MINING AND ENVIRONMENTAL PROTECTION

PROCEEDINGS

Editor

Prof. dr Ivica Ristovic

Vrdnik

10 - 13. June 2015.

5th

International Symposium

MINING AND ENVIRONMENTAL PROTECTION

10 - 13 June 2015., Vrdnik, Serbia

PROCEEDINGS

5th International Symposium MINING AND ENVIRONMENTAL PROTECTION

Editor: prof. dr Ivica Ristovic, Faculty of Mining and Geology, Belgrade

Reviewers:

dr Michal Cehlar, BERG Faculty, TU Košice, Slovakia, dr Gabriel Fedorko, BERG Faculty, TU Košice, Slovakia, dr

Vieroslav Molnar, BERG Faculty, TU Košice, Slovakia, dr Daniela Marasova, BERG Faculty, TU Košice, Slovakia, dr

Milivoj Vulic, Faculty of Natural Sciences and Engineering, Ljubljana, Slovenia, dr Zeljko Vukelic, Faculty of Natural

Sciences and Engineering, Ljubljana, Slovenia, dr Goran Vizintin, Faculty of Natural Sciences and Engineering,

Ljubljana, Slovenia, dr Evgen Dervaric, Faculty of Natural Sciences and Engineering, Ljubljana, Slovenia, dr Milan

Medved, University of Maribor, Slovenia, dr Vladimir I. Galkin, MISIS Moscow, Russia, dr Evgenia. E Sheshko,

MISIS Moscow, Russia, dr Nikolaj M. Kachurin, TulGU, Tula, Russia, dr Oleg N. Rusak, Sankt-Peterburg, Russia, dr

Zoran Panov, Goce Delcev University Stip, Macedonia, dr Zoran Despodov, Goce Delcev University Stip, Macedonia,

dr Dejan Mirakovski, Goce Delcev University Stip, Macedonia, dr Viktor Kovalov, Donbas State Engineering

Academy, Ukraine, dr Valentin Nedeff, University of Bacau, Romania, dr Alexandru-Viorel Pele, University of

Oradea, Romania, dr Raycho Ilarionov, TU Gabrovo, Bulgaria, dr Malgorzata Malec, KOMAG, Gliwice, Poland, dr

Monika Hardygora, Wrocław University of Technology, Poland, dr Horst Gondek, VŠB Ostrava, Czech Republic, dr

Jiri Fries, VŠB Ostrava, Czech Republic, dr Neven Duic, University of Zagreb, Croatia, dr Nediljka Gaurina-

Medjimurec, University of Zagreb, Croatia, dr Vlatko Marusic, University of Osijek, Croatia, dr Vladimir Malbasic,

University of Banja Luka, Republic of Srpska, Bosnia and Hercegovina, dr Kemal Gutic, Faculty of Minig, Geology

and Civil Engineering,Bosnia and Hercegovina, dr Gordana Stefanovic, University of Nis, Serbia, dr Srdjan Jovic,

University of Pristina, Serbia, dr Blagoje Nedeljkovic, University of Pristina, Serbia, dr Gordana Vojkovic, University

of Belgrade, Serbia, dr Zoran Nikic, University of Belgrade, Serbia, dr Ivan Obradovic, University of Belgrade, Serbia,

dr Nikola Lilic, University of Belgrade, Serbia, dr Bozo Kolonja, University of Belgrade, Serbia, dr Dinko Knezevic,

University of Belgrade, Serbia, dr Milos Grujic, University of Belgrade, Serbia, dr Aleksandar Cvjetic, University of

Belgrade, Serbia, dr Ivica Ristovic, University of Belgrade, Serbia.

Editorial Board: Aleksandar Ganic; Ivica Ristovic; Rade Tokalic; Milena Kostović; Milos Tanasijevic;

Branko Lekovic; Branko Gluscevic; Milena Gojkovic.

Publisher: Faculty of Mining and Geology, Belgrade

For publisher: Prof. dr Ivan Obradovic, Dean

Technical desing: SaTCIP, Vrnjacka Banja

Printed by: SaTCIP, Vrnjacka Banja

Copies: 150

ISBN 978-86-7352-287-6

The publication of this Proceedings approved by the Council of Faculty of Mining and Geology, University of

Belgrade

All Papers in Proceedings are reviewed

This Proceedings was published with the financial assistance of the Ministry of Education, Science and

Technological Development of Republic of Serbia

ORGANIZER

UNIVERSITY OF BELGRADE, FACULTY OF MINING AND GEOLOGY, Belgrade

CENTER FOR ENVIRONMENTAL ENGINEERING, Mining Department

www.rgf.bg.ac.rs

COORGANIZERS

BERG FACULTY TU KOSICE, SLOVAKIA

www.fberg.tuke.sk

UNIVERSITY OF LJUBLJANA, FACULTY OF NATURAL SCIENCES AND ENGINEERING, SLOVENIA

www.ntf.uni-lj.si

GOCE DELCEV UNIVERSITY IN STIP, MACEDONIA

www.ugd.edu.mk

NATIONAL UNIVERSITY OF SCIENCE AND TECHNOLOGY “MISIS”, MOSCOW, RUSSIA

www.en.misis.ru

INTERNATIONAL ACADEMY OF SCIENCES OF ECOLOGY AND PROTECTION MANEB,

SANKT-PETERBURG, RUSSIA

SCIENTIFIC COMMITTEE dr Michal Cehlar, BERG Faculty, TU Košice, Slovakia, dr Gabriel Fedorko, BERG Faculty, TU Košice, Slovakia, dr

