ECOIST2020

Univer
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Techni
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28th I
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nat
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PROCEEDI
NGS
EDITOR
Prof.DrSnežanaŠer
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16-19June2020,Hot
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PROCEEDINGS
28th INTERNATIONAL CONFERENCE
ECOLOGICAL TRUTH AND ENVIRONMENTAL RESEARCH – EcoTER’20
Editor:
Prof. Dr Snežana Šerbula
University of Belgrade, Technical Faculty in Bor
Technical Editors:
MSc Jelena Milosavljević
Dr Jelena Kalinović
Asst. Prof. Dr Tanja Kalinović
Asst. Prof. Dr Žaklina Tasić
Asst. Prof. Dr Ana Simonović
Publisher: University of Belgrade, Technical Faculty in Bor

For the Publisher: Dean Prof. Dr Nada Štrbac
Printed: GRAFIK CENTAR, Beograd, 60 copies
Year of publication: 2020
ISBN 978-86-6305-104-1
CIP - Каталогизација у публикацији
Народна библиотека Србије, Београд
502/504(082)(0.034.2)
574(082)(0.034.2)
INTERNATIONAL Conference Ecological Truth & Environmental Research (28 ; 2020 ;

Kladovo)
Proceedings [Elektronski izvor] / 28th International Conference Ecological Truth and
Environmental Research - EcoTER'20, 16-19 June 2019, Kladovo, Serbia ; [organized by University
of Belgrade, Technical faculty in Bor (Serbia)] ; editor Snežana Šerbula. - Bor : University of
Belgrade, Technical faculty, 2020 (Beogad : Grafik centar). - 1 USB fleš memorija : ilustr. ; 9 x 6 cm
(u obliku kartice)
Sistemski zahtevi: Nisu navedeni. - Nasl. sa naslovne strane dokumenta. - Tiraž 60. - Bibliografija uz
svaki rad. - Registar.
ISBN 978-86-6305-104-1
а) Животна средина -- Зборници б) Екологија -- Зборници
COBISS.SR-ID 15372809
28th International Conference
Ecological Truth and Environmental Research 2020
is organized by:
UNIVERSITY OF BELGRADE, TECHNICAL FACULTY IN

BOR (SERBIA)
Co–organizers of the Conference:
University of Banja Luka, Faculty of Technology

– Banja Luka (B&H)
University of Montenegro, Faculty of Metallurgy and Technology

– Podgorica (Montenegro)
University of Zagreb, Faculty of Metallurgy

– Sisak (Croatia)
University of Pristina, Faculty of Technical Sciences

– Kosovska Mitrovica
Association of Young Researchers – Bor (Serbia)
iii
Conference is financially supported by
The Ministry of Education, Science and Technological
Development of the Republic of Serbia
v
HONORARY COMMITTEE
Prof. Dr Zvonimir Stanković, Bor (Serbia)
Dr. Petar Paunović, Zaječar (Serbia)
Dragan Ranđelović, Spec. MBA (Serbia)
Mihajlo Stanković, Special Nature Reservation of Zasavica, Sremska Mitrovica (Serbia)
vii
SCIENTIFIC COMMITTEE
Prof. Dr Radoje Pantović, President
Prof. Dr Nada Štrbac, Vice President
Prof. Dr Snežana Šerbula, Vice President
Prof. Dr Jan Bogaert (Belgium) Prof. Dr Šefket Goletić (B&H)
Prof. Dr Ladislav Lazić (Croatia) Prof. Dr Džafer Dautbegović (B&H)
Prof. Dr A. Nadgórska-Socha (Poland) Prof. Dr Jakob Lamut (Slovenia)
Prof. Dr Sebastián Bellú (Argentina) Prof. Dr Borislav Malinović (B&H)
Prof. Dr Giulia Guerriero (Italy) Prof. Dr Jelena Šćepanović (Montenegro)
Prof. Dr Saša Drmanić (Serbia) Prof. Dr Slavica Sladojević (B&H)
Prof. Dr Slobodan Jovanović (Serbia) Prof. Dr Nada Šumatić (B&H)
Prof. Dr Nataša Valentić (Serbia) Prof. Dr Jacques Yvon (France)
Prof. Dr Natalija Dolić (Croatia) Prof. Dr Dejan Filipović (Serbia)
Prof. Dr Milutin Milosavljević Kosovska
Prof. Dr Mirjana Rajčić Vujasinović (Serbia)
Mitrovica
Prof. Dr Nenad Stavretović (Serbia) Prof. Dr Snežana Milić (Serbia)
Prof. Dr Slaviša Putić (Serbia) Prof. Dr Dejan Tanikić (Serbia)
Prof. Dr Miodrag Žikić (Serbia) Prof. Dr Milan Trumić (Serbia)
Prof. Dr Ivan Mihajlović (Serbia) Prof. Dr Maja Vukašinović Sekulić (Serbia)
Prof. Dr Jovica Sokolović (Serbia) Prof. Dr Nenad Vušović (Serbia)
Prof. Dr Milovan Vuković (Serbia) Dr Jasmina Stevanović (Serbia)
Prof. Dr Nada Blagojević (Montenegro) Dr Mirjana Marković (Serbia)
Prof. Dr Darko Vuksanović (Montenegro) Dr Jelena Milojković (Serbia)
Prof. Dr Irena Nikolić (Montenegro)
ix
ORGANIZING COMMITTEE
Prof. Dr Snežana Šerbula, President
Prof. Dr Snežana Milić, Vice President
Prof. Dr Đorđe Nikolić, Vice President
Prof. Dr Slađana Alagić (Serbia) Jelena Milosavljević, MSc (Serbia)
Prof. Dr Milica Veličković (Serbia) Dragana Medić, MSc (Serbia)
Dr Ana Simonović (Serbia) Predrag Stolić, MSc (Serbia)
Dr Danijela Voza (Serbia) Aleksandra Papludis, MSc (Serbia)
Dr Tanja Kalinović (Serbia) Sonja Stanković, BSc (Serbia)
Mara Manzalović, English language teacher
Dr Maja Nujkić (Serbia)
(Serbia)
Dr Žaklina Tasić (Serbia) Enisa Nikolić, English language teacher (Serbia)
Dr Jelena Kalinović (Serbia)
xi
PREFACE
The world today is faced with the rapid changes in technology. The excessive unsustainable
consumption of fossil fuels and primary raw materials require a multidisciplinary approach
in finding adequate sustainable solutions. That is why environmental research and ecological
truth are at the focus of the 28th International Conference Ecological Truth & Environmental
Research 2020 (EcoTER’20), which will be held at Kladovo, Serbia, 16-19 June 2020. On
behalf of the Organizing Committee, it is a great honor and pleasure to wish all the
participants a warm welcome to the Conference.
We hope to convey the message of the conference, which is that a transformation of attitudes
and behavior would bring the necessary changes. This is also an opportunity for the
participants who are experts in this field to exchange their experiences, expertise and ideas,
and also to consider the possibilities for their collaborative research.
The 28th International Conference Ecological Truth & Environmental Research 2020 is
organized by the University of Belgrade, Technical faculty in Bor, and co-organized by the
University of Banja Luka, Faculty of Technology, University of Montenegro, Faculty of
Metallurgy and Technology – Podgorica, University of Zagreb, Faculty of Metallurgy –
Sisak, University of Pristina, Faculty of Technical Sciences – Kosovska Mitrovica and the
Association of Young Researchers, Bor.
These proceedings include 51 papers from the authors coming from the universities, research
institutes and industries in 7 countries: Russia, Lithuania, Nigeria, Croatia, Bosnia and
Herzegovina, Montenegro and Serbia.
As a part of this year's conference, the third student section is being held. We appreciate the
research of the students and their mentors who have made a contribution to the conference.
Abstracts of the students' papers have been included into the EcoTER’20 proceedings.
Financial assistance provided by the Ministry of Education, Science and Technological
Development of the Republic of Serbia is gratefully acknowledged.
We appreciate the effort of all the authors who have contributed to these proceedings. We
would also like to express our gratitude to the members of the scientific and organizing
committees, reviewers, speakers, chairpersons and all the Conference participants for their
support to EcoTER’20. Sincere thanks go to all the people who have contributed to the
successful organization of EcoTER’20.
On behalf of the 28th EcoTER Organizing Committee,

Snežana Šerbula, Professor
xiii
TABLE OF CONTENTS
Plenary Lecture
Velizar Stanković
AMDs FROM COPPER MINES – A DRAMATIC THREAT TO LOCAL
WATER FLOWS OR A VALUABLE SOURCE FOR COPPER
PRODUCTION 3
Conference Papers
Slavica Stevanović, J. Krstić, B. Stojanović, D. Paunović, D. Dimitrijević,
J. Veličković
THE EFFECT OF EFFLUENT ON THE WATER QUALITY IN THE
NIŠAVA 5
Ana Čučulović, J. Stanojković, R. Čučulović, S. Nestorović, N. Radaković,
D. Veselinović
THE DISTRIBUTION OF THE MASS CONCENTRATIONS OF
POTASSIUM, THORIUM AND RADIUM IN THE SOILS OF THE TEKIJA
REGION, THE NP ĐERDAP 11
Suzana Lutovac, M. Gligorić, J. Majstorović, L. Crnogorac
EXPERIMENTAL DETERMINATION THE PARAMETERS OF ROCK
MASS OSCILLATION EQUATION AT COPPER ORE USING
SIMPSONS'S RULE 17
Tatjana Anđelković, D. Bogdanović, I. Kostić, G. Kocić
COMPARISON OF THE INFLUENCE OF TEMPERATURE AND
ULTRASOUND ON DEHP MIGRATION FROM PLASTIC PACKAGING
INTO FOOD RECIPIENTS 24
Tatjana Anđelković, D. Bogdanović, I. Kostić, G. Nikolić, B. Kostić, T. Cvetković,
G. Kocić
DETERMINATION OF PHTHALATES IN PVC MEDICAL DEVICES BY
FOURIER TRANSFORM INFRARED SPECTROSCOPY 30
Milanka Negovanović, L. Kričak
REDUCTION OF DRILLING DUST USING DRY DUST COLLECTION
SYSTEMS IN SURFACE BLASTING OPERATIONS 36
Marija Petrović Mihajlović, Ž. Tasić, A. Simonović, M. Radovanović,
M. Antonijević
DETERMINATION OF PARACETAMOL USING CARBON BASED
SENSOR ELECTRODES 42
Jovica Sokolović, D. Marilović, S. Vasković
THE ROLE OF SUSTAINABLE DEVELOPMENT IN THE CEMENT
INDUSTRY IN SERBIA 48
xv
EcoTER'20, 16-19 June 2020, Kladovo, Serbia
Jelena Kalinović, S. Šerbula, T. Kalinović, J. Milosavljević, A. Radojević,

M. Nujkić
ANALYSIS OF Al, Cr AND Mn IN THE ROOT ZONE SOIL AND PLANT
PARTS OF WILD ROSE (Rosa spp.) IN THE BOR AREA 54
Tanja Kalinović, S. Šerbula, J. Kalinović, J. Milosavljević, A. Radojević
THE DISTRIBUTION OF Al, Fe, Cu, Zn, Pb, Ni, As AND Cd WITHIN THE
PINE TREES FROM THE CHEMICALLY IMBALANCED
ENVIRONMENT 60
Jelena Milosavljević, S. Šerbula, T. Kalinović, J. Kalinović, A. Radojević,
B. Spalović
THE RELATIONS BETWEEN SOIL PHYSICO-CHEMICAL PROPERTIES
AND SOIL ENZYME ACTIVITIES IN LONG-TERM CONTAMINATED
AREA 66
Igor Kodranov, M. Pergal, D. Manojlović
TOXICITY SCREENING AFTER DEGRADATION OF
ORGANOPHOSPHORUS PESTICIDES WITH CHLORINE DIOXIDE 72
Darko Anđelković, M. Branković, B. Zlatković, M. Radović-Vučić, G. Kocić
Pistia stratiotes HEAVY METAL UPTAKE POTENTIAL: A STUDY OF
MULTIPLY LEVEL CADMIUM POLLUTED WATER 77
Miljan Bigović, S. Krivokapić, D. Đurović, N. Cupara, I. Nikolić
AGRICULTURAL SOIL POLLUTION BY HEAVY METALS IN THE
MUNICIPALITY OF PLJEVLJA, MONTENEGRO 82
Miljan Vilimonović, V. Cvetković, M. Košanin, G. Grkajac, V. Bogojević
THE INFLUENCE OF THE PROCESS OF WASHING ORE OF BORN
MINERALS FROM THE "POBRDJE" DEPOSIT ON THE ENVIRONMENT 88
Nevena Čule, A. Lučić, Z. Miletić, M. Veselinović, S. Mitrović
REMOVAL OF PHOSPHORUS AND NITROGEN IN MODIFIED
FLOATING TREATMENT WETLAND 94
Jakov Baleta, L. Lazić, D. Pavlović, D. Cerinski
NUMERICAL ANALYSIS OF THE INDUSTRIAL POLLUTANTS
DISPERSION IN URBAN AREA 100
Maja Nujkić, S. Milić, A. Papludis, S. Stanković, A. Radojević, S. Alagić,
B. Spalović
WALNUT SHELL AS A BIOSORBENT FOR REMOVAL OF HEAVY
METAL IONS FROM DIFFERENT SAMPLE SOLUTIONS 106
Aleksandra Papludis, S. Alagić, S. Milić
DETECTION OF PAHs AS MICRO-POLLUTANTS IN ENVIRONMENTAL
SOIL AND PLANT SAMPLES 111
Sonja Stanković, M. Antonijević, S. Milić
SOURCES AND AVAILABILITY OF INORGANIC PHOSPHOROUS IN
THE SOIL 116
Mihajlo Stanković
CONTRIBUTION TO THE KNOWLEDGE OF THE DISTRIBUTION OF
Gias titanus SIMON, 1879 (OPILIONES, PHALANGIIDAE) IN THE
TERRITORY OF BOSNIA AND HERZEGOVINA 122
Mihajlo Stanković
23 YEARS OF THE NATURAL COLLECTION OF ZASAVICA RESERVES 128
Darko Anđelković, M. Branković, G. Kocić
SUITABILITY OF PROCEDURAL CALIBRATION STANDARDS AFTER
LONG-TERM STORAGE FOR PESTICIDE ANALYSIS IN APPLE PEEL 136
xvi
Darko Anđelković, M. Branković, G. Kocić

LABORATORY SCALED EVALUATION OF SORPTION BEHAVIOR FOR
FIVE PESTICIDES IN APPLE PEEL: EFFECT OF CONTACT TIME 143
Tatjana Anđelković, D. Bogdanović, I. Kostić, D. Anđelković, G. Kocić
THE MIGRATION OF DEHP FROM PLASTIC PACKAGING INTO DAIRY
PRODUCTS WITH DIFFERENT FAT CONTENT 148
Nena Velinov, M. Petrović, M. Radović Vučić, M. Kostić, J. Mitrović, D. Bojić,
A. Bojić
OPTIMIZATION AND APPLICATION OF LIGNOCELLULOSIC-Al2O3
BIOSORBENT FOR COPPER IONS REMOVAL FROM WATER 154
Miljana Radović Vučić, N. Velinov, M. Petrović, S. Najdanović, J. Mitrović,
D. Bojić, A. Bojić
REACTIVE DYE CONTAMINATED WATER TREATED BY PHOTO
DRIVEN ADVANCED OXIDATION PROCESSES 160
Milica Petrović, N. Velinov, M. Radović Vučić, S. Najdanović, M. Kostić,
J. Mitrović, A. Bojić
A NOVEL STAINLESS STEEL/Bi2O3 ELECTRODE FOR
ELECTROCHEMICAL DEGRADATION OF TEXTILE DYE 165
Đuro Čokeša, M. Marković, M. Gajić-Kvaščev, B. Kaluđerović, S. Radmanović,
S. Šerbula
ISOTHERMAL TITRATION CALORIMETRY STUDY OF As(III)
BINDING TO HUMIC ACIDS 171
Miljan Bigović, S. Krivokapić, I. Milašević, N. Cupara, D. Đurović
DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS
(PAHs) CONTENT IN FOOD AND HEY IN PLJEVLJA MUNICIPALITY,
MONTENEGRO 178
Adeleke Victor Adedayo
CORROSION BEHAVIOUR OF ZA27 AND ZA27/EGGSHELL
COMPOSITE IN SCOTCH BONNET PEPPER FLUID 184
Adeleke Victor Adedayo
CORROSION BEHAVIOUR OF ZA27 AND ZA27/EGGSHELL
COMPOSITE IN SIMULATED SEA WATER 189
Milena Tadić, I. Nikolić, D. Laković, D. Đurović, N. Cupara
MODIFIED FLY ASH AS A NEW ADSORBENT FOR Cu2+ REMOVAL
FROM AQUATIC SOLUTIONS 193
Branka Kaluđerović, Đ. Čokeša, M. Marković, V. Rajković, M. Srećković
HYDROTHERMAL CARBONIZATION–GREEN PROCESS FOR CARBON
MATERIAL PREPARATION 198
Žaklina Tasić, A. Simonović, M. Petrović Mihajlović, M. Radovanović,
M. Antonijević
THE APPLICATION OF PENCIL GRAPHITE ELECTRODE IN
ELECTROANALYSIS 203
Ivan Đorđević, S. Milić, D. Medić, M. Nujkić, A. Papludis
RECOVERY OF METALS FROM SPENT LITHIUM ION BATTERIES 209
Marina Pešić, S. Milić, M. Nujkić, D. Medić, S. Stanković
APPLICATION OF SIMULATION METHODS AND ANALYSIS OF THE
INFLUENCE OF PRECIPITATION REGIME ON TURBIDITY OF KARST
AQUIFER: A CASE STUDY OF KARST ZLOT’S SPRING (BOR, SERBIA) 215
Nataša Đorđević, S. Mihajlović, A. Patarić
DISPOSAL OF FLYING ASH FROM THERMAL POWER PLANTS 221
xvii
Marija Nešić, D. Obratov-Petković, I. Bjedov, D. Skočajić

EFFECTS OF ALLELOPATHY ON THE SPREAD OF INVASIVE SPECIES
Aster Lanceolatus WILLD. COMPLEX 225
Ivana Bjedov, D. Obratov-Petković, M. Nešić, S. Belanović-Simić, J. Beloica
CHANGES IN THE DISTRIBUTION OF Vaccinium L. GENUS IN
RELATION TO THE SOIL ACIDIFICATION SCENARIO 231
Veselin Bežanović, M. Novaković, M. Živančev, D. Milovanović, D. Adamović
ADSORPTION OF METHYLENE BLUE FROM AQUEOUS SOLUTION
USING ACTIVATED CARBON PREPARED FROM HAZELNUT SHELL 237
Miodrag Živančev, D. Milovanović, V. Bežanović, M. Novaković, M. Petrović,
D. Ubavin
CONTRIBUTION OF WASTE MANAGEMENT SECTOR IN NOVI SAD
TO CLIMATE CHANGE 243
Ljiljana Stosic, D. Stojanovic, K. Lazarevic
OPINIONS AND ATTITUDES OF THE CITIZENS OF NIS ON
COMMUNITY NOISE 249
Zoranka Malešević, R. Krgović, M. Jovović
PHYSICAL-CHEMICAL CHARACTERISTICS OF SM "VELIKI CRLJENI"
COAL AND ITS EFFECT ON THE ENVIRONMENT 255
Daniela Urošević, Z. Sovrlić, I. Svrkota, M. Mikić, R. Kovačević, M. Šteharnik
IMPLEMENTATION OF QUALITY CONTROL ON SAMPLED SOIL
WITH TRIP AND FIELD BLANK 261
Miomir Mikić, D. Urošević, N. Stanić, M. Jovanović, S. Petrović
ENERGY, RENEWABLE ENERGY SOURCES, POTENTIALS AND
APPLICATIONS 269
Jovana Bošnjaković, I. Jelić, V. Komadinić
APPLICATION AND PROPERTIES OF NATURAL FIBER-BASED
BIOCOMPOSITE MATERIALS – A REWIEV 275
Maja Radić, S. Ćemer, M. Avdagić
PLANET PRESERVATION THROUGH CLIMATE ACTIONS AND
CREATING QUALITY JOBS ONLY 281
Senad Čergić, H. Husić
PREVENTION OF CONTAMINATION OPEN WATERCOURSES FROM
EVACUATION MINE WATER FROM SURFACE MINE TURIJA 286
Ligita Baležentienė
CROP' CONTRIBUTION TO SEASONAL CARBON EXCHANGE IN
TEMPERATE CLIMATE OF CENTRAL LITHUANIA 292
Student section
Student: Damnjan Trifunović

Mentor: Maja Nujkić
HONEY BEES AS BIOINDICATOR OF ENVIRONMENTAL POLLUTION 299
Student: Nemanja Milošević
Mentor: Snežana Milić
THERMOSTABLE PLASTIC POLYMERS 301
Author Index
304
xviii
Plenary Lecture
AMDs FROM COPPER MINES – A DRAMATIC THREAT TO LOCAL WATER
FLOWS OR A VALUABLE SOURCE FOR COPPER PRODUCTION
Velizar Stanković1*
1
University of Belgrade, Technical Faculty in Bor, V.J. 12, 19210 Bor, SERBIA
*
stankovic.velizar@gmail.com
Abstract
Maintenance of mining wastes, produced in heavy metal mines (dumps, abandoned mining works, not
excavated ore body edges), represents significant costs for a company, as well as a serious concern
for society, due to environmental problems closely related to a company's mining activities. Active,
closed, or abandoned, metal or nonmetallic mines produce more or less volumes of mine waters,
contaminated with dissolved minerals residues. The supposition is that there are >10,000 active or
abandoned mines and mining waste sites of different kinds across Europe, discharging spontaneously
5 to 10 bilions m3/year of mine waters into surface water streams. These waters need to be purified,
which causes a necessity of investing large amount of money for this purpose. Therefore, mine waters
remain a major concern, for which neither the European Community, nor the rest of world have found
a proper solution yet. This is one of the aspects of the European ecological truth! What is ours?
Special attention is paid to mine waters, originating from copper mines, known as acid mine
drainages (AMDs) containing, besides heavy metal ions, a certain amount of sulphuric acid which
makes them acidic. AMDs cause environmental problems on a global level. Some studies suggest that
up to ca. 19,300 km of rivers, and around 72,000 ha of lakes and similar water reservoirs around the
world have been polluted with various metal-sulphate salts and sulphuric acid.
Situation in the Balkan countries is even worse than the above, because of mining works in more than
20 active heavy metal mines. In each of them there are some AMDs affecting the surrounding water
flows heavily and irretrievably. The process of AMD generation is complex and involves chemical,
biochemical and electrochemical reactions.
On the other hand, mine dumps, as a cause and AMDs as their consequence, must be considered as
valuable secondary raw materials that could be further exploited, in order to extract metal residues
from them, and to reduce the existing mine waters overburden on the surface water flows. New
approaches are presented in implementation of some emerging technologies, in combination with
conventional techniques, for copper mine waters purification.
3
Conference Papers
THE EFFECT OF EFFLUENT ON THE WATER QUALITY IN THE NIŠAVA
Slavica Stevanović1*, Jovana Krstić1, Branka Stojanović1, Dušan Paunović1,

Danica Dimitrijević1, Jasmina Veličković1
1
University of Union-Nikola Tesla, Belgrade, Faculty of Applied Sciences,
Dušana Popovića 22a, 18000 Niš, SERBIA
*
slavlab@gmail.com
Abstract
From a general perspective, the sewage system in Niš is a combined type system. After mixing with
fecal and atmospheric water effluent is discharged directly into the Nišava via the two main outlets
(the left and right collectors). This research presents the influence of untreated wastewater on the
recipient’s quality (surface water). Surface and wastewater quality testing is carried out in
accordance with the relevant directives, national and international regulations. Physical
(temperature, turbidity, pH and electrical conductivity) and chemical (chlorides, ammonia, nitrites,
nitrates, sulfates, iron, manganese and chromium in the form of Cr6+ and Cr3+ ions) parameters are
analyzed as indicators of quality. Yearly sample quality monitoring indicated river degradation, which
necessitates wastewater treatment in the left and right collectors before the discharge into the Nišava.
Keywords: wastewater, surface water, monitoring, spectrophotometry
INTRODUCTION
During recent years, there has been an increasing awareness and concern about water
conservation all over the world. Hence, new approaches towards achieving sustainable
development of water resources have been advanced internationally [1].
Due to industrial development, domestic effluent and urban run-off account for the bulk of
the wastewater generated in Niš. Domestic sewage contains a wide variety of dissolved and
suspended impurities and is the primary source of pathogens (disease-causing
microorganisms) and putrescible organic substances. Because pathogens are excreted in feces
all sewage from cities and towns is likely to contain pathogens of some type, potentially
presenting a direct threat to public health. Putrescible organic matter has posed a different sort
of a threat to water quality in recent years.
India is recognized as having major problems with water pollution, predominantly, due to
untreated sewage. Rivers such as the Ganges and the Yamuna, all flowing through highly
populated areas, are polluted. 80% of the sewage in India is untreated and flows directly into
the nation's rivers, polluting the main sources of drinking water. Indian cities produce nearly
40,000 million liters of sewage every day and barely 20 percent of it is treated. Hence,
treatment of sewage and its reuse is the need of the hour [2].
From a general perspective, the Niš sewage system is a combined type system. A large
section of the city, in particular, the central region of the city on the left and right banks of the
Nišava possesses general (mixed) type collectors whereas for Niška Banja and certain
5
peripheral and newly-built parts of the city a separation system was constructed. After mixing
with fecal and atmospheric water wastewater is discharged directly into the river Nišava via
the two main outlets: outlet 1 - the left collector in Ivan Milutinović street and outlet 2 - the
right collector in Beograd mahala.
The purpose of this study is to estimate the effect of untreated sewage effluent on the
recipient’s water quality (the Nišava) via physical and chemical water quality indicators.
MATERIALS AND METHODS

Water quality is tested according to the corresponding directives and regulations of
national and international authorities –regulations (Official Gazette of RS, No: 33/2016;
67/2011, 48/2012 1/2016; 50/2012; 24/2014; 74/2011 and Official Gazette of SRS, No.
31/82).
The Nišava water quality is also monitored following drinking water regulations (EU
Council Directive 98/83/EC 1998; Official Gazette SRJ No: 42/1998, 44/1999, 28/2019;
WHO 2011a; US EPA 1999a; US EPA 2012) considering that river water (at the entrance to
the city) is used as the water intake.
The quality analysis of the wastewater in the left (L) and right (R) city collectors and the
Nišava water quality analysis before (N- the water intake) and after the discharge of the left
city collector (Nk - around 300 m downstream), was carried out in the laboratory of the
sanitary control sector with the PUC ‘Naissus’ laboratory in Niš. The laboratory is accredited
according to the standard SRPS ISO/IEC 17025:2006.
The water samples for physico-chemical examinations were taken by experts in accordance
with the standards: SRPS EN ISO 5667-1:2008, SRPS EN ISO 5667-3:2017, SRPS EN ISO
5667-4:1997, SRPS EN ISO 5667-6:1997, SRPS EN ISO 5667-10:1997.
The analysis of wastewater and surface water encompassed the appointment of the
following parameters:
Physical parameters (methods): water temperature (SRPSH.Z1.106:1970), turbidity (EN
ISO 7027: 1999), pH value (EN ISO 10523: 2008) and electrical conductivity (SRPS EN
27888:2009).
Chemical parameters (methods): chloride (SRPS ISO 9297/1:2007 revision 1), ammonia
(SRPS.H.Z1.184:1974), nitrite (SRPS ISO 26777:2009), nitrate (Standard methods for testing
hygienic correctness "Drinking water"1990), sulfate (USEPA 375.4:1978), iron (SRPS ISO
6332:2003), manganese (Standard methods for testing hygienic correctness "Drinking
water"1990) and chromium in the form of Cr6+ and Cr3+ ions (ISO 11083:1994(E)).
The wastewater and surface water quality analysis was conducted from January to
December 2017 with a monthly sampling frequency.
RESULTS AND DISCUSSION

The results of the physical and chemical parameters are shown in Tables 1-3.
The highest surface water and wastewater temperatures were measured in the wastewater
samples (R) 23.8°C in August while the lowest water temperature was measured in the
6
samples of surface water at the water intake location (N) 6.4°C in December (Table 1). No
national or international standards have been set for the temperature of surface water and
wastewater, because they don’t have an immediate effect on human health, but they influence
the chemical and microbiological processes in water.
Table 1 Yearly temperature, turbidity, pH values and electrical conductivity in surface and
wastewater: (N) the Nišava- water intake, (L) the left city collector, (R) the right city collector, (Nk)
the Nišava downstream from the left collector
Month Temperature Turbidity Electrical conductivity
pH value
°C NTU µS/cm
N L R Nk N Nk N L R Nk N L R Nk
January 11.2 14.0 14.1 13.8 22.1 28.9 7.90 7.96 7.95 8.02 352 886 1062 468
February 6.5 13.2 15.6 8.9 12.6 10.4 8.18 8.00 8.00 8.30 375 922 1072 400
March 8.0 14.9 13.8 9.5 15.2 27.0 7.79 7.60 7.95 7.90 354 727 933 412
April 9.8 16.2 15.1 11.4 5.2 11.1 8.02 7.61 7.82 8.06 384 870 1184 398
May 12.0 15.9 16.1 14.3 17.1 25.0 8.01 7.90 7.50 8.04 372 860 1022 407
June 17.2 18.1 17.7 19.1 16.1 16.7 8.10 7.92 7.52 8.39 467 803 1027 513
July 19.5 21.8 22.5 21.7 11.1 30.0 8.04 7.80 7.87 8.30 457 840 1045 522
August 16.9 18.8 23.8 18.2 6.0 26.0 8.00 7.81 7.94 8.10 403 876 1008 464
September 17.4 22.7 23.8 17.7 1.8 4.4 8.08 7.80 7.94 8.20 411 884 970 460
October 13.2 17.6 14.7 13.8 4.3 4.4 8.05 7.65 7.62 8.06 471 886 1289 491
November 8.2 14.4 13.8 8.6 10.2 15.2 7.96 7.88 7.65 7.72 380 823 840 405
December 6.4 12.4 11.3 6.7 18.3 25.1 7.98 7.85 7.94 8.20 307 890 792 328
The turbidity values measured in each surface water sample ranged from 1.80 NTU
(Nephelometric turbidity units) - at the water intake area to 30.00 NTU in the Nišava
downstream from the wastewater discharge point (Table 1), which points to a deterioration of
river water quality.
The toxicity of many components depends on the pH value. For instance, HCN toxicity
increases with the decline of pH values while the toxicity of NH3 grows with the elevation of
pH values. Simultaneously, with the elevation of pH values, heavy metals in effluent get
deposited in the form of their hydroxides. The measured pH values (Table 1) in all effluent
and surface water samples with the highest value of 8.39 are within the recommended values.
The electrical conductivity of water depends on the geology of the area through which
water flows and the ionizing particles in it. The highest values of electrical conductivity in the
wastewater were 1289 µS/cm (the right collector), which did not affect the drastic increase of
conductivity in the surface water: from the highest value 471 µS/cm at the water intake (N) to
the highest value of 522 µS/cm in the river downstream from the discharge point (Nk) (Table
1). The EU directive (1998) limited conductivity to 2500 µS/cm at 20°C under the condition
that the water is not aggressive. In Turkey, in 177 samples of groundwater electrical
conductivity is within the interval of 332 μS/cm to 3004 μS/cm with the average value of
1573 μS/cm [3].
7
Table 2 Yearly chloride and ammonia ion concentration in surface and wastewater: (N) the Nišava-
water intake, (L) the left city collector, (R) the right city collector, (Nk) the Nišava downstream from
the left collector
Month Cl- NH4+
mg/l mg/l
N L R Nk N L R Nk
January <5.0 45.8 67.5 12.8 0.2 35.6 30.6 7.9
February 6.6 53.7 62.7 7.5 0.1 26.7 30.1 0.6
March <5.0 62.6 84.0 5.2 0.1 35.6 28.9 0.5
April <5.0 46.8 81.9 5.1 0.1 30.8 34.4 6.1
May 6.5 45.5 63.1 7.4 0.2 45.3 60.0 3.9
June 6.7 42.8 50.9 8.5 0.1 24.7 28.3 0.7
July 6.5 40.8 77.5 6.6 0.1 25.6 26.5 6.2
August 5.3 42.0 55.0 14.7 0.1 31.2 35.1 6.7
September 6.5 54.3 59.5 12.2 0.1 23.5 27.4 1.4
October 6.6 57.3 140.5 11.4 0.1 33.5 42.9 2.3
November 5.2 41.2 92.8 5.1 0.1 26.2 36.2 0.4
December <5.0 44.8 107.2 <5.0 0.1 29.1 39.2 2.3
Chloride concentrations in all the river water samples (N and Nk - Table 2) are below the
maximum allowed concentration values of 100 mg/l. Chloride concentration increases with
the rise of mineral content. Chloride increases water’s electrical conductivity and thus
corrosiveness in water is also increased [4]. Wastewater samples (L and R) contain chloride in
higher concentration, but lower than 100 mg/l (Table 2). In Banat, Serbia, groundwater has
low chloride content ranging from 5 mg/l to 50 mg/l [5].
The presence of ammonia in concentrations higher than the geological level is an important
factor for fecal contamination and can be utilized for the assessment of overall water quality
[6,7]. Ammonia nitrogen concentrations (NH4+-N) in all wastewater samples ranged between
23.5 (L) to 60.00 mg/l (R) (Table 2) and this affected the increase of this parameter in the
river: from 0,1 mg/l (at the water intake) to 7.9 mg/l in the Nišava after the wastewater
discharge, which is considerably higher than the maximum allowed concentration in a river.
Nitrates and nitrites in wastewater and surface water can appear naturally but
anthropogenic processes like the overuse of inorganic nitrogen fertilizers, municipal
wastewater, septic tanks, farm runoff, industrial effluent, and others comprise the most
common causes. Inorganic nitrogen analysis enables the assessment of these activities
influence on water quality [8]. The highest nitrate concentration (NO3-N) of 21.3 mg/l and
nitrite nitrogen (NO2-N) concentration of <2.24 mg/l in the Nišava (Table 3) show water
quality deterioration after the discharge of untreated wastewater into the river. These values
are above the maximum allowed concentration for surface water. In the United States of
America, Texas, a region that aside from oil and natural gas production also engages in
agriculture, the groundwater nitrate concentration varies from <0.44 mg/l to 149 mg/l
whereby in 3 out of 40 water samples nitrate concentration exceeds the national standard of
44 mg/l. Statistics show that nitrate concentration drops with well depth [9].
8
Table 3 Yearly nitrite, nitrate and sulfate concentration in surface and wastewater: (N) the Nišava-
water intake, (L) the left city collector, (R) the right city collector, (Nk) The Nišava downstream from
the left collector
Month NO3-N NO2-N SO42-
mg/l mg/l mg/l
N L R Nk Nk N L R Nk
January 4.7 7.1 10.6 7.5 <0.71 13.2 58.2 50.0 22.9
February 4.5 4.5 6.3 4.8 <0.65 21.3 141.6 178.7 21.2
March 4.5 7.1 11.2 5.4 <0.03 10.0 34.7 18.1 10.9
April 3.8 3.6 3.7 3.7 <0.85 9.4 93.0 143.0 16.5
May 5.4 3.0 4.5 21.3 <0.75 15.3 46.3 71.8 14.1
June 6.5 2.7 2.5 5.5 <1.15 14.9 46.4 65.2 18.9
July 5.0 1.1 1.9 4.9 <2.24 24.5 45.7 70.1 28.7
August 4.9 1.1 0.7 4.5 <0.22 16.9 35.7 47.4 17.3
September 4.3 1.3 6.3 5.4 <0.17 13.6 29.9 16.9 20.4
October 7.7 6.0 4.3 7.7 <0.14 16.4 15.8 28.9 13.1
November 4.8 5.2 6.1 2.2 <0.62 8.4 24.8 19.5 11.6
December 3.8 4.2 8.4 3.9 <0.88 8.9 31.8 29.6 9.1
Studies suggest that in concentrations between 1000 mg/l and 1200 mg/l sulfates have a
laxative effect but without diarrhea, dehydration and weight loss (WHO). The highest
concentration of sulfate was measured in (R) (178.7 mg/l) in February while the lowest
sulfate concentration was measured in (N) (8.4 mg/l) in November. Despite the mild increase
of sulfate after the wastewater discharge all measurements in this location are far below the
maximum allowed concentration of 100 mg/l for surface water.
Iron concentration in all surface water samples (the Nišava after wastewater discharge) is
below the maximum allowed concentration (<0.5 mg/l).
Manganese in water behaves similarly to iron. Manganese concentration in all samples of
analyzed surface water is below the method’s detection threshold (<0.025 mg/l) and thus
satisfies the recommended values and the maximum allowed concentration (0.1 mg/l).
Also, the Cr6+ and Cr3+ concentrations in all water samples from the river Nišava are
below the method’s detection threshold (<0.01 mg/l) and therefore meet the recommended
values and the maximum allowed concentration (0.05 mg/l).
Even though all of these contaminants have not yet reached toxic levels, they still represent
a long term risk to public health [10].
Although the analyzed values of Fe, Mn and Cr are below the method’s detection
threshold, an increase in river water turbidity, as well as elevated values of nitrogen (ammonia
ion, nitrates), indicate that the untreated wastewater discharge continually deteriorates the
Nišava water quality. Due to higher values of ammonia ions, which indicate fecal
contamination, there is a risk of pathogenic bacteria.
Numerous studies [11] show the efficacy of various technical and technological
wastewater treatment processes. They mostly refer to filtration, aeration, disinfection [12] and
other processes depending on the degree and type of wastewater contamination. This is
9
certainly applicable to the wastewater in Niš and the result would be the preservation of the
environment and river quality.
CONCLUSION
The physical and chemical analysis of the wastewater and surface water quality indicates
deterioration in the Nišava after the discharge from the city wastewater collectors.
Contaminant concentration in the effluent has been a factor in the deterioration of the
recipient’s water quality. This can be stated because of the elevated turbidity values and fecal
contamination indicators (ammonia ion, nitrates) in the river after the discharge from the
collectors. These values are considerably increased in comparison to the values before the
discharge of wastewater and in comparison to the limit values for a good ecological status
according to the regulation on contaminant limits in surface water, groundwater, sediment and
the time limit for reaching them (Official Gazette RS no 50/2012) - for a good ecological
status, i.e. class II - river type 2; natural level.
As the aforementioned regulations stipulate time limits for reaching the threshold values,
in the following period it is necessary to adjust the emissions of contaminants to the threshold
values. To achieve this, a central wastewater facility must be constructed with the view of
preserving water from contamination and maintaining public health.
REFERENCES
[1] F. Burton, G. Tchobanoglous, H. D. Stensel, Wastewater Engineering, treatment and
reuse, IV Ed. Metcalf and Eddy, Tata McGraw-Hill Publishing Company Limited, New
Delhi (2010).
[2] S.Vrushali, C. Kaustav, International Science Journal; 1 (2) (2003).
[3] K. D.Tank, S.C.P. Chandel, Nature and Science; 8 (10) (2010) 1–7.
[4] E.G. Stets, C.J. Lee, D.A. Lytle, et al., Sci. Total. Environ; 613–614 (1) (2018) 1498–
1509.
[5] P. Papic, M. Ćuk, M. Todorović, et al., Pol. J. Environ. Stud; 21 (6) (2012)1783–1790.
[6] T. Maekawa, N. Omura, K Fujita, et al., Environ. Technol; 22 (2) (2001) 157–164.
[7] X. Hao, D. Wang, P. Wang, et al., Environ. Monit. Assess; 188 (1) (2016) 24.
[8] V. Furtula, H. Osachoff, G. Derksen, et al., Water. Res; 46 (4) (2012) 1079–1092.
[9] P.F. Hudak, Texas. Int. J. Environ. Res; 6(3) (2012) 663–668.
[10] V. Gvozdic, Lj. Caciv, J. Brana, et al., Med. Glas. Ljek. komore. Zenicko-doboj kantona;
9 (1) (2012) 91–96.
[11] E. Amanatidou, G. Samiotis, E. Trikoilidou, et al., Environ. Technol; 37 (2) (2016) 265–
278.
[12] A.H. Mahvi, Iran Journal of Environmental Health Sciences and Engineering; 5 (2)
(2008) 79–90.
10
THE DISTRIBUTION OF THE MASS CONCENTRATIONS OF POTASSIUM,
THORIUM AND RADIUM IN THE SOILS OF THE TEKIJA REGION, THE NP
ĐERDAP
Ana Čučulović1*, Jelena Stanojković1, Rodoljub Čučulović2, Saša Nestorović3,

