj j metallo, gRe. n&y K of co,p Dpe. r2 0a0n2d. Mgoolrdp hdoegpeonsiettsi cianl ttyhpee sB orf Stratigraphy and tectonics of Veliki Krš pmoertpahllyorgye ncoicp pzoern em”.i nReTrBa liBzoatri ohno lidni nthge cBoomr pmaentya, llCoogpepneicr and Stol in eastern Serbia zinosntiet.u te, Bor,

nTOnijEVić a , i. 1979.

. Rasprave ”Geozavoda”, X, aRaMaTa aSK2O9 V–i ć56. VETKOVi ć nE žEVi ć OR ĐEVi ć TaBnaeCoKgOrVaićd (in SerbianR).i sk assessment of water pollution K Geološ, kSi., Vanali ,B na.l,k Canskoga , Vp. o&l uKostrva -Đ , a caused b,y n a. b2a0n1d8o. nPerdo cmeninai nrgiz oikpae roadt izoangsa idnj iSvearnbjiaa vod - V. 1994. upper Cretaceous and Tertiary magamitites nih resursa pod uticajem napuštenih rudarskih radova of central and eaRsatejkronv aS ecrabviae and their metalogeny na prostoru Srbije [ , 58 (1):

– in aZa1R5E9 V–ić175. Serbian, with an English abstract ]. unpubl. PhD Thesis, L , R. 1976. Internatio.n aMl Z Jo. uBro nžaal oSft oSjcainenocvei ćs:,

Faculty of Mining and Geology, uGneiovleoršskiit ya noaf lBi eBlaglrkaadn e-, DOBMRaO asjidca annpde kA,p 6ipT1liiK epa dp R. (eisne aSercrhbian). an2sjkE9šo5EgV paić pp. oluostrva, n , O.T. & W Ge,o Klo.Lg.y 2 o0f0 e7a.s ate Rrne vSieerwbi aof the Flotation B , M. 201H0y.d uropgpeeorlo Cgrye otaf tcheeo cuosp mpearg dmepaotiscit s uoift Eeas sot -f of Copper Minerals.

tehrne STeirmbioa k Magmatic Complex. ETKOVi ć , 34 (2): 145–165. RaGišić 71: 13 –22. P , V. 1935. . Pos . izd . SKa , D , V. 1992. CHBuLeToZgE rad (inO ESHeRrEbR ian). RiESE PrOoScCeHeOdRiRnEgCsK of the TSaixSitK h . Spec ed. of the institute of Hydrogeology, The S Inter,n M.E Cn.,Do B Tnf. OoTnT HMO, iBFnF .e, F Closu,r eK,. ,1 K 8-21 Septem, Mbe.r, S 2011, Faculty of Mining and Geology, BelgradPer o(cine eSdeirnbgiasn o)f, 2t1h1e LS.a &ke W Louise-P, Alberta , K. 2011. Disposal of Waste Mate -

RaXpGXpišV.i ć II IAH CiLoanDginrOesVsi ć“GroundwiLaEtneirć in the Urban Environ - rials at the Bottom of Pit Lakes. D ment,” VN. Mottingham , B. & M , D. 1997 . Pollution of ground water in Donji Milanovac. , VoSlt. a1t:u Mtoinrye aScitte o Rne dcrlainmkaintigo wn,a atuer- staranldianrd C eonf ttrhee FRoerp Guebolimc eocfh Saenribcsia (acg), nedlands,

RaGišić , iLiPOVić , 1: 39T5 E–V3an9O9V. ić ujaSinOVić L 5L5a5S–n5iK 64. D iLaD, iV n.O, VFić Pro, cB e.e, dSings of Int,e rZ n.,. SVymp. “Imp,a cS t. o& f S . G RS 1999, 20H19yd. rogeology of karst aquifer of MIndustrial Ac, tBiv.i t1ie9s9 o4 n. Girnofulunedn Wcea toerf Qmuianliet yw”, IaAteHr, sA HoRn Carpathian-Balkanides of Eastern Serb, ian aon. d4 w4/a9te9r saunp d -

gUrnoiuvenrds iwtya pterre sqsu, aCloitnys toann ezxa ample of copper deposits in TEV2pal8yn/ Op2Vo0i sć1si9b.i l ities eastern Serbia. Hydrogeological S , Z. 1991. study of copper ore field „Majdanpek ”

iLiPOVi ć iMiTRijEVi ć OM, 1i ć39 –148. . Spec ed. of the institute of Hydrogeology, F , B., D , n. & T , V. 1975. The Faculty of Mining and Geology, Belgrade. 245 pp. (in Geol. an. Balk. poluos., 2020, 81 (2), 49–61 59 , Zbornik radova Serbian ). Zoran StEVanoVić , V EljKo MarinoVić & B raniSlaV PEtroVić