Vieroslav Molnar, BERG Faculty, TU Košice, Slovakia, dr Daniela Marasova, BERG Faculty, TU Košice, Slovakia, dr

Milivoj Vulic, Faculty of Natural Sciences and Engineering, Ljubljana, Slovenia, dr Zeljko Vukelic, Faculty of Natural

Sciences and Engineering, Ljubljana, Slovenia, dr Goran Vizintin, Faculty of Natural Sciences and Engineering,

Ljubljana, Slovenia, dr Evgen Dervaric, Faculty of Natural Sciences and Engineering, Ljubljana, Slovenia, dr Milan

Medved, University of Maribor, Slovenia, dr Vladimir I. Galkin, MISIS Moscow, Russia, dr Evgenia. E Sheshko,

MISIS Moscow, Russia, dr Nikolaj M. Kachurin, TulGU, Tula, Russia, dr Oleg N. Rusak, Sankt-Peterburg, Russia, dr

Zoran Panov, Goce Delcev University Stip, Macedonia, dr Zoran Despodov, Goce Delcev University Stip, Macedonia,

dr Dejan Mirakovski, Goce Delcev University Stip, Macedonia, dr Viktor Kovalov, Donbas State Engineering

Academy, Ukraine, dr Valentin Nedeff, University of Bacau, Romania, dr Alexandru-Viorel Pele, University of

Oradea, Romania, dr Raycho Ilarionov, TU Gabrovo, Bulgaria, dr Malgorzata Malec, KOMAG, Gliwice, Poland, dr

Monika Hardygora, Wrocław University of Technology, Poland, dr Horst Gondek, VŠB Ostrava, Czech Republic, dr

Jiri Fries, VŠB Ostrava, Czech Republic, dr Neven Duic, University of Zagreb, Croatia, dr Nediljka Gaurina-

Medjimurec, University of Zagreb, Croatia, dr Vlatko Marusic, University of Osijek, Croatia, dr Vladimir Malbasic,

University of Banja Luka, Republic of Srpska, Bosnia and Hercegovina, dr Kemal Gutic, Faculty of Minig, Geology

and Civil Engineering,Bosnia and Hercegovina, dr Gordana Stefanovic, University of Nis, Serbia, dr Srdjan Jovic,

University of Pristina, Serbia, dr Blagoje Nedeljkovic, University of Pristina, Serbia, dr Gordana Vojkovic, University

of Belgrade, Serbia, dr Zoran Nikic, University of Belgrade, Serbia, dr Ivan Obradovic, University of Belgrade, Serbia,

dr Nikola Lilic, University of Belgrade, Serbia, dr Bozo Kolonja, University of Belgrade, Serbia, dr Dinko Knezevic,

University of Belgrade, Serbia, dr Milos Grujic, University of Belgrade, Serbia, dr Aleksandar Cvjetic, University of

Belgrade, Serbia, dr Ivica Ristovic, University of Belgrade, Serbia.

ORGANIZING COMMITTEE:

dr. Ivica Ristovic, Belgrade, Serbia, president, dr. Gabriel Fedorko, Košice, Slovakia, vice president, dr. Milivoj

Vulic, Ljubljana, Slovenia, vice president, dr. Vasilii Zotov, Moscow, Russia, vice president, dr. Zoran Despodov,

Štip, Republic of Macedonia, vice president, dr. Vjeroslav Molnar, Košice, Slovakia, dr. Olga O. Sheshko, Moscow,

Russia, dr. Jiri Fries, Ostrava, Czech Republic, dr. Dejan Mirakovski, Štip, Republic of Macedonia, dr. Aleksandar

Cvjetic, Belgrade, Serbia, Miroslav Ivkovic, TE-KO Kostolac, Kostolac, Serbia, Danko Beatovic, TE-KO Kostolac,

Kostolac, Serbia, MSc Ivana Filipovic, Belgrade, Serbia, MSc Milena Lekic, Belgrade, Serbia, MSc Uros Pantelic,

Belgrade, Serbia, BSc Bojana Simic, Belgrade, Serbia, BSc Nadežda Petrović, Lazarevac, Serbia

http://www.fberg.tuke.sk/bergweb/http://www.fberg.tuke.sk/bergweb/http://www.ntf.uni-lj.si/http://www.ugd.edu.mk/index.php/en/http://en.misis.ru/

C O N T E N T S:

PLENARY SESSION

Ivica Ristovic:

Mining and Environmental Protection - Experiences and Challenges.........................................

1

Daniela Marasová, Michal Cehlár, Nikoleta Husáková, Slovakia:

Procedure of Creation and Design of Simulation Model of Calcined Ore Conveyance...........