Nenad Radaković3, Dragan Veselinović4
1
University of Belgrade, Institute for the Application of Nuclear Energy – INEP,
Banatska 31b, 11080 Zemun, SERBIA
2
University of Union Nikola Tesla, Faculty of Business and Low, Cara Dušana 62-64,
11000 Belgrade, SERBIA
3
Public Company Đerdap National Park, Kralja Petra I 14a, 19220 Donji Milanovac,
SERBIA
4
University of Belgrade, Faculty of Physical Chemistry, Studentski trg 12-16, P. Box 137,
*
anas@inep.co.rs
Abstract
Soil samples (24) were collected in June 2018, on the territory of NP Đerdap (from region the Tekija,
4 management units). In this study, the mass concentrations of potassium, radium and thorium, were
calculated based on specific activities of these radionuclides measured by gamma-ray spectrometry.
The mean values of elemental mass concentrations in analyzed soil samples were found to be 1.75%
for potassium, 2.54 mg kg-1 for radium and 8.88 mg kg-1 for thorium. The strength of the absorbed
gamma radiation dose originating from the activity of radionuclides in the soil and the yearly effective
dose were determined. Values of the strength of the absorbed gamma radiation dose and the yearly
effective dose from external exposure to gamma radiation based on the content of natural
radionuclides in soil were in the range of the expected values and close to the average values in the
world.
Keywords: NP Đerdap, mass concentration, potassium, thorium, radium
INTRODUCTION
National parks (NP) are large areas incorporating a number of diverse natural ecosystems
of national interest from the view point of preservation, complexity and biographical
characteristics with different forms of original flora and fauna, representative physico-
geographical objects and events, and cultural-historical values, representing exceptional
natural entities of national significance [1]. There are five natural parks (NP) in Serbia, and
the Đerdap is one of them since 1974, with an area of 63,350 ha. It is located in the Northeast
of Serbia on the boundary with Romania and occupies 100 km of the right bank of the middle
course of the river Danube. The complex relief in this NP, specific gorge mesoclimate, large
number of relic species and phytocenosis, and exceptional diversity in view of lithological
rock compositions, genetic origin and geological age [2], lead to the formation of a number of
11
different types of soil with different properties and production potential [3]. All organisms of
planet Earth are exposed to radiation that is classified by place of origin into earth and cosmic.
Sources of ionization radiation by their genesis and occurrence in the environment are
classified as: natural, anthropogene and radioactive waste. Natural radionuclides in soil (40K,
232
Th, 226Ra, 238U…) give the highest contribution to gamma radiation (96%) in the
environment. They are formed during the nucleosynthesis process and have a long half-life
and different physical, geochemical properties, half-life types, radiation intensities, isotropic
prolific quantities, occurrence method and geochemical cycles [4]. The activity levels of
radionuclides in soil depend on: the mineral composition and physicochemical properties of
soil, meteorological conditions and possible translocations and migrations of radionuclides.
Natural radioactivity is part of the environment and is changed from place to place and acts on
the population over a long time period. According to the UNSCEAR report the average mass
concentrations (concentration span) of uranium, radium, thorium and potassium in soil in the
world are: 2.82 (1.29–8.87) mg kg-1; 3.18 (1.53–5.45) mg kg-1; 7.32 (2.68–15.61) mg kg-1 and
1.54 (0.54–3.28) (%), respectively [5]. Research has shown that average mass concentrations
in brown woodland soil in Serbia were: potassium 1.74 %; thorium 7.88 mg kg-1 and uranium
1.78 mg kg-1 [6]. Our research of soil in the Tekija region (NP Đerdap) in the period 2015 and
2016 has shown that the mean values of mass concentrations of potassium, radium and
thorium were in the range: from 1.41 to 2.11% (mean 1.67%); from 0.37 to 3.02 mg kg-1
(mean 1.91 mg kg-1) and from 1.27 to 11.22 mg kg-1 (mean 6.98 mg kg-1) that is within the
range of measurements made in the world [7,8].
In order to obtain a real picture of the radioactivity state of the soil, the most important and
vulnerable component of the environment in the Tekija region (NP Đerdap), samples of soil
were collected in 2018 and the obtained results are presented in this work.

Soil samples (24) were collected in the Tekija region NP Đerdap from 4 management units
(GJ) (Tekija, Crni vrh, Manastirički gaj and Prapezišće), to the depth of 10 cm, in June 2018.
The management units for soil sampling were carefully selected based on radioactivity
bioindicator from previous years. Samples were transported to the laboratory and cleaned
from visible dirt, dried, homogenized and packed into 0.5 L Marinelli vessels that were
hermetically closed, sealed with wax and left for at least 40 days to establish radioactive
equilibrium of post-radon series members 238U, prior to gammaspectrometric analysis. Sample
mass was up to 600 g. A high purity semiconducting germanium detector ORTEC–AMETEK,
USA with 8192 channels, resolution 1.65 keV and relative efficiency of 34% at 1.33 MeV for
60
Co was used for determining radionuclide activity levels. Spectra were analyzed using the
Gamma Vision 32 software package.
Specific activity of 40K, 228Ra and232Th were converted into mass concentrations of
elemental potassium, radium and thorium [9], respectively, using equation (1):
(1)
12
where: FE - participation of element E in the sample, ME - atomic mass (kg mol-1), λE,i -
constant of radioactive isotope i half-life of element E (1/s), fE,i - isotope i representation in
nature, AE,i - measured specific activity (Bq kg-1) of radionuclides (40K, 226Ra, 232Th), NA -
Avogadro number (6.023 × 1023 atom mol-1) and C - constant with values of 106 for Ra and
Th (mass concentration mg kg-1) or 100 for K (mass concentration in %).
According to the recommendation of UNSCEAR [5], based on measured activity levels
(ARa,ATh,AK) (Bq kg-1) of natural radionuclides in investigated soil samples calculation of the
strength of the absorbed gamma radiation dose (D) 1m above soil level can be performed
according to equation (2) assuming that all descendants are in equilibrium with their
precursors and that radionuclides contribute only slightly to the total dose due to external
exposure, using the conversion factor for 226Ra, 232Th and 40K 0.462; 0.604 and 0.042
(nGyh-1/(Bq kg-1) respectively:
D (nGyh-1) = 0.462ARa+0.604ATh+0.042AK (2)
Knowing the total strength of the gamma absorbed radiation dose (D) equation (3) can be
used to calculate the yearly effective dose for an adult H (mSv):
H (mSv) = D×0.7×0.2×8760 (3)
where: 0.7 (SvGy-1) conversion coefficient (relation between the yearly effective dose
received by the pollution and absorbed dose in air); 0.2 – exposure factor for external
radiation (it is assumed that the population spends on average 20% time in the open); 8760 –
number of hours in one year [5].

Natural radioactivity of soil depends on the radiation type and geological structure of the
area. Table 1 shows mass concentrations of potassium (%), radium and thorium (mg kg-1) in
soil collected in 2018 in the Tekija region (NP Đerdap), the total strength of the gamma
absorbed radiation dose and the yearly effective radiation dose.
The average content of potassium in the lithosphere is 2.59% and its content in soil
depends on the geological base, the base substrate whose decomposition creates the soil and
on pedogenetic processes. Taking into account the data in Table 1 it follows that the mean
mass concentration of potassium in soil samples collected in 2018 in the Tekija region (NP
Đerdap) is 1.75% that is somewhat higher than the mean mass concentration in the world [5].
The minimal mass concentration of potassium was measured in the soil sample from GJ
Manastirički gaj, division 8a (0.65%), while the maximum value was measured in the soil
sample from Tekija, division 41a (2.83%) that is within the measurement range in the world
[5]. Mean values of mass concentrations of potassium (%) in GJ increase in the following
order: Manastirički gaj (0.68) < Crni vrh (1.62) < Tekija (1.9) < Propezešće (2.27).
13
In nature radium is found in uranium ores in the form of oxides and hydroxides. It is a
descendant of uranium and member of the radioactive series 228U. From Table 1 it follows
that the mean mass concentration of radium in soil from the Tekija region is 2.54 (mg kg-1)
and it is lower than the world average (3.18 mg kg-1) [5]. The minimal mass concentration of
radium was measured in the soil sample collected in GJ Manastirički gaj, division 8a (1.20 mg
kg-1), and the maximum in the sample from GJ Propezešće, division 25a (3.79 mg kg-1). The
values of mass concentrations of radium in the Tekija region are in the range of values
determined during research in the world [5]. Mean values of mass concentration of radium
(mg kg-1) in GJ increase according to the following order: Manastirički gaj (1.36) < Crni vrh
(2.54) < Tekija (2.69) < Propezešće (3.04).
Table 1 Mass concentrations of potassium (K), radium (Ra) and thorium (Th) in soil collected in 2018
in the Tekija region (NP Đerdap), the total strength of the gamma absorbed dose (D) and
effective yearly radiation dose (H)
No. Management unit, K Ra Th D H
division -1 -1
(%) (mg kg ) nGyh mSv
1. Tekija, 41a 2.83 2.93 6.98 71.3 0.087
2. Tekija, 41a 2.42 2.27 7.32 62.9 0.077
3. Tekija, 67 2.31 2.74 8.17 66.3 0.081
4. Faca Tekija, 48b 1.72 3.10 9.98 65.0 0.080
5. Faca Tekija, 48b 1.91 3.00 9.85 66.6 0.082
6. Tekija, 78 1.89 2.62 9.02 62.1 0.076
7. Tekija, 78 1.94 2.32 9.95 63.4 0.078
8. Tekija, Kosovica 1.63 2.29 8.24 54.9 0.067
9. Tekija, Kosovica 1.58 2.48 9.20 57.7 0.071
10. Tekija, Dafin 1.67 3.11 10.59 65.9 0.081
11. Crni vrh, 1 0.83 1.88 5.95 36.3 0.045
12. Crni vrh, 3 1.70 2.64 9.22 60.2 0.074
13. Crni vrh, 4 1.16 3.23 10.95 60.8 0.075
14. Crni vrh, 13 1.65 2.91 10.71 64.9 0.080
15. Crni vrh, 17 1.89 3.29 10.56 69.8 0.086
16. Crni vrh, 45 1.60 3.07 10.71 65.1 0.080
17. Crni vrh, 47 1.49 2.88 11.20 63.7 0.078
18. Crni vrh, 57 2.02 1.51 9.73 59.3 0.073
19. Crni vrh, 59 2.11 1.73 9.07 60.0 0.074
20. Crni vrh, 59 1.70 2.26 7.98 55.0 0.067
21. Manastirički gaj, 8a 0.65 1.20 3.20 23.2 0.028
22. Manastirički gaj, 8a 0.71 1.52 3.98 27.8 0.034
23. Propezešće, 25a 2.58 3.79 13.78 89.7 0.110
24. Propezešće, 25a 1.95 2.28 6.71 55.3 0.068
Thorium is obtained from uranium treatment. Thorite and alanite are the most significant
thorium minerals found in granite. From Table 1 it follows that the mean mass concentration
of thorium in soil in the Đerdap region is 8.88 (mg kg-1) and it is higher than the world
14
average (7.39 mg kg-1) [5]. The minimal mass concentration of thorium was measured in the
soil sample collected in GJ Manastirički gaj, division 8a (3.59 mg kg-1), while the maximum
was measured in GJ Propezešće, division 25a (10.25 mg kg-1). The obtained values of mass
concentrations of thorium are in the range of world values [5]. Mean mass concentrations of
thorium (mg kg-1) in GJ increase according to the following order: Manastirički gaj (3.59) <
Tekija (8.93) < Crni vrh (9.61) < Propezešće (10.25).
High values of the Pearson coefficient among radionuclides Ra-Th (0.777) in soil indicate
their common origin and strong linear bond. The values of the Pearson coefficient for K-Ra
(0.433) and K-Th (0.437) indicate their medium connectivity.
The total strength of the absorbed gamma radiation dose (D (nGyh-1)) can be calculated
based on equation (2). From Table 1 it follows that in the Tekija region D values (nGyh-1)
originating from potassium are from 8.48 to 37.25 (mean 23.00); originating from radium
from 6.84 to 21.6 (mean 14.51) and originating from thorium from 7.91 to 34.13 (mean
21.98). The total absorbed gamma radiation dose (nGyh-1) in the Tekija region was from 23.0
to 89.7 (mean 59.47) and is in the range of world values (32–107, mean 57.6) [5]. Mean
values of the total strength of gamma radiation dose (Gyh-1) in management units increase in
the following order: Manastirički gaj (25.50) < Crni vrh (59.52) < Tekija (63.59) <
Propezešće (72.51). From the results presented in Table 1 it follows that mean values of D
(nGyh-1) in all GJ, except Manastirički gaj, are somewhat higher than average world values.
Knowing D (nGyh-1), and based on equation (3) the calculated yearly effective radiation
dose H (mSv) in the Tekija region was from 0.028 to 0.110. Mean values of H (mSv) in all GJ
increase in the following order: Manastirički gaj (0.031) < Crni vrh (0.075) < Tekija (0.078) <
Propezešće (0.089). The yearly effective doses originating from terrestrial gamma radiation in
GJ Crni vrh, Tekija and Propezešće are higher than the mean world values (0.070 mSv), but in
the measuring range in the world. This research is in agreement with the research of other
scientists [10,11]. The mean value of H in the Đerdap region is 0.073 mSv and in accordance
with the mean world value 0.070 mSv. Based on the Rule book [12] the yearly effective dose
for the population is increased if it is higher than 1 mSv for a year. In the territory of the
Tekija region the mean value of the yearly effective radiation dose is 0.073 mSv for a year
and is significantly lower than 1mSv.
CONCLUSION
The mean values of the mass concentration of potassium (%), radium and thorium (mg kg-
1
) are the lowest in GJ Manastirički gaj and the highest in GJ Propezešće.
High values of Pearson coefficients for radionuclides Ra-Th (0.777) in soil indicate their
common origin and strong linear bond. The values of Pearson coefficients for K-Ra (0.433)
and K-Th (0.437) indicate their medium connectivity.
Mean values of the total strength of absorbed gamma radiation doses (nGyh-1) are the
lowest in GJ Manastirički gaj and the highest in GJ Propezešće. Mean values of the yearly
effective dose (mSv) are the lowest in GJ Manastirički gaj and the highest in GJ Propezešće.
The mean value of H in the Đerdap region is 0.073 mSv and is in accordance with the mean
value on the world level of 0.070 mSv.
15
ACKNOWLEDGEMENT
This work was financed by the Ministry for Education, Science and Technological Development of
the Republic of Serbia (Project III43009).
REFERENCES
[1] Zakon o zaštiti životne sredine Srbije, Službeni glasnik Republike Srbije br 66/91, 83/92,
53/93, 67/93, 48/94 i 53/95, (in Serbian).
[2] M. Medarević, Šume Đerdapa, JP Nacionalni park Đerdap – Donji Milanovac i IP
Ecolibri, Beograd, (2001), ISBN: 86-7905-037-7 (in Serbian).
[3] M. Knežević, R. Milošević, O. Košanin, Glasnik šumarskog fakulteta; 102 (2010) 57–68
(in Serbian).
[4] A. Dangić, Geohemijski procesi u prirodi i radionuklidi, Monografija Jonizujuća zračenje
iz prirode, Beograd, (1993) (in Serbian).
[5] UNCSEAR (2000), United Nations Scientific Committee on the Effects of Atomic
Radiation, Sources and Effects of Ionizing Radiation. UNSCEAR 2000 Report to the
General Assembly, with Scientific Annexes, New York, (2000).
[6] B. Gajić, Fizika zemljišta, Univerzitet u Beogradu, Poljoprivredni fakultet, Beograd,
(2006) (in Serbian).
[7] A. Čučulović, R. Čučulović, S. Nestorović, et al., Ecologica; 93 (26) (2019) 10–14.
[8] A. Čučulović, J. Stanojković, R. Čučulović, et al., Ecologica; 94 (26) (2019) 136–140.
[9] IAEA, Construction and use of calibration facilities for radiometric field equipment,
Technical Report Series 309, International Atomic Energy Agency (IAEA), Vienna (1989).
[10] S. Dragović, Lj. Janković, A. Onjia, et al., Radiat. Measur; 41 (2006) 611–616.
[11] S. Dragović, Lj. Janković, A. Onjia, Radioat. Prot. Dosim; 121 (3) (2006) 297–302.
[12] Pravilnik o granicama izlaganja jonizujućim zračenjima i merenjima radi procene nivoa
izlaganja jonizujućim zračenjima, Službeni glasnik RS, 86/2011 i 50/2018 (in Serbian).
16
EXPERIMENTAL DETERMINATION THE PARAMETERS OF ROCK MASS
OSCILLATION EQUATION AT COPPER ORE USING SIMPSON'S RULE
Suzana Lutovac1, Miloš Gligorić1*, Jelena Majstorović1, Luka Crnogorac1

1
University of Belgrade, Faculty of Mining and Geology, Đušina 7, 11000 Belgrade, SERBIA
*
milos.gligoric@rgf.bg.ac.rs
Abstract
In mining practice, as a way of the hard rock exploitation, massive blasting has an increasing
application. During exploitation, the use of explosives increases the quantity of the blasted rock mass
and decreases the production costs. However, the use of great quantities of explosive brings about
increase of negative blasting effects. By negative blasting effects we understand seismic effect of
blasting, the effect of the air blast wave, sound effect, scattering of blasted rock mass, etc. To estimate,
to control and plan seismic effects of blasting it is necessary to determine rock mass oscillation
equation. One of the most frequently used is the equation of M.A. Sadovskii, which defines the change
of rock mass oscillation velocity depending on the distance from blasting point, quantity of explosive,
conditions for performing blasting and geological characteristics of the rock mass. In this paper,
analysis of the methods for the determination the parameters of the rock mass oscillation equation
have performed, for the equal reduced distances at experimental blastings. To determine parameters
in the Sadovskii equation, besides the usual model – Method of Least Squares, one more model has
been presented applying Simpson’s rule.
Keywords: working environment, negative effects of blasting, oscillation velocity, rock mass
oscillation equation, Simpson’s rule
INTRODUCTION
Dynamic characteristics of the oscillation, in the elastic deformations zone of the rock
mass, is the most defined by the oscillation velocity. As the relation between the rock mass
oscillation velocity and basic parameters affecting its magnitude, such as: the amount of
explosive, the distance from the blast site, characteristics of the rock material and the type of
blasting, the equation of M.A. Sadovskii.
By applying the equation of rock mass oscillation while blasting, the determination of the
rock mass oscillation velocity is enabled for each blast operation in advance, thus blasting is,
as regards seismic effect, under control, and that gives an opportunity to plan the magnitude
of shock waves for each future blast operation. In this way adverse blasting effects are
reduced 1.
ROCK MASS OSCILLATION EQUATION

In the equation of Sadovskii, rock mass oscillation velocity is given in the following form [2]:
(1)
where there are:
17
– velocity of rock mass oscillation cm/s,

– coefficient conditioned by rock mass characteristics and blasting conditions,
where the amount of explosive is given by way of the volume. is determined by
terrain surveying,
– exponent, conditioned by rock mass properties and mining conditions and
determined by field measurements as well,
– distance from the blast site to the monitoring point m,
– amount of explosive kg,
– reduced distance, expressed as .
The Sadovskii equation is determined based on test blasting for the concrete working
environment.
MODELS OF DETERMINING THE PARAMETERS OF EQUATION OF ROCK

MASS OSCILLATION VELOCITY
In the equation (1) two parameters appear, and , which need to be determined for a
specific work environment and specific blasting conditions.
Model 1 - determining the parameters by applying the Least Square Method
The Least Square Method is mainly used to obtain the parameters and which
represents the most commonly model [3].
Model 2 – determining parameters by applying Simpson’s rule
In this paper, as model 2, we will use Simpson’s formula to approximate the values of the
definite interval functions [3,4].
Let the values for the negative function be known as for
, ; . Then
(2)
Formula (2) is Simpson’s formula for the finding approximative values of the definite
integral function in the given interval .
In order to verify this model, experimental blasting is performed. Ten explosions are
registered during the blasting operation, with corresponding reduced distances and oscillation
velocities.
For we have ; ; which means that according to Equation (1)
we have:
, . (3)
Equation (3) is written in the following form:
, (4)
from where we have:
. (5)
By logarithm operation of Equation (5) we get
18
, (6)
from where we find:
. (7)
According to Simpson’s formula (2) we have:

, (8)
where represents the right side in formula (2).
. (9)
How it is:
, (10)
from Equation (10) we find:
. (11)
By substituting from Equation (11) into Equation (1) we get the following formula:
. (12)
For Equation (1) is reduced to:

. (13)
DEFINING STATISTICAL CRITERIA

For the above-mentioned models 1 and 2, based on experimental data, we have obtained
equations, which make possible to determine the oscillation velocities of the rock mass
depending on the reduced distance .
In order to assess the degree of connection between the reduced distance and rock mass
oscillation velocity , we have used the curved line dependency index [5,6].
METHODOLOGY OF RESEARCH
General characteristics of the work environment in Majdanpek open pit
Experimental researches were performed on copper ore at open pit Majdanpek, eastern
Serbia [7]. By examining the physical and mechanical properties of the work environment,
the following values were obtained: compressive strength ; bending strength
; tensile strength ; cohesion ; strength
coefficient ; volume density ; angle of internal friction ;
porosity .
19
Method of blasting in Majdanpek open pit

The measurements of shocks resulting from blasting in Majdanpek open pit were
performed during blasting using half-second electric detonators. Blasting of 10 boreholes with
a depth of 0.5 m was performed. Delay time of initiation between boreholes was 0.5 s. It led
to ten explosions and appropriate rock mass oscillation velocities.
The boreholes were arranged in a single line at the distance of 1 m. One cartridge of
explosive amonex 1, with a weight of 0.1 kg, was placed in each borehole. The distance
between measuring point and the first borehole was 5 m.
Seismographs are instruments used for seismic parameters observation. From
seismographs maximum values for three oscillation velocity components can be recorded:
– rock mass oscillation velocity horizontal transversal component,
– rock mass oscillation velocity vertical component,
– rock mass oscillation velocity horizontal longitudinal component.
Maximum, i.e. resulting rock mass oscillation velocity was determined with the
following formula:
(14)
CALCULATION FOR PARAMETERS OF ROCK MASS OSCILLATION

EQUATION IN THE OPEN PIT MAJDANPEK
The values of distance from the blasting point to the point of observation , amount of
explosive , calculated values of reduced distances , registered values of rock mass
oscillation velocities by components , , and resulting rock mass oscillation velocities
for a total of ten explosions, are given in Table 1.
Table 1 Review of blasting parameters and measurement results

No m kg
1 5.0 0.1 10.7722 0.700 0.900 1.150 1.6194
2 6.0 0.1 12.9266 0.300 0.925 1.150 1.5060
3 7.0 0.1 15.0810 0.255 0.540 0.850 1.0388
4 8.0 0.1 17.2355 0.260 0.350 0.650 0.7827
5 9.0 0.1 19.3899 0.245 0.325 0.550 0.6842
6 10.0 0.1 21.5443 0.155 0.240 0.405 0.4956
7 11.0 0.1 23.6988 0.205 0.275 0.440 0.5579
8 12.0 0.1 25.8532 0.110 0.200 0.285 0.3651
9 13.0 0.1 28.0077 0.085 0.190 0.230 0.3102
10 14.0 0.1 30.1621 0.090 0.130 0.200 0.2550
Based on data given in Table 1, the rock mass oscillation equation is calculated by the
formula (1) – by the models 1 and 2. The calculation of the curve was carried out for values of
reduced distances from to . Thus, curve parameters were
calculated enabling us to determine the equation of rock mass oscillation in the form of:
20
 Model 1
(15)
Graphic review of the rock mass oscillation equation is shown in figure 1.
Oscillation velocities, v(cm/s) 2.0
1.8
1.6
1.4 v1 = 146.7047 R-1.8326

1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 20 40 60 80 100
Reduced distance, R
Figure 1 Graphic review of oscillation velocity and reduced distance in the open pit Majdanpek
 Model 2
(16)
Based on the obtained equations for rock mass oscillation (15) and (16), it is possible to
calculate values of rock mass oscillation velocities for the corresponding reduced distances
for models 1 and 2.
Review of reduced distances , registered rock mass oscillation velocities , calculated
rock mass oscillation velocities , , as well as the difference between registered and
calculated oscillation velocities for models 1 and 2 are given in Table 2.
Table 2 Review of recorded and calculated rock mass oscillation velocities for models 1 and 2
No
1 10.7722 1.6194 1.8821 2.0148 -0.2627 -0.3954
2 12.9266 1.5060 1.3475 1.4361 0.1585 0.0698
3 15.0810 1.0388 1.0159 1.0787 0.0229 -0.0399
4 17.2355 0.7827 0.7954 0.8418 -0.0127 -0.0591
5 19.3899 0.6842 0.6410 0.6764 0.0432 0.0078
6 21.5443 0.4956 0.5284 0.5563 -0.0328 -0.0607
7 23.6988 0.5579 0.4437 0.4660 0.1142 0.0919
8 25.8532 0.3651 0.3783 0.3965 -0.0132 -0.0314
9 28.0077 0.3102 0.3267 0.3417 -0.0165 -0.0315
10 30.1621 0.2550 0.2852 0.2978 -0.0302 -0.0428
21
Based on the data in Table 2, a statistical analysis i.e. between the reduced distance and
rock mass oscillation velocity :
 for model 1: (there is a strong correlation between and , given in the
formula (15)).
 for model 2: (there is a strong correlation between and , given in the
formula (16)).
CONCLUSION
In this paper, parameters and in the Sadovskii equation have been determined by way
of two models in the given working environment. First model represents the usual method of
the Least Squares, and the second model has been derived by applying Simpson’s rule. Thus,
we obtained the adequate functions which represent rock mass oscillation velocity depending
on reduced distance.
Comparing values of the recorded oscillation velocities of the rock mass with the
corresponding calculated ones, it is visible that they are approximately the same. Calculated
corresponding indices of curvilinear correlation show that between the reduced distance and
the rock mass oscillation velocity there is a significant and very strong curvilinear relationship
expressed by the functions obtained.
Based on the values obtained by statistical analysis we conclude that this new model can
be used for equal reduces distances with application of Simpson’s rule, at experimental
blastings.
ACKNOWLEDGEMENT
The authors are grateful to the Ministry of Education, Science and Technological development of
the Republic of Serbia for financial support (ТR 33025 and ТR 33029).
REFERENCES
1] M. Savić, Blasting at of the Open Pits, Monograph, RTB Bor, Cooper Institute Bor, Indok
center, Bor, 2000, pp. 317–319.
[2] S.V. Medvedev, Seismika gornwh vzrwvov, Nedra, Moskva, 1964, pp. 42–43.
[3] D. Simeunović, Mathematics, Faculty of Mining and Geology, Mining department,
Belgrade, 1985, pp. 101–103.
[4] A. Jeffrey, Mathematics for Engineers and Scientists, University of Newcastle upon –
Tyne Nelson, Copyright © Alan Jeffrey 1969, 1971, pp. 334–336.
[5] M. Žižić, M. Lovrić, D. Pavličić, Methods of Statistical Analysis, Faculty of Economics in
Belgrade, Belgrade, 1996, pp. 141–150.
[6] Ž. Petrović, Business Statistics, Megatrend, University of Applied Sciences, Belgrade,
Faculty for Management, Zaječar, 2004, p.182.
22
[7] S. Trajković, Area of Application of Laws of Rock Mass Oscillation Caused by Blasting,
with Particular Reference to Mining Works, PhD thesis, Faculty of Mining and Geology,
Belgrade, 1993, pp. 82-88, pp. 53–57.
23
COMPARISON OF THE INFLUENCE OF TEMPERATURE AND ULTRASOUND
ON DEHP MIGRATION FROM PLASTIC PACKAGING INTO FOOD RECIPIENTS
Tatjana Anđelković1, Danica Bogdanović1*, Ivana Kostić1, Gordana Kocić2

1
University of Niš, Faculty of Science and Matematics, Department of Chemistry,
Višegradska 33, 18000 Niš, SERBIA
2
University of Niš, Faculty of Medicine Department of Biochemistry,
Bulevar dr Zorana Đinđića 81, 18000 Niš, SERBIA
*
dannica.milojkovic@gmail.com
Abstract
Aim of this research was to determine the amount of migrated di-(2-ethylhexyl) phthalate (DEHP)
from plastic packaging materials into food recipients with different fat content under the influence of
increased temperature and ultrasound as a type of agitation. Investigated food products were infant
formula, milk powder and water. The results were obtained using liquid-liquid extraction (LLE)
followed by gas chromatography-mass spectrometry (GC/MS). The base peak ion of DEHP (m/z 149)
was selected for further research and recording was performed in the selected ion monitoring mode
(SIM). The response of the mass-selective detector (MSD) was linear for the considered range of
DEHP concentrations, 0.25 – 2.50 µg mL–1. Obtained results showed that the amount of migrated
DEHP from plastic packaging materials into dairy products was higher for dairy products with higher
percentage of fatboth in the case of influence of temperature and in the case of combined effect of
increased temperature and ultrasound agitation. The largest amount of DEHP migrated to infant
formula, followed by milk powder and water. Since phthalates being just incorporated into plastics
and not chemically bound to plastics, migration of DEHP was increased when ultrasound as type of
agitation was applied.
Keywords: DEHP, plastic packaging materials, migration, LLE, GC/MS
INTRODUCTION
Phthalates are compounds that are widely used for plasticizing polymers to produce
suitable plastic material with specific properties – soft, flexible, resistant. As such, plastic can
be used in production of toys, medical equipment and many household products, including
plastic wrap, plastic containers, and other things made of vinyl or PVC.The most commonly
used phthalate is di-(2-ethylhexyl) phthalate (DEHP) and plastics can contain from 1 to 40%
of this phthalate [1]. Since phthalates are not chemically bound to the plastics they are
continuously released into the air, food or liquid. Human are exposed to the effects of
phthalates in various ways: through ingestion, absorption and inhalation. Animal studies show
a harmful effect of phthalates, phthalates represent endocrine disruptors and affect
reproduction, induce cancer, cause liver disorders [2,3]. Due to easy release of phthalates in
the environment and because of their negative effects, it is of great importance to constantly
analyse the food and drink on the phthalate content. It is also important to determine the
conditions under which phthalates migration takes place.
24
In this paper, the effect of temperature and ultrasound on the migration of DEHP from
plastic packaging into food recipients with different fat content were investigated.

Reagents and materials
HPLC grade n-hexane was purchased from Sigma–Aldrich (St. Louis, MO, USA). Di(2-
ethylhexyl) phthalate (DEHP) was purchased, in the highest available purity, from Sigma–
Aldrich (St. Louis, MO, USA). Dibutyladipate (DBA) was purchased from Fluka (Buchs,
Switzerland) and used as an internal standard.
Water from a Milli-Q system (Millipore, Bedford, MA, USA) was used. Dialysis bag
(Baxter, USA) was used. Milk powder and infant formula were purchased from commercial
manufacturers offered at the Serbian market.
Calibration standard series with DEHP concentration range 0.25, 0.50, 1.00, 1.50 and 2.50
µg mL-1 with DBA, as the internal standard, at a concentration of 1 µg mL-1, was obtained by
dilution of working solutions of DEHP in n-hexane.
GC-MS analysis
Gas chromatograph 6890 (Hewlett-Packard) equipped with a mass selective detector
(MSD) 5973 (Agilent, USA) and a DB-5 MS capillary column (30 m × 250 mm × 0.25 mm)
(Agilent, USA) was used forDEHP determination. The gas chromatograph was operated in
the split less injection mode. The oven temperature was programmed from 60 °C (1 min) to
220 °C (1 min) at a rate of 20 °C min-1 and then to 280 °C (4 min) at a rate of 5 °C min-1.
Helium was the carrier gas (1.0 mL min-1) and the inlet temperature was 250 °C. The
operating temperature of the MSD was 280 °C with the electronic impact of 70 eV. The MSD
was used in the single ion-monitoring mode (SIM) at m/z 149 for DEHP and ion m/z 185 for
DBA. The identification and quantification of DEHP was based on the relative retention time,
the presence of target ion and its relative abundance.
Sample preparation
The following dairy products with different fat content were used as food recipients: infant
formula (fat content 22.8 %) and powdered milk (fat content 20 %). Also, phthalate migration
was carried out in water as food without fat. Milk powder (45 g) and infant formula (45 g)
were dissolved in 1 L of water from a Milli-Q system, respectively, following to the producer
instruction. The dialysis bag was used as plastic packaging material with the high content of
DEHP. This reliable source of phthalate contains about 35.8 % of DEHP compared to the
total weight [4].
Dairy samples (35 mL) and the exact weight of the dialysis bag (1 cm2) were set in the
vessel and heated to a temperature up to 60 °C, for 60 min. In parallel, the set of samples were
exposed to temperature up to 60 °C, for 60 min but with agitation in ultrasonic bath. Pieces of
dialysis bag, were subjected to repeated migration tests into dairy products, providing total
heating time of 60 hours. The experiment was performed until the plateau was reached on the
curve m = f (t), where m is mass of the migrated DEHP and t exposure time.
25
After each heating, cooling and filtering, liquid-liquid extraction (LLE) with n-hexane (20
mL) as extraction agent was done. LLE conditions were: 15 minutes of manually shaking and
30 minutes of extraction agitation on the ultrasonic bath. After clarification and separation of
two layers, the n-hexane layer concentrated to the volume of 1 mL. Addition of DBA was
performed so that the concentration of DBA was 1 µg mL-1. Thus, prepared samples were
immediately analysed by GC-MS. All analyses were performed in triplicate and quantification
on GC-MS was repeated twice.

