exchanging experiences in the fields of ...the charachterization and the utilization of cement kiln...

XXIIVV••YYuuCCoorrrr INTERNATIONAL CONFERENCE

Međunarodna konferencija

EXCHANGING EXPERIENCES IN THE FIELDS OF CORROSION, MATERIALS AND ENVIRONMENTAL PROTECTION

Razmena iskustava u oblastima korozije, zaštite materijala i životne sredine

PROCEEDINGS KNJIGA RADOVA

Under the auspicies of Pod pokroviteljstvom

The MINISTRY OF EDUCATION AND SCIENCE OF THE REPUBLIC OF SERBIA MINISTARSTVA PROSVETE I NAUKE REPUBLIKE SRBIJE

17–20. April, 2012, Tara, Serbia

CIP - Каталогизација у публикацији Народна библиотека Србије, Београд

620.193/.197(082)(0.034.2) 621.793/.795(082)(0.034.2) 667.6(082)(0.034.2) 502/504(082)(0.034.2)

МЕЂУНАРОДНА конференција YUCORR (14 ; 2012 ; Тара) Razmena iskustava u oblastima korozije, zaštite materijala i životne sredine [Elektronski izvor] : knjiga radova / XIV YuCorr [Jugoslovenska korozija] Međunarodna konferencija 17-20. April, 2012, Tara ; [organizatori Udruženje inženjera Srbije za koroziju i zaštitu materijala ... et al. ; urednici Miomir Pavlović, Vladimir Panić] = Exchanging Experiences in the Fields of Corrosion, Materials and Enviromental Protection : proceedings / XIV YuCorr International Conference ; [organized by Serbian Society of Corrosion and Materials Protection ... et al.]. – Beograd : Udreženje inženjera Srbije za koroziju i zaštitu materijala, 2012 (Beograd : Foto futura). – 1 elektronski optički disk (CD-ROM) ; 12 cm

Sistemski zahtevi: Nisu navedeni. - Nasl. Sa naslovnog ekrana. - Radovi na srp. i engl. jeziku. – Bibliografija uz svaki rad. - Abstracts.

ISBN 978-86-82343-17-2 1. Удружење инжењера Србије за корозију и заштиту материјала (Београд) a) Премази, антикорозиони - Зборници b) Превлаке, антикорозионе - Зборници c) Антикорозиона заштита - Зборници d) Животна средина - Заштита - Зборници COBISS.SR-ID 190106124 INTERNACIONAL CONFERENCE XIV YUCCOR

IZDAVAČ UDRUŽENJE INŽENJERA SRBIJE ZA KORZIJU I ZAŠTITU MATERIJALA (UISKOZAM) Kneza Miloša 7a/II 11000 Beograd, , tel/fax: +381 11 3230 0 28, E-mail: [email protected]; www.sitzam.org.rs

ZA IZDAVAČA: Prof. dr MIOMIR PAVLOVIĆ, predsednik UISKOZAM

UREDNICI: Prof. dr Miomir Pavlović i Dr Vladimir Panić

OBLAST: KOROZIJA I ZAŠTITA MATERIJALA

ORGANIZACIONI ODBOR | ORGANIZING COMMITEE

Dr Vladimir Panić – president, Prof. dr Miomir Pavlović Jelena Slepčević, B.Sc. Dr Nebojša Nikolić Zagorka Bešić, B.Sc. Gordana Miljević, B.Sc. Miomirka Anđić, B.Sc. Prof. dr Branko Đukić Dr Zorica Stanišić Dr Miodrag Stojanović Prof. dr Dragica Jevtić Dr Zoran Avramović Dr Aleksandar Dekanski Milja Božić – secretary Lela Mladenović – secretary

NAUČNI ODBOR | SCIENTIFIC COMMITEE

Prof. dr M. Pavlović, President, Serbia Prof. dr D. Vuksanović, Montenegro Prof. dr Đ. Vaštag, Serbia, Prof. dr J. Marku, Albania Prof. dr D. Čamovska, Macedonia Prof. dr M. Jotanović, Bosnia and Herzegovina Prof. dr M. Antonijević, Serbia Prof. dr V. Alar, Croatia Prof. dr R. Zejnilović, Montenegro Dr N. Nikolić, Serbia Prof. dr Č. Lačnjevac, Serbia Prof. dr J. Bajat, Serbia Dr I. Krastev, Bulgaria Docent dr R. Fuchs Godec, Slovenia Prof. dr S. Hadži Jordanov, Macedonia Dr V. Panić, Serbia Dr H. J. Gores, Germany Prof. dr D. Jevtić, Serbia Dr M. Stojanović, Serbia Dr. S. Bernik, Slovenia Prof. dr I. Esih, Croatia

GODINA IZDANJA: 2012.

KOMPJUTERSKA OBRADA: Vladimir Panić i Aleksandar Dekanski

TIRAŽ: 200 primeraka

XIV YUCORR IS ORGANIZED BY ORGANIZATORI XIV YUCORR-a

UDRUŽENJE INŽENJERA SRBIJE ZA KOROZIJU I ZAŠTITU MATERIJALA

Serbian Society of Corrosion and Materials Protection

INSTITUT ZA HEMIJU, TEHNOLOGIJU I METALURGIJU

Institute of Chemistry, Technology and Metallurgy, Belgrade

SAVEZ INŽENJERA I TEHNIČARA SRBIJE

Union Of Engineers And Tehnicians Of Serbia, Belgrade

INŽENJERSKA KOMORA SRBIJE Serbian Chamber Of Engineers

INŽENJERSKA AKADEMIJA SRBIJE Engineering Academy Of Serbia

XIV YUCORR UNDER THE AUSPICIES OF THE XIV YUCORR JE FINANSIJSKI POMOGLO

MINISTRY OF EDUCATION AND SCIENCE OF THE REPUBLIC OF SERBIA

MINISTARSTVO PROSVETE I NAUKE REPUBLIKE SRBIJE

MAIN SPONSORS | GLAVNI SPONZORI • STOPAQ ADRIATIC, Zagreb, Hrvatska • PA –EL, d.o.o, VELIKO TRGOVIŠĆE, Zagreb, Hrvatska • GALFOS, d.o.o., Beograd