9

Evgen Dervaric, Zeljko Vukelic, Slovenia: Can Coal Survive......................................................................................................................

15

Aleksandar Cvjetic, Serbia:

Environmental Noise in Serbian Open Cast Lignite Mines......................................................

23

Predrag Dasic, Ivica Ristovic, Jovan Dasic, Serbia:

Analysis of bibliometric indicators for category Mining & Mineral

Processing for 2013 based on JCR and Scopus data.................................................................

30

WORKS SESSIONS

Gabriel Fedorko, Vieroslav Molnar, Nikoleta Husakova, Slovakia: Analysis of Variable Pipe Conveyor Belt Motion by the Help of CAX Tools.........................

40

Gabriel Fedorko, Vieroslav Molnár, Dragan Medenica, Slovakia, Serbia:

Modelling of Stress-Deformation States for Conveyor Belts of Classic Belt Conveyors........

48

Gabriel Fedorko, Ivana Filipovic, Ivica Ristovic, Slovakia, Serbia:

Utilization of CAD and CAE Technologies by Research of Shifting of Pipe Conveyors........

55

Peter Michalik, Vieroslav Molnár, Slovakia:

Scripting – Effective Tool for Acceleration of FEM Analysis in the Program Abaqus...........

64

Nikoleta Husáková, Slovakia:

Eco-logistics – a Tool for Environmental Protection................................................................

73

Evgenia E. Sheshko, Russia:

Substantiation of Efficiency of Application of Sandwich Belt High Angle

Conveyors in the Schemes With Cyclic and Line Technology in Deep Open Pits..................

79

Vladimir I. Galkin, Russia:

Features of Designs of Belts for Pipe Belt Conveyors..............................................................

86

Olga E. Sheshko, Russia:

Tendences of Reducing Harmful Emissions Into Atmosphere in Deep Open Pits...................

91

Svjetlana Sredic, Nada Prerad, Slobodanka Malbasic, Vladimir Malbasic,

Igor Knjeginic, Republic of Srpska, Bosnia and Hercegovina:

Possibility of Biomass Production from Fast-Growing Plantations at the

Degraded Areas of Iron Ore Mines Around Prijedor................................................................

97

Amor Husic, Rijad Sisic, Zvjezdan Karadzin, Bosnia and Hercegovina:

Possibilities of Utilizing Ventilation Air Methane from FBIH Coal Mines................................

106

Dragana Jelisavac Erdeljan, Serbia: Mining Waste Management.........................................................................................................

112

Milos Grujic, Serbia:

Basic Principles of Quantifying the Criteria for Identifying Priorities

in Solving the Environmental Protection Problems in Mining....................................................

115

Bogoljub Vuckovic, Biljana Radovanovic, Nadezda Petrovic, Serbia:

Kolubara Lignites Combustible Sulphur Environmental Impact – Naturall

and Artificial Selected Sources Comparison................................................................................

120

Zeljko Prastalo, Dragan Milosevic, Sasa Mitic, Milinko Radosavljevic,

Nenad Makar, Serbia:

Exploitation Measures Aimed in Preserving the Quality of Humus............................................

130

Nikolai M. Kachurin, Sergei A. Vorobev, Sergei M. Bogdanov, Russia:

Evaluating Polluting Atmosphere by Mining Enterprises and

Optimizing Prophylactic Measures Resources.............................................................................

135

Nikolai M. Kachurin, Sergei A. Vorobev, Dimitryi N. Shkuratckiy,

Sergei M. Bogdanov, Russia:

Environmental Danger of Worked and Liquidated Coal Mines Open Areas...............................

141

Edward M. Socolov, Tatiyna S. Sviridova, Russia:

Polluting Soils by Heavy Metals and Radionuclides...................................................................

150

Zorica Ivkovic, Dejan Dramlic, Vladica Dragosavljevic, Serbia:

Legislation to preserve and faciliate biological resources in underground coal exploitation......

154

Biljana Milutinovic, Gordana Stefanovic, Srdjan Jovic, Hivzo Skrijelj, Serbia: Development of Mathematical Model for Estimation of Economic

Indicators of Waste Treatment.....................................................................................................

162

Dragana Savic, Jelena Majstorovic, Dejan Nikolic, Dejan Zivkovic, Serbia:

Geological Investigations of Conceptual Project of Regional Landfill on Kalenic.....................

171

Drago Potocnik, Janez Roser, Milivoj Vulic, Slovenia:

Analysis of Occupational Injuries in the Velenje Coal Mine Using

Modified Sigmoid Function.........................................................................................................

179

Gregor Novakovic, Simon Kovacic, Milivoj Vulic, Slovenia:

Applicability of 3D Laser Scanning Data in Underground Constructions...................................

184

Janja Vrzel, Nives Ogrinc, Goran Vizintin, Slovenia:

Development of the Conceptual Model – Ljubljansko Polje Aquifer (Slovenia)........................