GC/MS acquisition
The obtained GC/MS chromatogram shows good separation of DEHP and DBA with
retention times for DBA and DEHP 9.990 and 18.426 min, respectively.Figure 1 shows the
linear analytical curve obtained for DEHP within concentration range 0.25 – 2.5 µg mL-1 with
correlation coefficient of R2 = 0.990 and linear equation y = (505228 ± 9612) x – (8473 ±
13465). The limit of determination (LOD) and the limit of quantification (LOQ) values,
calculated from the signal/noise ratios which were multiplied with the factor 3 and 10
respectively [5], for DEHP are 0.04 µg mL–1 and 0.12 µg mL–1 with relative standard
deviation (RSD) value 3.6 % (n = 3).
Figure 1 The analytical curve for DEHP within concentration range 0.25 – 2.5 µg mL-1
Comparison of influence of temperature and ultrasound on the migration of DEHP

The aim of this study was to compare the effect of temperature and ultrasound on the
repeated migration of DEHP from plastic packaging material into food recipients with
different fat content. Obtained results, mass of migrated DEHP and percentage of migrated
DEHP, were given in Table 1. By comparing the various food receiving matrices, the food
with the highest fat content was the best recipient for the migrated DEHP, because DEHP is a
non-polar molecule and has a greater tendency to dissolve in a non-polar medium. For this
reason, the best recipient for migrated DEHP was the infant formula (fat content 22.8%),
followed by milk powder (fat content 20%) and water (fat content 0%). The same trend of
DEHP migration was observed in cases when the migration was carried with
26
increasedtemperature, as well as by influence of temperature assisted with ultrasound

agitation. The maximal amount of migrated DEHP under the influence of increased
temperature was 601.29 µg, 384.66 µg and 135.67 µg for the following food recipients, infant
formula, milk powder and water in the order. The amount of migrated DEHP under the
influence of ultrasound-assisted migration, followed the same trend, only the maximum
amount of migrated DEHP was higher for all food recipients, due to the additional influence,
as shown in Figure 2. The obtained data show that ultrasound-assisted migration had greater
effect on the migration of DEHP then effect of temperature alone.
Table 1 Migration of DEHP into different food recipient influenced by (1) temperature and (2)
temperature assisted with ultrasound agitation
Mass of Mass of DEHP Maximal amount Percentage of
Food receiving
dialysis bag in dialysis bag of migrated migrated
matrix
(g) (g)[4] DEHP (µg) DEHP (%)
Water 1.7410 0.6233 135.67±1.23 0.02
(1) Milk powder 1.6200 0.5800 384.66±3.61 0.07
Infant formula 1.4560 0.5212 601.29±2.73 0.12
Water 1.4709 0.5266 292.16±1.37 0.06
(2) Milk powder 1.6049 0.5745 1170.33±1.96 0.20
Infant formula 1.4502 0.5192 1323.36±1.87 0.25
a) b)
Figure 2 The effect of temperature and ultrasound on DEHP migration into food recipient with
different fat content
When it comes to the exposure time of a given plastic packaging material to a certain
effect, it was observed that with increasing of exposure time, the mass of migrated DEHP also
increases. The mass increases linearly to a certain point, after which saturation was reached. A
saturation indicated a plateau on the curve m=f(t) where m is mass of migrated DEHP and t is
exposure time, and this plateau showed that the migration no longer occurred due to the
application of the corresponding effect (Figure 3). Maximal amount of migrated DEHP was
reached faster due to the combined effect of increased temperature and ultrasound compared
27
with applied increased temperature alone. When water was a recipient, ultrasound application
reduced exposure time from 2500 min to 1450 min, plateau was reached almost 1000 min
faster (Table 1). The time to achieve saturation, when the ultrasound was applied was shorter
than when only temperature was applied for about 200 minutes for milk powder and infant
formula, as recipients. Expected reason was that water, as polar molecule, only “washed”
molecules of DEHP from plastic surface. On the other hand, non-polar milk samples can
dissolve DEHP from all plastic material and for this is necessary longer period.
Figure 3 Mass of the migrated DEHP under the influence of ultrasound a) in time period of 3500 min
and b) in time period of 450 min
In a first time period (450 min) correlation between mass of migrated DEHP and exposure
time was almost linear and in this period about 30 % of the total migration was taken place
under the both influences. But, taking any time period during the DEHP migration under both
influences, a higher mass of DEHP was always obtained, under the influence of ultrasound.
This increased efficiency of DEHP migration was a consequence of the power and energy
provided by oscillations produced by ultrasound. In this way, the plastic pieces of the dialysis
bag came in better contact with the sample, the sample under the influence of the energy of
the ultrasound infiltrates deeper into the plastic, and soils DEHP in a larger quantity.
CONCLUSION
Obtained data shows that DEHP migration from plastic packaging materials into food
products depends on fat content of these products, increased temperature and applied
ultrasound as an adjunct to increased temperature. In both cases, when temperature alone was
applied and when effects of temperature and ultrasound was combined, amount of migrated
DEHP decreases by following order: infant formula, powdered milk, water, indicating the
effect of fat content of dairy products. The highest DEHP migration occurred into dairy
product with highest fat content. The influence of combined increased temperature and
ultrasound on the DEHP migration from plastic packaging materials into dairy products is
higher than the influence of temperature, for all dairy products. By comparing these effects,
28
conclusion is that ultrasound disrupts structure of plastic material and accelerates diffusion
and release of phthalate from plastic packaging materials into different recipient medium.
ACKNOWLEDGEMENT
This study was supported by the Ministry for Education, Science and Technological Development
of the Republic of Serbia and was performed as a part of Project TR 31060. This investigation was
done under agreement 451-03-68/2020-14/200124.
REFERENCES
[1] R. Rudel, L. Perovich, Atmos Environ; 43 (1) (2009) 170–181.
[2] S. Benjamin, E. Masai, N. Kamimura, et al., J. Haz. Mat; 340 (2017) 360–383.
[3] S. Rowdhwal, J. Chen, Biomed. Res. Int; 2018 (18) (2018) 1–10.
[4] I. Kostić, T. Anđelković, D. Anđelković, et al., Bulg. Chem. Commun; 49 (2) (2017) 360–
365.
[5] Wisconsin Department of Natural Resources Laboratory Certification Program,
Analytical Detection Limit Guidance & Laboratory Guide for Determining Method
Detection Limits, Available on the following link: http://dnr.wi.gov/regulations/labcert/
documents/guidance/-lodguide.pdf
29
DETERMINATION OF PHTHALATES IN PVC MEDICAL DEVICES BY FOURIER
TRANSFORM INFRARED SPECTROSCOPY
Tatjana Anđelković1, Danica Bogdanović1*, Ivana Kostić1, Goran Nikolić2,

Bojana Kostić2, Tatjana Cvetković3, Gordana Kocić3
1
University of Niš, Faculty of Science and Mathematics, Department of Chemistry,
2
University of Niš, Faculty of Technology, Department of Chemistry and Chemical
Technology, Bulevar oslobođenja 124, 16000 Leskovac, SERBIA
3
*
Abstract
The aim of this work was to determine phthalates in PVC medical devices using the FTIR
spectroscopy, as a rapid pre-screening test. Phthalates were isolated from the PVC samples by
tetrahydrofuran and then plastic is precipitated by the addition of an excess of methanol. The FTIR
spectrum of PVC samples were recorded and on the basis of specific absorbance bands occurring in
the spectra, the existence of phthalates in the PVC samples was checked. The characteristic
adsorbance bands for phthalates in FTIR spectrum were at 743 cm-1, 1579 cm-1 and 1599 cm-1. Based
on the intensity of absorption for three investigated PVC samples, it could be concluded that tubing
for infusion set contains the most phthalates, following by tubing for dialysis set and dialysis bag,
respectively. The absence of these characteristic peaks in the FTIR spectra obtained by the
precipitation method demonstrated the effectiveness of this method in the removal of phthalates.
Comparison of obtained amount of phthalates in tetrahydrofuran/methanol solution, PVC precipitate
and in PVC sample showed that FTIR method can be used as a rapid pre-screening test for qualitative
determination of phthalates.
Keywords: phthalates, PVC, FTIR, precipitation
INTRODUCTION
Phthalates are the esters of 1,2-benzene dicarboxylic acid that are formed by the addition
of an aliphatic or aromatic alcohols to phthalic anhydride in the presence of a catalyst. The
resulting ester groups are in the ortho- position. Phthalates are a family of chemicals used to
make plastics (primarily polyvinyl chloride - PVC) more flexible, elastic and soft, and for this
reason phthalates are also called plasticizers. Because of that, phthalates are used in hundreds
of products in households, hospitals and other spheres. Since phthalates are not chemically
bonded to PVC, they can leach out of plastic under appropriate conditions. The consequences
of phthalate migration from PVC are: the plastic becomes rigid and brittleand the phthalates
reaches the environment. Due to their properties (non-polar molecules, easily soluble in fats),
they are easily dissolved in food, dairy products, beverages, blood, urine, etc. This way
30
human are exposed to the harmful effects of phthalates. Research has shown that phthalates
cause infertility in men, cause testicular cancer, and affect the secretion of glands, thereby
classifying phthalates as endocrine disruptors [1–3].
In order to determine phthalates in various media due to their harmful effects, different
methods have been developed, among which gas chromatography-mass spectrometry
(GC/MS) is the most common used method for this analyse [4]. Phthalate structure with the
ester groups in the ortho- position has great importance for the further phthalates
determination by Fourier Transform Infrared Spectroscopy (FTIR). FTIR method as non-
destructive, reliable, rapid, not expensive, without the need of special sample preparation, can
be considered as significant in the pre-screening for phthalate determination in PVC [5].
The aim of this work was the qualitative determination of phthalates in medical devices,
made of PVC. By removing phthalates from the plastic packaging materials by the
dissolution/precipitation method, the phthalate content qualitatively checked in phthalates free
– plastic and phthalate plastic by FTIR technique, while phthalate content in THF/methanol
system was checked by GC/MS technique.
Comparison of obtained amount of phthalates in tetrahydrofuran/methanol solution, PVC
precipitate and in PVC sample showed that FTIR method can be used as a rapid pre-screening
test for qualitative determination of phthalates.

Chemicals and reagents
The tetrahydrofuran (THF) with HPLC purity was purchased from Fischer scientific
(USA). The methanol with HPLC purity was purchased from Carlo Erba (France).
Medical devices made of PVC was taken from local Clinical Center Niš, Serbia. Dialysis
bag with coupled dialysis tubing which constitute a set for peritoneal dialysis (Baxter, USA)
and tubing for infusion set (Mediaset, Spain) were used for analysis.
FTIR technique
FTIR spectra were scanned on a laser Fourier Transform Infrared Spectroscope (BOMEM
Hartman & Braun — Michelson MB series 100).
The manual hydraulic press (Graseby Specac) was used to create pellet samples for further
analytical determination by analytical equipment such as FTIR.
Amalgamator (Wig-L-Bug) was used for mixing precipitates from this analysis with
appropriate substance.
Gravimetric technique
Methanol was used to produce the PVC precipitate from THF solution. The centrifuge
(Jouan C4I Benchtop, Termo Fisher) was used to separate precipitates from the aliquot. Mass
of PVC precipitate after drying was measured on the analytical balance with accuracy of
±0.00001 g.
31
Sample preparation
Dissolving PVC sample in THF
Accurately weighed mass of PVC medical equipment (0.01 g) was dissolved in 4 ml of
THF. This was the first step in qualitative phthalates determination using the FTIR
instrument. Dissolution of PVC was accelerated by heating, with caution not to evaporate
THF. The next step was to evaporate THF solution in order to form a polymer film of PVC.
The formed Phthalate-PVC polymer (PPVC) filmon the evaporating dish was mounted on an
IR cell holder on FTIR instrument and FTIR spectrum was scanned. Each analysis was
repeated three times.
Precipitation of PVC by methanol
The same mass of the sample (0.01 g) as in the previous experiment was dissolved in 4 ml
of THF. After dissolution, 10 ml of methanol was added to form PVC precipitate without
phthalates (P-free PVC), leaving dissolved phthalates in the supernatant above the precipitate.
The P-free PVC precipitate was separated by centrifugation (3500 rpm). In order to confirm
the complete release of phthalates from PVC samples by THF/methanol, the analysis was
conducted in three directions:
(1) P-free PVC precipitate (pre-dried at 80°C in the oven) was mixed with KBr to form
pellets using manual hydraulic press and amalgamator and scanned on FTIR
instrument.
(2) P-free PVC precipitate was dissolved in THF. After evaporation of THF, the obtained
polymer film was scanned on FTIR instrument.
(3) Evaporation of the dissolved phthalates supernatant into evaporating dish was done.
Obtained disk was gravimetrically measured. The weight of the disk represented mass
of the phthalates in PVC. In this way the mass percentage of phthalates in PVC
samples was calculated.
Safety precautions and reduction of sample contamination by phthalates
Due to the volatility and flammability of the used solvents, care must be taken.
Evaporation of THF must be done in the digester due to the toxicity of THF. Only glassware
equipment was used, because THF dissolves PVC and in order to reduce laboratory phthalates
contamination. All glassware was washed with soap, tap water and ultrapure water, then
washed with acetone and n-hexane and dried at 200 °C in the oven for 4 hours [6].

Characterization of FTIR spectra of PVC samples
Given that the phthalates aromatic ring was substituted in the ortho- position, the expected
absorbance band at 743 cm-1, characteristic of that group appeared on the FTIR spectrum.
This strong absorbance band at 743 cm-1 identifies the phthalates. On the FTIR spectrum
doublet bands at 1599 cm-1 and 1579 cm-1 appeared as a result of the aromatic ring quadrant
stretching vibration and also were useful for infrared analysis of phthalates. Frequency and
intensity of these bands depends on the aromatic ring substitution. Other useful and
32
characteristic FTIR spectra absorption bands for PVC are: 2960 cm-1 (for -C-H bond), 1718
cm-1 (for the phthalate ester), 1450 cm-1 (for -CH2- and -CH3), 1278 cm-1 (for -CH2-), 1073
cm-1 (for -CH3). In Figure 1 FTIR absorption spectrum of dialysis bag was given.
Figure 1 The FTIR spectrum of dialysis bag with qualitative bands identified
In Figure 2 two regions of the FTIR spectra of the investigated medical devices were
given, region from 730 to 760 cm-1 and region from 1590 to 1610 cm-1. Based on the graphs
Absorbance=f (Wavelength), it can be concluded which PVC sample contains the most
phthalates. The tubing for infusion set contains the most phthalates, followed by tubing for
dialysis set and dialysis bag, respectively.
a) b)
Figure 2 The FTIR spectrum of PVC samples: a) region 730-760 cm-1 b) region 1590-1610 cm-1
Characterization of FTIR spectra of P-free PVC sample

Prepared the KBr pellets, were scanned on FTIR instrument to confirm complete release of
the phthalates into methanol-THF aliquot and given spectra show absence of characteristic
33
absorbance bands for phthalates at 743 cm-1, 1579 cm-1 and 1599 cm-1. In Figure 3 FTIR
spectrum of KBr pellet was given. The absence of these absorbance bands showed that the
precipitation method by methanol completely released phthalate from PVC samples. The
same FTIR spectrum was obtained by recording a polymer film obtained by evaporation of
the dissolved P-free PVC precipitate in THF.
Figure 3 The FTIR spectrum of dialysis bag without phthalates
Determination of dissolved phthalates in methanol-THF supernatant

Analysis of methanol-THF supernatant given the following results. The weight of polymer
film obtained after evaporation of THF/methanol was measured. The weight of this polymer
film represented the total mass of phthalates in the sample. Obtained calculated mass
percentage of phthalates in investigated PVC samples was given in Table 1.
Table 1 Mass % of phthalates of PVC sample

Sample Mass % of phthalates
Tubing for infusion set 25.96±0.53
Tubing for dialysis set 20.95±0.41
Dialysis bag 19.2±0.36
Qualitative comparison of obtained polymer films

In this investigation two different polymer films were obtained. The PPVC polymer film
with phthalates, obtained by evaporation of THF from the THF solution of PVC, was elastic
and flexible, because phthalates have the function of plasticizers in PVC plastic. The P-free
PVC polymer film, obtained by evaporation of THF-methanol, was rigid and brittle, which
was a consequence of removal of phthalates from the PVC sample.
34
CONCLUSION
Considering the impact of phthalates on human health, determination of phthalates in
various food, beverage, plastic packaging, medical equipment, etc. is of great importance.
Given that determination methods generally are expensive and complicate, it is important to
develop a method that is fast, reliable and inexpensive. Such a method uses FTIR technique
described in this paper. The disadvantage of this method is that it is not specific method,
because the obtained characteristic absorbance band at 743 cm-1 and absorbance doublet at
1579 cm-1 and 1599 cm-1 in FTIR spectra are characteristic of each phthalate. However, this
method is useful, because it can be used in pre-screening, after which the GC/MS analysis can
be performed.
Also, the precipitation method was used in this work to remove phthalates from plastic,
and evidence of the removed phthalates was provided by the FTIR method. The free
phthalates-plastic film was brittle and rigid, unlike the phthalate-containing plastic that was
flexible and elastic. Comparison of obtained amount of phthalates in
tetrahydrofuran/methanol solution, PVC precipitate and in PVC sample showed that FTIR
method can be used as a rapid pre-screening test for qualitative determination of phthalates.
ACKNOWLEDGEMENT
of the Republic of Serbia and was performed as a part of Project TR 31060 and Project III 41018.
This investigation was done under agreement 451-03-68/2020-14/200124.
REFERENCES
[1] J. Axelsson, L. Rylander, A. Rignell-Hydbom, et al., Environ. Res; 138 (2015) 264–270.
[2] R. Waring, R. Harris, Maturitas; 68 (2) (2011) 111–115.
[3] E. Gray, J. Ostby, J. Furr, et al., Toxicol. Sci; 58 (2) (2000) 350–365.
[4] C. Sablayrolles, M. Montréjaud-Vignoles, D. Benanou, et al., J. of Chrom. A; 1072 (2005)
233–242.
[5] S. Lowry, M. Bradley, Using FT-IR Spectroscopy to Characterize Plastics and Other
Materials, Available on the following link: https://www.asminternational.org/documents/
10192/1883419/amp16904p22.pdf/33ef982b-db56-4f84-8a92-a05cbd37dc14
[6] A. Fankhauser-Noti, K. Grob, Anal. Chim. Acta; 582 (2) (2007) 353–360.
35
REDUCTION OF DRILLING DUST USING DRY DUST COLLECTION SYSTEMS
IN SURFACE BLASTING OPERATIONS
Milanka Negovanović1*, Lazar Kričak1

1
University of Belgrade, Faculty of Mining and Geology, Đušina 7, 11000 Belgrade, SERBIA
*
milanka.negovanovic@rgf.bg.ac.rs
Abstract
Drilling and blasting are still the most effective and cheapest methods of the exploitation of solid
mineral raw materials in surface mines. The quality of drilling process reduces the drilling costs and
increases the productivity. However, drilling dust can be a serious health hazard, not only to
operators, but also to worksites in general. Respirable dust generated by drilling operations can lead
to high exposure levels for the drill operator, drill helper, and other personnel in the local vicinity
during operation. This negative effect of every drilling process in surface mines cannot be avoided
and should be controlled by the efficient dust suppression or collection systems. Reduction of dust
during drilling operation is carried out to improve work conditions and to increase productivity. The
paper mostly deals with dry dust collection systems.
Keywords: dust, drilling, collector, rock blasting, surface mine
INTRODUCTION
The drilling process is applied in surface mines for blasting operations which are
conducted for the fragmentation of rock. The drilling methods that are mostly used in surface
mines are rotary percussion drilling and rotary drilling with rolling tricone bits. Rotary
percussion drilling is based upon the combination of the following [1]:
– Percussion. The impacts produced by repeated blows of the piston generate shock waves
that are transmitted to the bit through the drill string (in top hammer) or directly upon it
(down the hole).
– Rotation. With the movement, the bit is turned so that the impact is produced on the rock
in different positions.
– Feed or thrust load. In order to maintain the contact of the drill bit with the rock, a thrust
load or feed force is applied to the drill string.
– Flushing. Flushing removes the drill cuttings from the blasthole.
Rotary drilling with rolling tricone bits is the most widely used method for drilling large
diameter blastholes in large surface mining operations [2]. This drilling method is applicable
to a wide range of soft to hard rock materials. Rotary blasthole drill rigs have large size and
high weight and their masts are sturdy enough to withstand high forces generated by the
pulldown mechanism and stresses due to vibration that develop in the rotary head. Rotary
rock drills essentially comprise a power source; a string of pipes which transmit the load; and
rotation and flushing air supplied to a bit with steel teeth or tungsten carbide inserts, which in
36
EcoTER'20, 16–19 June 2020, Kladovo, Serbia
turn acts upon the rock [1,2]. The components in a rotary blasthole drill string are a tricone
bit, stabilizers, drill pipes, shock absorbers and crossover subs [2,3].
Drilling dust poses a serious health hazard, not only to operators, but also to worksites in
general [4]. Respirable dust from drilling operations can lead to high exposure levels for the
drill operator, drill helper, and other personnel in the local vicinity during operation [5].
Silicosis can be caused by stone dust containing quartz particles with a granular size less than
0.005 mm. In view of this health risk, many countries have introduced stringent standards and
measures concerning dust separation in rock drilling [4].
Operator cabs are increasingly becoming an acceptable method for protecting the drill
operator from respirable dust generated by the drilling operation. However, the protection
provided, is only available to the personnel inside the cab. Other personnel working in the
vicinity of the drilling operations, the drill helper, shotfirer, mechanics, etc., cannot be
protected in this manner [5].
The empirical formula for determining the dust emission in drilling of boreholes is
presented in the form [6]:
E = i V0 d02 ρ f K1 K2 K3, (mg/s) (1)
where:
E – dust emission in drilling (mg/s), i – coefficient taking the drilling and cleaning method of the
borehole (i = 155∙10–8 in normal drilling and borehole washing with water, i = 90∙10–8 when the water
softeners are added, i = 16∙10–8 at optional drilling and borehole washing with water), Vo – drilling
speed (mm/s), do – diameter of borehole (mm), ρ – rock density, f – strength coefficient according to
Protodjakon, K1 – coefficient of simultaneous operation for multiple drilling hammers (K1 =1 for one
drilling hammer, K1 =1.7 for two drill hammers, K1 =2.7 for three drilling hammers, for drillers in the
open pit exploitation K1 =1), K2 is the coefficient of inclination angle of borehole (K2 =1 for horizontal,
K2 =1.3 for inclined and vertical upwards, K2 =0.7 for inclined and vertical downwards), K3 –
coefficient taking into account the impact of the type of hammer drill or drill (K 3 =1.3 for working
with manual drilling hammer, K3 =1 for drilling hammer or chisel on rack, K3 =0.5 for pivot drill
hammer or hydraulic pushing drilling accessories).
REDUCTION OF DRILLING DUST

The reduction of dust during drilling is carried out to improve work conditions and to
increase productivity. Other technical and economic reasons that justify the elimination of
dust during drilling are [1]:
– lower maintenance of the motor–compressor equipment, giving higher mechanical
output. Uncontrolled drilling dust can clog motors and filters on adjacent machinery,
promoting faster wear through abnormal friction and overheating. This can lead to more
servicing and repairs, and a costly decline in production [4];
– higher drilling rate (about 2 to 10% more), due to the fact that the cuttings are removed
from the blasthole, therefore avoiding their regrinding. Besides, the operator can be closer to
the controls of the machine, increasing the efficiency and control of drilling;
– lower drilling costs because of higher output as well as less wear on the bits.
There are two basic methods for controlling dust on drills [5]:
37
– wet suppression system or,

– dry cyclone/filter type collector.
Wet systems operate by spraying water into the bailing air as it enters the drill stem. Dust
particles are conglomerated as the drill cuttings are bailed out of the hole [5].
Dry collectors operate by withdrawing air from a shroud or enclosure surrounding the area
where the drill stem enters the ground. The air is filtered and exhausted to the atmosphere.
When dust controls are implemented effectively at drilling operations, both wet suppression
and dry collection systems can achieve good dust control efficiency [5].
DRY DUST COLLECTION SYSTEMS

Dust collectors basically consist of:
– Suction head that is placed on the surface at the blasthole collar where the dust is
aspirated and sent through the suction hose to the separation and filter unit [1];
– System of separation and filtering which is carried out in two stages: first with cyclone,
where bigger particles and most of the dust is separated by means of centrifugal force, and
secondly, the filtering is carried out that retains the dust particles under 5 µm;
– Depression or partial vacuum system, with a fan placed behind the filter unit that is
operated by hydraulic or electrical energy, or pneumatically on occasions.
Medium– to large–diameter drill dust collection systems
Typical dry dust collection system on a medium– to large–diameter drill is shown in Figure
1. Drill dust is generated by the bailing air, which is compressed air that is forced through the
drill steel out the end of the drill bit and used to flush the cuttings from the hole. In a properly
operating collection system, these cuttings are contained by the drill deck and shroud located
over the drilling area. This dusty air from underneath the shrouded drill deck is removed by
the dust collector system [5]. The collector is composed of an exhaust fan and filters which
filter the air from underneath the shroud area. It is generally self–cleaning, using compressed
air to pulse through the filters at timed intervals to clean them and prevent clogging. The
filtered fine–sized material then drops out the bottom of the collector to the collector dump
[5].
a) b)
Figure 1 Typical dry dust collection system on Figure 2 Hydraulic ILMEG dust collectors
a medium– to large–diameter drill [5] a) ILMEG X–150; b) ILMEG X–200 [7]
38
The ILMEG X–150 and X–200 hydraulic dust collectors (Figure 2) are used in rock
drilling applications for improved productivity and working conditions with regards to dust
[7]. A typical application is for blast hole drilling with top hammer rock drills or down the
hole rock drills. The filter cleansing function is carried out with reversed air [7].
Table 1 Technical specification of ILMEG hydraulic dust collectors [7]

Specification ILMEG X–150 ILMEG X–200
Max hole size (mm) 165 203
Filter area (m²) 16 24
Number of filters: 4 4 6
Oil flow requirement (l/min) 44 76
Oil pressure requirement (bar) 200 160
Width x depth x height (mm) 1078 x 897 x 1133 1263 x 1065 x 1133
Approx. weight (kg) 220 350
Filter cleansing i–clean: Reversed air through filters in Reversed air through filters in
sequences while drilling sequences while drilling
Rec. working pressure (bar) 7 7
Dust collection system used for small– to medium–diameter drill rigs

A dust collection system used for small– to medium–diameter surface crawler drills is
shown in Figure 3. The difference from the large diameter drill dust collection system is that
this system collects all the drill cutting material, sends it to a large separation cyclone on the
drill boom to drop out the large diameter material, and then sends the remainder to the dust
collector at the back of the drill where the fine–sized material is discharged [5].
Figure 3 Dust collection system used for small– to medium–diameter surface crawler drill rigs [5]
Dust collection system on surface crawler drill rig FlexiROC T35

FlexiROC T35 (Figure 4) is flexible and versatile tophammer drill rig for hole diameter:
64–115 mm, developed and designed for high performance in demanding construction
applications. It can also be applied in small and medium size quarries [8].
39
a) b)
Figure 4 Drill rig FlexiROC T35 [8] Figure 5 Dust collection system on
surface crawler drill rig FlexiROC T35
a) heavy cuttings; b) dust and fine
cuttings
DCT dust collectors (Figure 5) operate via a two–stage filtration process. A coarse
separator isolates 90% of dust in the first stage, thus reducing the risk of overload of the
filters. Then the remainder is separated in secondary filters to get rid of the highly injurious,
microscopic stone dust of particle size less than 0.005 mm [4]. DCT dust collectors [4] have
very few moving parts. The drive ejector has been positioned behind the filters, creating a
partial vacuum in the entire system. As a result, there is no dust leakage, even in the event of a
suction hose becoming damaged. The drive ejector operates continuously in clean, filtered air,
eliminating risk of erosion by drill dust. Steady, high airflow speed in the suction hose
counteracts blockage of the suction hose. Compressed air to the ejector does not pass by way
of the filters, reducing their load [4].
Table 2 Technical specification of drill rig FlexiROC T35 [8]

Main Components Dust collector DCT 110
Track frames with single Aluminium profile feed Filter area 11 m2
grouser pads and cleaning holes beam
Hydraulic track oscillation Hydraulic cylinder feed Suction capacity 560 l/s
and two speed traction system at 500 mm wg
Atlas Copco screw Carousel type rod Suction hose 127 mm
type compressor handling system, 1 + 7 rods diameter
Operator’s cabin, ROPS Hydraulic rock Cleaning air 7.5 bar
and FOPS approved drill pressure, max
LED work Dust collection Cleaning 2–4
lights system air consumption l/pulse
Folding boom Dust pre Number of 11 pcs
system separator filter elements
40
Field experience has shown that, using DCT dust collectors, nett penetration rates can
improve by 5–10%. This is partly because the drill cuttings are removed from the drill hole,
reducing recrushing, and improving bit performance [4].
DCT dust collectors remove virtually 100% of all drilling dust, and, most important of all,
separate the microscopic stone particles.
CONCLUSION
The drilling process is applied in surface mines for blasting operations which are
conducted for the fragmentation of rock. The accuracy of drilling process according to design
drill pattern reduces the drilling costs and increases the productivity.
However, drilling dust poses a serious health hazard, not only to operators, but also to
worksites in general. Reduction of drilling dust can be done by wet suppression system or dry
cyclone/filter type collector. Dust collectors offer effective, reliable dust separation with
operational simplicity, while improving the working environment and increasing productivity.
ACKNOWLEDGEMENT
the Republic of Serbia for financial support the Project TR 33003.
REFERENCES
[1] C.L. Jimeno, E.L. Jimeno, F.J.A. Carcedo, Drilling and Blasting of Rocks, A.A. Balkema,
Rotterdam (1995), p. 408, ISBN: 9789054101994.
[2] L. Kricak, M. Negovanovic, S. Mitrovic, et al., J. S. Afr. I. Min. Metall; 115 (11) (2015)
1065–1071.
[3] B.V. Gokhale, Blasthole drilling technology, Multi Fields, Mumbai, India (2003).
[4] ATLAS COPCO, Surface Drilling in Quarry and Construction, Third edition 2006, Available
on the following link: www.surfacedrilling.com
[5] A.B. Cecala, A.D. O’Brien, J. Schall, et al., Dust Control Handbook for Industrial Minerals
Mining and Processing, Report of Investigations 9689, (2012), Available on the following link:
https://www.cdc.gov/niosh/mining/
[6] M. Mikić, M. Jovanović, I. Jovanović, et al., MMI Bor; 1–2 (2017) 35–40.
[7] ILMEG, Dust Control Solutions for the Construction and Mining Industry, Available on the
following link: http://ilmeg.se/products
[8] EPIROC, FlexiROC T35 and T40, Surface drill rigs for quarrying and construction,
Available on the following link: https://www.epiroc.com/en–id/products/drill–rigs
41
DETERMINATION OF PARACETAMOL USING CARBON BASED SENSOR
ELECTRODES
Marija Petrović Mihajlović1*, Žaklina Tasić1, Ana Simonović1, Milan Radovanović1,

Milan Antonijević1
1
*
mpetrovic@tfbor.bg.ac.rs
Abstract
Paracetamol (acetaminophen, APAP) is commonly used analgesic and antipyretic medication. Hence,
it is interesting to evaluate its amounts in commercial tablets and syrups, as well as in human body
fluids. As a consequence of its widespread application it is found in the environment as well, where it
presents a potential risk and also should be monitored. One of the possible approaches includes
application of various electrochemical methods. It is presented within the paper that carbon based
electrodes can be efficiently used for its determination. These methods can include expensive
electrodes such as glassy carbon electrodes or modifications of other types of carbon electrodes and
on the other side pencil graphite electrodes that are low cost variation, and equally adequate. Due to
the facts that they are cheap and easy to work with the pencil graphite electrodes receive increasing
attention.
Keywords: paracetamol, pencil graphite electrode, modified carbon electrodes,
electrochemical techniques, voltammetry.
INTRODUCTION
Paracetamol (also known as acetaminophen and APAP), which structure is presented in
Figure 1, is a pharmaceutical compound very often used as analgesic and antipyretic
medication. Hence, there is interest to provide efficient techniques for its qualitative and
quantitative determination, either to test the accuracy of the amounts present in
pharmaceuticals or to monitor its presence in human fluid samples and in the environment.
Figure 1 Structure of paracetamol

42
There are numerous studies [1–5] that distinguish pharmaceuticals, amongst which is
paracetamol one of the most frequent ones, as environment pollutants and a potential risk to
the ecosystem. The results like these bring out the question of monitoring of pharmaceutical
compounds such as paracetamol in water systems. The application of some electroanalytical
techniques can be one of the possible ways to do that. Electrochemical techniques can be very
convenient since the measurements are fast so results are very quickly obtained and there is a
possibility to make them cost effective by use of some low cost electrodes such as pencil
graphite electrodes. This paper presents a summary of literature data on determination of
paracetamol (PAR) using carbon-based electrodes, with special attention paid to pencil
graphite electrodes.

