ContentsMiodrag ZlatitForeword

LANDCON KEYNcTp PeppRMartin Haigh qnd J.S. RawatLandslide Activity and Environmental change in theHimalaya

Cnaprsn ILexo DecRaoATIoN

olivera Koianin, Miran Kneievic and Rade cvieticqninBasification process in some Forest s"iir in ?rr. Areaof Mountain Mirod

sneiana Belanovt simic, Jerena Beroica, vefko perovic,lVuri S. Alnaass, Milan Knezevic, Ratko Kadovic andBranislava Mihailoviccurrent State and rhreats of soil Resources in Rasinacatchment upstream from o'fekije', w;;ReservoirEmiliya G. Velizarove, Krasimira M. Ihikolova,Irene G. Ilcheva-Michajrova, Ivan Ts. Marinov and lvan L lvikorovDetermination andlripping of the Hyd.oiogi. soil Croupsfor Representative wat^ersnEos of the St.u-? River Basin, BurgariaP et ar P ap ic, Zvo n i m ir Mi t ij it, Jorygs toj kovitc, Jov ane Mil o s av lj evit,Maja Todorovic, Marina iuk and Zetiio koiiurori,Geoenvironmental Investigations at a Smelter Locationin Bor (Serbia)

!u!y lopa, Dumitru Jfiistor and Romur Mircea MargineanuSoil Erosion Estimates in a smail Agricurtuiut wutershedMilica V. Marcovic and Jelica M. DjurdjanovicFlood Risk Assessmelt []s.ing Grsi A 'case study of theNisava River Sector, SerbiaMilutin

.s t efanov ic, yit:y_ Miloj ev ic, Irina Mil ov anovit and Je I ena co tritAnalysis of Torrential Floods on the River pdinja and itsTributaries in Trgoviste, southern Serbia in May 2010Pre!1?s Yo!g/?ric,.sanja Mustafit, Ivana carevit, Jerena Lukovicctnd Mqrko MiloievicTransport of Dissolved Load and Suspended Load in theMlava River Basin (Eastern Serbia)

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Ratko Kadovic, Sneiana Belanovit, I{ada Dragovic,Jelena B eloica, Mirj ana To do s ij evic, Tij ana Andrij anic andBoban MilojkovicInfluence of Soil Organic Carbon on Soil Erodibility inForest Soils in Rasina Catchment

Ivon BlinkovAn Approach for Conversion of Erosion Data Produced byEPM Method in Weight Measure

Ilyusya Gabbasova, Manfred Fruehouf, Ilgiz Khabirov,Ruslan Suleymanov and Peter LiebeltChanges in the Properties of Eroded Soils in a Long Time Period

Cnaprpn 2LENI CONSBnvATION

Sevilay Haciyakupoglu, A. Beril Tugrul, A. Filiz Boytas,Ferhat Gokbulak, Nesrin Altinsoy, Ir{ilgun Baydogan,Nilgiln Karatepe, Sema Erentiirk, Billent Buyuk and Ertrugrul DemirBehaviour of KNOs Fertilizer in Soil by the View of LandConservation

Mirjona Todosijevic, Miodrag Zlatic, Itlado Dragovic,Vukaiin Milianovit, Tijana Vulevic and Gordana VukelicSustainable Management of Soil Resources in MountainousAreas of Western Serbia Using Conservation Measures

Panagiotis Stefanidis, Marios Sapountzis, Fani Tziaftoniand Stefano s StefonidisTorrent Control Works at the Region of Peloponnese (Greece)After Forest Fire of 2007

Stanimir Kostadinov, Ano Borisavljevic and Dragan MladjanTorrents and Torrential Floods in Serbia: Characteristicsand Possibilities of its Control

Slobodan PetkovicSediment Management in the Catchment of the River Ibar in Serbia,Related to the Project of Hydropower System

CsaprEn 3InapRcT oF CLIMATE CHANGE

Jana Podhrdzskd, Josef Kuiera, Filip Chuchma, Tomds Stieda,Hana Stiedova and Miroslav DumbrovslgtAffect of Changes in Selected Climatic Factors on WindErosion Risks