189

Zeljko Vukelic, Evgen Dervaric, Goran Vizintin, Slovenia:

Well Optimization in Velenje Coal Mine Using 3D

Finithe Elements Modeling..........................................................................................................

193

Cvjetko Stojanovic, Biljana Borovic, Republic of Srpska, Bosnia and Hercegovina:

Exploitation of Natural Resources in Function of Sustainable Development..............................

199

Zoran Despodov, Dejan Mirakovski, Nikolinka Doneva,

Stojance Mijalkovski, Zoran Panov, Republic of Macedonia:

Regulation of Saska River with Aim for Environmetal Protection at

No.4 Flotation Tailing Damp Construction in the Sasa Mine.......................................................

203

Todor Serafimovski, Goran Tasev, Republic of Macedonia:

Soil Metal Pollution Related to Active Zletovo Pb-Zn Mine...........................................................

209

Dejan Mirakovski, Marija Hadzi-Nikolova, Zoran Despodov,

Nikolinka Doneva, Stojance Mijalkovski, Republic of Macedonia: Guidelines for Preparation of Mine Waste Management Plan.....................................................

216

Marija Hadzi-Nikolova, Dejan Mirakovski, Zoran Despodov,

Nikolinka Doneva, Stojance Mijalkovski Republic of Macedonia:

Verification of the Environmental Noise Dispersion Model in Mining.......................................

226

Aleksandar Simic, Radoje Lausevic, Ana Popovic, Mirjana Bartula, Serbia:

Environmental Management and Information System for Surface Lignite Mining....................

232

Marija Zivkovic, Dejan Ivezic, Aleksandar Madzarevic, Serbia: The Role of Ecological Indicators in Processes of Strategic

Planning-Case of The City of Nis................................................................................................

238

Vesna Karovic Maricic, Branko Lekovic, Dusan Danilovic,

Miroslav Crnogorac, Serbia:

Environmental Benefits of Enhanced Oil Recovery by CO2 Injection........................................

247

Dusan Danilovic, Vesna Karovic-Maricic, Branko Lekovic,

Miroslav Crnogorac, Serbia:

Preventing Harmful Emissions Into the Atmosphere Upon Manipulation Oil Derivatives.........

253

Snezana Savkovic, Jelena Majstorovic, Predrag Jovancic, Serbia:

Analysis attainable technical-technological results word open pit mines

Elecktrical industry - EPS of Serbia.............................................................................................

258

Jelena Malenovic Nikolic, Ana Vukadinovic, Vojin Cokorilo, Serbia:

Energy Management and Systems of Environmental Safety in Mining-Energy Complexes......

262

Jelena Malenovic Nikolic, Dejan Vasovic, Serbia:

Improving Systems of Environmental Safety in Mining-Energy Complexes:

Project Management.....................................................................................................................

267

Dejan Vasovic, Jelena Malenovic Nikolic, Stevan Musicki, Serbia:

Water Framework Directive, Industrial Emissions Directive, Seveso Directive:

A Triangle of Equal Sides............................................................................................................

272

Radule Tosovic, Serbia:

Expert Economic Evaluation of Mineral Resources in Environmental Protection......................

278

Tomislav Subaranovic, Vladimir Pavlovic, Ivan Jankovic, Serbia:

Planning and Options of Mine Closure........................................................................................

285

Milorad Stojanovic, Slavica Stojanovic, Serbia:

The Impact of the Construction of Phase II of the Coal Preparation Plant

(Crusher) Tamnava-East Field and Dump Fine Coal on the Environment..................................

289

Gordana Milentijevic, Blagoje Nedeljkovic, Milan Milojevic, Serbia:

Exploration of Pb-Zn ore on Surrounding Areas of the Crnac Mine...........................................

296

Gordana Milentijevic, Blagoje Nedeljkovic, Milan Milojevic, Serbia:

The Impact of Flotation Processing of the Pb-Zn ore one the Living Environment

of the MIF Kopaonik in Leposavic..............................................................................................

301

Snezana Aleksandrovic, Aleksandar Cvjetic, Serbia:

Analysis of Noise Sources in Power Transformers and Rotating Electrical Machine.................

307

Jovan Zdravkovic, Mladen Vojnic, Serbia: Deep Well Dewatering on the Open Pit Drmno with Reference to Environmental Protection..........

313

Radisa Djuric, Dragan Stevic, Filip Todorovic, Serbia:

Impact of Modern Technology Application of New Machines of the Auxiliary

Mechanization for Reduction of Environmental Pollution at the Open-Pit Coal Mine Drmno...

318

Radisa Djuric, Dragan Milosevic, Zoran Maksimovic, Serbia:

Rational Maintenance of Machinery in the Open Pit Drmno Using

the New Concepts of Vehicles Used for the Collection and Distribution of New Oil.................

323

Miodrag Denic, Veselin Dragisic, Sasa Stojadinovic, Vladimir Zivanovic, Igor Svrkota,

Dragan Jokovic, Serbia:

Isolation of Old Works and the Possibility of a Durable Solution for the

Drainage of the Pit Mine Soko.....................................................................................................