Pencil graphite electrode as the electrochemical sensor for paracetamol
There are numerous different approaches and electrochemical techniques used for
paracetamol determination and different electrode pretreatments. For instance, Özcan and
Şahin [6] used N-acetyl-p-benzoquinoneimine (NAPQI) reduction on the electrochemically
treated pencil graphite electrode (ETPG) to determine paracetamol. The electrochemical
treatment was potential cycling between −0.3V and +2.0V with a scan rate of 50mVs−1 for 5
scans in 0.1M H3PO4. NAPQI was formed by electrochemical oxidation of paracetamol on
ETPG. Mechanism of paracetamol oxidation to NAPQI and its reduction is presented in
Figure 2. Since paracetamol can adsorb on ETPG the method adsorptive transfer stripping
differential pulse voltammetry (ATSDPV) can be used for its determination in body fluids in
the presence of uric acid. Values of limit of detection and linear range are shown in Table 1.
Figure 2 Mechanism of paracetamol oxidation/reduction according to Özcan and Şahin [6]
The same authors [7] previously prepared and tested molecularly imprinted polypyrrole
modified pencil graphite electrode (MIP) as paracetamol sensor using differential pulse
voltammetry (DPV). The MIP was obtained by the process of electrodeposition on the surface
of the PGE using cyclic voltammetry in aqueous solution containing 0.1M LiClO4, 0.05M
43
pyrrole and 0.02M paracetamol. The embedded paracetamol were afterwards extracted to give
a surface complimentary in shape and functionality to the original template paracetamol. The
best results are obtained in phosphate buffer medium at pH 7.0, with 0.05M phosphate and
0.1M KCl. This electrode can be used to determine paracetamol even if commonly known
interferences such as phenol, glucose, phenacetin, dopamine and ascorbic acid are present.
Recently, Keskin and Ertürk [8] investigated electrochemical behavior of paracetamol on
the oxidative pretreated pencil graphite electrode (OP-PGE) using cyclic voltammetry (CV)
and electrochemical impedance spectroscopy (EIS). It is found that acetate buffer solution
(0.1M, pH4.8) provided optimal conditions for determination of paracetamol. It is proposed
that the electrochemical improvement of OP-PGE occurs due to the increase in oxygenated
functional groups, microporosity and surface area on the electrode surface. The focus of the
research was also on the effect of the interferences commonly present in real samples on
determination of paracetamol under the optimized experimental conditions. The results
indicated that molecules such as glucose, fructose, sucrose, saccharin and cations such as Na+,
K+, Ba2+, Ca2+, Fe2+, Cu2+, Zn2+ did not affect the peak current of PAR up to 1000-fold-
excess. Acetylsalicylic acid did not interfere up to 11-fold-excess and at higher concentration
interference occurred and decreased peaks of PAR. Oxidation peaks of PAR and dopamine
merged and disabled the determination of PAR when dopamine concentration was higher than
1.23 times of PAR concentration. In their research Mondal et al. [9] constructed nickel ferrite-
modified pencil graphite electrode (NF-PGE) that showed good sensor characteristics, shown
in Table 1, for determination of paracetamol alone and in the presence of ascorbic acid in
phosphate buffer solution (pH 7.4).
Table 1 Limit of paracetamol detection and linear range for pencil graphite electrodes
Electrode Limit of detection Linear range Reference
-9
ETPG 2.5×10 M 0.05-2.5μM [6]
MIP 7.9×10-7M 5-500μM [7]
OP-PGE 14.8×10-9M 0.052-2.85μM [8]
NF-PGE 0.106×10-6M 0.8-55.5μM [9]
AuNPs−PA−PGE 5.0×10-8M 0.2-6.0μM [10]
In order to improve usual approach based on the laboratory experiments, Güzel et al. [10]
applied the experimental design and optimization (EDO) methodology for finding the optimal
electrochemical conditions for paracetamol determination. This methodology have several
advantages such as diminishing of the duration of analysis and use of reagents for
experiments and the opportunity to obtain the exact optimal electrochemical conditions for the
best determination results. They developed gold nanoparticles–polyaniline modified pencil
graphite electrode (AuNPs−PA−PGE) and used it for the quantitation of paracetamol in
commercial syrup and tablet. Satisfactory results were obtained for the determination of
paracetamol using differential pulse voltammetry (DPV) method under the optimal
electrochemical conditions provided by EDO technique which were: the optimal values for
the accumulation potential –524 mV, 294 s accumulation time and 0.1 M phosphate buffer
44
solution medium at pH 8.69. The results obtained by all the above-mentioned studies are
summarized in Table 1.
Glassy carbon electrode and other carbon electrodes as the electrochemical sensors
for paracetamol
Even bare glassy carbon electrode can be efficiently used for paracetamol determination as
Engin et al. [11] demonstrated using glassy carbon electrode for the electroanalytical study of
paracetamol by cyclic voltammetry and differential pulse voltammetry (DPV) techniques.
Optimal results were obtained in 0.2M acetate buffer (pH 4.51). The proposed technique can
be applied for paracetamol determination in commercial medicaments. The obtained results
can be seen in Table 2.
However, there are numerous possibilities to improve characteristics of the electrodes by
various modifications. Graphene and graphene oxide gave good results for modifications of
the electrode surfaces. For example, Kang et al. [12] modified glassy carbon electrode (GCE)
with ethanol suspension of graphene that was cast on electrode surface and dried in air. The
conclusion was that the modified electrode shows superior characteristics as paracetamol
sensor and exhibits very well defined redox peaks in cyclic voltammetry (CV) graph in pH
9.3 buffer (NH3×H2O-NH4Cl, 0.1M, scan rate 50mVs-1). In order to provide high sensitivity
accumulation potential of 0.0 V was applied for 240 s when square-wave voltammetry (SWV)
was used. This method can be used in the presence of ascorbic acid or dopamine. On the other
hand, Li et al. [13] successfully applied electrochemical impedance spectroscopy (EIS), cyclic
voltammetry (CV) and differential pulse voltammetry (DPV) for paracetamol determination
on glassy carbon electrode modified with Pd/graphene oxide (Pd/GO/GCE) in 0.1M
phosphate buffer solution (pH 6.8). The effect of commonly present interferences is also
evaluated and it was found that this method has an excellent selectivity towards paracetamol
since the response of paracetamol is not distinctly affected in the presence of 10-folds of
ascorbic acid, dopamine, uric acid and 4-aminophenol, 20-folds of tyrosine, tryptophan and
guanine, 30-folds of adenine and vitamin B1, and 50-folds of glucose, and 100-folds of K+,
Ca2+, Cu2+, Cd2+, Pb2+, Al3+, Fe3+, SO42- and Cl-. The presented method was also successfully
applied to the determination of paracetamol in practical analysis of commercial tablets and
human urines. Summary of the experimental results is presented in Table 2. Fan et al. [14]
developed the Nafion/TiO2–graphene (TiO2-GR) composite film modified glassy carbon
electrode (GCE) and tested the possibility of its application as paracetamol sensor.
Electrochemical behaviour of paracetamol was studied in 0.1M phosphate buffer solution (pH
7) by application of cyclic voltammetry and for determination differential pulse voltammetry
was applied with good results presented in the Table 2. Whereas, Santos et al. [15] succeeded
in the simultaneous determination of paracetamol and ciprofloxacin using glassy carbon
electrode modified with graphene oxide and nickel oxide nanoparticles (NiONPs-GO-CTS:
EPH/GCE). Square wave adsorptive anodic stripping voltammetry (SWAdASV) was the
method of choice developed firstly in 0.2M phosphate buffer solution (pH 6) and afterwards
applied with success in synthetic biological fluids. Parameters are presented in Table 2.
Cheemalapati et al. [16] used glassy carbon electrode (GCE) modified with multiwalled
carbon nanotubes (MWCNT)/ graphene oxide (GO) nanocomposite for the simultaneous
determination of paracetamol and dopamine. They use cyclic voltammetry and amperometric
45
i–t technique and successfully determined studied compounds in pharmaceuticals and human
urine samples. Similar modified electrode MWCNTs-graphene nanosheet nanocomposite
modified glassy carbon electrode (MWCNTs-GNS/GCE) was used by Arvand and
Gholizadeh [17] for the simultaneous determination of paracetamol and tyrosine in phosphate
buffer solution (pH 7) using differential pulse voltammetry (DPV). The established method
was also successfully applied for their determination in human blood serum and
pharmaceutical samples.
Table 2 Limit of paracetamol detection and linear range for glassy carbon and other carbon
electrodes
Electrode Limit of detection Linear range Reference
graphene modified GCE 3.2×10-8M [12]
Nafion/TiO2–GR/GCE 2.1×10-7M 1-100μM [14]
Pd/GO/GCE 2.2×10-9M 0.005–0.5μM and 0.5–80μM [13]
NiONPs-GO-CTS: EPH/GCE 6.7×10-9M 0.1-2.9μM [15]
MWCNT/GO/GCE 0.05×10-6M 0.5-400μM [16]
MWCNTs-GNS/GCE 0.1×10-6M 0.80–110μM [17]
GCE 3.69×10-7M 4-100μM [11]
iron oxides/G 13×10-6M 13-320ppm [18]
CNP/CPE 0.015×10-6M 0.1-1000μM [19]
PyC 1.4×10-6M 15 - 225μM [20]
According to Benchettara et al. [18] graphite electrode modified with iron oxides can be
used to successfully determine paracetamol in an alkaline solution of pH 12. Amiri et al. [19]
studied the possibility to simultaneously determine paracetamol, phenylephrine and
dextromethorphan since they are commonly found in pharmaceutical used against the
common cold. The authors applied electrochemical techniques such as: cyclic voltammetry
and differential pulse voltammetry using tosyl carbon nanoparticles (CNP) for modifying
carbon paste electrode (CNP/CPE). Solution used for experiments was 0.1 M phosphate
buffer of pH 7.0, human serum and solutions of different pharmaceuticals. The modified
electrode was able to separate overlapping voltammetric peaks of PHE and DX into two well-
defined voltammetric peaks. Keeley et al. [20] studied the electroanalytical properties of thin
pyrolytic carbon (PyC) films prepared by chemical vapor deposition (CVD) on Si/SiO2. They
were found to be competitive with the best commercial carbon electrodes and have the
advantage of being inexpensive, disposable, high-performance nanostructured electrodes for
sensors, fuel cells and energy conversion. They also demonstrated the simultaneous detection
of dopamine and paracetamol using these pyrolytic carbon electrodes. Values of obtained
limit of detection and linear range are shown in Table 2.
CONCLUSION
The survey of the literature dealing with the topic of paracetamol detection and
determination in various media on carbon-based electrodes is presented. It can be concluded
that different electrochemical techniques can be efficiently employed, however, differential
46
pulse voltammetry is the dominantly used one. Different types of carbon-based electrodes are
tested and showed good sensor characteristics, but in the view of cost and the simplicity of
work pencil graphite electrodes stand out. They are much cheaper and the limit of detection
for paracetamol is in the range of other tested electrodes, also there are numerous ways to
improve their properties by different modifications.
ACKNOWLEDGEMENT
The research presented in this paper was done with the financial support of the Ministry of
Education, Science and Technological Development of the Republic of Serbia, within the funding of
the scientific research work at the University of Belgrade, Technical Faculty in Bor, according to the
contract with registration number 451-03-68/2020-14/ 200131.
REFERENCES
[1] B. Morasch, F. Bonvin, H. Reiser, et al., Environ. Toxicol. Chem; 29 (8) (2010) 1658–
1668.
[2] S. Wu, L. Zhang, J. Chen, Appl. Microbiol. Biotechnol; 96 (2012) 875–884.
[3] S. Fekadu, E. Alemayehu, R. Dewil, et al., Sci. Total Environ; 654 (2019) 324–337.
[4] Y. Kim, K. Choi, J. Jung, et al., Environ. Int; 33 (2007) 370–375.
[5] E. Vulliet, C. Cren-Olivé, Environ. Pollut; 159 (2011) 2929–2934.
[6] A. Özcan, Y. Şahin, Anal. Chim. Acta; 685 (2011) 9–14.
[7] A. Özcan, Y. Şahin, Sens. Actuators B; 127 (2007) 362–369.
[8] E. Keskin, A.S. Ertürk, Ionics; 24 (2018) 4043–4054.
[9] S. Mondal, M. Kumari, R. Madhuri, et al., Appl. Phys. A; 123 (7) (2017) article: 494, DOI
10.1007/s00339-017-1107-y.
[10] R. Güzel, H. Ekşi, E. Dinç, et al., J. Anal. Chem; 74 (3) (2019) 296–305.
[11] C. Engin, S. Yilmaz, G. Saglikoglu, et al., Int. J. Electrochem. Sci; 10 (2) (2015) 1916–
1925.
[12] X. Kang, J. Wang, H. Wu, et al., Talanta; 81 (2010) 754–759.
[13] J. Li, J. Liu, G. Tan, et al., Biosens. Bioelectron; 54 (2014) 468–475.
[14] Y. Fan, J-H. Liu, H-T. Lu, et al., Colloids Surf. B; 85 (2011) 289–292.
[15] A.M. Santos, A. Wong, A.A. Almeida, et al., Talanta; 174 (2017) 610–618.
[16] S. Cheemalapati, S. Palanisamy, V. Mani, et al., Talanta; 117 (2013) 297–304.
[17] M. Arvand, T.M. Gholizadeh, Colloids Surf. B; 103 (2013) 84–93.
[18] A. Benchettara, M. Sidoumou, R. Mehdaoui, et al., Portugaliae Electrochimica Acta; 37
(6) (2019) 383–391.
[19] M. Amiri, F. Rezapour, A. Bezaatpour, J. Electroanal. Chem; 735 (2014) 10–18.
[20] G.P. Keeley, N. Mc Evoy, H. Nolan, et al., Anal. Methods; 4 (2012) 2048–2053.
47
THE ROLE OF SUSTAINABLE DEVELOPMENT IN THE CEMENT INDUSTRY
IN SERBIA
Jovica Sokolović1*, Dragana Marilović1, Sandra Vasković1

1
*
jsokolovic@tfbor.bg.ac.rs
Abstract
The cement industry is one of the largest carbon emitting industrial sectors in the world. The carbon
dioxide emissions in this sector should be significantly reduced due to their high environmental impact
and climate change. Accordingly, the cement industry in Serbia is taking all the measures necessary to
reduce the impact of incineration of fossil fuels and to reduce their use. Cement plants in Serbia are
increasingly turning to the use of alternative fuels and waste as a raw material for thermal energy.
This paper presents the results of the use of alternative fuels in Serbian cement industry and their
positive environmental impact.
Keywords: cement plants, alternaive fuels, cement production
INTRODUCTION
Sustainable development has been defined in many ways, but the most frequently quoted
definition is from Our Common Future, also known as the Brundtland Report:
"Sustainable development is development that meets the needs of the present without
compromising the ability of future generations to meet their own needs" [1].
Social development in modern conditions is linked to the model of sustainable
development. The concept of sustainable development itself was adopted as a global concept
of the development at the Rio de Janeiro Conference in order to overcome the problems
related to the development of modern civilization and to find a possible path for industrial and
economic development, as well as for the environmental protection.
One of the first industries to apply the concept of sustainable development is the cement
industry. Cement is certainly one of the most important building materials today. World
cement production in 2017 was estimated at approximately 4.1 billion tonnes. China produces
57% of the world’s cement, with EU28 representing 4.2% and CEMBUREAU members
representing 6.3% of the world’s production [2]. According to the IMF World Economic
Outlook, the 2018 global growth was estimated at 3.7%, and projected to grow at 3.5% in
2019 and 3.6% in 2020 [2].
The increasing use of cement enabled rapid development of construction, especially of
concrete structures, but on the other hand, the progress of construction was set before the
cement industry had increasingly demanding tasks, and nowadays it is gradually overcome
[3]. Cement is the building material of our future, making it sustainable. Cement companies
48
that have integrated sustainable development into their global goals are industry leaders and
innovators in reducing CO2 emissions.
As the environment is polluted in the cement production process, the cement industry has
set the principle of sustainable business and aims to produce as much cement as possible with
as little waste and pollution per ton of material produced. The cement industry accepted the
challenges of sustainable development very early and with full responsibility. The guidelines
developed by the Cement Sustainability Initiative (CSI) are supported and applied by the
Cement Industry of Serbia (CIS), whose representatives are LafargeHolcim group Serbia and
TITAN Cement Plant Kosjeric. In 2011, they signed a Sustainable Development Statement
and thus supported the Cement Sustainability Initaitive [4].
SUSTAINABLE DEVELOPMENT IN CEMENT PRODUCTION

Lafarge Serbia has a tradition in cement production for more than a century. The annual
capacity of the cement plant is 1,350,000 tonnes of cement and binder [5]. On the other hand,
Titan cement plant produces about 750,000 tonnes of cement annually [6]. These factories
initially met with environmental problems. However, they also showed a high level of
readiness in this field. In order to improve their environmental performance, they focused on
the following areas: energy efficiency, use of alternative fuels, climate change, and waste
management.
Energetic efficiency
Cement production is one of the industries with the highest specific consumption of
electricity and heat per unit of product. In the dry portland cement clinker production process,
3.3 to 3.6 GJ of heat is consumed to produce 1 ton of clinker with approximately 100 kWh/t
of cement consumed [5]. For this reason, the cement industry is particularly interested in the
use of cheaper (alternative) fuels. The following alternative fuels are used [7]:
-Waste tires
-Waste oil
-Municipal industrial waste
-Oil sludges
-Biomass
-Meat bone flour
In the past year, TITAN Cement Plant Kosjeric has used thermal energy from the
combustion of fossil fuels and biomass, and electricity. Compared to 2017, the consumption
of thermal energy and electricity in 2018 was higher (thermal energy by 2.6% and electricity
by 8.2%) resulting from an increase in production volume. However, energy efficiency was
actually improved, as indicated by a decrease in specific energy consumption (by -0.2% and -
5.0%, respectively) [8].
49
Use of alternative fuels

Tires have a high caloric value, which makes them suitable for the clinker production
process. Based on the 2018 Environmental Impact Assessment Study, Lafarge used waste
tires with a share of heat substitution up to 30% of total needs. The waste oil content was at
most 12%, of the total heat demand energy [9]. Municipal, industrial waste and biomass could
replace 30% of the heat generated from fossil fuels. Meat bone flour was also used as
alternative fuel which replaced conventional fuel consumption by 13% per year [9]. The use
of alternative fuel in the Lafarge cement group and CRH cement plant is shown in Figures 1
and 2, respectively.
Figure 1 Percentage share of alternative fuels in Lafarge cement group [9]
Figure 2 Percentage share of alternative fuels in CRH cement plant [10]
Due to the positive effects in the EU countries, a high percentage of alternative fuels is
represented (Figure 3) [8].
50
Figure 3 Percentage share of alternative fuels in EU countries [8]
Reduction of carbon dioxide emissions

The cement industry has faced problems of environmental pollution. The negative
environmental impacts that characterize the production of all building materials occur in the
expensive cement production process. The use of non-renewable natural resources to obtain
raw materials, the emission of harmful gases (CO2, NOx and SOx) and energy consumption
are the most important aspects of the sustainability of the cement industry. The cement
industry must be actively involved in implementing the Kyoto Protocol to reduce CO 2
emissions. In cement production, CO2 emissions are caused by the decarbonisation reaction
from the feedstock and the combustion of fuel [5].
Lafarge aims to reduce by 2030 CO2 emissions by 40% per ton of cement compared to
1990, or an additional 19% reduction when compared to 2014 [11]. On the other hand, CRH
Popovac aims to reduce carbon dioxide emissions by 25% in 2020 [10]. In Titan cement plant
total direct carbon dioxide emissions in 2018 were about 1.4% higher than in 2017, due to
increased production volumes. In the same period, total biogenic CO2 emissions from wood
pellet combustion were 553 tonnes. Specific direct carbon dioxide emissions per tonne of
product were 3.5% lower than in 2017 [12].
Waste management
In accordance with its waste management in innovative ways, with a focus on alternative
energy sources, some of these factories have a platform for pre-treatment of non-hazardous
waste. Table 1 shows the total quantities of waste generated at the cement plant [9].
Today, a large amount of non-hazardous waste at the Lafarge Serbia cement plant is
recycled, where some of it is used as an alternative fuel and the rest is landfilled.
51
Table 1 Total amount of waste

Types of waste Amount of waste (t)
Hazardous waste 466.78
Non-hazardous waste 1,055.74
CONCLUSION
In line with the EU commitment to fighting climate change, the cement industry, as one of
the largest carbon emitting industrial sector, needs a more sustainable future. The use of
alternative raw materials in the process of clinker production or as a substitute for clinker in
cement has a significant positive contribution to the environment. The use of alternative raw
materials reduces the consumption of natural, non-renewable raw materials and CO2
emissions (caused by the decarbonisation reaction from the raw material and the combustion
of fuel). Cement plants in Serbia are implementing all necessary arrangements in accordance
with the EU law to reduce the emission of carbon dioxide into the atmosphere. They also have
a long-term plan for protecting the environment and reducing the impact of production and
the emission of harmful gases into the atmosphere.
ACKNOWLEDGMENT
REFERENCES
[1] World Commission on Environment and Development, 1987. Our Common Future,
Oxford University Press.
[2] The European Cement Association (Cembureau), 2019. Activity Report Cement Industry
2018. Brussels.
[3] K. Popović, R. Rosković, D. Bjegović, Proizvodnja cementa i održivi razvoj. Građevinar;
55 (04) (2003) 201206.
[4] Poslovno Udruženje Cementne Industrije Srbije, 2012. Upotreba alternativnih goriva i
sirovina u cementnoj industriji.
[5] Lafarge Srbija doo, Available on the following link: https://www.lafarge.rs/
[6] Titan cementara Kosjerić, Available on the following link: http://www.titan.rs/
home/page/1/Titan-Cementara-Kosjeric.
[7] Lafarge, 13. Netehnički prikaz podataka na kojima se zasniva zahtev za izdavanje
integrisane dozvole, 2018, Available on the following link:
http://www.ekourbapv.vojvodina.gov.rs/wp-
ccontent/uploads/2018/10/III_Netehni%C4%8Dki -prikaz-III-13_LBFC-2018.pdf
52
[8] Titan cementara Kosijerić, Integrisani godišnji izveštaj za 2018. godinu,

Available on the following link: http://www.titan.rs/public/uploaded_files/
TCK_Izve%C5%A1taj_2018_SRB_WEB.PDF
[9] Lafarge, 3. Detaljni podaci o postrojenju, procesima i procedurama, Available on the
following link: http://www.ekourbapv.vojvodina.gov.rs/wp-content/uploads/2018/10/III_
Detaljni-podaci-o-postrojenju_LBFC-2018.pdf
[10] Innovating for a sustainable built environment CRH Sustainability Report 2018,
Available on the following link: https://www.crh.com/media/1437/crh-sustainability-
report-2018-1.pdf
[11] Lafarge Srbija doo, Available on the following link: https://www.lafarge.rs/klima
[12] Titan cementara Kosijerić, Rezultati kontinualnih merenja, Available on the following
link: http://www.titan.co.rs/ekomonitor/2019
53
ANALYSIS OF Al, Cr AND Mn IN THE ROOT ZONE SOIL AND PLANT PARTS OF
WILD ROSE (Rosa spp.) IN THE BOR AREA
Jelena Kalinović1*, Snežana Šerbula1, Tanja Kalinović1, Jelena Milosavljević1,

Ana Radojević1, Maja Nujkić1
1
*
jkalinovic@tfbor.bg.ac.rs
Abstract
Concentrations of Al, Cr and Mn in the root zone soil and plant parts of wild rose (Rosa spp.,
predominantly Rosa canina L.) were determined by ICP-AES in order to assess their origin. The
sampling of soil and plant material was performed in the city of Bor and its surroundings which is
known for mining and smelting of copper ores. According to the concentrations of Al, Cr and Mn in
the soil, as well as the Enrichment factor, it can be considered that these elements were naturally
present in soil from the study area. However, the origin of Al in the plant material was from
resuspended particles from the soil, while the concentrations of Cr and Mn in plants from the sites
around the open pits and rural area were influenced by mining and smelting activities.
Keywords: Al, Cr, Mn, wild rose, Rosa spp.
INTRODUCTION
The usage of herbs is widespread all over the world due to their mild features and low side
effects [1]. The fruits of wild rose (Rosa spp.) are used for strengthening of the body and
protection from infections and cold, as well as like a supplement in the treatment of some
diseases [2]. The rosehips are great source of vitamin A, B3, D, E, and especially vitamin C
[3]. Herbs may be contaminated with toxic elements (Pb, Cd, Al, Hg and other elements like
Cr), and their usage in human consumption could cause some health problems [1,4].
Mining and smelting activities represent one of the main anthropogenic sources of the
environmental pollution in the study area (the city of Bor and its surroundings). Particulate
matter which contains large quantities of toxic elements, as well as the waste gases emitted
from industrial activities pose a great risk for living organisms and plants. In our earlier study
performed in the selected area, results indicated that the origin of As, Cd, Cu, Pb, Mo and Zn
in the soil and plant parts of wild rose was anthropogenic [5].
The aim of this study was to determinate the concentrations of Al, Cr and Mn in the root
zone soil and parts of wild rose sampled in Bor area in order to assess their origin. Also, the
obtained results were compared with some relevant literature data.

The sampling of plant material and root zone soil was performed in the city of Bor and its
surroundings. The sampling site B was characterized as background due to its distance of 17
54
km from Bor. The sampling site TR was located along the traffic road 20 km from the city of
Bor (traffic pollution). The sites T1 and T2 were in Brestovac spa and Bor lake, respectively.
These sites were located in the direction of the dominant winds that transmit the pollution
from the mining-metallurgical complex (MMC) in Bor. The sampling site UI was in the center
of Bor, while the site U was located on the broader area of Bor (pollution from MMC). The
settlement Brezonik was denoted as the sampling site SU, while Oštrelj and Slatina were the
sites R1 and R2, respectively (pollution from MMC and flotation tailing ponds). Sampling
site I1 was located close to the quarry, I2 and I3 were in the surroundings of the copper mine
Cerovo, I4 was in the surroundings of the copper mine Veliki Krivelj and I5 was in the
vicinity of the flotation tailing ponds of the copper mine Veliki Krivelj. Position of the
sampling sites and pollution sources are given in Figure 1.
Leaves (washed and unwashed), branches, fruits and roots of wild rose (Rosa spp.,
predominantly Rosa canina L.) as well as root zone soil were sampled and prepared as
described in Kalinovic et al. [5] and afterwards digested according to the U.S. EPA method
3050B [6]. Concentrations of Al, Cr and Mn were determined by ICP-AES at the Mining and
Metallurgy Institute Bor.
Figure 1 Position of the sampling sites of the root zone soil and plants in regard to the pollution
sources

The concentrations of Al, Cr and Mn in the root zone soil of the wild rose from the
sampling area are shown in Figure 2. The concentrations of Al in root zone soil were within
world average level [7]. The lowest concentration was at the I1 site and the highest at the T1
site. The concentrations of Cr in root zone soil were below the limit value (100 mg/kg)
according to the Serbian Regulation [8], except at the sampling site UI (100.4 mg/kg). The
lowest concentration of Cr in root zone soil was found at the sampling site I1. The
concentrations of Mn in root zone soil were above the world average level (411-550 mg/kg)
55
[7]. The highest concentration of Mn was detected in the soil from the site I4, while the
lowest concentration was found in the soil from the site R2. The highest concentrations of the
examined elements were not observed in the areas affected by the pollution from the mining-
metallurgical copper production (except for Cr at the UI site), as well as the lowest
concentrations were not recorded at the B site which was characterized as unpolluted. This
observation could indicate natural presence of Al, Cr and Mn in the soil.
The ratio of element concentration in the soil sample and the corresponding element
concentration from the background site represents the Enrichment factor (EF) [9]. Figure 3
shows the EF values for Al, Cr and Mn in soil from the study area. The soil samples from all
the 14 sites were not enriched with Al and Cr (EF<2), while the moderate enrichment with
Mn was noticed only at the sites I4, U and T2 (2≤EF<5). Considering the EF values, which
were used to assess the origin of the elements in the soil, it could be noticed that Al, Cr and
Mn were naturally present in soil of the study area.
a) b)
c)
Figure 2 Concentrations of a) Al b) Cr and c) Mn in root zone soil of wild rose from the sampling
sites in the study area
Figure 3 Root zone soil Enrichment factor for Al, Cr and Mn in the study area
56
The concentrations of Al, Cr and Mn in plant material of wild rose (Rosa spp.,
predominantly Rosa canina L.) from the sampling area are shown in Figure 4. Among the
analyzed plant parts, branch was characterized with the lowest content of analyzed elements
at all sampling sites. The highest concentration of Al in root was at the UI site, while the
highest concentrations in leaves and fruits were at the sites I2, I4 and I5. Site I2 was located in
the vicinity of the copper mine Cerovo, while the sites I4 and I5 were located in the vicinity
of the copper mine Veliki Krivelj and flotation tailing ponds, respectively. Based on this, it
could be considered that the origin of Al in the plant material was from resuspended particles
of soil. The highest concentration of Cr in root of wild rose was at the T2 site, while in leaves
the highest concentrations were at the I3 and I4 sites. The concentration of Cr in fruit was
detected only in samples from R2 and I4 sites. In the root of wild rose, the highest
concentration of Mn was in the sample from I3 site, while the concentrations of Mn in leaves
were higher in the samples from the SU, R2 and sites located in the industrial zone (I) and in
the vicinity of open pits and flotation tailing ponds, compared to the other sites. The highest
concentration of Mn in fruit samples was found at the I3 site. According to the obtained
concentrations of Cr and Mn in parts of wild rose, it can be considered that mining and
smelting activities influenced higher concentrations of these elements in samples from the
sites in the vicinity of open pits Cerovo and Veliki Krivelj and in the rural zone.
a) b)
c)
Figure 4 Concentrations (mg/kg) of a) Al; b) Cr and c) Mn in plant parts of wild rose
Comparing the content of Al, Cr and Mn in washed leaves and fruits of wild rose obtained
in this research with the data from the literature (Table 1) it can be seen that concentrations of
Al and Cr in the leaves were approximate, while the concentration of Mn was higher in the
samples from the study area in Bor and the surroundings. Concentrations of Al, Cr and Mn in
fruit samples analysed by Başgel and Erdemoğlu [1] were several times higher than the
concentrations in this study.
57
Table 1 Literature data for the element concentrations (mg/kg dw) in the parts of wild rose
Al Cr Mn References
Washed leaves
*
0.022±0.005 2.441±0.16 110 ±10.97 [10]
Fruit
Al Cr Mn References
157±12 0.92±0.07 244.0±13.8 [1]
13.70±11.24 1.33±1.14 13.93±11.71 [11]
/ 0.79±0.02 35.8±0.7 [4]
*
dw - dry weigh basis; concentrations are given in %; / not determined.
CONCLUSION
Concentrations of Al, Cr and Mn in the root zone soil and parts of wild rose sampled in
Bor area were determined in order to assess the origin of these elements. Based on the
obtained concentrations of the examined elements in root zone soil of wild rose and values of
Enrichment factor it can be noticed that Al, Cr and Mn were naturally present in soil.
Regarding the concentration of elements in the plant material it was observed that Al
originated from resuspended particles of soil, because this element is surely present in soil.
Higher concentrations of Cr and Mn in the plant material were influenced by mining and
smelting activities especially at the sites around the open pits and rural area.
ACKNOWLEDGEMENT
REFERENCES
[1] S. Başgel, S.B. Erdemoğlu, Sci. Total Environ; 359 (2006) 82‒89.
[2] F. Demir, M. Özcan, J. Food Eng; 47 (2001) 333‒336.
[3] S. Ercisli, Genet. Resour. Crop Ev; 52 (2005) 787‒795.
[4] Ş. Tokalıoğlu, 2012) Food Chem; 134 (2012) 2504‒2508.
[5] J. Kalinovic, S. Serbula, A. Radojevic, et al., Environ. Monit. Assess; 191 (2019) 15.
[6] U.S. EPA, Acid Digestion of Sediments, Sludges and Solids (3050B), Washington, USA
(1996).
[7] A. Kabata-Pendias, Trace Elements in Soils and Plants, (4th ed.), CRC Press, Boca Raton
(2011), ISBN: 978-1-4200-9368-1.
[8] Regulation No. 88/10, "The Official Gazette of Republic of Serbia", The soil quality
monitoring programme using indicators for assessing the risks from the soil degradation as
well as the methodology for working out the remediation programme (2010).
58
[9] A. Enuneku, E. Biose, L. Ezemonye, J. Environ. Chem. Eng; 5 (2017) 2773‒2781.

[10] A. Vural, Environ. Monit. Assess; 187 (2015) 486.
[11] M.M. Özcan, A. Ünver, T. Uçar, et al., Food Chem; 106 (2008) 1120‒1127.
59
THE DISTRIBUTION OF Al, Fe, Cu, Zn, Pb, Ni, As AND Cd WITHIN THE PINE
TREES FROM THE CHEMICALLY IMBALANCED ENVIRONMENT
Tanja Kalinović1*, Snežana Šerbula1, Jelena Kalinović1, Jelena Milosavljević1,

Ana Radojević1
1
*
tkalinovic@tfbor.bg.ac.rs
Abstract
Estimation of Al, Fe, Cu, Zn, Pb, Ni, As and Cd distribution among the roots, branches and needles of
the pine trees from the zones in the chemically imbalanced environment due to the soil and air
pollution from the copper production processes and unpolluted zone, was presented. Distribution of Al
throughout the pine tree in the most cases was characteristic for the natural environmental conditions
probably due to the absence of a nonpoint source of Al pollution in the examined area. Higher Fe
concentrations in the pine branches than in the needles could be attributed to rougher branches
surfaces, which contributed to higher ability for retaining Fe from the atmospheric deposition.
Differences in the distribution of Cu, Zn, Pb, As and Cd among parts of pine from the extremely
polluted urban-industrial relative to the background zone, point out the different ways of plant
adaptations in the environmentally stressed habitats. Cu was predominantly accumulated in the
branches, while the roots had the lowest Zn, Pb and Ni content.
Keywords: pine, distribution, environmental pollution, copper production
INTRODUCTION
Plants respond to chemical stress caused by both deficiencies and excesses of nutrients in
ecosystems. During evolution and course of life, plants have developed several biochemical
mechanisms that have resulted in the adaptation to and the tolerance of new or chemically
imbalanced environments. Therefore, this relations should always be investigated for the
particular soil–plant, as well as the air–plant systems [1]. Contents of certain elements in the
plant parts can be indicative of (1) atmospheric pollution via incorporation through the
stomata or (2) soil pollution taken up via roots and transported to the leaves [2,3]. The transfer
and accumulation of heavy metals into the plant organs is usually substantially influenced by
the various factors: primarily by soil heavy metal content and soil characteristics, by soil
reaction, by cation exchange capacity, or by Ca/Mg content ratio [4]. However, the ability to
transfer metals from the soil/air to the plant organs makes some tree species suitable for the
colonization and vegetation restoration of the contaminated areas [5].
Chemically imbalanced environments due to the soil and air pollution are the most
attractive for the investigations of the interactions in the soil–plant and air–plant systems.
However, little attention was given to the distribution of the essential elements, as well as
heavy metals and metalloids within the parts of trees. The aim of this research was to estimate
distribution of Al, Fe, Cu, Zn, Pb, Ni, As and Cd among the roots, branches and needles of
60
pine trees from the different zones located in the area affected by the polluting substances
from the copper production processes relative to the unpolluted background zone.

Plant material was sampled from 10 sampling sites distributed in 7 zones. The urban-
industrial (UI) zone/sampling site was located in the city of Bor (Serbia). This zone was
characterized by decades of the extreeme air pollution from the copper smelter, flotation
tailing ponds, heating plant and traffic [6]. The urban (U) zone/sampling site characterized
with the periodical impact of the polluting substances from the copper production proceses
was situated in the most populous part of the city. The suburban (SU) zone/sampling site was
polluted predominantly with the pollution from the copper smelter. The I1 and I2 sampling
sites within the industrial (I) zone represented area in the vicinity of the Copper mines Veliki
Krivelj and Cerovo, respectively. Polluting substances at these sampling sites predominantly
originated from the flotation tailing ponds and overburden dumps, as well as from the acid
mine drainage waters. Two sampling sites, T1 (Brestovac spa) and T2 (Bor lake), represented
the tourist zone (T). The rural (R) zone (R1 and R2 sampling sites) under the pollution from
the copper smelter, flotation tailing ponds and acid mine drainage was the most vulnerabled
area, due to the ussage of agricultural land for food production. The background (B)
zone/sampling site represented the unpolluted area, about 17 km from the facilities for the
copper production.
Plant material was sampled during September and the first half of October. Samples were
collected under the stable weather conditions, after prolonged periods without rain, and during
days without winds. Three to five healthy individuals were sampled from the each sampling
site. Needles and branches (about 2 cm thick) were sampled at the high of 1.5 to 2 m, from the
outer of the canopy, on the east, west, north and south sides. Needles and branches remained
unwashed. Roots (up to 4 cm thick) were sampled at a depth of 1020 cm, with several sides
of the canopy depending on the availability. The composite root samples were repeatedly
washed in distilled water with brushing. Plant samples were air dried at the room temperature
and then milled. Microwave digestion of the plant material was performed according to the
US EPA method [7]. The concentrations of Al, Fe, Cu, Zn, Pb, Ni, As, and Cd in the needles,
branches and roots were determined on the atomic emission coupled plasmainduced
spectrometer, with radial and axial plasma observations, (Atomic Emission Spectrometer with
dual view simultaneous Inductively coupled plasma, ICPAES) manufactured by SPECTRO
model Blue.