SPONSORS | SPONZORI

• ZVEZDA HELIOS, Gornji Milanovac

• UNIVERZITET U BEOGRADU, TEHNIČKI FAKULTET BOR

• SITS, Beograd

• SZR «GALVA», Kragujevac

• ALFATERM d.o.o., Čačak

• E.W.E. ECOSYSTEMS, Beograd

• TEHNOSAM d.o.o, Subotica

• INSTITUT «JAROSLAV ČERNI», Beograd

• »AMAL» S.R. d.o.o, Inđija

• DRINSKO LIMSKE HIDROELEKTRANE d.o.o., Bajina Bašta

• SUR TEC d.o.o., Čačak

• PLAMING SKUPINA, d.o.o., Slovenija

• FABRIKA MAZIVA, Kruševac

• »HIGRAP», Beograd

• KTD, d.o.o., Beograd

• RV »METAL», Beograd

• »DARTOS», Obrenovac-Zvečka

• »RIO» d.o.o., Kostolac

• TIKKURILA ZORKA d.o.o., Šabac

• HOPEX INTERNATIONAL d.o.o., Zemun

• INSTITUT ZA PREVENTIVU, Novi Sad

• TARKETT d.o.o., Bačka Palanka

XIV,YuCorr, 17–20 April, 2012, Tara, Serbia I

CONTENTS | SADRŽAJ

Derivati tiazola kao inhibitori korozije bakra u kiseloj sredini | Thiazole derivatives as copper corrosion inhibitors in acidic medium Đenđi Vaštag ...................................................................................................................................................... 1 The charachterization and the utilization of cement kiln dust (CKD) as partial replacement of Portland cement in mortar and concrete production J. Marku, I. Dumi, E. Liço, T. Dilo, O. Çakaj .................................................................................................. 11 Removal of petroleum-type pollutants from the environment by bioremediation | Uklanjanje zagađivača životne sredine na bazi nafte remedijacijom Branimir Jovančićević, Miroslav Vrvić ............................................................................................................ 28 Analiza zaštitnih svojstava premaza na vodenoj bazi na metalnim podlogama | Analysis of the protective properties of waterborne coatings on metallic substrates I. Stojanović, V. Alar, I. Juraga ........................................................................................................................ 35 Application of polyaniline in corrosion protection of metals | Polianilin u zaštiti metala od korozije Milica Gvozdenović .......................................................................................................................................... 43 Mogućnost dobijanja prevlaka za bescementne implantate atmosferskim plazma-sprej postupkom | The possibility of coatings for non-cemented implants obtaining by atmospheric plasma-spraying Marija Mihailović, Aleksandra Patarić, Zvonko Gulišija, Zoran Janjušević, Miroslav Sokić ........................ 50 Utucaj izduvnih gasova aviona na sumu gasova staklene bašte atmosfere | Effect aircraft exhaust gases on sum of green-house atmosphere gases Božidarka Arsenović, Zoran Janjuš, Emil Banjac ............................................................................................ 56 Mikroskopski prikaz erozije maghromitne vatrostalne opeke livnig lonca usled dejstva troske | Microscopic demonstration erosion magchromic refractory bricks from casting ladles by the action slag Snežana Dević, Mira Cocić .............................................................................................................................. 62 Investigation of corrosion and electrochemical characteristics of alloy unmodified system AlZnSnGa in drinking water | Istraživanje korozionih i elektrohemijskih karakteristika nemodifikovanih legura sistema AlZnSnGa u vodi za piće Dragan Radonjić, Darko Vuksanović, Jelena Pješčić ...................................................................................... 66 Ispitivanje korozije rezervoara za dizel gorivo | Corrosion inspection on diesel storage tank Andrej Češnovar, Ružica Manojlović ............................................................................................................... 73 Болести које настају услед загађења воде | The diseases caused by contaminated drinking water Сафет Муратовић, Емина Муратовић ........................................................................................................ 82 Ocena otpornosti na koroziju zavarenih cevi u naftnim bušotinama | Estimation of the corrosion resistance of welded pipes in oil wells Živče Šarkoćević, Miodrag Arsić, Marko Rakon, Bojan Međo, Milan Mišić ................................................... 89 Primena fluoropolimera u antikorozionoj zaštiti organskim premazima | The application of fluoropolymers in corrosion protection by organic coatings V. Milovanović, K. Rončević ............................................................................................................................ 99 Biosorption – technology for improving environment for the new century | Biosorpcija – tehnologija unapređenja životne sredine za novi vek Jelena Milojković, Zorica Lopičić, Mirjana Stojanović, Časlav Lačnjevac, Marija Petrović ....................... 106 SEM–EDS analiza korozijskih naslaga unutarnje strane naftovoda | SEM–EDS analysis of corrosion products deposited onto inner side of oil pipelines A. Ivanković, V. Grozdanić, S. Martinez ........................................................................................................ 114