331

Dusko Djukanovic, Igor Svrkota, Serbia:

Influence of Accidents in Underground Coal Mining to Environment........................................

338

Radoje Pantovic, Nenad Vusovic, Igor Svrkota, MarkoVukovic, Serbia:

Monitoring of Displacements in Support of Kriveljska Reka Collector......................................

341

Novica Momcilovic, Jadranka Vukasinovic, Serbia: Construction and Exploitation of a Landfill for Ash and Slag Disposal from the

Heating Plant Vreoci for the Purpose of Environmental Protection............................................

349

Dinko Knezevic, Nikola Lilic, Dragana Nisic, Milos Stanic, Vladan Kuzmanovic, Serbia:

Using Previously Polluted Sites for Waste Storage, Prahovo Phosphogypsum

Storage Case Study.......................................................................................................................

356

Nikola Lilic, Vladimir Milisavljevic, Uros Pantelic, Ljiljana Kolonja,

Dragan Medenica, Serbia:

Dispersion Modeling of Particulate Matter in Surface Lead and Zinc Mine Suplja Stijena.....

366

Suzana Lutovac, Cedomir Beljic, Zoran Gligoric, Branko Gluscevic, Serbia:

Parameter Determination of Soil Oscillation Law Using Quotient of the Relative Growth

Increments of Oscillation Velocity and Reduced Distances at Kovilovaca Surface Mine..........

376

Bozo Kolonja, Dejan Stevanovic, Milica Pesic Georgiadis, Mirjana Bankovic,

Ljiljana Kolonja, Serbia:

Uncertainty in Open Pit Optimization..........................................................................................

385

Ljiljana Kolonja, Ranka Stankovic, Ivan Obradovic, Olivera Kitanovic,

Uros Pantelic, Serbia:

Development of a Business Intelligence Tool For Accident Analysis in Mines..........................

393

Ranka Stankovic, Nikola Vulovic, Nikola Lilic, Ivan Obradovic, Radule Tosovic,

Milica Pesic-Georgiadis:

Webgis Cadastre Of Abandoned Mines In Autonomous Province Of Vojvodina.......................

400

Sasa Ilic, Serbia:

Selective Mining and Dumping of Overburden on Opencast Coal Mining.................................

407

Aleksandar Cvjetic, Ljubica Figun, Vladimir Milisavljevic, Uros Pantelic,

Aleksandra Tomasevic, Serbia:

Noise Management at the Buvac Open Cast Mine.......................................................................

410

Milena Lekic, Ivana Filipovic, Zoran Nikic, Serbia:

Biological Planning Prospects of Municipal Waste Landfills in Serbia...........................................

420

POSTER SESSION

Vrhovnik Petra, Recnik Aleksander, Dolenec Matej, Daneu Nina,

Grom Nina, Slovenia:

Magnetite Ore Deposit Mala Kopa..............................................................................................

427

Vrhovnik Petra, Serafimovski Todor, Tasev Goran, Rogan Smuc Nastja,

Dolenec Matej, Slovenia, Republic of Macedonia: Metal Contamination in Makedonska Kamenica Region:Relevance to Human Health..............

428

INDEX OF AUTHORS

209

SOIL METAL POLLUTION RELATED TO ACTIVE ZLETOVO Pb-Zn

MINE, REPUBLIC OF MACEDONIA

Todor Serafimovski, Goran Tasev

University "Goce Delčev", Faculty of Natural and Technical Sciences, Stip, Republic of Macedonia

Abstract: Within this study a total content of 20 elements was determined in 24 soil samples taken from the vicinity of

the "Zletovo" mine, Republic of Macedonia, covering an area of 24.5 km2. However, in this paper we present four

elements significant from anthropogenic point of view. In that manner, in soils of the “Zletovo” mine area Fe values

ranged 19.3-76.9 g kg-1

with 24 above the optimum (18 g kg-1

) and 1 above action value (72 g kg-1

), Mn values ranged

643-28000 mg kg-1

with 24 above optimum (33 mg kg-1

) as well as 24 over the action value (330 mg kg-1

), Pb with

range of 42.3-529.66 mg kg-1

with 23 over optimal (85 mg kg-1

) and none above action value (530 mg kg-1

), and Zn

with range 138-3240 mg kg-1

with 23 over optimal (140 mg kg-1

) and 14 above action value (720 mg kg-1

).