Pine roots from 6 sampling sites had higher Al concentrations, compared to the rest
analyzed pine parts (Figure 1a). This was in accordance with the results by Zhang et al. [8]
and Wang et al. [9] who found that Al mainly accumulates in the pine roots. Pine branches
contained higher Al concentrations than the needles at the most sampling sites. Distribution of
Al in the pine parts from the most polluted (UI) and unpolluted (B) sampling sites differed,
althouth nonpoint source of Al pollution in the examined area did not existed [3].
61
a) b)
c) d)
e) f)
g) h)
Figure 1 Distribution of: a) Al, b) Fe, c) Cu, d) Zn, e) Pb, f) Ni, g) As and h) Cd in the roots, branches
and needles of pine
62
Pine branches (except from the UI and I2 sites) retained higher Fe concentrations relative
to the roots and needles (Figure 1b). Branches have rugher surface than the needles which
could be the cause of higher Fe concentrations in the pine branches. Kalinovic et al. [3]
noticed significant decrease of Fe concentrations resulting from the washing of tree leaves
which indicated the presence of Fe in the atmospheric deposition.
Pine branches contained more Cu, compared to the rest examined plant parts, except at the
sampling sites UI, I2 and B (Figure 1c). Skonieczna et al. [10] detected the highest Cu
concentrations in the branches of pine growing in the environmentally stable area. Pine from
the sampling sites I2 and B, had the highest Cu concentrations in the roots, while branches
and needles had similar Cu contents. Cu has low mobility relative to other elements in plants
and most of this metal appears to remain in the root and leaf tissues until they senesce [11].
Such behaviour in this investigation was observed only for the sampling sites with the lowest
environmental pollution, esspecially for the sampling site B with natural environmental
conditions. Differences in Cu distribution depending on the plant part and sampling site, point
out the different ways of adaptation which plants develop to survive in the habitats with high
Cu contents. This observation was based on the data from the most polluted zone (UI
sampling site) and the background zone. Kalinovic et al. [3] found that soil from the vicinity
of the copper smelter was the most polluted with Cu, while soil from the background zone
had the lowest Cu content. Also, the washing procedure resulted in the significant reduction
of the Cu content in the needles from the examined area [3], which indicated environmental
pollution with Cu.
The determined Zn concentrations were the lowest in the pine roots compared to the other
parts, at 6 out of 10 sampling sites (Figure 1d). From this regularity deviated Zn
concentrations in the plant material from the suburban, industrial and background zone. Pine
roots from the unpolluted area (B zone) had higher Zn content compared to the branches and
needles, which was contrary to the results from the UI zone. That indicated the specific
behavior of the pine tree under different environmental conditions, similarly to the results for
Cu. Kalinovic et al. [3] detected the highest Zn contents in the pine soil from the UI zone,
while statistically significant Zn content was washed from the pine needles. In the conditions
of hight levels of Zn in soil, this element may be translocated from the roots and accumulated
in the tops of the plant [11], which was in agreement with the results of this study.
The lowest Pb content was detected predominantly in the pine roots, except for the
sampling sites I2 and B, where Pb content in the roots was higher compared to the other parts
(Figure 1e). According to KabataPendias and Mukherjee [12] a great proportion of Pb was
accumulated in the pine roots, which was the case only at the sampling sites with the lowest
environmental pollution (i.e. I2 and B). Pine branches contained the highest Pb levels, except
at the sampling sites UI, I2 and B. The variations in the Pb distribution among the roots,
branches and needles from the urbanindustrial and background zone, point to the different
mechanisms of Pb accumulation and translocation in the pine tree, under the specific
environmental conditions, similar as in the case of Cu and Zn.
The lowest Ni concentrations were observed in the pine roots from 7 out of 10 sampling
sites, including the sampling site B which represented the unpolluted zone (Figure 1f). The
63
aerial pine parts contained the highest Ni concentrations. Distribution of Ni among the pine
parts from the UI and B zone did not differ greatly.
Branches and needles had higher As contents than the roots, except from the sites T1 and B
(Figure 1g). These results indicated that pine tree used the same mechanisms for accumulation
and translocation of this nonessential element, in almost the entire study locations. The
differences in the distribution between UI and B zones, as in the case of Cu, Zn and Pb, were
observed. The copper smelter had enormously influence on the pollution of soil and air with
As in the entire study area [6]. Jana et al. [13] concluded that the pine roots retained more As
than the trunk, branches and needles. These results were contrary to the our findings, probably
because of the different source and level of pollution.
The distribution of Cd in the pine parts very greatly in all the investigated zones (Figure
1h). It is important to point out that the needles from the urbanindustrial zone contained the
highest Cd concentrations, while the roots had the highest concentrations in the background
zone. The results from the background zone were in agreement with the statement by Kabata-
Pendias and Mukherjee [12] who reported that Cd concentrations are ussually the highest in
the roots and decreases towards the top of plants. These results indicated specific mechanisms
of pine adaptation depending on the degree of the environmental pollution by Cd. The trend
of the environmental pollution with Cd was similar as in the case of Cu and As reported by
Kalinovic et al. [3].
CONCLUSION
The contents of Al, Fe, Cu, Zn, Pb, Ni, As and Cd in the pine roots, branches and needles
from 9 sampling sites under the pollution from the copper production processes, and one
unpolluted site were determined and compared in order to evaluate the elements distribution
through the pine tree. Aluminum accumulated predominantly in the roots (at 6 out of 10
sampling sites). The distribution of Al throughout the pine tree in the most cases was in a
compliance with the results from the literature data, probably due to the absence of a nonpoint
Al pollution source in the examined area. Pine branches contained higher Fe concentrations
than the needles, which could be effect of the rougher surface which captured more Fe from
the atmospheric deposition. The differences in Cu, Zn, Pb, As and Cd distribution among the
parts of pine from the extremely polluted urban-industrial and unpolluted background zone,
point out different ways of adaptation which plants develop to survive on the chemically
imbalanced habitats. Cu was accumulated predominantly in the branches, while the roots had
the lowest Zn and Pb content (at 8 out of 10 sampling sites), and Ni content (at 7 out of 10
sampling sites).
ACKNOWLEDGEMENT
Education, Science and Technological development of the Republic of Serbia, as part of the funding of
scientific research at the University of Belgrade, Technical faculty in Bor, according to the contract
with registration number 451-03-68/2020-14/ 200131.
64
REFERENCES
[1] A. KabataPendias, Trace Elements in Soils and Plants, Boca Raton, Florida (2011),
ISBN: 978-1-4200-9368-1.
[2] M.I. Rucandio, M.D. Petit-Domínguez, C. Fidalgo-Hijano, et al., Environ. Sci. Pollut.
Res; 18 (2011) 51–63.
[3] T.S. Kalinovic, S.M. Serbula, A.A. Radojevic, et al., Geoderma; 262 (2016) 266–275.
[4] P. Andráš, I. Turisová, G. Buccheri, et al., Web Ecol; 16 (2016) 81–87.
[5] M. Mleczek, P. Goliński, M. Krzesłowska, et al., Environ. Sci. Pollut. Res; 24 (2017)
2183–22195.
[6] S.M. Serbula, J.S. Milosavljevic, A.A. Radojevic, et al., Sci. Total Environ; 586 (2017)
1066–1075.
[7] US Environmental Protection Agency, 1996. Acid Digestion of Sediments, Sludges, and
Solids (3050B), Washington, DC. Available on the following link:
https://www.epa.gov/sites/production/files/2015-06/documents/epa-3050b.pdf
[8] H. Zhang, Z. Jiang, R. Qin, et al., BMC Plant Biol; 14 (2014) 264.
[9] S. Wang, P. Wang, C.Q. Fan, et al., Atmos. Environ; 47 (2012) 358–364.
[10] J. Skonieczna, S. Małek, K. Polowy, et al., Drewno; 57 (192) (2014) 77–87.
[11] A. Kabata-Pendias, H. Pendias, Trace Elements in Soils and Plants, Boca Raton, Florida,
(2001), ISBN: 0-8493-1575-1.
[12] A. Kabata-Pendias, A.B. Mukherjee, Trace Elements from Soil to Human, Springer-
Verlag Berlin Heidelberg (2007), ISBN-13: 978-3-540-32713-4.
[13] U. Jana, V. Chassany, G. Bertrand, et al., J. Environ. Manage; 110 (2012) 188–193.
65
THE RELATIONS BETWEEN SOIL PHYSICO-CHEMICAL PROPERTIES AND
SOIL ENZYME ACTIVITIES IN LONG-TERM CONTAMINATED AREA
Jelena Milosavljević1*, Snežana Šerbula1, Tanja Kalinović1, Jelena Kalinović1,

Ana Radojević1, Boban Spalović1
1
*
jmilosavljevic@tfbor.bg.ac.rs
Abstract
This study aims to evaluate the influence of selected soil properties on soil enzyme activities in the
area characterized with long-term contamination originating from the mining-metallurgical
processes. Sampling of Plantago spp. root zone soil was performed at five sites. Selected soil
properties, such as soil pH, soil organic carbon and soil moisture were determined. The activities of
five hydrolases (i.e. ß-glucosidase, urease, arylsulphatase, acid and alkaline phosphatase) with
essential roles in soil nutrient cycling were assessed. Calculated total enzyme activity index (TEI)
inhibition rate denoted soil enzyme activities inhibition at the site Brezonik, while the other sites were
characterized with higher soil enzyme activities in comparison to the control site. Spearman’s
correlation coefficients between soil properties, soil enzyme activities and TEI were also calculated.
Among the five studied enzymes, Arl activity was found to be sensitive to distance from the main
pollution source. Assessed soil properties (pH, organic carbon and moisture) did not significantly
influence soil enzyme activities. On the other hand, soil properties determination along with soil
enzyme activities is necessary considering the complexity of interrelations between these variables.
Keywords: soil enzyme activities, hydrolases, soil properties, TEI, copper smelter, Plantago
spp.
INTRODUCTION
Contaminants emitted during different anthropogenic activities are primarily accumulated
in the upper soil horizons where most organic matter is found and microbial processes are
occurring [1]. Different soil properties are affected by contamination, such as the amount and
quality of potential organic inputs, as well as soil microbial processes [2]. Unlike soil
physico-chemical properties, soil biological properties (i.e. soil enzyme activities) are
sensitive indicators responding rapidly to the environmental disturbances of both natural and
anthropogenic origin [3,4]. Soil processes mediated by enzymes are regarded as integrators of
soil physical, chemical and biological characteristics, and represent excellent candidates to
reflect changes in soil properties [5]. The methods for determination of soil enzyme activities
are considered to be relatively easy and fast, thus soil enzyme activities represent cost-
effecting monitoring tools [2,6]. Soil enzymes are catalysts of different reactions, and have
crucial roles in the stabilization of soil structure, organic matter formation and nutrient
cycling [4]. Nutrient cycling is one of the most important soil functions, whereby the
processes catalyzed by enzymes provide the basis of fundamental elements cycling in soil
[2,5].
66
Soil properties including pH, organic carbon content and soil moisture level, beside the
presence of soil contaminants (i.e. heavy metals), highly influence soil enzyme activities
[2,4,5,7]. The investigations based on the identification of the relations between soil physico-
chemical properties and soil enzyme activities can improve current knowledge of soil
biogeochemical dynamics and cycles [7]. The evaluation of soil hydrolytic enzymes activities
provides the measure of the effects of soil alteration on the biological processes related to C,
N, S and P cycling [3]. Special emphasis is given to the assessment of the soil enzyme
activities in long-term contamination areas with the specific environmental conditions [2].
Taking into account aforementioned, this study aims to evaluate the influence of selected soil
properties on the soil enzyme activities with crucial roles in essential element cycling, namely
ß-glucosidase, urease, arylsulphatase, acid and alkaline phosphatase, in the long-term
contaminated area.

Soil sampling
Soil sampling was performed at the 5 sites in the Bor area previously described with the
highest amount of heavy metals in air and soil: Town park, Brezonik, Oštrelj and Slatina,
while site Gornjane was used as control [8–10]. At each selected site, root zone soil of
Plantago spp. (predominantly Plantago lanceolata) from 5-10 individual plants was sampled,
and combined into one composite sample. Sampled soil was further air dried in the laboratory
and physico-chemical properties were determined. One part of the soil was sieved (<2mm),
kept at 4°C and used for the analyses of soil enzyme activities.
Soil physico-chemical properties
Air dried soil samples were sieved (<2 mm), grinded and further analyzed. Soil pH was
determined in 1M KCl solution [2,4,11]. Standard pH meter (Model MU 6100L) was used to
determine pH of soil:KCl suspension. The ratio used for pH determination was 1:5
mass/volume [12]. Soil water content (moisture) was determined from the loss of weight after
drying of field moist soil samples (<2 mm) at 105°C until constant mass. In order to calculate
soil organic carbon content, soil organic matter was first determined from the loss-on-ignition
method (550°C for 2 h) [13]. Soil organic carbon (OC) was calculated by using the
conversion factor of 2, based on the assumption that organic matter is 50% carbon [14].
Soil enzyme activities determination
The activities of ß-glucosidase (Glu), urease (Ure), arylsulphatase (Arl), acid and alkaline
phosphatase were determined on the basis of product released after the specific reaction
between the enzymes and substrates [15]. The specific substrates were salicin (for Glu
determination), urea (Ure), p-nitrophenylsulfate (Arl) and p-nitrophenyl phosphate (AcP and
AlP). The enzyme activities are expressed as released products per unit of dry soil mass (dm).
Total enzyme activity index (TEI) was calculated according to expression:
TEI  X i / X i , where X i represents the measured activity of the soil enzyme i, while X i
represents the average activity of the soil enzyme i in all samples [3,16]. TEI inhibition rate
proposed by Fang et al. [16]: [1–(TEIpolluted/TEIunpolluted)]*100 was also calculated.
67
Data analysis
All statistical analyses were conducted and graphs were created using R programming
language, v 3.5.2, R core team 2018 [17]. Non-parametric correlation analysis (Spearman’s
coefficients) was used to assess the relationships between soil enzyme activities, soil physico-
chemical properties and TEI. The correlation matrix of data was plotted by the R package
corrplot [18].
RESULTS AND DISCUSSIONS

Soil properties
The results of analyzed soil physico-chemical properties are given in Table 1. Soil pH
values were in the range of 4.22 to 7.20, whereby the sampling site Slatina was characterized
with the lowest and site Gornjane with the highest pH. Moisture content in the soil samples
was in the range from 9.22% (at the site Gornjane) to 20.24% (at the site Town park). The
lowest organic carbon content was determined in the soil samples from the site Gornjane
(1.88%), while the highest was in the samples from the site Slatina (5.52%).
Table 1 Physico-chemical properties of the sampled soils

Sampling site Distance (km)* pH (KCl) Moisture (%) OC (%)
Town park 0.5 6.81 20.24 5.52
Brezonik 2.5 6.26 14.31 3.30
Oštrelj 4.5 7.19 18.79 4.67
Slatina 6.5 4.22 18.32 5.53
Gornjane 17 7.20 9.22 1.88
*
From the copper smelter
Total enzyme activity index (TEI) and TEI inhibition rate

Soil enzyme activities across the study area were: 309.83 μg saligenin g-1 dm (Glu); 96.04
μg N g-1 dm (Ure); 75.10 μg p-nitrophenol g-1 dm (AlP); 548.71 μg p-nitrophenol g-1 dm
(AcP) and 442.18 μg p-nitrophenol g-1 dm (AlP). The lowest TEI value was calculated for the
sampling site Brezonik, while the highest for the site Oštrelj (Table 2). Contrary to our results,
Fang et al. [16] found the highest TEI for the unpolluted area.
Table 2 Calculated TEI and TEI inhibition rate

Sampling site TEI TEI inhibition rate (%)*
Town park 4.24 -0.33
Brezonik 3.73 11.67
Oštrelj 7.85 -85.66
Slatina 4.95 -17.08
Gornjane 4.23 /
*
calculated in comparison to the control site
68
TEI inhibition rate for the site Brezonik amounted to 11.67% indicating inhibition of soil
enzyme activities compared to the control site (Table 2). TEI inhibition rate calculated for the
other sampling sites amounted to -0.33, -85.66 and -17.08% for the sites Town park, Oštrelj
and Slatina, respectively. Negative TEI inhibition rate indicated the enhancement of the soil
enzyme activities in comparison to the control site.
The influence of soil properties on the soil enzyme activities
Correlation matrix between soil enzyme activities, soil properties and TEI is given in
Figure 1. The positive correlation found between Arl activity and distance from the main
pollution source (r=0.900, p<0.05) was in accordance with the previous studies [4,11,19].
Statistically significant positive correlation was found between TEI and Ure activity (r=1.000,
p<0.001) (Figure 1), which was in accordance with the study by Tan et al. [3]. Soil properties
did not exhibit significant influence on TEI. However, Tan et al. [3] found that TEI was
strongly influenced by soil OM and pH levels (OM content had positive, while pH had
negative effect on TEI) in comparison to the individual soil enzyme activities. Also, Fang et
al. [16] found that soil properties (i.e. electrical conductivity) negatively influenced TEI.
Soil pH value was in positive relation with the activities of AcP and Glu and in negative
relation with the activities of AlP and Arl, although relations were not significant. This
finding was supported with statistically significant negative correlations (r=-0.900, p<0.05)
between AcP and AlP activities, as well as between Glu and Arl (Figure 1). Our results are in
accordance with the previous studies which indicated that AlP activity was predominant in
neutral or alkaline soils, whereas AcP activity was predominant in acid soils [5].
The results from this study indicated that soil enzyme activities are poorly related to soil
pH, in contrast with the previous studies highlighting influence of pH on the soil enzyme
activities [4,5]. The changes in soil pH values influence soil enzyme activities through direct
and indirect effects [5]. On the other hand, Garcia-Gil et al. [1] stated that it is very difficult
to distinguish between the effects of pH changes on soil biological properties and the effects
resulting from the presence of soil pollutants.
OC was negatively correlated with Glu, Ure and AcP activity, while positively with Arl
and AlP, although not statistically significant (Figure 1). The absence of significant influence
of organic C on the soil enzyme activities, Angelovičová and Fazekašová [6] attributed to the
quality of the organic inputs into the soil. Niemeyer et al. [2] denoted positive relations
between soil enzyme activities and soil organic carbon in the surrounding area of lead smelter
plant in Brazil. According to the literature [2,4], organic matter acts like an energy and C
source for microbes, as well as the substance-complexing heavy metals and thus protecting
soil enzymes. Also, regarding the influences of organic matter on the soil capacity for water
retention, soil enzyme activities are considered to be positively related to soil organic carbon.
Taking into account moisture level and soil enzyme activities, there were no significant
correlation (Figure 1), which was in contrast to the previous study by Weintraub et al. [7] who
denoted positive correlations between soil moisture level and enzyme activities. According to
the study by Pereira et al. [20], low correlation coefficients indicated that the moisture level
was not a limiting factor affecting soil enzyme activities in the mining area. Alvarenga et al.
[21] stated that low enzymatic activities in soil sampled at the São Domingos mine, could be
69
attributed to the specific climatic conditions resulting in the low soil moisture content. Soil
moisture affects soil enzyme activities directly by influencing water availability to microbial
activity, as well as by indirect effects related to changes in soil levels of oxygen and the flux
of labile C and nutrients [7].
Figure 1 Correlation matrix between soil enzyme activities, distance from the smelter, soil properties
and TEI in the root zone soil of Plantago spp. based on Spearman’s correlation coefficients. Purple
and green colors indicate negative and positive correlations, respectively. The size of the circle is
proportional to the correlation coefficients. Asterisks indicate statistical significance (*p<0.05,
**
p<0.001). Glu: ß-glucosidase, Ure: urease, Arl: arylsulphatase, AcP: acid phosphatase, AlP:
alkaline phosphatase, OC: organic carbon content, TEI: total enzyme activity index.
CONCLUSION
The influence of selected soil properties on the enzyme activities in soil sampled at five
sites with distinct distance from the main pollution source was assessed. TEI inhibition rate
denoted reduction of soil enzyme activities at the site Brezonik, while at the sites Town park,
Oštrelj and Slatina soil enzyme activities were higher in comparison to the control site.
Arylsulphatase activity was negatively correlated to the distance from the main pollution
source, which indicated the reduction of the activity in the soil sampled in the close vicinity of
the copper smelter. In general, soil enzyme activities were poorly related to soil pH, organic
carbon and moisture content. Taking into account direct and indirect influences on the soil
enzyme activities, the soil properties should be determined in the studies involving evaluation
of soil enzyme activities as indicators.
ACKNOWLEDGEMENT
70
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6550.
71
TOXICITY SCREENING AFTER DEGRADATION OF ORGANOPHOSPHORUS
PESTICIDES WITH CHLORINE DIOXIDE
Igor Kodranov1, Marija Pergal2*, Dragan Manojlović1,3

1
University of Belgrade, Faculty of Chemistry, Studentski trg 12-16, 11000 Belgrade,
SERBIA
2
University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Njegoševa 12,
3
South Ural State University, Lenin prospekt 76, 454080 Chelyabinsk, RUSSIA
*
marijav@chem.bg.ac.rs
Abstract
Effectiveness, mineralization and toxicity of four organophosphorus pesticides (OPPs) azamethiphos
(AZA), dimethoate (DM), fenitrothion (FEN) and malathion (MAL) in water with chlorine dioxide
(ClO2) as degradation agent were investigated. Analyses included toxicity tests of parent pesticides
and their degradation products (DPs), using Daphnia magna test organisms, and total organic carbon
(TOC) analysis. Toxicity tests showed that all four pesticide DPs were less toxic than parent
pesticides, but DM had higher toxic DPs compared to parent AZA, FEN and MAL. All DPs were
classified as category III (on a scale from I to V) of toxicity as acutely toxic. TOC analysis showed
that AZA has lowest (only 18%) and MAL has highest mineralization (56%). Considering the obtained
results, it could be concluded that ClO2 efficiently degrades AZA, DM, FEN and MAL and represents
good solution for a safer environment.
Keywords: organophosphorus pesticides, chlorine dioxide, TOC, toxicity
INTRODUCTION
According to US EPA estimates, organophosphorus pesticides (OPPs) represent about 40%
of the world market value [1]. They are the most popular and most used pesticides because of
their low cost, wide spectrum of application and multi-pest control capability. The widespread
application of the OPPs represents a great potential risk to environment and human life [2].
They could easily reach and contaminate the underground and surface water by leaching or
runoff [3].
It has been found that OPPs could be very toxic to human health [2]. They can cause minor
and major disruptive disorders, such as allergies, nausea, pancreatitis, spontaneous abortions
and death [2,4]. It was reported that OPPs are neurotoxic and high doses of them involve
inhibition of acetylcholinesterase [4]. Many researchers have suggested association between
post natal exposure of children with OPPs and caused health disorders. Attention deficit
hyperactivity disorder was noticed [5], also poorer short-term memory and attention [6],
slower motor speed [7], and developmental delay [8]. Because of this and many other health
disorders, significant number of OPPs has been restricted by Environmental Protection
Agency (EPA) and European Union (EU) [9].
72
Among the oxidants, chlorine dioxide (ClO2) has been increasingly employed as
disinfectant in water treatment systems due to its antibacterial and antiviral properties [10]. As
a powerful oxidant, ClO2 can remove many organic and inorganic pollutants [11,12]. Previous
studies reported oxidative degradation using ClO2 of some pesticides and pharmaceuticals
[3,13,14].
The aim of this study was to investigate effectiveness, mineralization and toxicity of four
OPPs (AZA, DM, FEN and MAL (Figure 1)) and their DPs, in water using ClO2 as
degradation agent. Toxicity screening was examined with the test organisms D. magna. Also,
the mineralization degree was obtained by total organic carbon (TOC) analysis.

Chemicals
In this research AZA, DM (Makhteshim Agan, 98%, obtained from the Institute for Plant
Protection, Belgrade), FEN and MAL (Sigma Aldrich, 97%) were used. Concentrations of
pesticides in experiments were 10 mg/L for AZA and DM and 20 mg/L for FEN and MAL.
Reason why we used 20 mg/L AZA and DM, not 10 mg/L like FEN and MAL, was the
quantification limit on high performance liquid chromatography (HPLC) for these two
pesticides which becomes important for trace monitoring in the final steps of degradation.
For toxicity test pesticides were diluted in medium, prepared according to standard procedure
OECD Guideline 202, 2004 [15, 16]. ClO2 was prepared by dissolving sodium chlorite
(TwinOxide®) and sodium bisulphate (TwinOxide®) in 1 L of deionized water and
standardized with 0.1000 mol/dm3 standard solution of sodium thiosulphate according to the
Standard Method SRPS EN 12671:2009 [17].
Figure 1 Structures of organophosphorus pesticides
Experimental
Optimization of pesticide degradation and preparation of samples for TOC analysis
The optimal conditions for degradation of OPPs with ClO2 in deionized water had to be
determined. Degradation using different concentrations of ClO2 (5 and 10 mg/L), degradation
73
time (0.5, 1, 2, 3, 6 and 24 h) and pH values (2, 3, 7, 9) was studied. The percentage of
degradation was determined by HPLC analysis with photodiode array detection (DAD) as
described previously by Pergal et al. [3]. Samples with the highest degree of degradation for
each pesticide were analyzed by TOC analysis. TOC analysis was done on Zellweger
LabTOC 2100 TOC Analyzer in accordance with method ISO 8245:2007 [3]. The optimal
conditions for degradation of each pesticide were also applied to preparation of samples for
toxicity tests.
Sample preparation for toxicity tests
All samples were diluted in medium prepared according to Klüttgen et al. [16]. One part of
initial pesticide solution was taken for toxicity test and other part was set to optimal
parameters and treated with optimal concentration of ClO2 for obtaining of DPs. Test
organisms D. magna were exposed to solution of pesticides and their DPs. A detailed
examination using toxicity tests can be found in our paper Pergal et al. [3].

Results of degradation efficiency
Optimization of OPPs degradation (AZA, DM, FEN and MAL) was performed in
deionized water under sunlight conditions described previously by Pergal et al. [3]. In Table 1
are presented summarized optimal conditions for OPPs degradation (ranged from 81 to 100%
in efficiency) and which were determined using HPLC-DAD analysis.
Table 1 Optimized conditions for degradation of pesticides with ClO2

Concentration Degree of
Concentration of pH Duration of
Sample name of sample degradation
ClO2 (mg/L) value degradation (h)
(mg/L) (%)
Azamethiphos 10 10 9 0.5 100
Dimethoate 10 10 7 24 97
Fenitrothion 20 10 2 24 81
Malathion 20 5 7 24 98
Toxicity test results

Toxicity tests of the pesticide solutions and their DPs were evaluated using test organisms
D. magna.
After a 48 h of test period number of live and dead neonates was determined, and LC50
(lethal concentration which causes 50% mortality in the daphnids) was calculated for each
pesticide and its DP. Results of LC50 for parent pesticides and DPs are shown in Table 2.
Solution of parent AZA has the highest mortality of neonates and FEN has the lowest
mortality as compared to other parent pesticides, but it was still high. For DPs of pesticides,
AZA has higher LC50 value, while DM has the lowest LC50 value compared to other
pesticides. DM has the highest and AZA has the lowest mortality. The pesticides degradation
products were less toxic than parent pesticides. When compared the toxicity results of
pesticide solutions with their DPs, it could be concluded that ClO2 degradation of AZA was
74
successful. Also, there should be noted that in case of other tested pesticides toxicity of DPs
was noticeable lower in comparison to starting pesticide solutions.
Table 2 LC50 values of pesticides and their degradation products (DPs) after 48 h of ClO2 treatment
Sample name LC50 ( %, v/v) 48h Sample name LC50 ( %, v/v) 48h
Azamethiphos 2.5 Fenitrothion 23.2
Azamethiphos DP 61.3 Fenitrothion DP 45.8
Dimethoate 12.2 Malathion 12.9
Dimethoate DP 35.4 Malathion DP 42.6
A toxicity unit (TU) was calculated for each sample using the LC50 results. On the scale
from I to V [18] all DPs can be categorized in class III as acutely toxic.
Results of mineralization analysis
Mineralization percent was determined by TOC analysis for each pesticide and its DP. The
results of mineralization are presented in Table 3. Results show that AZA and DM have low
level of mineralization and MAL has the highest mineralization level as compared to other
pesticides. But, low level of mineralization does not always mean that something is harmful
or toxic. When all results have been compared (HPLC analysis, D. magna test and TOC
analysis), we could see that AZA has a good degradation percent (100%) and its DP relatively
high LC50 (61%). It means that ClO2 degrades AZA very efficiently, with significantly less
toxic DPs but they are still of organic origin. FEN and MAL both have good degree of
degradation (81 and 98%, respectively) and mineralization (45 and 55%) and less toxic DPs.
In case of DM, even ClO2 degrades this OPP with degradation efficiency of 97%, ClO2
creates relatively toxic DPs and they are mostly of organic origin (mineralization of only
23%).
Table 3 Mineralization degree of degradation products (DPs) of pesticides

Sample name Degree of mineralization (%)
Azamethiphos DP 17.7
Dimethoate DP 22.5
Fenitrothion DP 45.2
Malathion DP 55.8
CONCLUSIONS
In this research, toxicity of AZA, DM, FEN and MAL pesticides and their DPs, after
degradation with ClO2 under optimal conditions for each pesticide, was studied. The toxicity
test was done on D. magna neonates. Degree of mineralization was also obtained by TOC
analysis for pesticides and DPs.
Results showed that AZA has a good degradation percent (100%) and relatively high LC50
(61%). It means that ClO2 degrades AZA very well, with significant less toxic DPs but they
are still of organic origin (18% of mineralization). FEN and MAL both have good degree of
75
degradation (81 and 98% respectively) and mineralization (45 and 56%) and less toxic DP. In
case of DM, ClO2 degrades this OPP with degradation degree of 97%, ClO2 creates relatively
toxic DPs and they are mostly of organic origin (mineralisation of only 23%).
The results of toxicity tests showed that all DPs of pesticides belong to class III as acutely
toxic. Further research should be directed towards obtaining less toxic products.
ACKNOWLEDGEMENT
This work was financially supported by the Ministry of Education, Science and Technological
Development of the Republic of Serbia, (Grant No. 451-03-68/2020-14/200026; 451-03-68/2020-
14/200168). The authors would like to thank TwinOxide-RS d.o.o. for providing components for the
preparation of ClO2 (TWINS preparation).
REFERENCES
[1] D. Atwood, C. Paisley-Jones, Pesticides industry sales and usage 2008-2012 market
estimates, Available on the following link: https://www.epa.gov/sites/production/files/
2017-01/documents/ pesticides-industry-sales-usage-2016_0.pdf
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[14] P. Wang, Y.L. He, C.H. Huang, Water. Res; 44 (2010) 5989–5998.
[15] OECD Guideline for testing of chemicals (2004) Daphnia sp. Acute Immobilisation Test.
OECD Guideline 202. Available on the following link: https://www.oecd-
ilibrary.org/docserver/9789264069947-en.pdf?expires=1588348144&id=id&accname=gue
st &checksum=7AEA23DC800CF46AA9078F82C28225B5
[16] B. Klüttgen, U. Dülmer, M. Engels, et al., Water. Res; 28 (1994) 743–746.
[17] SRPS EN 12671:2009, Chemicals used for treatment of water intended for human
consumption–Chlorine dioxide. Available on the following link: https://www.iss.rs/la/
standard /?natstandard_document_id=17165
[18] G. Persoone, B. Marsalek, I. Blinova, et al., Environ. Toxicol; 18 (2003) 395–402.
76
Pistia stratiotes HEAVY METAL UPTAKE POTENTIAL: A STUDY OF MULTIPLY
LEVEL CADMIUM POLLUTED WATER
Darko Anđelković1, Milica Branković2*, Bojan Zlatković3, Miljana Radović-Vučić2,

Gordana Kocić4
1
University of Niš, Faculty of Agriculture, Kosančićeva 4, 37000 Kruševac, SERBIA
2
University of Niš, Faculty of Sciences and Mathematics, Department of Chemistry,
3
University of Niš, Faculty of Sciences and Mathematics, Department of Biology,
4
University of Niš, Faculty of Medicine, Bulevar dr Zorana Đinđića 81, 18108 Niš, SERBIA
*
milica.chem@outlook.com
Abstract
Commonly found heavy metals in waters are As, Pb, Hg, Cd, Ni and Cr. The promising green
technique for heavy metal removal from the environment is phytoremediation. Regarding polluted
water, the best choice for phytoremediation are the free-floating macrophytes such as Pistia stratiotes.
The aim of this study was to evaluate the time trend and sorption capacity of P. stratiotes with respect
to increased cadmium concentration in aqueous cultivation medium. Sorption capacity of P. stratiotes
towards cadmium with respect to the growth period, increases linearly in the first 4 day of growth; the
linear correlation becomes weaker with the increasing pollution. Sorption capacity of P. stratiotes
towards cadmium with respect to the level of pollution, increases linearly, up to 11 th day, after which
the adverse effect of prolonged plant exposure to cadmium was observed.
Keywords: water pollution, phytoremediation, Pistia Stratiotes
INTRODUCTION
Plants, animals and ultimately humans are negatively affected by heavy metal pollution of
water supplies. Commonly found heavy metals in waters are As, Pb, Hg, Cd, Ni and Cr. One
of the major consequences of this kind of pollution is bioaccumulation of heavy metals. There
are many functional changes that can be observed in plants, after being exposed to heavy
metals, such as plant membrane damage due to the formation of reactive oxygen species and
radicals, disrupted metabolic activities or growth retardations. For example, the accumulation
of cadmium in P. stratiotes stimulates malondialdehyde production, indicating that cadmium
indirectly leads to production of superoxide radicals and increases lipid peroxidative products
and oxidative stress [1]. However, toxicity degree of non-essential metals such as Cd, Pb, Hg
depends on their concentration.
Techniques of phytoremediation arise as a cost-effective and ‘green’ solution for
remediation of soils and water supplies contaminated by heavy metals. Many aquatic plants
are currently under investigation to determine their phytoremediation potential, particularly
high-growth rate plants i.e. macrophytes. P. stratiotes or water lettuce is a free-floating
77
macrophyte from the family Araceae. The key properties of its potential phytoremediation
effectiveness are high growth rate, high coverage of water surface and easy harvestability.
Mechanisms of phytoremediation varies between plant types. Metal uptake mechanisms
may include accumulation, exclusion, translocation, osmoregulation and distribution. Among
these accumulation, translocation and concentration of heavy metals in the aerial parts of
hyper-accumulator plants are mostly suspected to occur [2]. Beside the plant type, an
important factor of remediation capacity for a specific metal is the length of exposure, the
metal itself, its concentration, environmental parameters (e.g. temperature, salinity and pH)
and synergistic or antagonistic interactions with other metals in the environment [2].
P. stratiotes has been suggested for efficient removal of Cd and Pb from contaminated
water since it has good rhizofiltration potential accompanied by a high tolerance to heavy
metal stress, especially with respect to cadmium [3]. The aim of this study was to evaluate the
sorption capacity of P. stratiotes with respect to increased cadmium concentration in aqueous
cultivation medium.

Reagents: the source of cadmium was the 72.958 µg mL-1 solution of cadmium-chloride
[CdCl2]. Nutrients for plant growth were not used.
Biosorbent: The samples of aquatic macrophyte Pistia stratiotes were handpicked from the
natural freshwater habitat in Ostrovica, near Niš (Serbia), in the mid–June 2017.
Experimental setup
Collected plant samples were washed with tap water to eliminate the remains of pond
sediments and particulate matter, placed in five different plastic tanks (labeled from I to V)
and filled up to 35 L with tap water (Figure 1).
Figure 1 Construction of P. stratiotes growth medium
Each tank contained 15 specimens of Pistia stratiotes and different amount of Cd2+ ion (as
CdCl2), as given in Table 1. Plants were grown during 15 days in contaminated media. One
plant per day was removed from each tank and analyzed.
78
Table 1 Concentration of CdCl2 and Cd2+ ion and amount of plant material in each tank
Tank No. I II III IV V
2+
Cd ion concentration, ppm 1 5 10 15 20
Cd2+ ion total amount in tank, mg 35 175 350 525 700
Total mass of plant material at start
490 480 528 426 522
of experiment (fresh weight), g
Total mass of plant material at the
402 355 388 292 349
end of experiment (fresh weight), g
Sample preparation
After removal from tanks, samples of Pistia stratiotes were washed out of excessive
substrate solution with fresh water and left to dry indoor at ambient temperature until
complete dryness. Afterwards, in order to remove possible residual humidity, plants were
additionally dried in a laboratory oven, at 100 °C for 30 minutes, prior to weighing. Leaves
and root of each plant specimen, were separated, weighted, cut in small pieces and pulverized.
A weight of each specimen sample was then digested with 15 mL of a mixture (v/v 3:1) of
concentrated 63% nitric acid and 30% hydrogen peroxide and solution was evaporated until
dryness. The solid residue was re-dissolved in 13 mL of 0.1 mol/dm3 nitric acid, filtered
through filter paper, then through microfilter (0.45 µm), after which the mineralized plant
material was ready for instrumental analysis.
Instrumental analysis
In order to determine the metal content in plant material, obtained extracts were analyzed
by atomic absorption spectroscopy (AAS) using VARIAN Aanalyst 300 with acetylene/air
flame.