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Ildefonso Pla Sent[sConflicting Issues in Controlling Land Degradation andGlobal Climatic Changes

Dragoljub Cvijan Todit, Mirjana Todosijevic and Ana Vladimir GrbicLand Protection and Climate Changes in the Regulations of theRepublic of Serbia (Harmonization of the National Legislationwith EU Legislation) 211Lodo Kutnar and Andrej KoblerPossible Impacts of Global Warming on Forst Tree SpeciesComposition in Slovenia

lVenad Rankovic, Dragan I{onic, Jelena l,'ledeljkovic andSaia StamatovitRelationship of some Climate Elements and Collected Quantitiesof Non-Wood Forest Products in Serbia in the Period 1993-2011

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CHaprpn 4SOCTO-E,coNoMIC IssuBs AND PoLICY oF LRNo DBcneoATIoNAND LEXP COXSPNVATION

Ivctylo Velichkov, Bojan Srdjevic and Milena LakicevicAn Example of AHP Application in Forestry

Gordana Vukelic, Miodrag Zlatic and Mirjana TodosijevicEconomic Justification of the Model of Anti Hail Protectionof Multi-Year Plants

Jelena Tomicevic, Ana Kostic, Werner Konold and lvqna ZivojinovicLandscape Modification and Landscape Perception by the LocalPopulation in the Village of Kupinovo within a Protected Area

Slavoljub S. Dragicevi1, Marija P. Martinovit, Mikica Z. Sibinovic,Ivan D. Novkovit, Radislav S. Toiit and Stefana Lj. BabovitRecent Changes of the Erosion Intensity Caused bySocio-Demographic and Land Use Changes in KnjaZevacMunicipality, Serbia

Ljiliana M. Keca and l,lenad D. KecaInvestment Appraisal in Poplar Plantations in Serbia and itsRelations with Sustainable Land Management

Boris P. Radic, Ratko U. Ristit, Miodrag D. Zlatic,I\Ievena B. Vasiljevit and lvan MaluievitModification of Landscape Stability as Response on RuralDepopulation: Example of Watershed of Kupinovadka River,Serbia

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CHaprBn 5Itrztpl-pnapNrpo Grosnr/REcroNRrA{erroNAL PRorncrs

Ana Nikezic and Dragan MarkovitVisitor Center as a Viable Alternative for Cultural Landscape:The Case of the Remains of the Trajan Bridge on theRive Danube

CHepren 6E,NvTRONMENTAL Issups

Vesna DukitAnalysis of Groundwater Recharge of the Basin ofKolubara River in Serbia

Branko Glavonjit, Milan Neiit, Slavica Petrovic andSneiana Belanovi1Environmental Aspects of Charcoal Production in Serbia:Current Situation and Assessment of Harmonization withISO Declaration 14025

Dragica D. Obratov-Petkovi1, IvanaR. Bjedov, Branislav G. Jurisrc,Marija M. Neiit and Verica B. StojanovitRelationship between Invasive Plant Species and Species Richnessin Urban and Suburban Habitats of Belgrade (Serbia) 348

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Advances in GeoEcology 43

Geoenvironmental Investigations at aSmelter Location in Bor

Petar Papic, Zvonimir Milijic, Jana Stojkovic,Jovana Milosavljevit, Maja Todorovic, Marina Cuk and