TEVanOVi ć Lithospheric water mineral resources S in Serb,i aZ. 1995. Karst ground waters in Serbia – present таaтZ aјRеE Vиić нтензивTнEоVг anпOVрiоć цеса карстификације aTnEdV anpOoVtieć ntial uses in regional water supply. in: (L , 1976; S , 1991). Карстна издан S Z. (Ed.). се прихрањује падавинама, али и понирућим . Spec ed. of the institute of Hydrogeology, The површинским токовима који се формирају на Theoretical and applied Karstology TEVFaancOuVltićy of MinRinaGgi šainć d Geology, Belgrade, 77 –120. водонепропусним палеозојским стенама и стена - Opera - S , Z . & D , V . 1995. Some cases of accidental ма ТВК. Значајнији извори и карстна врела (Ка - tional monitoring of groundwater in Serbia karst water pollution int the Serbian Carpathians , луђерица, Ваља Фундата, Башчао, Штамета , TEVanOVi ć ETROVić aRinOV,i 8ć : 137 –144. врела Рајкове и Паскове пећине ) настала су на S , Z., P , B. & M , V. 2020. контакту титонских кречњака и слабопропусних . Final Re - палеозојских и вулканогено -седиментних стена. port of 3-year research (2017 –2020). Ministry of У циљу креирања квалитетнијих подлога за Environmental Protection, Belgrade. приступне преговоре са Европском Унијом (ЕУ) у (https://www.ekologija.gov.rs/dokumenti/) области животне средине, као и проширења мо - WFD, 2000. Water Framework Directive, Official journal ниторинг мреже подземних вода ради примене Реoзfи Eмu,е 2000/60, L 327/1, Brussels. Оквирне директиве о водама ЕУ ( WFD , 2000), реализован је пројекат „Опера тивни мониторинг Опасне супстанце у водама карстних подземних вода Репу блике Србије“ који је подр - издани – један од резултата жало МинTEи VсaтnаOрVсićтво за зашти ту животне средине оперативног мониторинга подземних Србије (S et al., 2020). У склопу поменутог вода у Србији пројекта два карстна врела – Ваља Фундата и Калуђерица, у оквиру водног тела под земних вода „Крш–север“, била су укључена у тзв. оперативни мониторинг у циљу оцене утицаја рударских активности на квалитет подземних вода. Рударска активност на подручју Мајданпека Утицај рударских активности на подземне има дугу традицију. Тренутно се експлоатише воде настао је услед остварене хидрогеолошке руда бакра и у мањој мери руде сребра и злата . веiзLеiP иOзVмić еђу слепе карстне долине Ваља Фундата Шира околина лежишта бакра Мајданпек у гео - (F et al., 1975 ), која је одабрана као лока - лошком (Слика 1) и морфолошком EсTмKиOсVлić у пред- ција за формирање флотацијског одлагали - стRаuвBљić а део Карпато-Балканида ( P , 1935; шта/језера и истоимене пећине (Слика 2, 3), G , 1974). На истражном терену су присутни односно врела Калуђерица (Слика 5). Теренска прекамбријумски и старије палеозојски гнајсеви мерења параметара квалитета, као и извршене и шкриљци , местимично испробијани гранитима хемијске анализе у акредитованој лабораторији херцинске орогенезе. Дебели комплекс карбо - Института за јавно здравље Крагујевац (Табела натних седимената формиран јеn нTOаnјвijеEћViиć м делом 1, Слика 4), потврдиле су да постоји значајан током горње јуре (титон) (a , 1979). антропогени утицај на квалитет подземних вода Источни делови терена су настали током дугог у оквиру истраживане карстне издани. Концен - периода турон–палеоген, када је формиран тзв. трације нитрита, амонијака, сулфата, гвожђа, Тимочки вулканогено -седиментни комплекс мангана и никла забележене су изнад макси - (ТВК ) од андезита, пирокластита, туфова и пор - мално дозвоLљенLиaSхn кiK онцентрација (МДК) за воду фирита богатих рудоaмnK OбVаiкć ра који aдRоaсMтaиTжa е де - за пиће (S . G RS , 1999, 2019) . Знатно бљине EиL EдnоK O2V0ić00 mO ( žjELj , 199a0nj;E KšEVić et al., повећане вредности мутноће указују на продор 1994; j & K , 2002; B , 2010). висококолоидног флуида из флотације Ваља Формирање бројних површинских и подзем - Фундата лоциране у карстној депресији слепе них карстних облика (Рајкова и Паскова пећина, долине за коју је још 1974. констатовано да је 6В0 аља Фундата) и карстне издани у оквиру титон - главни узрочник екоGлeоolш. anк. оBгal kи. pнolцuoиsд., 2е0н20т, а81 к (2о),ј 4и9 –ј6е 1 ских кречњака шире области Мајданпека резул - довео до уништења флоре и фауне у водотоку Hazardous Substances in Karst Aquifer Waters – One of the Results of the Operational Monitoring of Groundwater in Serbia