Effect of growth period in polluted water
Mass fraction of cadmium (mg kg-1) in whole plant unit was calculated by summing up
masses determined in roots and shoots, divided by mass of plant weighted prior to the
separation of roots and shoots (dry weight).
Within tank No. I, cadmium amount in plant increases up from 66.47 to 307.25 mg kg-1 up
to 4th day of growth (R2=0.9989, linear fit). From 5th to 15th day it becomes practically
uniform with average value of 303.90 mg kg-1 (RSD=25%). Similar was observed for tank
No. III (Table 2). Linear increase in Cd amount up to 4th day (R2=0.8876), after which it
reaches 1944 mg kg-1 (RSD=35%). Within tank No. II increase in cadmium amount in plant is
observed practically till 11th day of growth (R2=0.8059, linear fit). 4th day linear correlation
between Cd within-plant amount and growth period is weaker in tanks No. 4 and 5
(R2=0.7552 and 0.7870, respectively). In this highly polluted water mediums, Cd amount
through the period of 8 days (5th to 12th) reaches 3382 mg kg-1 in plants from tank IV
(RSD=11%) and 3752 mg kg-1 in plants from tank V (RSD=25%). There is no correlation
with measured amounts from 13th to 15th day of growth.
79
Table 2 Cadmium amount in plant in mg kg-1 (dry weight) after exposure to cadmium polluted water
Tank No.
Days I II III IV V
-1
Amount mg kg dry weight
1 66.47 295.65 485.20 791.43 1550.72
2 139.36 592.57 1633.18 2592.75 2966.52
3 225.84 556.52 1843.56 3805.47 2689.64
4 307.25 698.89 2271.33 3374.47 3627.80
5 255.54 844.99 1475.13 2653.41 3218.94
6 288.62 779.36 1632.30 3835.65 2380.39
7 272.05 678.52 2479.26 3378.60 4200.69
8 282.18 898.74 3174.27 3685.47 3979.59
9 421.28 884.87 2447.61 3205.55 3618.25
10 280.10 897.68 1534.69 3273.23 5563.82
11 459.43 1138.03 2141.86 3302.57 4072.68
12 254.82 768.19 1158.27 3721.03 2983.39
13 236.68 355.09 797.40 661.14 678.83
14 360.15 995.28 2313.79 2828.99 1660.28
15 232.06 503.40 2230.63 2417.45 1852.88
Effect of increased cadmium pollution

The degree of linear correlation between the calculated fraction and cadmium
concentration in aqueous solution is given in Table 3 for each day of the experiment and
visualized in Figure 2 in five-days intervals. Strong correlation exists almost after each day of
experiment, up to 11th day. Weaker correlation i.e. lesser mass fraction of cadmium at last
days of experiment, especially after 12th day was probably due to the adverse effect of
prolonged exposure to cadmium, since the destruction of plants was observed, mainly
evidenced in root biomass reduction, as it was also elsewhere noticed [4]. Weight
measurements showed that total mass of plant material measured from the beginning to the
end of experiment (Table 1) was reduced for about 18.00, 26.00, 26.50, 31.00 and 33 % in
tanks I, II, III, IV and V, respectively.
Table 3 Coefficients of correlation between cadmium concentration in aqueous solution and in plant
material (mg kg-1 dry weight) after each day during experiment
Day 1st 2nd 3rd 4th 5th 6th 7th
Correlation coefficient 0.918 0.979 0.756 0.951 0.987 0.666 0.974
Day 8th 9th 10th 11th 12th 13th 14th 15th
Correlation coefficient 0.897 0.956 0.933 0.996 0.794 0.609 0.482 0.639
At the end the percentage of cadmium removal from experimental solutions by the total
mass of plant can be pointed out. In the hypothetic case of a 100 % cadmium removal, the
mass fraction of cadmium based on total plant mass from tank No. I would be 71.42 mg kg-1
of fresh weight. Experimentally determined fraction was 5.085 mg kg-1 of fresh weight; thus,
the percentage of cadmium adoption/removal is 7.12%. The percentage for tanks No. II, III,
IV and V was 3.75, 5.08, 5.25, 4.25%, respectively. However, it should be kept in mind that
80
the removal percentage represent an uptake potential of 15 plant units, where each of them
has been in contact with the polluted water for only 24 hours.
Figure 2 Cd concentration in plants vs. concentration in tanks, for different exposure periods
CONCLUSION
Sorption capacity of P. Stratiotes towards cadmium with respect to the growth period,
increases linearly in 1, 10, 15 and 20 ppm cadmium polluted medium, but only in the first 4
day of growth. Furthermore, with increasing pollution linear correlation becomes weaker. The
exception is water medium with 5 ppm of cadmium, where sorption capacity linearly
increases up to 11th day.
Sorption capacity of P. Stratiotes towards cadmium with respect to the level of pollution,
was reflected through strong correlation almost after each day of experiment, up to 11 th day.
Weaker correlation, especially after 12th day, was probably due to the adverse effect of
prolonged exposure to cadmium, since the destruction of plants was observed, mainly
evidenced in root biomass reduction.
ACKNOWLEDGEMENT
the Republic of Serbia for financial support (TR 31060). This investigation was done under Agreement
No. 451-03-68/2020-14/200124 between MPNTR and Faculty of Science and Mathematics in Niš,
University of Niš.
REFERENCES
[1] Y. Li, S. Zhang, W. Jiang, et al., Environ. Sci. Pollut. Res; 20 (2013) 1117–1123.
[2] E. Üçüncü, A. Devrim Özkan, T. Tarkan Ölmez, et al., Heavy Metal Remediation, Nova
Science Publishers, Inc., New York (2014), p.179, ISBN: 978-1-63321-568-9.
[3] T. Veselý, P. Tlustoš, J. Száková, Int. J. Phytorem; 13 (2011) 859–872.
[4] S. Das, S. Goswami, A. Das Talukdar, Bull. Environ. Contam. Toxicol; 92 (2014) 169–
174.
81
AGRICULTURAL SOIL POLLUTION BY HEAVY METALS IN THE
MUNICIPALITY OF PLJEVLJA, MONTENEGRO
Miljan Bigović1, Slađana Krivokapić1, Dijana Đurović2*, Nevena Cupara1,2,

Irena Nikolić3
1
University of Montenegro, Faculty of Natural Science, Džordža Vašingtona bb, 81000
Podgorica, MONTENEGRO
2
Institute of Public Health of Montenegro, Džona Džeksona bb, 81000 Podgorica,
MONTENEGRO
3
University of Montenegro, Faculty of Metallurgy and Technology, Džordža Vašingtona bb,
81000 Podgorica, MONTENEGRO
*
dijana.djurovic@ijzcg.me
Abstract
This paper aimed to investigate the agricultural soil pollution by heavy metals as a result of
anthropological activities in the municipality of Pljevlja, north part of Montenegro. The soil samples
contaminated by heavy metals (Zn, Cu, Cd, Cr, Pb, Hg and As) were taken from the settlement near
the coal fired station Pljevlja and from open pit mine of lead and zinc "Šuplja Stijena". The soil
pollution was evaluated using the ecological risk (RI) index and index of geo-accumulation (Igeo). The
results have indicated the extremely polluted soils by Pb, Zn and Cr, unpolluted or unpolluted to
moderately polluted soil by Cd, strongly to extremely polluted soil by As and unpolluted soil by Hg.
The low ecological risk values were mainly obtained but three sampling sites indicated moderate,
considerable and high ecological risk.
Keywords: Heavy metals, agricultural soil, ecological risk index, index of geo-accumulation
INTRODUCTION
The problem of heavy metal contamination in the environment is widespread. Significant
amount of pollutants from different sources can contaminate soil every year. Soil acts as
natural buffer by controlling the transport of chemical elements and substances to the
environment as well as a sink for the chemical pollutants. Toxic elements such as heavy
metals contaminate agricultural soil that attracts the interest of people, because metals can be
taken by plants and may enter the food chain, and therefore, humans can also be exposed to
this kind of contamination [1]. Different kinds of industries can be generators of heavy metals
and contribute their reaching in the soil through industrial effluent. The quality and
concentration of the heavy metals varies from industry to industry and has a direct concern
with nature of the product. Deficient environmental management have led to a large-scale
pollution in the environment especially in developing countries, due to rapid industrialization,
excessive application of metals and synthetic chemicals in the terrestrial environment.
Although some of heavy metals are essential for a different metabolic process, the high intake
of these elements lead to their accumulation in a human body and potential development of
82
different diseases. The body burden of Cd and Pb have been well documented as toxic to the
central nervous and renal systems while chronic exposure to Cu health problems such as:
nausea, head-aches and diarrhea [2].
Environment pollution by heavy metals is a result of different anthropological activities.
There are several sources of heavy metals pollution in the environment: 1) air sources from
mining, smelting and refining of fossil fuels, production and use of metallic commercial
products and vehicular exhaust, 2) water from domestic sewage, thermal power plants and
atmospheric fallout, sewage and industrial effluents, and 3) soil - like agricultural and animal
wastes, municipal and industrial sewage, coal ashes, fertilizers, discarded manufacture goods
and atmospheric fallout [3]. The two main industrial pollution sources in Montenegro are
located in the municipality of Pljevlja on the north part of Montenegro. The first one is a coal
fired power station Pljevlja and second one is an open pit mine of lead and zinc "Šuplja
Stijena". Since, both activity present a serious risk for a global community, this paper aimed
to investigate the pollution of agricultural soils in the surrounding settlement of coal fired
power station and mine. The sampling of agricultural soil at eleven locations was carried out
and heavy metals concentrations (Zn, Cu, Cd, Cr, Pb, Hg and As) were determined.

Materials and sampling
Soil samples were taken from maximum 20 cm depth, from agricultural fields near
households in November 2019. The households are located near two sources of pollution,
Thermal power plant (TE Pljevlja) and Zinc and lead mine (Gradir, Montenegro). Samples 1,
2, 3, 4, 6, 7 and 11 are located near Thermal power plant. Sample 5 is located between
Thermal power plant and surface Coal mine. Samples 8, 9 and 10 are located near Zinc and
lead mine. For metal analysis, wet soil was dried at 105°C and sieved through mesh 0.25 µm.
3 g of dried and sieved samples were digested with 25 ml of aqua regia, using reflux and
heating source (EPA method 3050B). Samples were filtrated through Whatman No. 41 and
flasks were washed with 5 ml of concentrated HCl and adjusted to final volume of 50 ml with
distilled water. Concentrations of heavy metals were measured using inductively coupled
plasma technique (ICP-OES), manufactured by Spectro Arcos with hydride technique for As
determination.
Assessment of Soil Contamination
Ecological risk (RI) index and index of geo-accumulation (Igeo) defined by Müller [4] were
used in order to define and determine soil contamination by arsenic by comparing current
concentrations with pre-industrial levels. Based on the value of RI there are low, moderate,
considerable and high risk contaminations while based on the value of Igeo there are seven
classes of pollution (Table 1) [2].
83
Table 1 Terminologies for the assessment of agricultural soil contamination by arsenic and
terminologies for contamination classes on pollution indices
Ci
Ecological risk index (RI) : RI = Σ Er ; Er  T i  C f ; Cf 
C ri
Low risk RI < 150
Moderate risk 150  RI < 300
Considerable risk 300  RI < 600
High contamination RI  600
 Ci 
Index of geo-accumulation (Igeo) I  log 2  
1.5  C ri 
geo
CLAS 0, unpolluted Igeo  0
CLASS 1, from unpolluted to moderately polluted 0 < Igeo  1
CLASS 2, moderately polluted 1 < Igeo  2
CLASS 3, from moderately to strongly polluted 2 < Igeo  3
CLASS 4, strongly polluted 3 < Igeo  4
CLASS 5, from strongly to extremely polluted 4 < Igeo  5
CLASS 6, extremely polluted Igeo > 5

Ci is the total metal content in soil, Cr is background level (reference threshold for sensitive soil [5])
and Ti is the toxic-response factor for a given substance by Håkanson [6] (Table 2), Cf is
contamination factor and Er is ecological risk factor.
Table 2 Toxic-response factor (Ti) by Håkanson Elements [6]

Elements Cu Cd Zn Cr Pb Hg As
Toxic-response factor 5 30 1 2 5 10 40

Total contents and descriptive statistics for the heavy metals measured in this study are
given in Table 3. The order of the total element content was Zn>Pb>Cu>Cr>As>Cd.>Hg. The
results have shown that the mean content of Pb exceeds the maximum allowed concentration
of metals prescribed by National regulation [7] while the values of mean contents of other
metals are below the prescribed limits.
84
Table 3 Total contents and descriptive statistics of elements in agricultural soil samples
Element (mg kg-1)
Site
Pb Cd Cu Zn Cr Hg As
1 11.73 0.92 15.78 43.3 6.14 0.06 4.06
2 21.07 0.99 52.35 96.54 16.35 0.425 10.52
3 20.00 1.26 59.43 129.85 13.8 0.08 8.11
4 17.43 0.24 22.32 30.73 13.76 0.11 4.33
5 35.76 1.78 49.67 92.55 17.47 0.12 7.12
6 23.97 0.63 52.92 117.98 18.86 0.17 9.54
7 37.65 3.08 56.79 140.27 28.24 0.93 12.7
8 37.82 0.52 37.82 81.57 15.7 0.07 8.24
9 837.4 2.8 18.85 1150.3 18.95 0.62 57.71
10 27.37 0.51 51.76 55.28 13.28 0.18 9.42
11 39.97 0.75 52.35 80.87 28.53 0.18 2.00
MAC* 50 2 100 300 50 1.5 20
Min 11.73 0.24 15.78 30.73 6.14 0.06 4.06
Max 837.4 3.08 59.43 1150.3 28.24 0.93 57.71
Mean 100.9 1.23 42.73 183.6 17.37 0.268 12.16
SD** 244.4 0.945 16.2 322.5 6.48 0.279 15.4

MAC* maximum allowed concentration.
SD** Standard deviation.
Geo-accumulation index (Igeo) and ecological Risk Index (RI)

According to geo-accumulation index (Igeo) (Figure 1) values for Pb, Zn, Cu and Cr the
agricultural soil in the municipality of Pljevlja belong to Class 6 i.e. extremely polluted soils.
The values for Igeo for Cd indicated the unpolluted (Class 0) or unpolluted to moderately
polluted soil (Class 1). The soil belongs to the extremely polluted (Class 6) and the Class 5 i.e.
strongly to extremely polluted soil with respect to the value of Igeo for As while there is no
contamination by Hg since the values of Igeo indicated unpolluted soil.
85
Pb Cd
15 1.5 CLASS 2
14
13 1
12 CLASS 1
11 0.5
10 CLASS 6 0
9
8 1 2 3 4 5 6 7 8 9 10 11
Igeo
-0.5
7
Igeo
6 -1
5
4 -1.5
3 CLASS 0
2 -2
1
0 -2.5
1 2 3 4 5 6 7 8 9 10 11
-3
Location Location
Cu Zn
11 11
CLASS 6 CLASS 6
10 10
9 9
8 8
7 7
6 6
Igeo
Igeo
5 5
4 4
3 3
2 2
1 1
0 0
1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11
Location Location
Cr As
10 CLASS 6 8
9 7
8 CLASS 6
6
7
6 5
CLASS 5
Igeo
Igeo
5 4
4 3
3
2
2
1 1
0 0
1 2 3 4 5 6 7 8 9 10 11 1 2 3 4 5 6 7 8 9 10 11
Location Location
Hg
Location
1 2 3 4 5 6 7 8 9 10 11
0
-1
-2
-3
-4
Igeo
-5
-6
-7
-8 CLASS 0
-9
Figure 1 Geo-accumulation index (Igeo) values of heavy metals in agricultural soil samples in the
municipality of Pljevlja (Montenegro)
86
The results obtained for ecological risk assessment (Figure 2) showed that RI values were
mainly lower than 150 indicating the low ecological risk. However, the RI values at location 2,
7 and 9 indicated moderate, considerable and high ecological risk, respectively. Zinc, lead,
copper and arsenic are the main contributors to RI values.
750
700
High risk
650
600
550
500
450 Considerable risk
400
RI
350
300
250 Moderate risk
200
150
100 Low risk
50
0
1 2 3 4 5 6 7 8 9 10 11
Location
Figure 2 Ecological risk index (RI) values of heavy metals in agricultural soil samples in the
municipality of Pljevlja (Montenegro)
CONCLUSION
The results of investigation have shown that the values of Igeo indicated the agricultural soil
is extremely polluted by Pb, Zn, Cu and Cr, extremely polluted or strongly to extremely
polluted by As, unpolluted or unpolluted to moderately polluted by Cd while pollution by Hg
was not registered. With respect to the values of RI agricultural soil in the municipality of
Pljevlja in Montenegro are characterized mainly by low ecological risk. However, the results
obtained at three locations indicated moderate, considerable and high ecological risk.
ACKNOWLEDGEMENT
This work was supported by the Montenegrin Ministry of Science under grant no. 01-779/2.
REFERENCES
[1] S.S. Huang, Q.L. Liao, M.Hua, et al., Chemosphere; 67 (2007) 2148–2155.
[2] O. Barbier, G. Jacquillet, M. Tauc, et al., Nephron-Physiol; 99 (2005) 105–110.
[3] A.K. Chopra, Chakresh Pathak, G. Prasad, J. Nat. Appl. Sci; 1(2009) 99–108.
[4] G. Muller. Geol. J; 2 (1969) 108–118.
[5] Directive proposal establishing a framework for the protection of soil - COM (2006) 232.
[6] L. Hakanson, Water Res; 14 (1980) 975–1001.
[7] Rulebook on permitted quantities of dangerous and harmful substances in soil and
methods for their determination (Official gazette of Montenegro, no.18/97).
87
THE INFLUENCE OF THE PROCESS OF WASHING ORE OF BORON MINERALS
FROM THE "POBRDJE" DEPOSIT ON THE ENVIRONMENT
Miljan Vilimonović1*, Vladan Cvetković2, Milinko Košanin2,

Goran Grkajac2, Vladan Bogojević2
1
University of Belgrade, Faculty of Technology and metallurgy, Karnegijeva 4,
2
JP PEU Resavica, Ibar coal mines, Steve Kačara 4, 36344 Baljevac, SERBIA
*
schultze_78@yahoo.com
Abstract
Pine ore deposits in Pobrdje and Piskanja, Baljevac - Serbia, are unique in this part of Europe so far.
Trial excavation of trench ore by underground mineral extraction methods was organized at the
„Pobrdje“ ore deposit. After excavation, the trench ore is transported by truck to the disposal site at
the location of the Piskanja site. The hand-picked ore is taken to the customers and the tailings go to
the landfill. There are small classes of ore in the tailings that could not be separated by hand, so the
use of trench ore is about 20 to 30%, depending on geological conditions. The low utilization in the
manual extraction of ore deposit "Pobrdje" indicates that for the future exploitation of ore from the
"Piskanja" deposit, technical and technological solutions must be provided that will improve the
utilization. Some of the possible solutions are: magnetic separation, optical separation, electrostatic
separation, decryption, etc. To determine the optimal solution researchs and industrial tests must be
performed. Each of these methods require the removal of impurities from the trench ore, that is, the
trench ore washing, which will produce a certain amount of waste water. This paper will present the
results of the analysis of wastewater used in the process of washing the primary trench ore in order to
define the environmental impact.
Keywords: boron ore, trench ore washing, wastewater, environmental impact
INTRODUCTION
Since boric acid is widely used in many fields of industry, pharmacy, agriculture, etc.,
there is a real need for its production. One of the production possibilities is a technological
process that uses a mixture of colemanite and haulite minerals, enriched with B2O3 at least
42%, for the feedstock. Boron oxides are present everywhere in nature, but boron minerals are
very rare. Such deposit in which the boron minerals haulite and colemanite are represented is
in the Jarandol basin.
The Jarandol Tertiary Basin is located in the valley of the Ibar river, territorially belonging
to the Raska Municipality, about 14 km away. The basin is elongated in the W-NW-E-SE
direction. The Ibar river is divided into two parts: the eastern, the Piskanjski which contains
the deposit of the Piskanja boric minerals and the western, wich contains the Jarandol coal
horizons, the mineral deposit of the "Pobrdje" in the Pobrdje stream and the boron
mineralization in Raspopovic. The deposit of the boric minerals "Pobrdje" is located west of
88
Baljevac, about 1.6 km away. Traffic communications with „Pobrdje“ deposit are very
convenient [1].
An ore body consisting of cholemanite and haulite is genetically related to younger
volcanism, that is, volcanic gas fumaroles and hydrothermal solutions containing significant
concentrations of boron. The accompanying rocks of the ore layers are: volcanogenic breccias
and conglomerates of marls, tuff-sandstones, sandstones and clays, which often form larger
and smaller layers in the ore layer, which negatively affects the depletion of the trench ore [2].
Balance ore reserves as of 31.12.2019. amounted to 124.701 t. Taking into account mining
and geological conditions, the excavation of pine ore in the "Pobrdje" deposit is done by
underground exploitation, and the trench ore in the pit "Pobrdje" is obtained by the process of
drilling and mining operations. The mined ore from the pit is transported to the surface by a
conveyor system, ie by chain conveyors and belt conveyors, from where it is transported by
truck to a location in the area of Piskanja. The hand-picked ore is taken to the customers and
tailings go to the landfill. Due to the presence of a lot of fine particles of both ore and tailings
and the presence of moisture and bitumen, the very fractions of ore and tailings occur in the
process of exploitation and transportation. They adhere to both the tailings surface and the ore
surface, so it is difficult to visually distinguish the ore from the tailings. Ore itself is often
very similar to tailings, especially sandstones that have a greyish color. The exception is
haulite, which has a snow-white color and is no problem to spot and separate from the
tailings. During the manual extraction of ore, the effects are very small due to the difficult
distinction between ore and tailings. Better results are achieved when washing the ore, ie, by
washing with water, it is easier to distinguish between ore pieces and tailings pieces.
Although much better results have been shown in practice when the ore was previously
washed, manual ore selection due to low utilization is not an option and is unlikely to apply in
the future. The methods used in the world to obtain boron ore concentrates, that is, colemanite
concentrates, which in commercial form should contain from 35 to 43% of useful component
B2O3, are magnetic separation as a very cheap form of separation, decryption, electrostatic
separation, for optical separation or separation on optical sorters. For each of these types of
separation, it is necessary to separate the ore and tailings grains from tiny micro particles in
order to distinguish them. For example, in the case of magnetic separation, this is necessary
because if the tailings were not removed from the ore, which, due to the content of the iron,
were magnetic, the magnetic separator would attract them altogether. No matter which
method of concentrate production is adopted, the need to wash ore is inevitable.
The purpose of this paper is to determine whether water can be discharged into
watercourses after the process of washing trench ore, or whether a treatment facility or a
wastewater treatment plant is required. To determine the correctness of such water, we took
one quantity of trench ore and washed it with a certain amount of water.

The trench ore from the pit, previously ground on a crusher with a hammer to a particle
size of -16.0 + 0.00 mm, was used for the experiment. Thereafter, a measured amount of 1 kg
of ore of such a granulometric composition was inserted into a plastic balloon. Then the water
89
was poured into the balloon, shaken and cast. On this occasion, 9 liters of water was
consumed to wash 1 kg of trench ore. The used washing water was taken from the city water
supply system, for which the competent institution daily analyzes the water quality. Such
water was poured into special balloons and collected. The process itself was repeated several
times until a water of barely noticeable slight turbidity was obtained. The water was collected
in two balloons, which were sent for testing to the Institute MOL d.o.o. During the test, the
water was filtered and on this occasion sludge was obtained as a solid residue and a clearer
liquid residue.

According to the analyzes done earlier, the content of B2O3 in water after the first ore
washing is 0.0856 mg/l, which indicates that boron ore can be washed because it is insoluble
in water, more precisely it is poorly soluble [3]. During the ore washing, the water removes
the dirt, dust and micro particles from the ore and tailings that are generated during the
exploitation and transportation of the ore.
A balloon containing a sample of shredded trench ore was used in the experiment, and the
appearance of such a sample before washing is shown in Figure 1a. As we emphasized, the
water from the city water supply system was poured into a balloon containing trench ore. The
balloon was shaken several times to make contact between water and all fractions of trench
ore more intense. Afterwards, such water is drained and a new amount of water is poured into
the balloon. When the first quantity was drained, the water was extremely turbid and parts of
the wooden pit support that were floating on the water were present. The appearance of such
turbid water is shown in Figure 1b.
a) b)
Figure 1 Initial phase of trench ore washing a) the appearance of shredded trench ore before
washing; b) the appearance of turbid water during washing when the first quantity is outflow
90
This process was repeated several times until the watered water became almost clear, that
is, until it had a slight turbidity. The appearance of such slightly turbid water is shown in
Figure 2a, and the appearance of the sample of shredded trench after washing in Figure 2b.
Visual differences between tailings and ore were noticeable, confirming the conclusion that
trench washing would be of great benefit in the preparation phase for the selected separation
method.
a) b)
Figure 2 Final stage of trench ore washing a) the appearance of slightly turbid water after
removal at the end of washing; b) the appearance of shredded trench ore after washing
In order for water to be allowed to enter the watercourses after washing, it must meet a
certain ecological status according to the classification given in the ordinance, which
prescribes ecological and chemical status parameters for surface waters. Decree on limit
values of pollutants in surface and groundwater and sediment and deadlines for their
attainment (Official Gazette RS No. 50/2012) defines limit values for parameters for a certain
ecological status, ie class of surface waters [4].
After submitting the wastewater sample for testing, the MOL Institute d.o.o. did the
analysis and produced the test report. The parameter concentrations were determined from the
clear portion of sample I.b. 803, and the results of these analyzes are shown in Table 1.
Methods which used to find parameter values are also shown in Table 1.
Comparing the limit values of the parameters for good ecological status, that is, for the II
class of surface waters with the obtained results, it was found that the pH and ammonium ion
values were increased [5]. Namely, the pH limit for the mentioned surface water class is 6.5-
8.5, while the found value is 8.86. Also, the limit value for ammonium ions for the mentioned
surface water class is 0.10 mg N/l, while the value of 0.28 mg N/l was found. The values
found for other parameters were within the allowed values.
91
Table 1 Test results for the clear portion of the sample I.b. 803, Mol Institute d.o.o. [5]
Measurement Found
Parameter Method
unit value
pH SRPS H.Z1.111:1987 8.86
Specific conductivity ASTM D 1125A:1999 µS/cm 335
2)
Total residue after evaporation Manual met. 2540 B:98 mg/l 318.0
2)
Suspended matter Manual met. 2540 D:98 mg/l <15.0
Sedimentary matter VM 068 ml/l <0,1
Chemical oxygen demand
EPA M 410.2:1978 mg O2/l 9.77
(COD)
Biochemical oxygen demand
SRPS EN 1899-1:2009 mg O2/l <3.0
(BOD)
Consumption of potassium
SRPS EN ISO 8467:2007 mg/l 5.69
permanganate
Chlorides VM 057-2 mg/l 4.51
Sulfates VM 057-2 mg/l 38.12
Phosphates VM 057-2 mg P/l <0.1
Nitrates VM 057-2 mg N/l 0,98
Nitrites VM 057-2 mg N/l <0.1
Ammonium ion SRPS H.Z1.184:1974 mg N/l 0.28
Total inorganic nitrogen calculated mg N/l 1.26
Oils and fats EPA M 1664 A:1999 mg/l <1.4
Phenols SRPS ISO 6439 B:1997 mg/l <0.002
Mineral oils C10-C40 VM 056-2 mg/l <0.05
Detergents SRPS EN 903:2009 mg/l <0.1
Iron VM 090 mg/l <0.01
Chrome VM 090 mg/l <0.007
Zinc VM 090 mg/l <0.006
Copper VM 090 mg/l <0.006
Nickel VM 090 mg/l <0.008
Lead VM 090 mg/l <0.005
Cadmium VM 090 mg/l <0.003
Total phosphorus SRPS EN ISO 6878:2008 mg/l 0.017
TOC VM 093 mg/l 1.51
Sulphides EPA M 376.2 mg/l <0.1
Cyanides SRPS H.Z1.139 mg/l <0.01
Mercury EPA M 245.1 mg/l <0.0007
Arsenic VM 090 mg/l 0.008
Since ammonium ion occurs in the presence of organic matter, one of the assumptions for
increased ammonium ion concentration may be the appearance of residual parts of the
wooden pit support and bitumen. For increased pH, a more detailed analysis would have to be
done to explain why such water is alkaline to this extent. Such information would assist in the
treatment of wastewater.
92
CONCLUSION
In order to improve the technical and technological procedure for the separation of pine
ore, the procedure for trench ore washing is imposed as a first step. As a product of the
washing of pine ore, a certain amount of waste water is generated which has to be tested and
determined whether it can freely enter the watercourses. This experiment was performed to
serve as an initial assumption of water quality for further exploration of the possibility of
treating such wastewater. The test results show that the found pH values and the found values
of ammonium ion concentration increased in relation to the limit values prescribed by the
Decree on limit values of pollutants in surface and groundwater and sediment and deadlines
for their attainment (Official Gazette RS No. 50/2012), indicating that such filtered water
does not qualify for discharge as such into watercourses. It is necessary to create a plant for
the preparation of mineral raw materials where the water would be brought to a condition that
would meet the legal requirements during the technological purification process, so that it
could flow into the watercourses. This should be a mandatory part of all future projects that
would address any type of separation in raising the quality of boron concentrate.
REFERENCES
[1] D. Zečević, M. Ivković, M. Popović, Some lessons learned from the mining of boron ore
in the deposit of Pobrđe, Committee for Underground Mining - Mining papers, 2 (2009)
29–34.
[2] D. Đukanović, “MMP for the opening and exploitation of ore minerals in the reservoir of
Pobrdje, Ibar coal mines-Baljevac”, Design and Development Bureau-Belgrade (2008).
[3] S. Milosević, Environmental impact of pine minerals during the exploitation and
preparation of pine ore from the “Pobrdje” Mine, Institute for technology of nuclear and
other mineral raw materials, Belgrade (1997).
[4] Decree on limit values of pollutants in surface and groundwater and sediment and
deadlines for their attainment (Official Gazette RS No. 50/2012).
[5] Test Report I 926/19–1, Institute of MOL Ltd., Stara Pazova (2019).
93
REMOVAL OF PHOSPHORUS AND NITROGEN IN MODIFIED FLOATING
TREATMENT WETLAND
Nevena Čule1*, Aleksandar Lučić1, Zoran Miletić1, Milorad Veselinović1,

Suzana Mitrović1
1
Institute of forestry, Kneza Viseslava 3, 11000 Belgrade, SERBIA
*
nevena.cule@yahoo.com
Abstract
There is a recognised need for the protection of water integrity by using environmentally friendly,
efficient and cost-effective solutions. Floating treatment wetlands (FTW) have emerged as a powerful
and innovative technology for the removal of a vast spectrum of pollutants from contaminated water.
This research set out to determine the efficiency of P and N removal in modified FTW constructed on
the bank of the polluted urban river. The results showed that after the whole treatment P
concentrations in polished water were reduced by 87%. This green technology was also very efficient
in removing NH4-N, NO2-N, NO3-N and total N by decreasing its concentrations 96%, 97%, more than
94% and more than 86%, respectively. Further studies should focus on the research on the required
number and arrangement of cells with aerobic and anaerobic conditions in FTW.
Keywords: floating treatment wetlands, water pollution, phytoremediation, nutrient removal
INTRODUCTION
Finding an efficient, environmentally friendly and economically justified solution for the
treatment of degraded urban rivers and lakes has received increased attention across many
disciplines in recent years. Floating treatment wetlands (FTW) are one of the innovative
phytoremediation techniques [1] that are often described as more cost-effective and efficient
compared to widely used constructed wetlands [2,3]. Floating treatment wetlands consist of a
series of cells with floating islands. The platform, which carries the substrate for the growth
of terrestrial and aquatic plants forms the floating island. To start the revitalization of the
polluted urban river, pilot-scale FTW was constructed on its bank. Because of numerous
sources of anthropogenic pollution this river is mainly classified as a river with bad ecological
status (class V) based on its chemical, physiochemical and microbiological water parameters
[4]. Phosphorus (P) and nitrogen (N) are one of the most important elements in ecosystems.
However, the problem arises when the excess amounts of these macronutrients occur in water.
This will lead to a deplete of dissolved oxygen in the water and the appearance of
eutrophication [5]. This paper evaluates the efficiency of modified FTW in the removal of P
and N.

The FTW consisted of a pump for drawing water from the river, a closed collection tank,
four open rectangular cells with floating islands, and one open rectangular cell with algae [4]
94
(Figure 1). In each of 4 cells, there were 3 floating islands with seedlings planted in the
substrate (stone wool). The coverage of the cells with plants was 100%.
a) b)
Figure 1 The cells with plants a month after the planting (a) and the cell with algae (b)
The floating islands of the Cell 1 were planted with 25 seedlings of

Phragmites australis (Cav.) Trin. ex Steud each. The Cell 2 was planted with 25 seedlings of
Canna indica L. per floating island. The Cell 3 contained a mix of those 2 species, with 25
seedlings on each island. Each floating island of the Cell 4 was planted with 30 seedlings of
mix decorative macrophytes: Iris pseudacorus L., Iris sibirica 'Perry's Blue', Alisma plantago
- aquatica L., Lythrum salicaria L. and Menyanthes trifoliata L. The algae (Cladophora sp.)
were introduced to the Cell 5 directly from the river.
A 12-day treatment was conducted to assess efficiency of modified FTW for removal of P
and N from water. The treatment cycle began with the pumping of polluted water from the
river to the collection tank. Water was then simultaneously transported by gravitation to 4
open cells with floating islands. Polluted water stayed in Cells 1 - 4 for 6 days and then it was
moved to the Cell 5 for the same period. At the end of this phase, the treatment cycle was
completed. Samples of polluted water were collected at the beginning of the treatment cycle at
the outlet of the pump. Treated water was sampled in cells with plants after 6 days. Polished
water in the cell with algae was sampled at the end of the cycle (after 12 days). The composite
sample represented 1L of water collected from 5 spots within each cell.
Temperature, pH and dissolved oxygen (DO) in water samples were measured with HACH
HQ 40d Digital Multi 2-channel Meter with automatic temperature calibration (HACH, USA)
according to US EPA 170.1:74, SRPS EN ISO 10523:2016 and HACH 10360 LDO methods,
respectively. Total P was determined by SRPS ENISO 6878:2008 method. Concentration of
ammonia nitrogen (NH4-N), nitrites (NO2-N), nitrates (NO3-N), and total N were determined
according to SRPS EN ISO 14911:2009, SRPS EN 26777:2009, APHA 4500-NO3- B and
SRPS EN 12260:2008 methods, respectively.