Zetjko Kamberovic

Abstract

The goal of the geoenvironmental investigations was to identify and determinethe degree of soil contamination present in the area of the plant planned forredevelopment. These investigations also included a determination whether thesoil underlying below the investigated area should be considere d a hazardouswaste. The secondary goal was to determine the level of contamination in sur-face dust accumulated on the abandoned buildings being prepared for demoli-tion. Soil samples from the investigated areas were analyzed for 15 differentmetals, fluoride and PHC concentrations, VOCs, PAHs, PCBs, pH, atrazine andsimazine. In addition, samples of dust, waste and topsoil were analyzed. Theresults of these analyses showed that the main contaminants were heavy metals.Lead, mercury, arsenic and PCB were above Action level (The New Dutchlist)in many borehole soil samples. Contaminated soils should mainly remain in situand undisturbed, since groundwater leaching would not appeario be a signifi-cant issue. According to TCLP (Toxicity Characteristic Leaching Procedure)there would be a potentially negative impact to workers during demolition andconstructions activities. According to geochemical and geomechanical investiga-tions consideration of the possibilify for a new location of the wastewater treat-ment plant was recommended and excavations for foundations and services arerequired.

Keywords: Geoenvironmental investigations, heavy metals, groundwater

Introduction

A11 primary and secondary industries impact the environment to a greater or les-ser extent, through the use of energy and raw materials. The main environmentalimpact is direct: as a result of emissions of pollutants into the air, water and soil.This impact may be local, transboundary or global, and it affects human health.

Soil is often seen as an inerl medium and as something that only helps peoplein their activities. However, soil represents a complex system in which key

ISBN 978-3-923381-61-6, US ISBN 1-59326-265-5@ 2014 CATENA VERLAG, 3544l Reiskirchen, Germanypeer reviewed paper

(Serbia)

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chemical and biochemical processes take place. In most European countries,reported soil data are qualitative in nature and the interpretation of such datarequires specialized knowledge. Study and classification methods vary fromcountry to country, and occasionally even within a single country. Informationon soil and terrain properties, which affect environmental processes, is oftenlacking.

A broad range of diverse industries impact the environment. Some naturalresources are often used in different ways by different manufacturing sectors.Table 1 contains a summary of the types of emissions generated by the non-ferous metal industry.

Table I : Summary of the types of emissions generated by the non-ferrous metal industry.

Non-ferrous metal industry facilities release diverse pollutants into the atmos-phere, resulting from various ore processing stages, as well as the production,smelting and purification of metals. The adverse impact of this industrial sectoron the environment and human health has been relatively well studied anddocumented (World Health Organrzation). The air most often receives heavymetals, gases and other substances. Apart from mercury, heavy metals are gene-rally not discharged into the atmosphere in their elemental form, but bound todust particles. The deposition of these substances often leads to contamination ofcrops near smelters and to exposure of the local population to diverse toxic sub-stances, depending on the type of ore processed. In the widest sense, pollutantsgenerated by factories reach the environment in two ways: (1) bV transportationof substances released into the air over small or large distances, and their sub-sequent deposition on the soil or water; and (2) by permeation of heavy metalsand other substances through the soil into groundwater or surface water, due toimproper storage of chemicals, runoff from solid waste landfills, and the like.The latter includes direct discharges of wastewater into surface water.

Many manufacturing companies have adapted their production processes toaddress environmental concerns. In practice, such changes are generally made inresponse to internal and external pressures.

One of the main and also the most difficult questions is: "Who is responsiblefor restoring the original state of, above all, the soil polluted by industry in thepast?" Polluted soil is found in many areas where various chemicals had previ-ously been discharged. In some countries there are hundreds of such sites where,notwithstanding the fact that the size of the individual sites is often small,pollutant concentrations are often extremely high. Some of these sites can beremediated, but remediation generally requires considerable spending.

Large industrial facilities, which were commissioned at the time when

NON-FERROUSMETALINDUSTRY

Air Water Soil

Emissions of SOz,NO,., Cd, Cr, Cu, Zn,

Hg, As, PAH, F;HF and Ni aerosols

Wastewater loadedwith metals and

other solidparticles, gases,

fluoride, etc.

Sludge from rawmaterial andwastewater

treatment plants

Advances in GeoEcology 43

Geoenvironmental investigations, smelter location, Bor (Serbia)

environmental issues were not addressed, are now generally obsolete. Industry iscapable of developing the new processes and machinery needed to effectivelyreduce pollution, by introducing new technologies and modifying products,thereby also improving product quality and boosting productivity.