Keywords: Zletovo Mine, Waste, Heavy Metals, Pollution, Soil

1. INTRODUCTION

Mine wastes represent the greatest proportion of waste produced by industrial activity. It is well known that

mining and metallurgical activities lead to enormous soil contamination with heavy metals [1, 2, 3, 4, 5, 6,

7, 8, 9, 10, 11, 12, 13]. In fact, the quantity of solid mine waste and the quantity of Earth’s materials moved

by fundamental global geological processes are of the same order of magnitude or approximately several

thousand million tonnes per year [14, 15]. Opposite to the fundamental global geological processes such as

oceanic crust formation, soil erosion, sediment discharge to the oceans, and mountain building, which

naturally move Earth’s materials around the Earth’s crust and shape our planet, the human extracts material

from the Earth during mining and discards most of the extracted crust as waste. Although the modern

mining industry is of considerable importance to the world economy as it provides a great diversity of

mineral products for industrial and household consumers. Therefore, it is necessary to take measures to

protect the environment from pollution with heavy metals from when it comes from such processes. This is

especially important for the proper waste management. There are several the most important approaches to

minimize the environmental impact, i.e. more sustainable mining operations, like proper deposition,

monitoring, reusing, bioremediation etc. [16]. Increased environmental awareness about the anthropogenic

input around the industrial facilities around the world induced the study of Zletovo Mine’s influence to the

adjacent environ. Here we are showing our work and analytical data of 2011 study of concentration of

different chemical elements in surface soil around one of the oldest Macedonian mines (Zletovo Mine) and

determination of its environmental impact to the adjacent vicinity (Fig. 1).

5th

International Symposium

MINING AND ENVIRONMENTAL PROTECTION

10 - 13. June 2015., Vrdnik, Serbia

210

Figure 1 Main sources of heavy metals pollution induced by work of Zletovo Mine, Macedonia

2. THE ZLETOVO Pb-Zn DEPOSIT SHORT FACTS

The Zletovo mine is located in the vicinity of the city of Probistip, Macedonia. The mine started operation

in 1940 and its production lasts until today with certain short-term interruptions. As it is well known the

mineralization is related to Tertiary calcalkaline magmatic rocks, mostly dacites and andesites.

Mineralization is found in a dacitic volcano-sedimentary suite that has been altered to clays and micas

[17, 18]. Detailed information about the mineral parageneses and geochemical features of major minerals

in ore veins is provided in extensive literature [19, 20]. The main ore mineral association is composed of

galena and sphalerite, followed by tetrahedrite, pyrrhotite, magnetite, chalcopyrite, pyrite, and Mn oxides

are also common. Production during certain periods have reached 300000 t of ore per annum, with ore

grades higher than 9% Pb and 2% Zn, and variable concentrations of Ag, Bi, Cd, and Cu. Ore was

concentrated by flotation at Probistip and tailings were disposed of in two impoundments situated in

adjacent river and stream valleys. One of them, the river Kiselica, drains the flotation plant at Probistip

while the Koritnica River drains the area containing the main workings of the Zletovo mine (Figure 1).

Both of them join the River Zletovska, which flows down into the River Bregalnica.

3. SAMPLING AREA AND METHODS

Sampling was carried out at the beginning of May 2011. Soil surface samples (0 cm to 5 cm depth) were

collected in around the Zletovo Mine and its surrounding region (Fig. 1). The main locations that have

been sampled were at the drainage systems of Zletovo, Koritnica River, Globica, Kiselica, Strmos,

Buciste, Ziganci and Ularci as well as sites around these streams-rivers. Soil samples were collected at

several locations, but in general perpendicular to the stream-river flows. In total, 24 samples were

collected from 24 locations, over an area of 24.5 km2. Samples were located using the Global Positioning

System (GPS) and topographic maps at scale of 1:25 000. Each sample represented the composite

material collected at the central sampling point itself together with at least four points collected around a

central one with а radius of 1 m towards N, E, S and W directions. The composite material of each sample

(about 0.5 kg) was placed into plastic self-closing bags and brought to the Faculty of Natural and

Technical Sciences, University “Goce Delcev” Stip, Republic of Macedonia, where they were prepared

for the analysis. Hot (80°C) concentrated nitric acid digest was used to leach elements from the soil.

Solutions were analysed by ICP-AES or ICP-MS, depending on concentrations. The precision was less

than 5%. A large number of analytes were determined but only those that are likely mining related and

environmentally significant are presented and discussed here. The concentrations were compared to

reference guidelines to assess their significance.

211

4. RESULTS AND DISCUSSION

Studying results and statistically processing them it was determined that representative are elements such are

lead, zinc, iron and manganese and they are given in more details within this paper while there are elements

such are chromium, vanadium, nickel, cobalt, have not displayed elevated concentrations and being without

any significant impact as direct product of geological setting and anthropogenetic activity (Table 1).

Table 1.Concentrations of particular heavy metals in soil samples from the vicinity of the Zletovo Mine, Macedonia

Sample Pb

(mg kg-1

)

Zn

(mg kg-1

)

Fe

(g kg-1

)

Mn

(mg kg-1

)