II XIV,YuCorr, 17–20 April, 2012, Tara, Serbia

Tehnologija baliranja u funkciji očuvanja energetske vrijednosti otpada | Baling technology in preservation of the energy value of the waste Veljko Đukić, Biljana Đukić ........................................................................................................................... 121 Plan uzorkovanja i analize lebdećih čestica u životnoj sredini | Sampling and analysis plan airborne particles in the environment Slobodan Bunić, Milena Marković, Aleksandar Stojaković, Kaća Mijić, Ranka Radić, Slavko Kuzmanović .................................................................................................................................................... 127 Contribution of electrostatic interaction in prevention and controlling deposition of corrosion products on heat exchange surfaces Sonja Vidojkovic, Antonije Onjia, Aleksandra Nastasovic ............................................................................. 133 Influence of the surface pretreatment on the anodic behavior of zirconium in H3PO4 solutions Zagorka Koneska, Ruzica Manojlovic, Dafinka Stoevska-Gogovska ............................................................ 137 Investigation of behaviour of some triazoline-3-thiones in sulfuric acid solution Vesna Dimova, Mirjana Jankulovska, Igor Jordanov, Dejan Dimitrovski .................................................... 142 Zaštita rashladnog sistema od stvaranja depozita | Protection of cooling system against deposit build up B. Đukić, S. Smiljanić, A. Došić ..................................................................................................................... 147 The inhibitive effect of vitamin-C on the corrosive performance of steel in HCl solutions Regina Fuchs–Godec, Miomir G. Pavlović, M. V. Tomić .............................................................................. 155 The need of Macedonian companies for the management of suppliers Elizabeta Mitreva ........................................................................................................................................... 162 National Eco-label criteria for indoor paints and varnishes Slavjanka Pejcinovska-Andonova, Dragica Chamovska ................................................................................ 167 Struktura i svojstva elektroprovodnih kompozitnih materijala na bazi lignoceluloze i bakarnog praha | Structure and properties of electroconductive composite materials based on lignocellulose and copper powder Miroslav M. Pavlović, Vladan Ćosović, Nadežda Talijan, Miomir G. Pavlović, Vaso Bojanić .................... 169 Mogućnost primene zelenih inhibitora za zaštitu čelika | Possibility of application of green inhibitors for steel protection M.G. Pavlović, M.V. Tomić, R. Fuchs Godec, M.M. Pavlović, B. Đukić, M.G. Riđošić ................................ 177 Immobilization of used sandblasting grit in the fly ash based geopolymers | Imobilizacija otpadnog grita u geopolimere na bazi pepela I. Nikolić, R. Zejak, V. Radmilović, S. Mitsche, D. Blečić, M. Krgović .......................................................... 191 Environmental issues in materials science and engineering Vineta Srebrenkoska, Emilija Fidancevska .................................................................................................... 196 Sustainable technologies as a basis of cleaner production Vineta Srebrenkoska, Kiril Lisichkov, Emilija Fidancevska, Jadranka Blazevska Gilev ............................... 202 Elektrohemijski postupci obrade otpadnih voda | Electrochemical processes wastewater treatment Borislav Malinović, Jovo Mandić, Slobodan Bunić, Draženko Bjelić ........................................................... 207 Mjerenje doza gama zračenja na ulaznom dijelu deponije u Banjoj Luci | Dosimetric measurement of gamma radiation on landfill’s entrance in Banja Luka Dragana Nešković-Markić, Željka Šobot Pešić, Vinko Lazić ......................................................................... 215 Praćenje ukupnog nivoa buke na regionalnoj deponiji Banja Luka | Monitoring the overall noise level at the regional landfill Banja Luka Dragana Nešković-Markić, Željka Šobot Pešić, Vinko Lazić ......................................................................... 219 Wastewater treatment using zeolite 4A Blagica Cekova, Darko Spasev ...................................................................................................................... 223 Discounting words as significant indicator of the need of changing the approach into a team management Beti Andonovic, Stanislav Petkovski ............................................................................................................... 227