This paper presents the final results of geoenvironmental investigations onthe locality of reconstructed smelter and sulfuric acid new factory, in the CopperMining and Smelting Complex Bor (RTB Bor), in eastern Serbia. The goal ofthe geoenvironmental investigations was to identif, and determine the degree ofcontamination present in the area of the plant planned for redevelopment. Theseinvestigations also included a determination whether the soil underlying beneathinvestigated area should be considered a hazardous waste. The secondary goalwas to determine the level of contamination in surface dust accumulated on theabandoned buildings being prepared for demolition.

Methods

The analytical program reported in this paper was developed in accordance witha sampling program. There are three sites where new industrial projects areproposed, and they represented sfudy areas for environmental pollution assess-ment. They include:a) Study Area 1: site of existing smelter slated for reconstruction'b) Study Area 2: site of new sulfuric acid plant;c) Study Area 3: site of new wastewater treatment plant.

A number of sampling points were selected in each study area, includingboreholes up to a depth of 10 m. The total number of these boreholes was 34,including three boreholes beyond the polluted zone, and there were only sixobservation wells (where groundwater was present). Most boreholes testednegative for groundwater, even during rarny periods.

The analytical program included: 101 analyses of metal concentrations (15elements) in soil samples; 68 analyses of fluoride and PHC concentrations; 34analyses of VOCs, PAHs, PCBs, pH, atrazine, and simazine; and analysis ofhazardots waste applying the TCLP method. In addition, 74 samples of dust,waste and topsoil were analyzed applying the X-RFA method in situ, while 10samples were tested for heavy metals by the TCLP method. Metal concentra-tions in the filtrate were compared with the filtrate quality criteria per theCanadian standard (Ontario, Canada).

Methodology: Sampling and mapping of soil, determination of coordinates(width, length and height), sampling of topsoil and subsoil, and samplehomogentzation. The following parameters were tested: humidity (%),pH level,fluorides, heavy metals, pesticides, PCBs, PAHs, PHCs, VOCs; TCLP methodfor the determination of hazardous waste. Equipment: GPS, dryer, analyticalscale, furnace, pH meter, water bath, ultrasonic bath, centrifuge, ICP-OES,turbotherm, vapodest VAP, GC/FID/PTV GC 6890N, GC/MSD HP 6890 GC,HP 5193 MSD, NITON X-ray fluorescent analyzer.

Quality control: The recommendation was that 1}Yo of all soil samples and20% of all groundwater samples be control samples. The analytical laboratories,

Miodrag Zlatic & Stanimir Kostadinov (Editors)

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accredited by the relevant ministry, followed environmental quality controlprocedures.

Results

The geological makeup of the investigated terrain is comprised of the so-calledBor Andesitic Massif, largely hornblende-biotite andesites. They are generallycovered with technogenic deposits of varying compositions.

Prior to the erection of the existing structures, a portion of the terrain desig-nated as Study Area 1 (locations of Study Areas are shown on Figures 1 and 2)was excavated by cutting into a slope and creating a platform which holds thefoundations. The thickness of the fill over this platform varies between 0.15 and1.5 m. The locations of boreholes BH-5 and BH-2 are exceptions, as the bedrockwas encountered at 2.5 m and 2.6 m, respectively, as a result of the fact thatexcavation was deeper within that zone for purposes of underground infra-structures. The technogenic deposits in Study Area 1 are generally comprised ofsandy material combined with building debris, smelter slag and concrete.

The portion of the terrain designated as Sfudy Area 2 is also largely(southwest part) a platform created by cutting into a slope. The andesite bedrockwas encountered at depths ranging from 0.15 and 1.3 m, except for the locationof borehole BH-E15 where beyond filled sand with building debris, drilling wasconducted in reinforced concrete for nearly 2 m.Technogenic deposits in thispart of Study Area 2 are generally comprised of concrete and filled materialswith building debris and slag. In another, norlheastern, part of this area, towardsan abandoned mining site, there are thicker deposits of smelter slag, such that thebedrock was encountered at depths between 5.5 and 9.0 m. Borehole BH-EI6 islocated within the border zone between the SW and NE parts of Study Area 2.