ZN-1 42.3 138 19.3 643

ZN-2 102 283 29.66 1980

ZN-3 153 163 31.66 8680

ZN-4 529.66 2300 44.5 8553

ZN-5 389 1800 29.45 5920

ZN-6 201 300 31.23 1842

ZN-7 116.3 298 29.36 2016

ZN-8 192 420 42.36 2090

ZN-9 209 265 37.89 2312

ZN-10 493.8 2333 61 28000

ZN-11 435 2400 61.12 5440

ZN-12 333 1390 37.45 8666

ZN-13 480 2320 76.9 4350

ZN-14 358 3007 63.32 21560

ZN-15 443 3240 55.22 18960

ZN-16 211 444 29.45 3320

ZN-17 198 489 31.22 5550

ZN-18 211 611 29.33 2750

ZN-19 283 1230 33.71 2630

ZN-20 233 1120 30.16 2610

ZN-21 229 1326 31.78 2590

ZN-22 190 745 34.23 6870

ZN-23 165 796 29.97 7540

ZN-24 200 910 28.63 6110

min 42.3 138 19.3 643

max 529.66 3240 76.9 28000

average 284.36 1303.54 40.67 7791.75

Dutch list (Optimum) 85 140 18 33

Dutch list (Action) 530 720 72 330

Above optimum 23 23 24 24

Above action 0 14 1 24

Lead (Pb). In mining areas, Pb may be dispersed due to the erosion and chemical weathering of tailings.

The severity of these processes depends on chemical characteristics, and the minerals present in the

tailings [6]. In general, several observations of Pb balance in various ecosystems show that the input of

this metal greatly exceeds its output. The strong Pb adsorption in soils may mean that Pb additions to soil

are permanent and irreversible. The average amount of Pb in the world’s soils is 35 mg kg-1

[21], in the

European topsoil is 33 mg kg-1

[6], in Macedonia (studied part) is 26 mg kg-1

[22]. As it is obvious from

the table above (Table 1), we would like to stress out that lead values ranged from the 42.30÷529.66

mg·kg-1

Pb, while the lowest values were determined near the Zletovo village the highest ones were

determined in samples from localities Koritnica, Kiselica and Strmos. Calculated enrichment factor and

index of geo-accumulation were 16.66 and 0.327, respectively. In the main polluted area the average

concentration of Pb is 8.6-times higher than the European Pb average and Macedonian average for 10.9-

times. Although the average content of lead in the topsoil for the entire study area was found to be about

212

284.36 mg kg-1

, there are areas with increased concentration up to 529.66 mg kg-1

, although even such

values were not above action values by the Dutch list (Table 1; Figure 2).

a) b)

c) d)

Figure 2 Measured concentrations of some heavy metals (Pb, Zn, Fe, Mn) vs. Dutch standard in

soils around the Zletovo Mine, Macedonia. (Note: all plots have logarithmic vertical scale)

Zinc (Zn). The most important anthropogenic sources of Zn are the metallurgy industry, burning of fossil

fuels, mines and Zn ore processing [1]. Zn is an essential element for most living organism (plants,

animals and humans) with important role in enzymes processes and cellular metabolism, in immune

function, protein synthesis, DNA synthesis, and cell division and daily intake of zinc is required to

maintain a steady state because the body has no specialized zinc storage system [23]. Even the toxicity of

Zn is relatively low, there are cases when poisoning with Zn can occur in both acute and chronic forms

[24]. The average amount of Zn in the world’s soils is 90 mg kg-1

[21], in the European topsoil is 68 mg

kg-1

[25], in Macedonia (studied part) is 55 mg kg-1

[22]. The highest concentrations of zinc were

determined near the Koritnica, Kiselica and Ziganci while the whole range was quite wide starting from

138 mg·kg-1

Zn and ending up to 3240 mg·kg-1

Zn with enrichment factor of 24.60 and index of geo-

accumulation of 0.135. For the main polluted area, the average concentration of Zn is 19.2-times higher

than the European Zn average and Macedonian average for 23.7-times. Similarly to the findings for lead,

although the average content of zinc in the topsoil for the entire study area was found to be about 1303.5

mg kg-1

, there are areas with very high level of contamination (Table 1; Figure 2).

Iron (Fe). Since about 3 000 years BC iron has been the most commonly used metal in all civilizations.

The common range of Fe contents in soils is between 0.1 and 10% (in forms of oxides and hydroxides, as

amorphous compounds and small particles) and its distribution in soil profiles is variable and controlled

by several soil parameters (ex. soil texture etc.). However, Fe plays a special role in the behavior of

several trace elements and is in the intermediate position between macro and micronutrients in plants,

213

animals and humans. As a very chemically reactive metal, Fe tarnishes rapidly in air or water. Effects of

corrosion processes, on a global scale, are a serious source of this metal in different environmental

compartments [26]. Contents of Fe in soils are both inherited from parent materials and/or resulted from

soil processes that are controlled by climatic factors. Must to mention fact in regards to iron is that it is an

excellent metallic material for environmental remediation because it is a strong and nontoxic reducer,

effective in coprecipitating and sorbing inorganic pollutants [27]. The average amount of Fe in the

world’s soils is 35 g kg-1

[21], in the European topsoil is 21.7 g kg-1

[25], in Macedonia in the considered

area is 33 g kg-1

[22]. As it is obvious from the table above (Table 1), we would like to stress out that iron

values ranged from the 19.3÷76.9 g·kg-1

Fe. Either the iron haven’t shown significantly increased values,

the highest ones were recorded for the locations such as Kiselica, Koritnica and Strmos. Also, for iron

were calculated enrichment factor of 2.15 and index of geo-accumulation of 0.193. In the main polluted

area the average concentration of Fe is 1.9-times higher than the European Fe average and Macedonian

average for 1.2-times. Although the average content of iron in the topsoil for the entire study area was

found to be about 40.67 g kg-1

, there are areas with increased concentration up to 76.9 g kg-1

, although

only one value was above action value by the Dutch list (Table 1; Figure 2).