The polluted water had the characteristics of a slightly alkaline medium (Table 1). There
was a decrease in pH in each cell with plants after the first six days of treatment. However,
the pH value increased again at the end of treatment (after 12 days). Extremely low DO values
were detected in Cells 1 - 4 due to 100% cell coverage with floating islands (Table 1). After
95
water polishing in Cell 5, the amount of DO increased and had higher values than DO
concentrations in the polluted water.
Table 1 Temperature, pH and dissolved oxygen in polluted and treated water

Parameter Tank Cell 1 Cell 2 Cell 3 Cell 4 Cell 5
o
t ( C) 14.50 12.80 12.10 12.40 12.10 14.00
pH 7.66 7.33 7.29 7.37 7.33 8.15
DO (mg/L) 6.98 0.40 0.63 1.33 1.43 18.77
Low concentrations of phosphorus (0.31 mg/L) were detected at the inlet of FTW. Content
of P increased within the cells with floating islands after 6 days of treatment. However, by the
end of treatment, the removal efficiency of total P in Cell 5 was 87% (Table 2).
Settling is the main physical process for the removal of P from polluted water [1,6]. During
this process, P binds to solid particles in water and sinks to the bottom of the FTW. The
removal of P is much more efficient in the FTW compared to other constructed aquatic
ecosystems [7]. The large free root surface of floating islands allows rapid filtration of solid
particles from the water which are then precipitated with P. White and Cousins [8] have
shown that the removal efficiency of P in the FTW can reach 81%. The results of this research
are in accordance with these claims if the efficiency of the entire FTW is considered.
However, the results also showed that there was no reduction of P concentrations in the Cells
1 - 4 and that there was higher content of P in the outlet of these cells than in the collection
tank. It was presumed that the anaerobic conditions in the cells with floating islands have led
to the release of sequestered and precipitated P back into the water body. It was also assumed
that at extremely low DO content in the water, sulfate was reduced, sulfides were created, and
thus prevent the binding of P to Fe and Al oxides [9]. Also, the cause of the additional P
resuspension in the FTW could be the turbulence caused by the introduction of new quantities
of water into the cells or the occurrence of gases (oxygen, methane and carbon dioxide) from
the bottom of the cells [5]. Algae have a high affinity for P removal from polluted water, and
the removal process is rapid [10]. The results have shown that algae accumulate large
amounts of P during the experimental period [4]. Since there was no removal of P in the Cells
1 - 4, it can be concluded that algae were responsible for the biological removal of P in the
modified FTW. Together with the settling and sorption processes in the aerobic environment,
algae were able to remove this element with high efficiency.
Confirmation of the high efficiency of the modified FTW in the removal of P can also be
supported by the following data. Based on the concentration of P as a parameter for the
assessment of the ecological status of waters [11] water at the inlet of the modified FTW was
classified as water with moderate ecological status (class III). After 12-day treatment, water at
the outlet of the modified FTW had characteristics of water with excellent ecological status
(class I).
96
Table 2 Efficiency of the removal of total phosphates, ammonia nitrogen, nitrite, nitrate and total
nitrogen (%)
Parameter Cell 1 Cell 2 Cell 3 Cell 4 FTW outlet
P -55 -294 -71 -58 87
NH4 - N 83 45 81 78 96
NO2 - N 15 -137 -26 -100 97
NO3 - N 79 56 63 67 >94
N 77 22 64 67 >86
The initial concentration of ammonia (NH4-N) in polluted water was 3.12 mg/L. After the
treatment cycle the concentration was reduced to 0.14 mg/L and thus a removal efficiency of
96% was achieved (Table 2). Reduction of NH4-N concentration was significant even after six
days of treatment in the cells with plants. The highest NH4-N removal efficiency in the Cells
1 - 4 was achieved in the Cell 1 where P. australis was planted (Table 2). The removal
efficiency of nitrite (NO2-N) and nitrate (NO3-N) was also high, considering the entire
treatment cycle, with NO2-N removed up to 97% and NO3-N by more than 94% (Table 2).
After six days of treatment, NO2-N concentrations decreased in the Cell 1 (15%) compared to
the inlet value (0.27 mg/L), while in other cells with plants concentration increased (Table 2).
The reduction of NO3-N content was significant in the cells with floating islands and ranged
from 56% to 79% (Table 2). The maximum removal efficiency was achieved in the Cell 1
with P. australis compared to other cells with plants. The concentration of total nitrogen (N)
in the inflow was 7.00 mg/L. As with nitrates, removal of N was significant after six days of
experiment in the Cells 1 - 4 (Table 2). The highest removal efficiency was achieved in the
Cell 1 with P. australis, and the lowest in the Cell 2 with C. indica. At the end of the
treatment and polishing of the water with algae, the removal efficiency of N was more than
86% (Table 2).
The removal of organic N in the modified FTW was accomplished primarily due to the
metabolism of nitrifying and denitrifying microorganisms [12]. The decomposition of these
pollutants in water begins with the process of ammonification. This process takes place in
both aerobic and anaerobic environments [1]. The rhizosphere of plants in the modified FTW
is a convenient place within which the organic N compounds can be decomposed to NH4-N
and CO2. An aerobic environment in which nitrification takes place is required for the further
decomposition process. Based on the obtained results about the efficiency of NH4-N removal
in the Cells 1 - 4 and the fact that cells had anaerobic conditions, it can be concluded that the
amount of oxygen present in the rhizosphere of the plants was sufficient for the unobstructed
execution of this process. Also, the decrease in the pH of the water in the Cells 1 - 4 can serve
as an indication that nitrification in the cells with plants took place despite the low DO in the
water surrounding the rhizosphere. However, when analysing the results obtained for the
efficiency of NO2-N removal, it can be noticed that the nitrification process was still not
complete thus that all available NH4-N was not utterly converted to NO3-N. Bernet et al. [13]
state that low DO concentrations in water can lead to the formation of toxic NO2-N, as an
intermediate phase for the conversion of NH4-N to NO3-N. The reduction of NO2-N
concentration occurred only in the Cell 1 with P. australis, with removal efficiency being
97
relatively low compared to removal of other forms of N from polluted water. Anaerobic water
conditions in the cells with plants enabled high NO3-N removal through denitrification.
Through their metabolism, denitrifying microorganisms have decomposed NO3-N to harmless
gaseous N and CO2. Despite the relatively low and seasonally dependent efficiency of plants
in N removal [14], it cannot be said that they had no significance in the removal of this
element from the polluted waters. The primary role of plants in FTW was water aeration.
However, plants also adopted inorganic N as a macronutrient thus removing it from water.
For its growth, C. glomerata can use N in both NH4-N and NO3-N form [15]. Although the
removal of various forms of N was mainly due to microorganisms, the efficiency of the Cell 5
with algae was very high for NH4-N, NO3-N and total N. Due to the aerobic conditions in the
Cell 5, NO2-N was reduced with an efficiency of 97% (Table 2).
Dodkins and Mendzil [1] state that the removal efficiency of total N and NH4-N in the
FTW is about 40% and 50%, respectively. By comparing the efficiency of the modified FTW
in this research with the results obtained by other authors [2,3,8,16] for a similar type of FTW
it can be concluded that the modified FTW was far more efficient in removing the various
forms of N, both in the cells with plants and algae, especially in the case of NH4-N.
The high efficiency of the modified FTW in the removal of various forms of N can also be
indicated by comparing the contents of NH4-N, NO2-N, NO3-N and total N, as a parameter for
the assessment of the ecological status of water [11], in inlet and outlet of modified FTW.
Based on the content of NH4-N, the polluted water had characteristics of waters with bad
ecological status (class V). According to the concentration of NO2-N polluted water had poor
ecological status (class IV). Based on the total N and NO3-N concentrations polluted water
was characterised as water with moderate ecological status (class III). After treatment in
modified FTW water had high ecological status (class I) for parameters NO2-N, NO3-N and
total N, and good ecological status (class II) based on NH4-N concentration.
CONCLUSION
The present study was designed to determine the removal efficiency of P and N in the
modified FTW. Taken together, presented results suggest that proposed green technology can
provide efficient removal of P and N from polluted water if appropriate conditions are created
for the unobstructed execution of the main physical and biological processes for the removal
of these pollutants. These findings have significant implications for the understanding of how
alternating changes in aerobic and anaerobic conditions can lead to successful treatment of
polluted water. The most important limitation for high P removal in this research lies in the
fact that the cell coverage with the floating island was 100%. There is, therefore, a definite
need for the reduction of the vegetation coverage in order to leave enough free space for the
contact between water and air, which will allow the necessary oxygen input into the water.
Since P is removed mainly through the processes of filtration and settling, to avoid its
resuspension to water it is important to organize periodical removal of the accumulated
sediments from the bottom of the cells. Another important practical implication of this study
is that for an efficient N reduction in the FTW it is necessary to provide both aerobic and
anaerobic conditions. This means that, as in the case of P, the percentage of the cell coverage
should be reassessed. Based on the presented results it is also recommended to provide a
98
series of cells with algae at the end of the FTW for additional water polishing. Further studies
should focus on the research on the required number and arrangement of cells with aerobic
and anaerobic conditions in FTW, bearing in mind that such biological systems should be also
able to remove a vast range of pollutants, other than P and N.
ACKNOWLEDGEMENT
This work was supported by the City of Belgrade - Belgrade City Administration - Secretariat for
Environmental protection by financing the project "Revitalization of Topčiderka River by biological
systems for purification of polluted waters" (2014 - 2016).
REFERENCES
[1] I. Dodkins, A. Mendzil, Enterprise Assist: Floating Treatment Wetlands: Treatment
efficiency and potential benefits of activated carbon, Swansea University, Swansea (2014),
p. 44.
[2] F. Stewart, T. Mulholland, A. Cunningham, et al., Land Contam. Reclamat; 16 (1) (2008)
25–33.
[3] A. Van de Moortel, E. Meers, N. Pauw, et al., Water Air Soil Pollut; 212 (2010) 281–297.
[4] A. Lucic, N. Cule, D. Drazic, et al., Project Revitalization of Topciderka River by
biological systems for purification of polluted waters, Available on the following link:
https://www.beograd.rs/images/data/98e470b6829e9ce1a59ff91b9a926ad2_1251546056.p
df
[5] U.S. EPA, Manual - Constructed Wetlands Treatment of Municipal Wastewater. U.S.
EPA, Office of Research and Development, Cincinnati (2000), p.165, EPA/625/R-99/010.
[6] U. Stottmeister, A. Wießner, P. Kuschk, et al., Biotechnol. Adv; 22 (1–2) (2003) 93–117.
[7] B. Masters, Water Pract. Technol; 7 (1) (2012) doi:10.2166/wpt.2012.022.
[8] S. White, M. Cousins, Ecol. Eng; 61 (2013) 207–215.
[9] R. Kadlec, S. Wallace, Treatment Wetlands (2nd Edition), CRC Press, Taylor & Francis,
Boca Raton (2009), p. 1016, ISBN: 978-1-56670-526-4.
[10] J. Vymazal, Sci. Total Environ; 380 (1–3) (2007) 48–65.
[11] Rulebook on parameters of ecological and chemical status of surface waters and
parameters of chemical and quantitative status of groundwater. Off. Gaz. of RS 74/2011.
[12] V. Groudeva, S. Groudev, A. Doycheva, Int. J. Miner. Process; 62 (1–4) (2001) 293–299.
[13] N. Bernet, P. Dangcong, J. Delgenes, et al., J. Environ. Eng; 127 (3) (2001) 266–271.
[14] C. Etnier, B. Guterstam, Ecological Engineering for Wastewater Treatment (2nd Edition),
CRC Press, Taylor & Francis, New York (1996), p. 207–116, ISBN: 9780873719902.
[15] G. Gerloff, G. Fitzgerald, The nutrition of Great Lakes Cladophora, U.S. EPA, Office of
Research and Development, Duluth, (1976), p. 111, EPA-6003-76-044.
[16] Z. Yang, S. Zheng, J. Chen, et al., Bioresour. Technol; 99 (17) (2008) 8049–8053.
99
NUMERICAL ANALYSIS OF THE INDUSTRIAL POLLUTANTS DISPERSION IN
URBAN AREA
Jakov Baleta1*, Ladislav Lazić1, Dominik Pavlović1, Damijan Cerinski1

1
University of Zagreb, Faculty of Metallurgy, Aleja narodnih heroja 3, 44000 Sisak,
CROATIA
*
baleta@simet.hr
Abstract
The concentration of pollutants in the atmosphere is constantly increasing every day which affects
human population, as well as complete ecosystem. Present work utilizes Computational Fluid
Dynamics based on the control volume to analyse influence of meteorological conditions on the
dispersion of pollutants from stationary industrial sources in populated areas. Measured emission
values from the Thermal Power Plant Sisak and INA Sisak Refinery were used as input data together
with the boundary wind conditions taken from the meteorological model. The computational domain
covers the area of the City of Sisak and the time horizon encompass period of 24 hours, i.e. one
characteristic day. Simulation results demonstrate spatial evolution of pollutant dispersion for the SO2
emissions along the domain height. It was concluded that the legally prescribed emission limit value
for SO2 in the populated part of the city is not exceeded during the simulation period, making the air
quality satisfactory.
Keywords: numerical simulation, SO2 emission, pollutant dispersion
INTRODUCTION
The increase in world population together with strong economic development has led to
the increase in environmental burden, especially pollutant emissions which have adverse
impact on human health. Most of the energy today is obtained through the combustion of
fossil fuels, which lead to an increase in the concentration of greenhouse gases, as well as
other harmful products such as CO, NOx and SOx. The negative impact of these substances
on the environment is reflected through the formation of photochemical smog, ozone
depletion, global warming, the occurrence of acid rain etc. [1]. Anthropogenic sources of
pollutants include traffic, industry, households, agriculture, energy sector etc., while forest
fires, volcano activity, dust dispersion caused by the action of wind, could be classified into
natural sources. During its development, humanity has recognized the negative impacts and
has begun to take action to control and reduce it. Today, environmental protection is receiving
greater attention and cases of such disasters are very rare [2].
The aim of the present work is to study the dispersion of pollutants from stationary
industrial sources by the control volume method. The emission data for simulation were taken
from the Sisak Thermal Power Plant and the INA Sisak Refinery, whereas for wind data the
meteorological model was employed. Those stationary industrial sources have a significant
influence on the pollution of the city of Sisak and the simulation of the movement of
100
pollutants under different wind speeds and directions was being studied. The rest of the work
is organized in a few steps. First, the research method is presented by giving the most
important conservation laws in differential form which lead to general transport equation as
the basis for numerical method. Afterwards, most important numerical settings are given
together with boundary conditions for emissions. Finally, most important results are presented
as spatial distributions and average values of SO2 and most important findings are
summarized in conclusion section.
RESEARCH METHOD
In this section, the most important equations behind the method are given together with
numerical simulation settings and boundary conditions.
Mathematical model
Mass conservation law for differential element of fluid in Cartesian coordinate system can
be expressed by the following equation:
 

t x j
 u j   0 (1)
where ρ is fluid density, t represents time, xj Cartesian coordinates and uj velocity vector
components. For incompressible fluid, equation (1) states that the divergence of velocity is
equal to zero. Momentum conservation law for differential, incompressible element of
Newtonian fluid can be written in the following form:
  p  2u
 ui    uiu j      i   fi (2)
t x j xi x j x j
Equations (1) and (2) are also known as Navier-Stokes equations. Energy conservation law is
written as:
  u   T    ji vi 
 i    iu j    p j       fi vi  (3)
t x j x j x j  x j  x j
where i is specific internal energy of fluid.
The observed commonalities between presented governing equations enable introduction
of a general scalar variable φ, with whom general conservative form of all fluid flow
equations can be stated:
     
     u j       S (4)
t x j x j  x j 
In the above equation four characteristic members can be distinguished each with distinct
physical meaning: first term on the left hand side represents time rate of change of scalar
variable φ, second term on the left hand side is convective transport of the same variable, first
term on the right hand side describes diffusional transport of φ, whilst the last term of the
equation is source/sink of the variable φ due to various other mechanisms. General transport
equation (4) represents foundation for the numerical theory of CFD. In this work conservation
equations of mass, momentum and energy based on Reynolds averaging were solved.
101
Simulation settings
Computational domain was made which encompasses boundaries of the city of Sisak
(Figure 1). The domain is 2000 m high, 8230 m wide and 5530 m long. The boundary
conditions for wind in the form of velocity components and turbulent kinetic energy were
taken from the Weather Research and Forecasting (WRF) model for locations of 4 boundary
points depicted in Figure 1 in red colour. Data were given for the entire height of the domain,
more precisely from the ground up to two kilometres in height. The boundary conditions
between those points were obtained by linear interpolation.
a) b)
Figure 1 City of Sisak a) satellite image; b) computational mesh [3]
Initial concentrations of chemical species were set within the domain, amounting to 79%
for nitrogen and 21% for oxygen. Emission sources in simulation domain come from 5
chimneys (Table 1), of which 2 chimneys belong to the thermal power plant (TE blok A and
TE blok B) and 3 belong to the refinery (FCC, WB3 and main chimney).
Table 1 Data for industrial chimneys used in the simulation as emission sources
Mass fraction
CHIMNEY Temperature Mass flow
SO2
K kg/h ppm
FCC 620 67980 695
WB3 484 47652 443
main chimney 423 361902 552
TE block A 433 202767 2142
TE blok B 433 271391 2046
At the top of the domain constant pressure of 0.8 bar was imposed which linearly increases
towards the bottom of the domain where adiabatic and no-slip boundary conditions were set.
Well established k-ε model was used for the description of turbulence which is numerically
robust and gives reasonable compromise between results accuracy and computational
102
demands. Solution is considered converged when residuals of conservation equations fall

below four orders of magnitude compared to initial guessed solution. SIMPLE algorithm was
used for pressure velocity coupling. Euler first order implicit scheme was utilized for the time
discretization. Central differencing scheme was used for continuity equation, whereas
combined scheme of central and upwind schemes with blending factor of 0.5 was used for
momentum equation. Energy and scalar equation employed upwind differencing scheme.

Following section presents spatial distribution of SO2 concentration at different hours of
simulated characteristic day and emission profiles at different domain heights.
Spatial distribution of SO2
The green area in the following Figures represents densely populated Sisak area. The
concentrations in the scales are set according to the limit values for SO2 emissions following
national legislation. The limit value for the concentration of SO2 in the air should be below
350 µg/m3 during the one-hour averaging period, and this value was converted to mass
fraction.
Figure 2 presents spatial distribution of SO2 concentration at 10th hour of characteristic
day. Smoke plums are quite narrow, which in combination with fairly uniform wind direction,
results in longer retention of pollutants in the air and low concentrations near the ground
surface emission concentration. The area around the chimneys is most affected at a height of 2
m, and considering the terrain, the area around the chimney is mostly affected. At 400 m, a
smoke plume is only visible from the thermal power plants chimneys.
Figure 2 Spatial distribution of SO2 mass concentration at various heights for 10th hour
Figure 3 presents results for 15th hour of the characteristic day and is selected because the
emissions cover a wider area, including the densely populated area of the city.
Also, it can be seen that fairly similar concentration pattern is conserved regardless of
height. The reasons for this can be reflected in the state of the atmosphere, the time of day,
meteorological conditions and other influences. Stationary industrial sources of the city of
103
Sisak present a potential risk of contamination even for areas located at larger distances from
the industrial zone. SO2 concentrations are increased compared to the 10th hour.
Figure 3 Spatial distribution of SO2 mass concentration at various heights for 15th hour
Emission profiles at different domain heights

Emission profiles along the line that goes across the green zone of the densely populated
part of the city (Figure 4a) is considered representative to check whether the SO2
concentration limits defined by law were surpassed.
a) b)
Mass fraction
Length, m
Figure 4 Concentration profiles a) line position within the city; b) SO2 profiles at various
heights
It can be seen that the conenctration is highest near the ground and becomes more uniform
and lower with increased height. Emission limit is not reached at any simulated hour in the
green zone, bringing the conclusion that air quality is satisfactory with respect to SO2
concentrations during the the cahracteristic day. It was also shown that numerical simulations
are valid tool for study of urban pollution which can be used for environmental studies and
urban planning.
104
CONCLUSION
The simulation performed within this work shows the results of the dispersion of pollutants
with the associated concentration values at specific parts of the domain and at certain
altitudes. The highest concentrations were noticed at the ground level at a height of 2 meters.
It should be pointed out, as an important conclusion, that the limit value for SO2 emissions in
the populated part of the city was not exceeded during any hour of simulated time period. The
recommendation for further work is to validate the presented method and to analyse the
dispersion of suspended particles that have a negative effect on human health. It was also
shown that numerical simulations are valid tool for study of urban pollution which can be
used for environmental studies and urban planning.
REFERENCES
[1] M. Martinjak, Numerička simulacija sustava za selektivnu katalitičku redukciju,
Sveučilište u Zagrebu Fakultet strojarstva i brodogradnje, Zagreb (2016).
[2] T. Sofilić, Ekotoksikologija, Sveučilište u Zagrebu Metalurški fakultet, Zagreb (2014).
[3] Available on the following link: https://www.google.com/maps
105
WALNUT SHELL AS A BIOSORBENT FOR REMOVAL OF HEAVY METAL IONS
FROM DIFFERENT SAMPLE SOLUTIONS
Maja Nujkić1*, Snežana Milić1, Aleksandra Papludis1, Sonja Stanković1,

Ana Radojević1, Slađana Alagić1, Boban Spalović1
1
*
mnujkic@tfbor.bg.ac.rs
Abstract
The purpose of this study was to investigate possibility of walnut shell for heavy metals ions removal
from rivers into which wastewater is discharged from Mining and Smelting Complex Bor, ZiJin Bor
Copper. Concentration of metal ions (Cu (II), Cr (II), Ni (II), Cd (II)), in treated sample solutions,
were determined using inductively coupled plasma optical emission spectrometer. Maximum
biosorption efficiencies for Cd (II), Cr (II), Cu (II) and Ni (II) of walnut shell was determined to be
96%, 91.6%, 97.6% and 91.5%. According to the results walnut shell can be used as an efficient
biosorbent for removal of metal ions from wastewater solutions.
Keywords: walnut shell, biosorption efficiency, biosorbent
INTRODUCTION
Industrial activities influenced the flow of materials in nature, so that in aquatic
environments, besides naturally occurring, appeared and some other substances, such as
textile dyes, phenols, pesticides, detergents, heavy metals, etc. Many industries, such as
mining, metallurgy, pesticide and fertilizer production, create wastewater with a relatively
high content of heavy metals whose impact on the ecosystem is of great economic and health
importance [1]. Today, wastewater treatment can remove 30-90% of harmful elements. Such
purified waters are further discharged into surface water, which is practically harmless if
wastewater treatment is applied, which is not yet the case in Serbia [2].
One of the most commonly used methods is adsorption with activated carbon, but its
application is limited due to the high cost of production and regeneration of activated carbon.
The last ten years have been invested in finding new, cheaper and more efficient materials for
wastewater treatment [3]. Most attention is paid to natural materials, most often to agro-
industrial waste that is readily available in large quantities. The biosorption as a method for
removal of heavy metals from water has been studied for more than twenty years [4]. The
advantages of this method relative to traditional methods are the low cost, high efficiency,
minimization of chemical or biological sludge, the ability to regenerate biosorbent and the
ability to extract metals. Jalayeri and Pepe, 2019 [5] showed that pistachio green hull is
sutible sorbent for Cu (II) removal from aqueous solutions. Corn silk can be used as efficiant
sorbent for effective removal of Cu (II) and Zn (II) and grape pomace waste is sutible for
cadmium ions removal from solutions [6,7].
106
Walnut shell is rich in lignin and cellulose that contains many functional groups which
have a strong affinity for heavy metal ions. So, it is widely used in the removal of heavy metal
in a solution. Some authors showed that the walnut shell have an adsorption effect on heavy
metals ions in aqueous solutions [8,9].
The purpose of this study was to investigate possibility of walnut shell for heavy metals
ions removal from seven sample solutions. Sampling was carried out from rivers into which
wastewater is discharged from Mining and Smelting Complex Bor, ZiJin Bor Copper. In this
study, by interpreting the results of biosorption experiments, the answers about the efficiency
of this biosorbent were obtained.

Seven different water samples were collected from rivers at locations Krivelj (K), spring of
Bor River (I), Timok (T), Slatina (S), Robule (P), Bor River (B) and Jaruga (J). The samples
were collected according to The Official Gazette of Republic of Serbia, no. 33/2016. Walnut
shell as biosorbent was collected from rural households. Biosorbents were previously air-
dried to constant mass, and then grounded in a vibrating mill with Mesh-Tyler rings.
Subsequently, the walnut shell samples were dried in a laboratory oven at 105° C for almost 1
hour. All the formed walnut shell samples were passed through a 200 mm sieve. A mass of
20 g/L of walnut shell was added in each water sample and stirred with magnetic stirrer (600
rpm) during 60, 120 and 240 min at the room temperature. After filtration, metal ions
concentration (Cu (II), Cr (II), Ni (II), Cd (II)), in treated sample solutions, were determined
using inductively coupled plasma optical emission spectrometer (ICP-OES Optima 8300;
Perkin Elmer, USA).
The biosorption efficiency, R (%) of heavy metal ions from wastewater was determined
according to equation (1):
R (%) = (1)
where Co and Cf are the initial and final heavy metal ion concentrations (mg/L) in aqueous
solution, respectively.

Heavy metal ion removal by the biosorbent was investigated at various initial
concentrations and the results obtained are presented in Table 1. The concentrations of metal
ions before treatment decreased with time. For example, the initial concentration of Cu (II)
ions, 76.7 mg/L in sample S is reduced to a value of 5.1 mg/L. While in the same sample a
reduction of Cd ions from 0.97 mg/L to 0.18 mg/L and Ni ions from 0.89 mg/L to 0.24 mg/L
was observed. The Cr concentration in initial sample B of 0.39 mg/L is reduced to 0.05 mg/L.
107
Table 1 Concentrations of metal ions in sample solutions before and after biosorption
Sample Cd(II) Cr(II) Cu(II) Ni(II)

solutions Concentrations (mg/L)
Jo 0.0863 0.0752 0.8933 0.3069
J1 0.0168 0.0447 0.5546 0.2547
J2 0.0078 0.0092 0.2004 0.1347
J4 0.0034 0.0063 0.1856 0.0262
Ko 0.0105 0.0086 0.7951 0.0125
K1 0.0078 0.0015 0.5006 0.0097
K2 0.0046 0.0010 0.2469 0.0076
K4 0.0027 0.0009 0.1865 0.0053
I0 0.0146 0.0066 0.6883 0.0894
I1 0.0090 0.0025 0.5843 0.0686
I2 0.0077 0.0016 0.2826 0.0526
I4 0.0070 0.0009 0.2549 0.0234
To 0.0105 0.0199 0.8861 0.5627
T1 0.0085 0.0191 0.7121 0.2886
T2 0.0073 0.0191 0.3364 0.1807
T4 0.0028 0.0157 0.2610 0.0418
So 0.9691 0.3733 76.676 0.8861
S1 0.6862 0.0907 7.5221 0.6186
S2 0.2271 0.0665 5.3418 0.3008
S4 0.1883 0.0709 5.0956 0.2379
Po 0.0040 0.0451 7.3515 0.1253
P1 0.0033 0.0408 1.3574 0.0951
P2 0.0022 0.0263 0.6666 0.0870
P4 0.0018 0.0206 0.1779 0.0229
Bo 0.0778 0.3954 40.076 0.5685
B1 0.0223 0.1238 3.3453 0.4884
B2 0.0205 0.1114 3.1804 0.3719
B4 0.0178 0.0532 2.7812 0.2824
Walnut shell showed high affinity for heavy metal ions in all samples (Figure 1). The
highest biosorption efficiency of the walnut shell for metal ions was determined after 4 h in
all water samples. Those results point out to best contact time between investigated biosorbent
and treated water. Maximum biosorption efficiencies for Cd (II) were detected in samples J
(96%), S (80.6%) and B (77%), respectively. In samples J, K, I, B and S, high efficiency of Cr
108
biosorption after 4h was determined: 91.6%, 89.9%, 86.9%, 86.5% and 80.9%, respectively.
Also, copper ions were effectively removed from the studied samples P (97.6%), B (93.1%)
and S (93%). Biosorption efficiency of Ni after 240 min was most effective in samples J
(91.5%), T (86.2%) and P (81.7%).
Figure 1 Efficiency of heavy metals ions removal from different sample solutions by walnut shell
CONCLUSION
Walnut shell has been found to have a high sorption capacity for Cd (II), Cr (II), Cu (II)
and Ni (II). The highest efficiency removal of Cu (II) with the walnut shell occurred in the
samples that contained the highest initial copper ions. According to the results, a high
biosorption efficiency for Cd (II), Cr (II), Cu (II) and Ni (II) removal from different sample
solutions revealed that the walnut shell can be used as an eco-friendly and low-cost adsorbent,
in particular in those areas where this material is abundant.
ACKNOWLEDGEMENTS
REFERENCES
[1] D. Kukić, 2016, Biosorpcija jona teških metala iz vode izluženim rezancima šećerne repe,
Doktorska disertacija, Univerzitet u Novom Sadu, Tehnološki fakultet, Novi Sad (in
Serbian).
109
[2] R. Milanov, 2014, Testing of contents of heavy metals and metalloids in tissues of river
fish as indicators of fish meat safety and environmental pollution, University of Belgrade,
Faculty of veterinary medicine.
[3] X.S. Li, S.L. Liu, Z.Y. Na, et al., Ecol. Eng; 60 (2013) 160–166.
[4] J.V. Milojković, Z.R. Lopičić, I.P. Anastopoulos, et al., J. Environ. Manag; 232 (2019)
97–109.
[5] H. Jalayeri, F. Pepe, Ecotox. Environ. Safe; 168 (2019) 64–71.
[6] M. Petrović, T. Šoštarić, M. Stojanović, et al., Ecol. Eng; 99 (2017) 83–90.
[7] M. Petrović, T. Šoštarić, J. Petrović, et al., The 50th International October Conference of
Mining and Metallurgy, 30 septembar-3 october 2018, Bor Lake, Bor, Serbia.
[8] X. Lu, Y. Guo, Environ. Sci. Poll. Res; 26 (2019) 12776–12787.
[9] F. Yang, Y. He, S. Sun, et al., J. Appl. Polym. Sci; (2016) 133.
[10] The Official Gazette of Republic of Serbia, no. 88/2010: The method and conditions for
measuring the quantity and testing the quality of waste water and the content of the
measurement report (in Serbian).
110
DETECTION OF PAHs AS MICRO-POLLUTANTS IN ENVIRONMENTAL SOIL
AND PLANT SAMPLES
Aleksandra Papludis1, Slađana Alagić1*, Snežana Milić1

1
*
salagic@tfbor.bg.ac.rs
Abstract
The examples of the exploitation of various methods for isolation and detection of polycyclic aromatic
hydrocarbons (PAHs), as typical micro-pollutants present in environmental soil and plant samples are
numerous, and over the years, their combinations became more and more original. It can be said that
during the latest decades of 20th century, the development of different procedures practically exploded,
especially in terms of screening of PAH presence in the environment, as well as for different risk
assessments. However, gas chromatographic-mass spectrometric (GC/MS) method, in combination
with various extraction/purification procedures, showed as one of the most appropriate because it
provides a fast, safe, and accurate analysis. In this work, a brief overview of some of the most
interesting and important examples of GC/MS application in PAH determination is represented,
including the descriptions of methods for PAH extraction from the investigated soil and plant samples
(together with the subsequent clean-up steps).
Keywords: PAHs, environmental samples, GC/MS
INTRODUCTION
Polycyclic aromatic hydrocarbons, PAHs, are hazardous substances belonging to a group
of the so called persistent organic pollutants, POPs. The number of individual PAH
compounds that can be found in the environment is pretty high (over 100) but 16 of them are
recognized as extremely dangerous and they are included in the list of priority pollutants; they
are: naphthalene (Nap), acenaphthylene (Acy), acenaphthene (Ace), phenanthrene (Phe),
fluoranthene (Flt), fluorene (Flr), anthracene (Ant), pyrene (Pyr), benzo[a]anthracene (BaA),
chrysene (CHR), benzo[a]pyrene (BaP), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene
(BkF), dibenz[a,h]anthracene (DhA), benzo[g,h,i]perylene (BgP), and indeno[1,2,3-cd]pyrene
(IcP); several compounds such as BaP, BkF, BbF, BaA, DhA, CHR, and IcP are anticipated
as possible carcinogenic and mutagenic [1].
Although present in micro-quantities in the environment, it was shown that PAHs may
pose serious risk for all living organisms. Their main natural sink is surface soil, where some
significant quantities may be accumulated over the years. Edible plants growing in PAH-
contaminated soil may also accumulate many PAH compounds representing in that way a
potential danger for human health [2]. In terms of protecting human health and the complete
environment, a constant monitoring of 16 priority PAHs is recommended by many relevant
world organizations, together with the related methods for their precise and accurate
detection. In most cases, gas chromatographic-mass spectrometric (GC/MS) method was a
method of choice and it was applied to different environmental matrices with great success
[3]. In this paper, a brief overview of some of the most interesting and important examples of
111
GC/MS application in PAH determination is represented, including the descriptions of

methods for PAH-extraction from the investigated soil and plant samples, as well as of the
subsequent clean-up steps.
VARIOUS COMBINATIONS OF ISOLATION AND DETECTION METHODS FOR