TE VВaеnлOиVкić и ПеRкa Gсiвšiеć до његовог ушћа у Дунав ( S - фидних минерала, који погоршавају квалитет & D , 1995) . Процуривање и активна флуида која се инфилтрира у карстну издан и филтрација отпадних флуида флотације оства - затим појављује на врелима Ваља Фундата и рује се и данас преко пукотина, каверни и круп - Калуђерица ( Слика 6). них пећинских канала Ваља Фундате. Резултати Висок ниво флотацијског језера у комбин - спроведених истраживања, такође, указују да је ацији са интензивним падавинама повећава квалитет подземних вода лошији у периоду ризик од продора загађења у карстну издан, што ниских вода, него што је то случај у периоду је забележено у претхTоEдVнanиOмV i ćинциRдaеGнišтić има из високих вода. Разлог је разблаживање подзем - 19R7aG4i.šиić 1996. године (S & D , 1995; них вода инфилтрираним водама од падавина и D et al. 1997). Иако у околини рудника не од топљења снега. Током спроведених истражи - постоји много погодних локација за флота - вања подземна вода врела Ваља Фундата је у цијско језеро , својевремена одлука да се оно свим узорцима имала високе концентрације лоцира у слепу карстну долину, која је и даље јона гвожђа и мангана, док је у узорку, који је хидрогео лошки активна, показала се као нео - узет у периоду ниских вода, концентрација гво - правдана и у данашње „еколошко“ време жђа била шест пута, а мангана десет пута виша сигурно не би уопште била могућа . У садашњим од МДК (Слика 4). Још неповољнија ситуација је условима ремедијација постојећег јаловишта забележена за подземне воде врела Калуђерица, Ваља Фунда та, осим што би изискивала огромна у периоду ниских вода концентрација гвожђа је финан сијска средства, скоро је и технички била чак 200 пута, а мангана 80 пута већа од неизводљива. Али би могло и требало да буде МДК (Слика 4). реализовано про јектовање и изградња мини У неизмењеним природним условима под - система за третман вода контаминираних карст - земна вода каTрEVсaтnнOеV iиćздани је обично одличног них извора. У циљу ублажавања утицаја рудар- квалитета ( S , 1995), међутим, у конта - ских активности на подземне карстне воде треба кту са рудним телом долази до њене измене применити и принцип Оквирне директиве о услед комплексних физичко -хемијских реакција водама ЕУ која је транспонована и у нашу леги - Manuscript received November 07, 2020 измене јона, смањењRaаG pišHić вредностRиa, Gпišоiвć ећања слативу, али се не примењује доследно - „загађи - Revised manuscript accepted December 05, 2020 минералDOиRзO ације iT( iDKa , 19C9H2u;L TDZE et al., вач плаћа“. 19Ta9n4a;C nKOVić & W , 2007; S et al., 2011; a , 2018). У случају флотацијског језера рудника Мајданпек долази до оксидације сул -

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