XIV,YuCorr, 17–20 April, 2012, Tara, Serbia III

Procjena zagađenja metalima sedimenata Skadarskog jezera | Metal pollution assessment of the Skadar lake sediments R.M. Zejnilović, V.R. Kastratović, D.D. Đurović, S.D. Krivokapić, Ž.K. Jaćimović, B.P. Mugoša, N.Z. Blagojević ....................................................................................................................................................... 234 Uticaj emisijskih i imisijskih koncentracija u tehnološkom postupku rada asfaltne baze na životnu sredinu | Influence of emission and ambient level concentrations in asphalt plant technological process on the environment J. Pješčić, D. Vuksanović, D. Radonjić .......................................................................................................... 243 Ispitivanje kumulativnih uticaja na kvalitet vazduha u toku istovremenog rada betonske baze, asfaltne baze i drobiličnog postrojenja | Examination of cumulative impacts on air quality in simultaneous progress of concrete production plant, asphalt plant and crusher plant D. Vuksanović, D. Radonjić, J. Pješčić .......................................................................................................... 250 Examination of reaction order and limiting step of reaction rate of naphthalene oxidation in presence of TiO2 photocatalyst obtained by sol-gel method Mirko Marinkovski, Perica Paunovic, Goran Nachevski, Kiril Lisichkov, Stefan Kuvendziev ...................... 255 Design of process control schemes for separation of unsaturated fish’ fatty acids Stefan Kuvendziev, Kiril Lisichkov ................................................................................................................. 259 Analysis of the process of production of solid pharmaceutical dosage forms by application of a process simulator Lisichkov Kiril, Zhezhov Gjorgji, Kuvendziev Stefan, Dejan Dimitrovski, Mirko Marinkovski ..................... 266 Adsorption of arsenic onto granular ferric hydroxide (GFH) in fixed-bed column Dejan V. Dimitrovski, Zoran Lj. Bozinovski, Kiril T. Lisichkov, Stefan V. Kuvendziev ................................. 272 Optimization of the process of consolidation for fly ash ceramics | Optimizacija procesa konsolidacije za keramiku od letećeg pepela Biljana Angjusheva, Emilija Fidancevska, Kiril Lisichkov, Vojo Jovanov .................................................... 275 Zaštita instalacija sa geotermalnom vodom od korozije i zaprljanja | Protection of the installations with geothermal waters of corrosion and fouling Predrag Milanović, Miomir Pavlović, Jovan Popić, Branislav Jaćimović, Srbislav Genić ........................... 282 Microstructural analysis of Ti-Ni shape memory alloy after corrosion testing in 0.9 % NaCl solution Mirko Gojić, Ladislav Vrsalović, Stjepan Kožuh, Diana Ćubela, Senka Gudić ............................................ 289 FTIR and GC-MS characterization of IR laser irradiated poly(phenylene ether-sulfone) Jadranka Blazevska Gilev, Josef Pola ............................................................................................................ 298 Durability investigation of cement mortars made with recycled rubber aggregate | Ispitivanje trajnosti cementnih maltera spravljenih sa recikliranim gumenim agregatom Dragica Jevtić, Aleksandar Savić ................................................................................................................... 302 Monitoring kvaliteta vazduha na regionalnoj sanitarnoj deponiji „Brijesnica“ Bijeljina | Air quality monitoring in regional sanitary landfill "Brijesnica" Bijeljina Danijela Knežević, Radun Marina ................................................................................................................. 308 Uticaj buke na fasadu stambenog objekta smještenog uz morsku obalu | Envirnonmental noise influence on residental premisse facade setteld near the sea coast Aleksandar Nikolić ......................................................................................................................................... 320 Valorizacija crvenog mulja kao komponente sirovinske mješavine za dobijanje konstrukcionih materijala metodom geopolimerizacije | Using of geopolymerization for the valorization of red mud as a component of raw mixture in constructive materials production Mira Vukčević, Milun Krgović, Ivana Bošković, Mileta Ivanović, Radomir Zejak ........................................ 326 The charachterization of the streams leaving separator in cement production Marku Jozefita, Noçka Enkela ........................................................................................................................ 333

IV XIV,YuCorr, 17–20 April, 2012, Tara, Serbia

Продужетак вијека депоније чврстог комуналног отпада регије Приједор издвајањем секундарних сировина прије депоновања отпада | Life extension municipal solid waste landfill Prijedor region separation of secondary raw materials prior to deposit waste Саша Дуновић, Синиша Цукут, Небојша Кнежевић ................................................................................ 341 Energane na otpad – rješenje problema urbanih sredina | The power plant waste solutions to the problem of urban areas Veljko Đukić, Vaso Bojanić ............................................................................................................................ 351 Propulzija električne bespilotne letelice – poređenje Li-jon kobalt i Li-jon čelik fosfat akumulatora | Propulsion of unmanned aerial vehicles – comparison of lithium-ion cobalt and lithium-ion iron phosphate batteries Kosta Velimirović, Ljiljana Gajić-Krstajić, Nemanja Velimirović ................................................................ 357 Prečišćavanje procjednog filtrata iz regionalne sanitarne deponije „Možura“, Opština Bar, Crna Gora | Leachate treatment at regional sanitary landfill „Mozura“, Municipality Bar, Montenegro Siniša Cukut, Nebojša Knežević, Saša Dunović, Vinko Lazić ........................................................................ 364 Optimization of cleaning process in breweries an important tool in cleaner production implementation Luljeta Xhagolli (Pinguli), Jozefita Marku ..................................................................................................... 373 Eksperimentalna istraživanja kvaliteta obrađene površine nerđajućih čelika pri elektrohemijskoj strugarskoj obradi | Experimental investigation of the surface quality of stainless steel in the electrochemical grating process Branko Pejović, Vladan Mićić, Vladimir Damjanović, Milorad Tomić ......................................................... 380 Heavy metals in sediments along the river Zletovska in Eastern Macedonia Orce Spasovski, Dejan Mirakovski, Emilija Ristova ...................................................................................... 389 Fizičko–hemijske osobine mlaznog goriva | Physical and chemical characteristics of jet fuel Božidarka Arsenović, Emil Banjac ................................................................................................................. 395 The specific surface area of the honeycomb-like structures obtained by the regime of pulsating overpotential in the second range | Specifična površina struktura pčelinjeg saća dobijenih režimom pulsirajuće prenapetosti u sekundskoj oblasti Nebojša D. Nikolić, Goran Branković, Miomir G. Pavlović .......................................................................... 401 Primjena anodne oksidacije u tretmanu otpadnih voda industrije boja | Application of anodic oxidation in paint wastewater treatment B. Malinović, J. Mandić, S. Dunović, N. Damjanović .................................................................................... 406 Zaštita od korozije predstavljena na primerima ukopanih metalnih konstrukcija | Protection from corrosion that is presented on examples of dug in metal construction Jagodinka Mitić, Slađana Đokanović, Miroljub Trifunović ........................................................................... 414 Tribološka i mehanička svojstva kompozita sa matricom na bazi legure bakar–cink | Tribology and mechanical properties of composites with a matrix based on alloys of copper–zinc Miroljub Trifunović, Novica Grujić, Branislav Nedeljković .......................................................................... 420 Ekološko vrednovanje proizvoda i politika integrisanog kvaliteta | Ecological evaluation of policy and integrated quality Dragiša Obradović, Miroljub Trifunović, Slobodanka Bursać ...................................................................... 426 Antikoroziona zaštita u pogonima Topionice i rafinacije bakra-Bor | Corrosion protection in the Copper smelting and refining plants-Bor Zoran Avramović, Milan Antonijević, Miloš Avramović ................................................................................ 432 Author Index | Indeks autora .......................................................................................................................... 439