Manganese (Mn). The major anthropogenic sources of Mn are: municipal wastewaters, sewage sludge, and

metal smelting processes. The combustion of fuel additives (MMT) is of a lesser importance. In soils irrigated

with water affected by acid mine drainage the soluble Mn fraction increases due to reductive dissolution of Mn

oxides [28]. Manganese has not been considered to be a polluting metal in soils; however, the MAC value for this

metal in agricultural soils is estimated at the range 1500–3000 mg kg-1. Manganese is a member of the iron

family and both elements are closely associated in geochemical processes (Mn cycles follow Fe cycles in various

terrestrial environments). The behavior of Mn in surfacial deposits is very complex and is governed by different

environmental factors, of which Eh–pH conditions are the most important. There the negatively charged

Mn(OH)4 and MnO2 are responsible for the high degree of association of Mn concretions with some trace metals,

in particular with Co, Ni, Cu, Zn, Pb, Ba, Tl, W, and Mo. In addition, the oxidation of As, Cr, V, Se, Hg, and Pu

by Mn oxides is likely to control the redox behavior of these elements in soils. On the world scale, the range of

Mn average contents was calculated at 488 mg kg-1, while for the U.S. soils the calculation is 495 mg/kg [24]

while in the European topsoil is 382 mg kg-1 [25], and in Macedonia in the considered area is averaging 650 mg

kg-1 [22]. Manganese analyses around the Zletovo mine area have shown the highest concentrations among

analyzed elements, ranging from 643 up to 28000 mg kg-1

Mn. Calculated enrichment factor was of respectable

203.3 while the index of geo-accumulation was 0.0246. In the main polluted area the average concentration of

Mn is 14.9-times higher than the European Pb average and Macedonian average for 11.9-times. Although the

average content of manganese in the topsoil for the entire study area was found to be about 7791.75 mg kg-1,

there are areas with increased concentration up to 28000 mg kg-1, however all the measured values were above

action value by the Dutch list (Table 1). Data from geochemical analyzes were statistically processed in regular

Excel calculations procedure going through the Data menu where we chose Data analysis option with an array of

Analysis tools where we continued with Correlation and selected data range for that particular type of data

analysis. Summarizing results and findings of this process, we have found that there are strong correlations

between the aforementioned elements (Table 2) and appropriate correlation plot (Figure 3).

Table 2 Correlation of Pb, Zn, Fe and Mn in soil samples from the vicinity of the Zletovo Mine, Macedonia

Pb (mg kg

-1) Zn (mg kg

-1) Fe (g kg

-1) Mn (mg kg

-1)

Pb (mg kg-1

) 1

Zn (mg kg

-1) 0,890744195 1

Fe (g kg

-1) 0,786717042 0,791725219 1

Mn (mg kg

-1) 0,587304633 0,693057484 0,585819281 1

The first suite encloses Pb-Zn with correlation coefficient of 0.89, Fe-Pb of 0.78 and Fe-Zn of 0.79. These

values indicate a high elemental correlation for this suite where lead and zinc have “historical” roots of

their high correlation even in their primary sources. The second elemental suite consists of Mn-Pb-Zn-Fe

with correlation coefficient for Mn-Pb of 0.58, Mn-Zn of 0.69 and Mn-Fe of 0.58. All these correlation

214

coefficients are relatively high and reflect the and the clear geochemical relationship of these elements,

which basically belong to their geochemical nature.

Figure 3 Correlation of Pb, Zn, Fe and Mn) in soils from the vicinity of the Zletovo Mine, Macedonia

(Note: all plots have logarithmic vertical scale)

However, here we are dealing with their anthropogenic input in soils around the Zletovo mine, which

clearly indicates their connection with the processing of lead-zinc ore from the mine.

5. CONCLUSION

Analytical data of the soil study around the Zletovo mine displayed contamination with heavy metals where

have been determined increased concentrations of Pb, Zn, Fe and Mn. These contaminations coincide with

the active exploitation of the mine and respective material discharges from the mining processes. Our study

confirmed that in soils of the “Zletovo” mine area Fe values ranged 19.3-76.9 g kg-1, Mn values ranged

643-28000 mg kg-1

, Pb with range of 42.3-529.66 mg kg-1 and Zn with range 138-3240 mg kg

-1, as well as

determined several geochemical pairs have shown correlation coefficients: Pb-Zn with correlation

coefficient 0.89, Fe-Pb of 0.78, Fe-Zn of 0.79, Mn-Pb of 0.58, Mn-Zn of 0.69 and Mn-Fe of 0.58. Increased

concentration of almost all analyzed metals in soil around the Zletovo mine implies direct correlation to the

processing of lead-zinc ore in the mine, while metal deposition in soil the most frequently comes through

the several medias (water, waste leachates and air).

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