Study Area 3 is the lower part of a previously natural slope or one of the topbenches of an abandoned open pit mine. While drilling to a depth of 12 m, nobedrock was encountered. From the ground surface to a depth of 5.4-9.2 m, anunconsolidated and unformed fill was found, underlain by smelter slag.

The surface of the andesite bedrock was found to be generally degraded up tothe depth investigated. The degree of degradation varied, from total grussifica-tion, where the characteristics of the rock were almost sand-like, to relativelysolid rock. The effects of degradation were found to be governed by the compo-sition and structure of the rock, as well as its depth relative to the previousnatural surface of the terrain.

Upon completion of investigations at the site of the smelter which is to bereconstructed and the site of the new sulfuric acid plant (which involved thedetermination of more than 4000 inorganic and organic geochemical andhydrogeochemical parameters), soil pollutants were identified and quantified.The results were compared with Serbian national standards, the new Dutchlist(The Netherlands) and the Leachate Quality Criteria (Ontario, Canada), and areshown, in part, in Table 2.

Advances in GeoEcology 43

Geoenvironmental investigations, smelter location, Bor (Serbia) 53

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54 Papic et al.

Table 2: Concentrations of heavy metals in soil sampledfromwith optimal and action concentrations, according to therequire action).

boreholes (mg/kg), alongDutchlist (bolded values

Parameter pH Pb Cd Zn Cu Cr Ni Hg As BaBH.8 6.6 186 1.3 95 806.4 10.4 t4.9 0.5 28 t26BH-9 7.9 19.5

Geoenvironmental investigations, smelter location, Bor (Serbia)

The Canadian standard (TCLP, Toxicity Characteristic Leaching Procedure)was applied to assess the toxic threat due to leaching. This procedure was usedto determine the mobility of inorganic and organic analytes present in the soil.The test does not address non-dispersive forms of metals. The proceduresimulates soil conditions. Over time, water and other fluids percolate into thesoil and react with solid waste, potentially impacting the environment andcreating a risk to human health, due to contaminant absorption. These analysesdetermine which contaminants have been identified and in which concentrations.If solid waste is characterized by one or several pollutants, it is considered to becharacter istic hazardous waste.

The heavy metal concentrations, following TCLP and comparison withstandards, show that there is no threat from potential activity of acidic agents,whereby some of the heavy metals would be transferred into solution. Excep-tions were noted at several boreholes, where lead was detected in concentrationsof up to 41.7 mglL (the quality criterion is 5 mglL). The concentrations of theother metals (Cd, Cr, Hg, As, Ba, Se and Ag) were far below respective criteria(pelL magnitude).

With regard to organic micropollutants in the soil sampled from the bore-holes, total PCBs were detected in concentrations of up to 6.63 mg/kg and theynecessitate action. In nearly all the samples the presence of PHCs was recordedin excess of the optimal concentration of 50 mg/kg, ranging up to 2893 mg/kg,meaning that action needs to be taken with regard to the PCBs, being persiitentorganic pollutants or the so-called POPs.

Fig. 3: Field determination of heavy metal content with NITOlrl X-ray fluorescenceanalyzer.

Topsoil samples were analyzed to determine the presence of 15 chemicalelements, applying the XRFA method (Figure 3). The samples included dust rich

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56 Papic et al.

in Fe and Cu, less represented elements Pb, Zn, V, Se, Sb and As, and slag withCaO and SiOz. Heavy metal concentrations in post-TCLP extracts, applyingCanadian criteria, showed that the concentrations of cadmium were elevated inseveral samples. Other concentrations were far below the respective criteria(Ontario, Canada).