XIV,YuCorr, 17–20 April, 2012, Tara, Serbia 389

Heavy metals in sediments along the river Zletovska in Eastern Macedonia Orce Spasovski1, Dejan Mirakovski1, Emilija Ristova2

1Faculty of Natural and Technical Science Stip, Macedonia, University “Goce Delcev” Stip, 2Faculty of Mechanical Engineering Vinica, Macedonia, University “Goce Delcev”, Stip

Soils according to the chemical composition and physic-chemical processes occurring in them represent the most complex systems in heterogeneous lithosphere. Both, soils and along the river sediments are subject to different research objectives, which analysis can come to the important information about the pollution of waters and soils with heavy metals, and thereby identify the effects on human health. In this paper the results of pollution by heavy metals in the sediments from the river Zletovska and its surroundings are presented. An attempt to identify the actual condition in the test area is made and the presence of the heavy metals in the sediments of the mentioned river and its tributaries to be determined. Analysis of samples was conducted as part of a series of samples of the instrument Atomic Emission Spectroscopy with inductive coupled plasma (AES-ICP). Past experiences of contamination of areas such as the area of interest indicate that the next group of elements should be taken into consideration: Mn, Fe, Al, Pb, Zn, As, Cd, Cu, Ni, Co, Ag, Cr, Ti, as well as some elements that present higher concentrations of maximum permitted amounts. In our case, the great influence on the activities of the contamination have Zletovo mines and some tailing ponds, which are a by - product of several decades of activity of the eponymous mines. INTRODUCTION Environmental pollution in the past few decades was a topic to which was given minimal importance. Unlike the recent years, this topic has a high priority [1]. Of particular interest is the problem of the presence of heavy and toxic metals in sediments [2,9,10]. Moreover, if the water supply wells for drinking water of the local population belong to such of areas, then the situation is alarming [3]. This research focuses to areas found in contemporary alluvium of the river Zletovska, on the confluence of the river Koritnica. The fact that the water supply wells for drinking water can be found to those areas, poses a serious problem for all residents that are in the municipality Probistip. Moreover, in the immediate vicinity of the mentioned area there are a number of agricultural lands used for production of various crops [11]. Past studies of geological, geochemical and environmental aspects indicate potential for natural contamination in researched area. Another important aspect is stricter legal standards for the quality of the environment in which people live and work in this region, as part of the mandatory EU environmental regulations implementation. The area that was the subject of research comprises sediments from the immediate surroundings of the river Shtalkovska, Koritnica, river Kiselicka and River Zletovska to its estuary in the river Bregalnica (Figure 1). The field marked with a rectangle representing the area of the sediment samples. In the past, the area that is the subject of research and its immediate surroundings has been studied by many researchers from different aspects [4,5,6,7,8]. METHODOLOGY Within the planned studies were carried out preliminary field activities consisted of an initial monitoring of the ground in order to get initial impressions of the situation on the ground. Starting with field activities, the points of research and also profile lines that describe the field of basic research are defined. Within the planned research, basic outreach activities that consist primarily of field monitoring by the topographic determinations of the points of research are carried out; also the profile lines from which the samples of sediments will be taken are determined. In this phase was processed ground covering the upstream of the river Zletovska and its tributaries, starting

390 XIV,YuCorr, 17–20 April, 2012, Tara, Serbia

from the river Shtalkovska by the valley Buchechki, to the estuary of the River Kiselica into river Zletovska, continuing to the part of Kocani (which includes the flow of the river Zletovska from the village Lepopelci to the village Zhiganci and until Ularci village), to the mouth of the river Zletovska into the river Bregalnica.

Figure 1. Map of Republic of Macedonia with the appointed position of the researching area The initial phase is consisted of sampling of sediments from the already mentioned points of researching. Samples are taken by profiles set perpendicular to the flow of rivers and longitudinal intervals of 25 meters on both sides of the rivers. Samples taken from sediments are placed into plastic bags with appropriate labels for samples, place and date of taking the sample. After the outreach activities, appropriate analysis is made. Preparation of sediment samples is consisted of four phases: drying of samples, crashing and sowing of samples, weighing the obtained sub-sample and dissolving of weighted samples. RESULTS AND DISCUSSION Within the planned research, 22 samples of sediments were taken at intervals twice in 25 m perpendicular to the river, on its left and right hand. Samples were collected in bags and further provided in the chemical laboratory of The Faculty of Mining Engineering and Geology in Stip for analysis. Each test is marked with a unique number and locations of samples taken in the field are shown on the topographic map (Figure 2). Table 1 shows the results of chemical tests performed on samples taken from sediments with an ordinal number from 1 to 22. The results are compared with the values of standards established of heavy metals in sediments. Based on the data in Table 1, certain conclusions about the presence of individual heavy metals in sediments in the vicinity of the river Zletovska and its tributary river Kiselicka as well as opinion about the reasons that contribute to the increased content of individual metals can be made.