The analyses showed that the main elements detected in the dust and wasteon the ground surface were Fe, Cu, Pb and Zn. The concentrations of copperwereupto 460A, of ironupto 560A,of zinc upto 4.4o , of leadupto 3.8o/o,ofantimony up to Io/o, of chromium up to 0.2oA, of selenium up to 0.2o/o and ofarsenic up to 0.3%. As such, the surface is contaminated to a certain degree. Thetest results indicate that the elements present in the surface samples of dust andslag belong to the group of toxic elements.

Six samples of groundwater were analyzed, including one QC sample. Theywere collected from four boreholes in Study Area 1 and two boreholes in StudyArea 2. Borehole profiles indicated the presence of groundwater generally fromdegraded andesite, found near the surface, and noteworthy chemical elementsfound in the groundwater included fluoride, arsenic and calcium. The concentra-tions of other heavy metals were extremely low. This is most likely a result if theinsufficient capacity of the groundwater to dissolve these substances (pH up to9.1), as well as adsorption to clay and degraded andesite particles. The ground-water samples were extremely turbid, while the presence of pesticides, PCBs,PAHs, PHCs or VOCs was not detected.

Conclusions

Geoenvironmental investigations were conducted at 34 boreholes at the site of asmelter of the Copper Mining and Smelting Complex Bor, in eastern Serbia. Thetest results allowed for very useful conclusions to be drawn about the qualify ofthe soil which will hold the new sulfuric acid plant. They unequivocally pointedto the degree of contamination, as a result of prior metallurgical activity. TCLPanalyses imparted confidence with regard to any leaching of heavy metals fromthe soil, through the action of atmospheric precipitation (whose pH levels maybe low) or groundwater. Based on the ecogeochemical test results, Sfudy Area 3is the primary arca characteristic of the presence of Pb, Hg, As and PCBs. Theresults indicated that the technogenic deposits (smelter slag and debris) were themain source of the identified highly-toxic elements, and that the presence ofPCBs was a result of operation of transformer stations, which were previouslylocated in this part of the terrain.

The main tasks placed before the ecogeological test program were to detectany presence of hazardous waste and determine any soil pollution. The mainconclusions suggest that hazardous waste is present. However, judging by theTCLP tests of heavy metals, only cadmium exceeds the quality criterion, in threedust samples. Regardless, there is the potential for an adverse impact on theworkers who will participate in the reconstruction of the smelter and the buildingof the new plant. The soil is polluted, given that the presence of Pb, Hg, As andPCBs in excess of action (removal) concentrations, based on the Dutchlist, wasdetected in many soil samples collected from the boreholes in Study Area 3.

Advances in GeoEcology 43

Geoenvironmental investigations, smelter location, Bor (Serbia)

Based on geomechanical and geochemical tests, the recommendation is toconsider another site for the wastewater treatment plant (Study Area 2 instead ofStudy Area 3).

References

Papii, P., Stojkovic, J. and Todorovii, M. (2011): Report of geoenvironmental investiga-tions on the locality for reconstructed smelter and sulfuric acid new plant (inSerbian), University of Belgrade, Faculty of Mining and Geology, Belgrade

Intervention values and target values - soil quality standards (The New Dutchlist), TheMinistry of Housing, Spatial Planning and Environment, The Netherlands

http://www.EHSO.com (The EPA TCLP: Toxicity Characteristic Leaching Procedureand Characteristic Hazardous Wastes)

Addresses of authors:Petar PapidJana StojkovidJovana Milosavljevi6Maja Todorovi6Marina CukUniversity of Belgrade, Faculty of Mining and GeologyDjusina 711000 Belgrade, Serbiappapic@rgf.bg.ac.rsj ana. stoj kovic@rgf.b g. ac.rsj ovana. d. milo savlj evic@, gmai 1. comma-i a. todorovic 8 7 (D, gmail. c ommarinacuk.rgf@ gmail. comZvonimir Miliji6RTB Bor GroupDjordja Yajferta2919210 Bor, SerbiaZvonimir. mi lij ic@ gmai l.com

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Zeljko KamberovidUniversity of Belgrade, Faculty of Technology and MetallurgyKarnegijeva 411000 Belgrade, Serbiakamber@,tmf.bg.ac.rs

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