Figure 2. Topographic map with the specified position of samples of sediments

The data for the iron content (Table 1) indicate increased its presence in most of the analyzed samples. The highest content of iron is found in the sample ZrS-16 (7.73), sample from the right side along the river Zletovska between the villages Zhiganci and Ularci. The lowest content of iron is found in the sample KrS-2 (3.10), sample of sediments from the right side of the river Kiselicka. In general, it can be concluded that the researched area is contaminated with iron. Increased iron content due to the presence of iron oxides and sulphide (pyrite and limonite). Particular attention is given to the high content of manganese in samples ZrS-15 (2.19 %) and ZrSr-16 (1 .. 84%), samples are taken from sediments in the right side of the river Zletovska between the villages Zhiganci and Ularci. The sample Kr/ZrS-5 taken at the estuary of the river Kiselicka into the river Zletovska and the sample ZrS-20 that is taken at the estuary of the river Zletovska into the river Bregalnica show a significant increase in manganese compared with standard content. The lowest content of manganese are found in sediments along the river Zletovska in the place called Lezovski Canton (sample ZrS-10). Contributions to the higher manganese contents in sediments of the rivers Kiselicka and Zletovska is the existing hydro slag that is located nearby mentioned rivers, and the presence of waste water from mines Zletovo where manganese is constant follower of lead - zinc mineralization. Increased content of lead were observed in all samples analyzed, but the highest content of lead occur in samples KrS-1 (2630 mg/kg), ZrS -15 (1830 mg/kg) ZrS-16 (2740 mg/kg).


Zinc also occurs in content increased in all samples analyzed. Particular attention is given to the high content of zinc in the samples ZrS -15 (3050 mg/kg) ZrS-16 (2050 mg/kg) compared with that default values are larger by about 100 times. Table 1. Concentrations of individual metals in sediments (mg/kg)

Elements Pb Zn Mn (%) Cu Co Cd V As Ag Fe

(%) Ni Cr

Samples marked

KrS-1 2630 1570 1.28 220 11 13 60 130 5 6.35 5.00 9.90 KrS-2 150 220 0.17 50 12 5 81 110 5 3.10 7.01 7.13

Kr/ZrS-3 920 990 0.38 100 13 10 69 120 3 4.69 15.76 20.0 Kr/ZrS-4 350 530 0.11 40 12 7 94 130 1 4.31 11.62 18.06 Kr/ZrS-5 1790 1680 1.01 200 8 13 110 170 5 6.10 5.22 12.53

ZrS-6 1350 1430 0.66 150 10 11 130 110 4 5.27 10.00 19.39 ZrS-7 570 900 0.36 69 15 9 170 28 2 4.81 15.44 19.09 ZrS-8 500 820 0.45 63 15 8 180 7 1 4.38 16.29 20.55 ZrS-9 140 280 .0.19 36 13 5 190 3 1 3.63 20.75 23.48 ZrS-10 56 130 0.10 48 13 5 200 5 1 3.74 20.00 24.83 ZrS-11 450 590 0.46 61 16 9 230 7 2 5.09 16.07 25.00 ZrS-12 400 670 0.29 59.87 11.78 8 150 1 1.48 4.22 19.14 20 ZrS-13 370 660 0.33 53.05 14.11 7 180 1 1.45 4.32 13.52 21 ZrS-14 440 760 0.37 62 15 8 190 1 2 4.54 16.00 23 ZrS-15 1830 3050 2.19 160 16.74 23 280 97.13 9.86 7.35 14.30 17 ZrS-16 2740 2050 1.84 190 18.45 23 240 53.88 9.26 7.73 10.74 17 ZrS-17 560 630 0.41 78.06 12.60 10 190 1 1.99 5.03 13.07 16 ZrS-18 250 260 0.15 44.45 14.43 6 200 1 1 4.09 13.57 20 ZrS-19 1000 1280 0.78 93.58 15.48 12 210 28.75 4.32 5.43 13.89 20 ZrS-20 1310 1080 1.11 120 15.63 14 150 36.59 4.75 5.83 12.54 22 ZrS-21 690 1050 0.65 80.65 14.79 10 200 7.33 2.14 4.64 16.15 24 ZrS-22 770 1190 0.62 84.66 14.45 10 100 5.33 2.77 4.30 15.75 21

Sampling: KrS – test sediments taken from the normal flow of the river Kiselicka; Kr/ZrS –samples from sediments taken in the estuary of the river Kiselicka into river Zletovska; ZrS – Samples from sediments taken downstream of the river Zletovska Note: Analyses were made in the laboratory of the Faculty of Mining and Geology in Stip in 2010 by AES-ICP, Analyst: MSc V. Zajkova Increased content of lead and zinc in sediments from the immediate environment of the rivers Kiselicka and Zletovska clearly confirm the high influence of hydro slag Zletovo and active operation of the lead and zinc mines Zletovo. Copper appears in content that are close to or greater compared with standard values. The highest content of copper is found in the test KrS - 1 (200 mg/kg) taken from the left side of the river Kiselicka and into the samples ZrS - 15 (160 mg/kg) and ZrS - 16 (190 mg/kg) taken from the right side of the river Zletovska between the villages Zhiganci and Ularci. Increased copper content is due to the presence of copper mineralization in the mines Zletovo and their immediate surroundings. Chromium occurs in the contents that are higher but very close to default values, except in samples as KrS-1 (9.90 mg / kg) and KrS-2 (7.13 mg / kg) taken from sediments in the river Kiselicka with lower values compared with default values. This kind of distribution of chromium suggests that


mines Zletovo not contaminate explored space with chrome, but the presence of chromium in sediments of the river Zletovska is a consequence of the presence of the mentioned elements in the range near the river Zletovska. Cadmium is a significant contaminant of the researched area because it occurs much more often than standard values. Contamination with cadmium is due to the presence of cadmium in the area in the immediate vicinity of the researched area, especially in mines Zletovo where it constantly monitor lead - zinc mineralization. Increased content of cadmium follows the parts that are contaminated with lead and zinc. Arsenic occurs in some samples in which the contents are identical to standard values, but in a larger number of samples increased significantly in content. This element appears due to its presence within the copper mineralization in the vicinity of Tursko Rudare and partly in the lead and zinc ore in the mines Zletovo. Cobalt is not a significant contaminant in the researched area because occurs in contents very close to standard values. The data obtained for silver (Table 1) indicate that the silver is contaminant in the whole researching area. The accompanying data also show that silver occurs in higher concentrations in all samples analyzed and that it follows lead. Vanadium occurs in contents significantly higher than standard values with the exception of samples taken at river Kiselicka and a test taken directly to the estuary of the river Kiselicka to the river Zletovska. The obtained values indicate significant contamination of the space with vanadium. Nickel in the researching area in most of samples occurs in contents higher, but very close to the standard values. In the samples taken from sediments near the river Kiselicka and in a test taken near the mouth of a river Kiselicka in the river Zletovska, nickel occurs in contents much lower than the standard values. The obtained values for nickel indicate that this element is not a significant contaminant of the researched area. CONCLUSION The results of chemical tests performed on samples taken from the sediments show that in all analyzed samples the heavy metals content is higher compared to standard values. There are several reasons for this behavior of the heavy metals in sediments of the researched area, as it a significant impact of the anthropogenic factors and the geology of the explored area. The highest values indicate the lead, the zinc, the copper, the iron and the cadmium; elements that are result of the contaminated region in a wider area. Also, a large share in the content of the analyzed elements has active operation of the mine Zletovo (it is about the lead zinc ore) and technological process of processing of lead and zinc ore that result in hydro slag Zletovo. Most of the examined elements occur in increased content as they tracking in lead zinc ore. Particular attention is given to samples ZrS-ZrS-15 and 16, taken from the sediments between the villages Zhiganci and Ularci where the most of the heavy metals show high contents, and the space is located at great distances from the mine Zletovo and hydro slag. We state that the increased content of analyzed elements in this part of the explored area is due to the long term activity associated with the transport of lead-zinc concentrate from the railway station in Krupiste. The storage of the concentrate (for ex., loading the truck to rail transport) often is part of the winds that concentrate can translate to larger distances and thus come to the contamination of the environment (soil, water, sediments, etc.). REFERENCES [1] Reeve R., 2002: Introduction to Environment Analysis, John Wily & Sons Ltd., UK. [2] Alloway B.J., 1990: Heavy metals in soils, John Wily & Sons, Inc.


[3] Fairall K., 2002: Chemistry of river water and sediments associated with mining in Macedonia, MSc Project, Royal Holloway, University of London (unpublished).

[4] Spasovski O., Doneva B., 2007: Heavy metals in the water of the river Zletovska and the vicinity, 2nd Balkan mining congress, Belgrade, Serbia.

[5] Spasovski O., Mitev, T., 2009: Heavy metals in waters along the river Bregalnica in the part oh hydroacumulation Kalimanci to Kocani, XI YUCOR International Conference, “Cooperation of researches of different branches in the fields of corrosion, materials protection and invironmental protection”, Tara, Srbija, PROCEEDINGS, 273-277.

[6] Spasovski O., Dambov R., 2009: Possibilities for ground and surface water pollution from the lead and zinc ore processing in the Zletovo mines, Annual of the University of Mining and geology “St. Ivan Rilski”, Vol. 52. Part II, Mining and Mineral processing, 175-178 pp.

[7] Spasovski O., Dambov R., 2009: Heavy metals and the River Kalnistanska and the Vicinty. 3 rd Balkan mining congress, Izmir, Turkey, pp. 667-670.

[8] Rogan N., Serafimovski T., Tasev G., Dolenec T., Dolenec M., 2009: Distribution of Pb and Zn and their chemical specifications in the paddy soils from the Kocani field (Macedonia), Geologica Macedonica, Vol. 23, pp.56-62.

[9] Spasovski O., Doneva B., 2007: Heavy metals in sediments and soills along the river Bregalnica in the part of hydroacumulation Kalimanci to Kocani, Geologica Macedonia.

[10] Spasovski O., Mitev T., Sovreski Z., 2011: Concentration of heavy metals in the environment around Zletovo mines, Proceedings of the XI-th National Conference with international participation of the open and underwater mining of minerals, Varna, Bulgaria. pp. 417-421.

[11] Rogan N., Serafimovski T., Dolenec M., Tasev G., Dolenec T. 2008: Heavy metal contamination of paddy soils and rice from Kocani field in Macedonia, Environ Geochem Health, Springer Science+Business Media B.V.

AUTHOR INDEX INDEKS AUTORA


Alar V. ................................................................ 35 Andonovic B. .................................................... 227 Angjusheva B. .................................................. 275 Antonijević M. .................................................. 432 Arsenović B. ............................................... 56, 395 Arsić M. .............................................................. 89 Avramović M. .................................................. 432 Avramović Z. .................................................... 432 Banjac E. .................................................... 56, 395 Bjelić D. ............................................................ 207 Blagojević N. Z. ............................................... 234 Blazevska Gilev J. .................................... 202, 298 Blečić D. ........................................................... 191 Bojanić V. ................................................. 169, 351 Bošković I. ........................................................ 326 Bozinovski Z. Lj. .............................................. 272 Branković G. .................................................... 401 Bunić S. .................................................... 127, 207 Bursać S. ........................................................... 426 Çakaj O. .............................................................. 11 Cekova B. ......................................................... 223 Češnovar A. ........................................................ 73 Chamovska D. .................................................. 167 Cocić M. ............................................................. 62 Ćosović V. ........................................................ 169 Ćubela D. .......................................................... 289 Cukut S. .................................................... 341, 364 Damjanović N. .................................................. 406 Damjanović V. .................................................. 380 Dević S. .............................................................. 62 Dilo T. ................................................................ 11 Dimitrovski D. .................................. 142, 266, 272 Dimova V. ........................................................ 142 Đokanović S. .................................................... 414 Došić A. ............................................................ 147 Đukić B. ............................................ 121, 147, 177 Đukić V. ................................................... 121, 351 Dumi I. ................................................................ 11 Dunović S. ........................................ 341, 364, 406 Đurović D. D. ................................................... 234 Fidancevska E. .................................. 196, 202, 275 Fuchs-Godec R. ................................................ 177 Fuchs–Godec R. ............................................... 155 Gajić-Krstajić Lj. .............................................. 357 Genić S. ............................................................ 282 Gojić M. ............................................................ 289 Grozdanić V. .................................................... 114 Grujić N. ........................................................... 420 Gudić S. ............................................................ 289

Gulišija Z. .......................................................... 50 Gvozdenović M. ................................................ 43 Ivanković A. .................................................... 114 Ivanović M. ...................................................... 326 Jaćimović B. .................................................... 282 Jaćimović Ž. K. ................................................ 234 Janjuš Z. ............................................................. 56 Janjušević Z. ...................................................... 50 Jankulovska M. ................................................ 142 Jevtić D. ........................................................... 302 Jordanov I. ....................................................... 142 Jovančićević B. .................................................. 28 Jovanov V. ....................................................... 275 Juraga I. ............................................................. 35 Kastratović V. R. ............................................. 234 Knežević D. ..................................................... 308 Knežević N. ..............................................341, 364 Koneska Z. ....................................................... 137 Kožuh S. .......................................................... 289 Krgović M. ................................................191, 326 Krivokapić S. D. .............................................. 234 Kuvendziev S. ........................... 255, 259, 266, 272 Kuzmanović S. ................................................. 127 Lačnjevac Č. .................................................... 106 Lazić V. ............................................ 215, 219, 364 Liço E. ............................................................... 11 Lisichkov K. ............. 202, 255, 259, 266, 272, 275 Lopičić Z. ......................................................... 106 Malinović B. .............................................207, 406 Mandić J. ..................................................207, 406 Manojlovic R. .................................................. 137 Manojlović R. .................................................... 73 Marinkovski M. ........................................255, 266 Marković M. .................................................... 127 Marku J. .............................................. 11, 333, 373 Martinez S. ....................................................... 114 Međo B. ............................................................. 89 Mićić V. ........................................................... 380 Mihailović M. .................................................... 50 Mijić K. ............................................................ 127 Milanović P. ..................................................... 282 Milojković J. .................................................... 106 Milovanović V. .................................................. 99 Mirakovski D. .................................................. 389 Mišić M. ............................................................. 89 Mitić J. ............................................................. 414 Mitreva E. ........................................................ 162 Mitsche S. ........................................................ 191 Mugoša B. P. ................................................... 234


Muratović E. ....................................................... 82 Muratović S. ....................................................... 82 Nachevski G. .................................................... 255 Nastasovic A. .................................................... 133 Nedeljković B. .................................................. 420 Nešković-Markić D. ................................. 215, 219 Nikolić A. ......................................................... 320 Nikolić I. ........................................................... 191 Nikolić N. D. .................................................... 401 Noçka E. ........................................................... 333 Obradović D. .................................................... 426 Onjia A. ............................................................ 133 Patarić A. ............................................................ 50 Paunovic P. ....................................................... 255 Pavlović M. G. .................. 155, 169, 177, 282, 401 Pavlović M. M. ......................................... 169, 177 Pejcinovska-Andonova S. ................................. 167 Pejović B. ......................................................... 380 Petkovski S. ...................................................... 227 Petrović M. ....................................................... 106 Pješčić J. ............................................. 66, 243, 250 Pola J. ............................................................... 298 Popić J. ............................................................. 282 Radić R. ............................................................ 127 Radmilović V.................................................... 191 Radonjić D. ......................................... 66, 243, 250 Radun M. .......................................................... 308 Rakon M. ............................................................ 89 Riđošić M. G. ................................................... 177 Ristova E. ......................................................... 389

Rončević K. ....................................................... 99 Šarkoćević Ž. ..................................................... 89 Savić A. ........................................................... 302 Smiljanić S. ...................................................... 147 Šobot Pešić Ž. ...........................................215, 219 Sokić M. ............................................................. 50 Spasev D. ......................................................... 223 Spasovski O. .................................................... 389 Srebrenkoska V. ........................................196, 202 Stoevska-Gogovska D. .................................... 137 Stojaković A. ................................................... 127 Stojanović I. ....................................................... 35 Stojanović M. ................................................... 106 Talijan N. ......................................................... 169 Tomić M. ......................................................... 380 Tomić M. V. .............................................155, 177 Trifunović M. .................................... 414, 420, 426 Vaštag Đenđi ....................................................... 1 Velimirović K. ................................................. 357 Velimirović N. ................................................. 357 Vidojkovic S. ................................................... 133 Vrsalović L. ..................................................... 289 Vrvić M. ............................................................. 28 Vukčević M. .................................................... 326 Vuksanović D. .................................... 66, 243, 250 Xhagolli (Pinguli) L. ........................................ 373 Zejak R. ....................................................191, 326 Zejnilović R. M. ............................................... 234 Zhezhov G. ...................................................... 266

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