PAHs IN THE SOIL AND PLANT SAMPLES
The development of different procedures practically exploded during the latest decades of
th
20 century, especially in terms of screening of PAH presence in the environment, as well as
for different risk assessments.
For example, at the end of 20th century, in far 1999, Kipopoulou et al. [4], applied the
method of high performance liquid chromatography, HPLC (with fluorescence detector) in
PAH detection in edible parts of several vegetables such as: carrot (Daucus carota), cabbage
(Brassica oleracea capitala), lettuce (Lactuca sativa), endive (Chichorium endivia), and leek
(Allium porrum), growing in an industrial area of Thessaloniki (Greece). PAHs were extracted
from the dried plant samples but also from the corresponding soils, in a Soxshlet-apparatus,
using solvents such as dichloromethane (for plants) and cyclohexsane (for soil). For each
sample clean-up, i.e. for the separation of PAHs from the polar compounds (chlorophyll, etc.),
solid-phase extraction, SPE, was applied, using Florisil cartridge (Florisil fibers are typical
silica micro-columns properly conditioned by n-hexsane, containing also anhydrous Na2SO4).
Only few years later, in 2004, Tao et al. [5] were investigating the content of 16 priority
PAHs in agricultural soil and plants in the area of Chinese town Tianjin, using the method of
GC/MS. The selected plants were celery (Apium graveolens), Chinese cabbage (Brassica
rapa, Pekinensis group), sweet violet (Coriandrum sativum), spinach (Spinacia oleracea),
turnip (Brassica rapa), cauliflower (Brassica oleracea), carrot (Daucus carota), and Chinese
mustard (Brassica juncea). Soil PAHs were extracted using accelerated solvent extraction,
ASE, with 1:1 mixture of dichloromethane and acetone. Clean-up was performed on silica gel
column (with anhydrous Na2SO4 and dichloromethane). The solvents used in different
procedural phases were as follows: cyclohexsane, n-hexsane, and pentane/dichloromethane.
Similar extraction and clean-up methods were also used for plant samples, with the
notification that the step of sulfonation was included during the clean-up (in terms of
removing the lipids and other co-extracted substances that could jeopardize PAH analysis).
Two years later, Tao et al. [6] were also investigating the content of 16 priority PAHs in
the samples of soil and different organs of rice (Oryza sativa) collected at the same territory
(Tianjin, China), and using the same GC/MS method together with the same extraction and
clean-up techniques. The applied procedure provided a safe evolving of important conclusions
related to the level of PAH bioaccumulation in the investigated rice organs, as the main food
in the region of interest.
In the same year, 2006, Meudec et al. [7] were using GC/MS method for the identification
and quantification of PAHs in marine plants, especially in halophytic Salicornia fragilis. For
elimination of pigments and other compounds that may endanger the analysis of PAHs, they
used the saponification method with KOH and SPE (with Florisil fibers). The solvents used in
different procedure steps were – ethanol, hexane, and dichloromethane.
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During 2006, Ratola et al. [8], collected and used Pinus pinea needles (from Barcelona,
Spain) for the analysis of 16 priority PAHs by GC/MS method. They also used this
opportunity for the development and comparison of the three different extraction methods:
Soxhlet, ultrasonic and pressurized liquid extraction, using always the same mixture of
solvents such as hexane/dichloromethane (1:1, v/v). Several clean-up procedures were also
tested, namely: Florisil, silica and alumina in cartridges or glass column format using the
same solvent mixture. Among several investigated extraction and clean-up methods tested,
ultrasonic extraction followed by alumina cartridge clean-up was the method that provided the
best recoveries of PAHs and limits of detection.
Already in 2010, Liao et al. [9] used an advanced GC/MS apparatus equipped with triple-
quadrupole in terms of the detection of PAHs in surface soils. Microwave-assisted extraction,
MAE, and SPE were used for PAH extraction and clean-up. Used solvents were
dichloromethane/hexane and acetone. The applied procedure provided average recoveries in
the range of 66.59–122.07% with relative standard deviations generally less than 20%.
In terms of investigating plant phytoremediation potentials, in 2011, Smith et al. [10] used
the method of HPLC with an UV diode array detector in the analysis of PAHs in 5 different
plant species: Festuca rubra (red fescue), Festuca arundinacea (tall fescue), Trifolium
pratense (red clover), Lolium perenne (perennial ryegrass), and Trifolium repens (white
clover). Extraction was accomplished by Soxhlet-method using dichloromethane/acetone (1:1,
v/v).
In 2012, Wang et al. [11] applied the method of GC/EI-MS (GC/electron-ionization MS)
in the investigation of PAH content in the samples of native plants, vegetables and rice (but
also in their corresponding soils) growing near the electronic (e-) waste situated at the
territory of Guangdong province in south China. PAH extraction from the soil samples was
accomplished by Soxhlet-method with dichloromethane as an extraction solvent, while plant
samples were extracted using mixture dichloromethane/acetone (3:1, v/v). After the
concentration, both kinds of extracts were dissolved in hexane. Their purification was
performed in a multi-layer silica gel - alumina column (with anhydrous Na2SO4) using eluent
hexane/dichloromethane (1:1, v/v). In terms of elimination of lipids, the extracts obtained
from the plant samples were additionally purified on a gel-permeation chromatography
column.
Three years later, Banach-Szott et al. [12] determined the content of the selected PAHs
(fluorene, anthracene, pirene, and chrizene) in the samples of agricultural soils from the
regions of Kujawy i Pomorze (Poland) using HPLC (with fluorescence detector). pAHs were
extracted in a standard way using Soxhlet-apparatus and cyclohexane as an extraction solvent.
Extracts were evaporated, whereas the residue was dissolved in acetonitrile.
In terms of investigating of the influence of PAH speciation in industrial soil on their latter
assimilation by plants (practicallt, Chinese cabbage, B. chinensis), in 2016, Zhang and Fan
[13] used the method of GC/MS and the accelerated solvent extractor with dichloromethane
as a solvent; it was later replaced with the series of different combination of solvents with the
aim of determination of PAH speciation in the samples of soil and plant). The extracts were
purified on an alumina and silica gel chromatography column and the extractable PAHs were
113
obtained through elution with 30 mL dichloromethane/n-hexane (2:1, v/v); the extractable

aliphatic hydrocarbons were obtained through elution with n-hexane.
In 2017, Shi et al. [14] monitored the content of 6 PAHs (phenanthrene, anthracene,
pyrene, benz[a]anthracene, benzo[a]pyrene, and benzo[g,h,i]perylene) in the samples of
leaves of 6 varieties of winter wheat (Triticum aestivum L.). Analyses were done on HPLC-
FLD aparatus with ultraviolet detector and a fluorescence detector. For the extraction,
Soxhlet-apparatus and mixture of solvents acetone/dichloromethane (1:3, v/v) were used. The
extracts were purified on Florisil column using mixture hexane/dichloromethane (1:1, v/v).
During 2013 and 2014, Sadowska-Rociek et al. [15,16] introduced a significant novelty in
PAH extraction from plant samples but also from the samples of different types of tea;
namely, they applied and optimized the QuEChERS (Quick, Easy, Cheap, Effective, Rugged
and Safe) methodology, a method combining the extraction: liquid–liquid with the later
purification on dispersive SPE. The method was originally developed for pesticide residues
analysis operating normally with the pollutant micro-quantities. Sadowska-Rociek et al. [15,
16] examined several types of solvents (acetonitrile, ethyl acetate), sorbents (PCA, GCB,
SAX, NH2), and preparation methods (solvent evaporation to dryness and dissolving of
residues in hexane and liquid–liquid extraction, LLE, with the solvent exchange). The results
showed that, for different types of teas, acetonitrile extraction, clean up with SAX and final
LLE represented the best approach providing the most purified extracts and the best
compound recoveries. The final extracts were analyzed by GC/MS.
A couple of years later, Cvetkovic et al. [17] adopted the QuEChERS methodology for
PAH analysis in real soil samples (collected in urban-industrial locations in Niš, Serbia),
applying again, different combinations of the extraction solvents (acetonitrile/water and
hexane/water) and purification sorbents (PSA, florisil, C18, diatomaceous earth and
clinoptilolite). Detection was done on GC/QqQ/MS system in the selected ion monitoring
(SIM) mode. The results showed that the most effective combination was: extraction by
acetonitrile/water as the extraction solvent and diatomaceous earth as the dispersive SPE
sorbent.
Following previous examinations, in 2016 and 2017, Alagić et al. [2,18] used the
QuEChERS method for PAH analysis in the samples of roots of wild blackberry from the
region of Bor (Serbia), as well as in the corresponding soil samples with the aim of estimating
the usability of this plant species in biomonitoring and phytoremediation. Practically,
extraction was performed using mixture acetonitrile/water (1:1, v/v), the clean-up was done
on a PSA-sorbent, while the detection of PAHs was done on the same GC/QqQ/MS system.
The results confirmed the proficient biomonitoring and phytostabilization potentials of the
investigated plant species.
CONCLUSION
Today, the researchers have mighty analytical instruments, which provide very precise
detection of organic pollutants such as PAHs, even in the case of their micro-quantities
(typically found in the environmental samples). However, GC/MS method is one of the most
appropriate because it provides a fast, safe, and accurate analysis; the detection of PAHs by
114
this method is of great importance for environmental preservation and protection. It should be
mentioned here that the preparation of samples also represent an important step in the
complete analysis, including the suitable methods for PAH extraction and later purification
where PAHs should be properly separated from other substances that may jeopardize the
correct final results. In recent time, the QuEChERS method appears as one of the best
solutions for micro-pollutants such as PAHs.
ACKNOWLEDGEMENT
the scientific research work at the University of Belgrade, Technical Faculty in Bor.
REFERENCES
[1] S.Č. Alagić, B.S. Maluckov, V.B. Radojičić, Clean Technol. Envir; 17 (3) (2015) 597–
614.
[2] S.Č. Alagić, V.P. Stankov Jovanović, V.D. Mitić, et al., Sci. Total Environ; 562C (2016)
561–570.
[3] Available on the following link: http://www.epa.gov/osw/hazard/wastemin/priority.htm
[4] A.M. Kipopoulou, E. Manoli, C. Samara, Environ. Pollut; 106 (1999) 369–380.
[5] S. Tao, Y. H. Cui, F. L. Xu, et al., Sci. Total Environ; 320 (2004) 11–24.
[6] S. Tao, X. C. Jiao, S. H. Chen, et al., Environ. Pollut; 140 (2006) 406–415.
[7] A. Meudec, J. Dussauze, M. Jourdin, et al., J. Chromatogr. A; 1108 (2006) 240–247.
[8] N. Ratola, S. Lacorte, A. Alves, et al., J. Chromatogr. A; 1114 (2006) 198–204.
[9] C. Liao, P. Yang, Z. Xie, et al., J. Chromatogr. Sci; 48 (2010) 161–166.
[10] M.J. Smith, T.H. Flowers, H.J. Duncan, et al., J. Hazard. Mater; 192 (2011) 1219–1225.
[11] Y. Wang, Z. Tian, H. Zhu, et al., Sci. Total Environ; 439 (2012) 187–193.
[12] M. Banach-Szott, B. Debska, A. Wisniewska, et al., Environ. Sci. Pollut. Res; 22 (2015)
5059–5069.
[13] J. Zhang, S. Fan, J. Hazard. Mater; 320 (2016) 114–122.
[14] T. Shi, K. Tian, H. Bao, et al., Environ. Sci. Pollut. Res; 24 (2017) 27215–27224.
[15] A. Sadowska-Rociek, M. Surma, E. Cieślik, B. Environ. Contam. Tox; 4 (2013) 508–
513.
[16] A. Sadowska-Rociek, M. Surma, E. Cieślik, Environ. Sci. Pollut. Res; 21 (2014) 1326–
38.
[17] J. Cvetkovic, V. Mitic, V. Stankov Jovanovic, et al., Anal. Methods-UK; 8 (2016) 1711–
1720.
[18] S.Č. Alagić, V.P. Stankov Jovanović, V.D. Mitić, et al., Environ. Sci. Pollut. Res; 24(18)
(2017) 15609–15621.
115
SOURCES AND AVAILABILITY OF INORGANIC PHOSPHOROUS IN THE SOIL
Sonja Stanković1*, Milan Antonijević1, Snežana Milić1

1
*
sstankovic@tfbor.bg.ac.rs
Abstract
Increasing needs for agricultural products require significant use of phosphorus fertilizers, that has
seriously disrupt natural cycle of this element in the soil. Phosphorus fertilizers are primarily used to
increase concetration and availability of phosphorus, as an essential element for plant development
and growth. However, more than 80% of phosphorus originating from fertilizers, soon after
application turn into the form that cannot be absorbed by the plants, due to very slow diffusion
process and high fixation degree. There are numerous factors influencing phosphorus availabilty in
soil solution, such as easily accessible Pi adsorption and desorption processes, soil texture, type and
pH value as well as method of soil treatment. It is necessary to understand dynamics and nature of the
process of phosphorus absorption and factor influencing phosphorus availiability in soil solution in
order to reduce production of phosphorus fertilizers and improve efficiency of its consumption. This
paper describes factors affect phoshorus availiability and concentration in soil solution and methods
for increasing phosphorus availability in soil solution.
Keywords: soil, inorganic P, phosphorus fertilizers, P availability, phosphorus activators
INTRODUCTION
In addition to nitrogen and potassium, phosphorus (P) is one of seventeen essential
elements required for normal plant growth and development [1,2]. Phosphorus stimulates seed
germination, root and stem development, flower and seed formation, crop yield and quality.
Also, it has significant role in numerous cell processes including maintenance of membrance
structures, synthesis of biomolecules and high energy molecules. Phosphorus deficiency
reflects in the disruption of many physiological, biochemical and metabolic processes, so the
plants growing under such conditions are underdeveloped with smaller, curled dark–green
leaves. Younger plants have greater need for phosphorus in relation to the plants that finished
their growth and development process, and that is the reason why the symptoms of its
deficicency are more visible at young plants [3].
As Balemi and Negisho [1], at more than 40% of the worldwide soil, P content available
for plants, is not sufficient to satisfy the needs of the plants [1]. During last decades, much
greater quantities of phosphorus fertilizer have been used, to satisfy needs for agricultural
products in the world. Shen et al. [4] indicated that consumption of phosphorus fertilizers in
China has been drastically increased from 1.18 Mt P in 1985 to 4.80 Mt P in 2005 [4].
Excessive application of phosphorus fertilizers can lead to an increase in the amount of
phosphorus that accumulates in the soil and/or leads to leakage from the soil into aquatic
systems, which can further lead to artificial eutropia and red tide [5,6]. In South China, about
116
68 kg P/h accumulates in agricultural land annually [5]. The results of study conducted by
Heckrath [7] indicate that if the amount of accumulated Olsen P is greater than 60 mg/kg,
there will be a loss of phosphorus from agricultural land to aquatic ecosystems [7]. The
disruption of natural phosphorus cycles imposes the risk to complete environment.
This paper present factors affecting phosphorus availability and concentration in soil as
well as methods for reducing phoshorus fertilizers and maximum recovery of the phosphorus
present in the soil.
PHOSPHORUS IN THE SOIL

Phosphorus in soil exists both in organic (Po) and inorganic (Pi) form. Literature data of
organic and inorganic phosphorus content is presented in Table 1. P concentration in the
surface layer of soil (0–15 cm) is from 50 to 3000 mg P/kg soil, whereas P concentration in
soil solution is from 0.05 to 0.30 µg/ml. Although most soil contains significant amounts of
phosphorus, only small part (<1%) of total P has been dissolved in soil solution [8]. Such low
phosphorus concentration and poor availability in soil solution has conditioned application of
phosphorus fertilizers [9]. Phosphorus fertilizers are primary used for increasing
concentration and availability of phosphate ion in soil solution. The most commonly used
phosphorus fertilizers are: shredded phosphate rock, super phosphate, triple super phosphate,
NPK and ammonium phosphate fertilizers [10]. P2O5 content in different types of phosphorus
fertilizers is given in Table 2.
Table 1 Content of organic and inorganic Table 2 P2O5 content in different types of
phosphorus in soil phosphorus fertilizers [2]
Content of P (%) Sapling location Ref. Types of phosphorus fertilizers Content (%)
Po 20–80 Newark (USA) [9] Single

17–20
superphosphate
Po 30–60
Beijing (China) [4]
Pi 35–70 Triple superphosphate 44–48
Po 30–50
Beijing (China) [8] Phosphate rock 26–37
Pi 60–80
Po 15–80 Novi Sad (Serbia) [11] Dicalcium phosphate 35–52
FACTORS INFLUENCING Pi CONCENTRATION AND AVAILABILITY IN

SOIL SOLUTION
The great number of reactions taking place in soil (Figure 1) affect P concentration and
availability in soil solution. Soon after application, more of 80% of P originating from
fertilizers, turns into form that cannot be absorbed by the plants, because of the sorption
process, precipitation or microbial immobilization [8].
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Figure 1 Phosphorus cycles in soil [8]
P concentration in soil solution is primarily controlled by balance between adsorption and

desorption process of labile Pi [8]. In acidic soil, P can be adsorbed at Al and Fe
oxides/hydroxides and clay mineral, whereas in neutral and carbonate soil, on the surface of
Ca carbonate and clay minerals [4]. Taking into consideration that clay minerals are
characterized by large surface for P adsorption, clay–rich soil is characterized by small
amount of P that can be extracted [12].
Phosphorus adsorbed at aluminium or iron oxide, as well as calcium phosphate minerals
are sensitive to changes of pH. Increasing of soil pH leads to increasing of Fe and Al
phosphate solubility (Figure 2), whereas the solubility of the Ca phosphate decreases until
pH=8. Increasing of soil pH (pH>8) leads to increasing of Ca phosphate solubility.
Figure 2 Influence of soil pH value to P availability [13]
Different forms of Ca, Al and Fe phosphates can influence P concentration in soil solution.
Dissolution of minerals in acidic, neutral and alkaline soil is presented in the following
reactions (1–9) [8]:
FePO4 ·2H2O(s) ↔ Fe3+ + PO43- + 2H2O (1)
2+ 3–
Fe 3(PO4)2·8H2O(s) ↔ 3Fe + 2PO4 + 8H2O (2)
AlPO4·2H2O(s) ↔ Al3+ + PO43- + 2H2O (3)
Ca3(PO4)2(s) ↔ 3Ca2+ + 2PO43- (4)
CaHPO4(s) ↔ Ca2+ + PO43- + H+ (5)
118
CaHPO4 · 2H2O(s) ↔ Ca2+ + PO43– + H+ + 2H2O (6)

2+ 3- -
Ca5(PO4)3F(s) ↔ 5Ca + 3PO4 + F (7)
+ 3- -
Ca5(PO4)3OH(s) ↔ 5Ca + 3PO4 + OH (8)
Ca8H2(PO4)6 · 5H2O ↔ 8Ca2+ + 6PO43- + 6H2O (9)
Some metal cations present in soil solution can form metal–phosphate complexes with
H2PO4- and HPO42- ions. Complexed P can present significant part of total P present in the soil
[14]. Low molecular weight organic acids can form organo–metal complexes with Fe, Mn,
Zn, Cu or Ca, whereby P releases from metal–phosphate complexes. Plants that grow on soil
rich in CaCO3 contribute to increase of organic acid content in the soil and thus affect the
concentration of P that plants can absorb [15].
METHODS FOR INCREASING Pi AVAILABILITY IN SOIL

Phosphorus activators transform insoluble P into forms that can be absorbed, leading to a
reduction in the amount of phosphorus that accumulates in the soil and/or flows into aquatic
ecosystems. They can be divided into three groups: (1) bio–inoculants and bio–fertilizers; (2)
organic substances and (3) zeolites and other substances [8]. The effect of applying different
bio-fertilizers is shown in Table 3.
Table 3 Effect of bio-fertilizers application

Microorganisms in bio-
Soil type Results of applied bio-fertilizers Ref.
fertilizers
Aspergillus versicolor
Bacillus licheniformis Silt clay soil The applied bio–fertilizer improved the uptake of P in maize and
[16]
Bacillus subtilis (India) rice by 25.95–50.56% and 18.58–44.09%, respectively
Streptomyces cellulosae
Pseudomonas Loamy soil
Improved phosphorus uptake by 103%
synxantha (India)
[17]
Loamy soil
Serratia marcescens Improved phosphorus uptake by 121%
(India)
Sandy soil Application with superphosphate improved P uptake by 29 mg/pot
Aspergillus niger
(Egypt) and 30 mg/pot for wheat and faba bean, respectively
Sandy soil Application with superphosphate improved P uptake by 129 mg
Aspergillus fumigatus [18]
(Egypt) /pot and 39 mg /pot for wheat and faba bean, respectively
Sandy soil Application with superphosphate improved P uptake by 125 mg/pot

Penicillium pinophilum
(Egypt) and 112 mg/pot for wheat and faba bean, respectively
The effects of applied organic acid on P transformation are shown in Table 4.

The use of humic acid, biochemical humic acid and lignosulfonate sodium as activators
reduced the amount of phosphorus that flows into aquatic ecosystems by 34.6%, 35.6% and
42.3%, respectively [5]. The impact of the application of phosphorus activators on the amount
of P that flows into aquatic ecosystems is shown in Figure 3 [5].
119
Table 4 Effects of applied organic acid on P transformation

Organic Ref.
Concentration Soil type Results
compound
Prevents the fixation of P in the soil
Humic acid 0.1 mg/kg soil Calcareous soil (Pakistan) and increases its availability to [19]
plants.
Maleic acid Natural forests or plantation from
Citric acid 10 mM/kg soil subtropical and tropical areas Effective in mobilizing P from soil [20]
Oxalic acid (Australia)
Figure 3 Cumulative phosphate loss via P leaching from the paddy soil [5]
(RCK0–without the addition of agents; RCK–superphosphate; HA–humic acid; LS– lignosulfonate
sodium; BCHA– biochemical humic acid)
In addition to activators, availability of phosphorus in soil solution can be affected by

changes in physical and chemical soil properties as well as crops planting approach. Results
of the study conducted by Shen et al. [4] indicated that if the corn and broad beans are grown
on the same agricultural land, the amount of absorbed P can be increased. Broad beans secrete
organic acids that leads to decreasing of rhizosphere pH value and contributes to increasing of
P concentration that can be absorbed by the plants [4]. Considering that P diffusion in the soil
is a very slow process, applying phosphorus fertilizers near the crop seeds can increase its
availability for the plants. By applying phosphorus fertilizer out of root area, the efficiency of
the applied fertilizer is reduced.
CONCLUSION
Due to the very low concentrations and poor availability of phosphorus in soil solution and
high demand for agricultural products, phosphorus fertilizers have been used in increasing
quantities in recent decades. In order to reduce quantity of phosphorus fertilizers in the world,
it is necessary to understand factors affecting P availability in soil, dynamics and nature of P
absorption from the soil. A number of factors influence phosphorus availability, such as: soil
pH value, method of soil treatment, content of Fe, Al, Ca, clay mineral and organic
substances. The activators, which facilitate phosphorus accumulated in the soil to be
transformed in the form easily absorbed by the plants, can be used in order to reduce the
quantity of phosphorus fertilizers application worldwide. Also, the use of activators can
reduce the amount of P that flows into aquatic ecosystems, thus preventing environmental
pollution.
120
ACKNOWLEDGEMENTS
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[2] C.B. Dissanayake, R. Chandrajith, JNSF; 37 (2009) 153–165.
[3] H. Malhotra, Vandana, S. Sharma, et al., Phosphorus nutrition: Plant growth in response
to deficiency and excess, In: M. Hasanuzzaman, M. Fujita, H. Oku et al., Plant nutrients
and abiotic stress tolerance, Springer, New Delhi (2018) ISBN: 978-981-10-9043-1
[4] J. Shen, L. Yuan, J. Zhang, et al., Plant Physiol; 156 (2011) 997–1005.
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[8] J. Zhu, M. Li, M. Whelan, Sci. Total Environ; 612 (2018) 522–537.
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[11] M. Jarak, J. Čolo, Mikrobiologija zemljišta, Univerzitet u Novom Sadu, Poljoprivredni
fakultet , Novi Sad (2007) 121–129, ISBN:978–86–7520–113–7.
[12] Z. Zheng, L. E. Parent, J. A. MacLeod, Can. J. Soil Sci; (2003) 395–403.
[13] G. Sandral, E. Tavakkoli, M. Barati, et al., Phosphorus and phosphorus stratification,
Available on the following link: https://grdc.com.au/resources–and–publications/grdc–
update–papers/tab–content/grdc–update–papers/2019/02/phosphorus–and–phosphorus–
stratification
[14] H. Hotlan, L. Kamp–Nielsen, A.O. Stuanes, Hydrobiologia, 170 (1988) 19–34.
[15] L. Ström, A.G. Owen, D.L. Godbold, et al., Soil Biol. Biochem; 37 (2005) 2046–2054.
[16] B. Ho, E.h. Huang, T.K. Ho, et al., Foshan Jinkuizi Plant Nutriment Co., Ltd., United
States (2013)
[17] M. Gupta, S. Kiran, A. Gulati, et al., Microbiol. Res; 167 (2012) 358–363.
[18] O. Abdul Wahid, T. Mehana, Microbiol. Res; 155 (2000) 221–227.
[19] M. Sarir, M. Durrani, I. Mian, J. Agric. & Biol. Sci; 1 (2006) 29–31.
[20] L. Wei, C. Chen, Z. Xu, Biol. Fertil. Soils; 46 (2010) 765–769.
121
CONTRIBUTION TO THE KNOWLEDGE OF THE DISTRIBUTION OF Gyas titanus
Simon, 1879 (OPILIONES, PHALANGIIDAE) IN THE TERRITORY OF BOSNIA
AND HERZEGOVINA
Mihajlo Stanković1*
1
Pokret gorana Sremska Mitrovica, Svetog Save 19, 22000 Sremska Mitrovica, SERBIA
*
trogloxen@gmail.com
Abstract
According to the literature so far, a total of Gyas titanus is present in nine localities in Bosnia and
Herzegovina. Our surveys from 2001 to 2018 recorded it in 21 localities. All our findings of Gyas
titanus do not deviate from other habitats of other authors where it is found, which is a forest on the
bank of a stream-river or terrain overgrown with shrubs and mostly beneath a rock or rotten tree. As
we can see, it mainly inhabits the forests of the most old age with a strong set, whose canopy cover is
not less than 70% and slightly smaller canyons and gorges with high almost vertical cliffs overgrown
with dense vegetation. During our study, the elevation zonation of this species ranged from about 600
above the sea level in Kozara to almost 1700 above the sea level in Mount Cincar. If we look at the
sites cited by Novak et al. [4] we notice that some localities are repeated, i.e. our research has
confirmed their presence in the wider area, which indicates our continuity of presence in the area. If
we compare the literature data with ours, we can see that for most of our localities these are new
findings in Bosnia and Herzegovina. It is reasonable to assume that the species and inhabits areas
that have not been extensively explored before, as these new localities in Bosnia and Herzegovina
show. Considering the findings from the literature as well as these new locations in Bosnia and
Herzegovina, we can conclude that G. titanus is more or less constantly present in the western and
central Balkans. In addition to some isolated mountains in the Pannonian Plain, the species
population has a continuous Alpine-Balkan-Carpathian distribution.
Keywords: Gyas titanus, Bosnia and Herzegovina, new location
INTRODUCTION
European phalangidae of the genus Gyas, are represented by two species Gyas titanus
Simon, 1879 and Gyas annulatus (Olivier, 1791) and both represent Mountainean species. In
the subalpine and hilly regions, G. titanus occurs in forests on the banks of streams and there
have been rare sporadic findings in caves. G. titanus species has been recorded in Croatia,
Bosnia and Herzegovina (B&H), Montenegro and Serbia.
In the description of the area we will stick to the Mountainean pre-alpine and hilly region,
which is cultivated and inhabited. The territory of B&H has an area of 51129 km2 and is an
integral part of the geomorphostructure of the Dinarides. The Dinaric Mountain
Morphosystem is a sub-continent of the western part of the Alpine-Himalayan belt. It
originated in the geotectonically moving, Mediterranean subduction zone (Mediterranean
geosynclinal area), during the Cenozoic phase of the Alpine cycle of orogenic closure by the
Neothetical Ocean. The formation of the Dinaric Orogen was influenced by complex tectonic
122
processes [1]. The relief structure of Bosnia and Herzegovina is expressed by: mountain
massifs and hills with foothill stairs, surfaces, mountain elevations and hills, karst fields,
valleys, bays and valleys. The high mountain dinaric zone morphologically expresses the
mountainous areas of northern Herzegovina, central, southeast and southwestern Bosnia.
Therefore, it is an extremely mountainous area with the highest altitudes (the peak of Maglic
2386 above the sea level) and the highest values of vertical distribution in B&H [2]. The
northeastern part of the high mountain Dinaric zone, in the area of the Central Dinarides, is
represented by mountain ranges and ridges of Vlasic (1943 above the sea level), Jahorina
(1913 above the sea level), Bjelašnica (2067 above the sea level), Zelengore (2015 above the
sea level), Maglića (2386 above the sea level). The southwestern highland frame is
represented by the boring-folding and scaly mountain morphostructures of the High Karst
zone in the Outer Dinarides. Orographically, the linear elevations of the mountain ridges
predominate. These are: Pljecevica 1645 above the sea level, Klekovača 1961 above the sea
level, Staretina 1607 above the sea level, Dinara 1912 above the sea level, Vitorog 1907
above the sea level, etc. The mountain massifs in the high Dinaric Orographics reflect
orographically: Tent 1873 above the sea level, Grmeč 1604 above the sea level, Prenj 2123
above the sea level, etc. The mentioned mountains are morphotectonically separated by relief
depressions of karst fields and larger bays. Morenan deposits are a reliable indicator of the
glacial process found in the high bays and low foothills of Pranja, Velez, Dinara, Tent, etc.,
while higher parts of the mentioned mountains are marked by forms of Pleistocene glacial
relief. The high mountain belt of the Dinarides of B&H is bordered from the northeast and
southwest, by slightly lower mid-mountain morphostructures of average altitudes of 1000-
1600 above the sea level. The southwestern highlands, extending to eastern and western
Herzegovina, represented by the backs and massifs of Radovan 1133 above the sea level,
Vranić 1117 above the sea level, Bjelašnica 1395 above the sea level, Viduše 1328 above the
sea level, etc., while the northeastern mountain range in central and eastern [1].
This paper aims to complete the picture on the distribution of Gyas titanus in B&H.

The material is ordered by rolling stones, rotting trees and stumps mainly in the bed of a
stream or mountain river in the forest. Specimens in most localities were not collected, only
photographed. It covers the period from 2001 to 2018 when field surveys were conducted in
the territory of Bosnia and Herzegovina. Determination was done according to Luhan [3].

According to the authors Novak et al. [4] Gyas titanus is present in Bosnia and
Herzegovina in eight localities:
Kupreška vrata, XJ87, Bugojno, 1200 m, 10.09.1983, Coll. BIOS 2606, SIVEC leg.: 1 m
(TN 406/1985; PMSL); Kozarac, XK48, Prijedor, 06.05.1987, SIVEC, HORVAT leg.: 2
subad. (TN 1096/1998; PMSL); Ravan, YJ38, Busovača, Zenica, 13.05.1986, SIVEC,
HORVAT leg.: 1 subad., 1 iuv. (TN 1234/1998; PMSL); Konjuh Mountain, CQ00, 890 m,
16 km north of Kladanj, 14.10.1990, SIVEC, HORVAT leg.: 2 iuv. (TN 1256/1998; PMSL);
123
Vranica Mountain., YJ27, 1400 m, 5 km southwest of Fojnice, 17.10.1990, SIVEC,

HORVAT leg.: 2 iuv. (TN 1264/1998; PMSL); Ponor cave Bijambare, Čevljanovići, BP37,
28.07.1968, PRETNER leg.: 1 iuv. (TN 233/1985; JH); Radačići, CP09, Kladanj, 680 m,
15.10.1990, SIVEC, HORVAT leg.: 1 iuv. (TN 1271/1998; PMSL); Maglić Mt., CN19, 25
km south of Foča, AUSOBSKY leg. (MARTENS, 1978).
The data of Jakšić [5], PhD for Prokoško Lake on Vranica Mountain, where the description
of biodiversity indicates the presence of this species. Thus, in total, Gyas titanus is present in
nine localities in Bosnia and Herzegovina. In the period 2001-2018 Gyas titanus was recorded
in 21 localities (Figure 1), which are listed as:
Zelengora Mountain: Canyon of Hršćanka River, 20. 08.2008, river bank below stone, 1
individual; Donje Bare Lake, 22.08.2008, lake shore, below stone, 2 individuals; rainforest
Perucica, 19.08.2009, forest, under rotting tree, 3 individuals; 23.05.2001, forest under stone
along Perucac creek, 5 individuals;
Maglić Mountain: Trnovac Lake, 19.08.2009, forest around the lake, under a rotting tree,
1 individual; Suha River Canyon, 19.08.2009, forest under a rotting tree, 2 individual;
Sutjeske canyon: 21.08.2009, coast, forest under stone, 1 individual;
Cincar Mountain: Dragnjic place, 17.08.2010, under the stone, 1 individual;
Šator Mountain: place Rare, under the stone, 18.08.2010, 1 individual; place Štekerovci,
19.08.2010, under the stone, 1 individual;
Lisine Mountain: Podrašnica, Zelenkovac, 24.08.2010, under a tree in the forest, 2
individuals; 25.08.2010, and 21.08.2011, along Zelenkovački creek below the stone, 1
individual each;
Krug Mountain: place Zagoričani, 25.08.2010, under the stone, 2 individuals;
Ljubuša Mountain: place of Mokronoge, 29.08.2010, under the stone, 2 individuals; the
surroundings of Rama Lake, 29.08.2010, below the stone 1 individual;
Livno: Jaruga River, 25.08. 2011, river bank below the rock, 2 individuals;
Zenica: Kraljeva Sutjeska, 20.04.2012, beneath the extinct tree in the forest, (one dry
specimen);
Kozara Mountain: Crna River, 17.08.2012, 20.08.2014. and 22.08.2013, under the
deciduous tree in the forest, 2 + 5 + 3 individuals; Pasini konaci, 21.08.2013. below the
extruded tree in a wet meadow (swamp) 2 individuals, Gumlin cave, 28.08.2015, in the
furnace walker in complete darkness, 3 individuals, Gumlin creek 28.08.2015, in the gorge of
the stream below the stone at coast, 3 individuals., Starenica river, 30.08.2018., below the
stone on the coast, 1 individual. Figure 2 shows Gyas titanus in Kozara NP in the Gumlin
creek gorge below a rock on the shore.
124
New data from 2001-2018

Figure 1 21 localities in Bosnia and Herzegovina where Gyas titanus was recorded
Localities surveyed: 1. Sutjeske Canyon (1); 2. Livno: Jaruga River (2); 3. Cincar Mountain: Dragnjic
Town (3); 4. Kozara Mountain: Black River (4), Pasha Strands (5), Gumlin Cave (6), Gumlinski brook
(7), Starenica River (8); 5. Krug Mountain: Zagoricani Town (9); 6. Lisina Mountain: Podrasnica,
Zelenkovac (10) and Zelenkovack creek (11); 7. Ljubuša Mountain: the place of Mokronog (12) and
the vicinity of Rama Lake (13); 8. Maglić Mountain: Trnovac Lake (14) and Suha Reka Canyon (15);
9. Šator Mountain: Rare (16) and Štekerovci (17); 10. Zelengora Mountain Canyon of the Christian
(Hršćanke) River (18); Donje Bare Lake (19); rainforest Perucica (20); 11. Zenica: Kraljeva Sutjeska
(21)
Figure 2 Gyas titanus in Kozara NP in the Gumlin creek gorge below a rock on the shore (Photo by
M. Stanković)
All our findings of Gyas titanus do not deviate from other habitats where it is found, which
is a forest on the bank of a stream or terrain overgrown with shrubs and mostly under rock or
125
decayed wood. As we can see, it mostly inhabits the forests of the most old age with a strong
set, whose canopy cover is not less than 70% and slightly smaller canyons and gorges with
high almost vertical cliffs overgrown with dense vegetation. In terrains that have a
predominantly open merocarst type where sparse shrubby or only grassy vegetation is present,
specimens are found under the rock, usually in slightly higher grass or denser shrub
assemblages.
The finding of the species in the Gumlin creek gorge and in the Gumlin Cave shows its
trogloxene character. That is, the species uses the interior of the cave temporarily during the
summer dry season. Visiting the cave itself, specimens were found in the cave corridor over
100 m from the entrance in complete darkness due to optimal humidity during the summer
when the temperature reached 40ºC and the water level in the stream was very low. This is
not the first case that opilions are found both around and inside the cave.
During fieldwork, it was observed that in vegetation terms Gyas titanus inhabits from
hardwood to mixed to purely coniferous communities as well as to communities in pastures
above the forest border, or from canyon communities with Salix, through mesophilic oak
communities, as well as from hilly and mountain beech communities to subalpine conifer or
mixed communities (Abieto-Fagetum, Abieto-Fageto-Picetum, Picetum submontanum, etc.)
The presence of this species was recorded in four localities belonging to the protected areas,
namely the Sutjeska and Kozara National Parks, while the Lisine Mountains are under
previous protection.
If we look at the sites cited by Novak et al. [4] we notice that some localities repeat like
Maglic (finding in 1978) where we also found it, which only confirms its continuity. At two
localities Kozarac near Prijedor (finding in 1987) and Ravan near Zenica (finding in 1986),
our research confirmed their presence in the wider area. In the work of Novak et al. [6] we
find data on the zoogeographical distribution of Gyas titanus where the authors state that it
belongs to the Alpine, Iberian, Central European, Dinaric and Carpathian elements.
During our study, the elevation zonation of this species ranged from about 600 above the
sea level in Kozara to almost 1700 above the sea level in Mount Cincar.
If we compare the literature data with ours, we can see that for most of our localities these
are new findings in B&H. It is reasonable to assume that the species and inhabits areas that
have not been extensively explored before, as these new localities in B&H show.
CONCLUSION
According to the literature so far, a total of Gyas titanus is present in nine localities in
Bosnia and Herzegovina. Our research in the period 2001-2018 recorded it in 21 localities.
All our findings of Gyas titanus do not deviate from other habitats of other authors where it
is found, which is a forest on the bank of a stream-river or terrain overgrown with shrubs and
mostly beneath a rock or rotten tree. As we can see, it mainly inhabits the forests of the most
old age with a strong set, whose canopy cover is not less than 70% and slightly smaller
canyons and gorges with high almost vertical cliffs overgrown with dense vegetation. During
our study, the elevation zonation of this species ranged from about 600 above the sea level in
Kozara to almost 1700 above the sea level in Mount Cincar.
126
If we look at the sites cited by Novak et al. [4] we notice that some localities are repeated,
i.e. that our research has confirmed their presence in the wider area, which indicates to us its
continuity in the area.
If we compare the literature data with ours, we can see that for most of our localities these
are new findings in B&H. It is reasonable to assume that the species and inhabits areas that
have not been extensively explored before, as these new localities in B&H show.
Considering the findings from the literature as well as these new locations in B&H, we can
conclude that G. titanus is more or less constantly present in the western and central Balkans.
In addition to some isolated mountains in the Pannonian Plain, the species population has a
continuous Alpine-Balkan-Carpathian distribution.
ACKNOWLEDGEMENT
I would like to thank the management of Sutjeska and Kozara National Park and all the
employees who assisted me in the field in the protected area, as well as the Zelenkovac
environmental society for logistical, technical and any other assistance during the research.
REFERENCES
[1] A. Lepirica, Reljef Bosne i Hercegovine, Zbornik radova Departmana za geografiju,
turizam i hotelijerstvo br. 41, Prirodno-Matematički fakultet, Univerzitet u Tuzli (2012).
[2] A. Lepirica, Reljef geomorfoloških makroregija Bosne i Hercegovine, Zbornik radova
Prirodno-Matematičkog fakulteta, Svezak Geografija br.6, Tuzla (2009).
[3] von W. Luhan, Zur Verteilung der Gyas-Arten im Ötztal (Nordtirol, Österreich)
(Opiliones: Phalangiidae, Gyantinae), Ber.nat.-med Ver.Innsbruck, Band 67, Innsbruck,
(1980) 89–94.
[4] T. Novak, S. Lipovšek, Lj. Slana, Natura Croatica, Zagreb, 9 (3) (2000) 189–194.
[5] Prof. Dr Predrag Jakšić - Prokoško jezero na planini Vranici, Available on the following
link: https://web.archive.org/web/20110616072556 /http://www.ekosela.com/dokumenti/
ANNEX%207%20Biodiversity%20Assessment%20BIH.pdf
[6] T. Novak, S. Lipovšek Delakorda, Lj. Slana Novak, Zootaxa; 1325 (2006) 267–276.
127
23 YEARS OF THE NATURAL COLLECTION OF ZASAVICA RESERVES
Mihajlo Stanković1*
1
Pokret gorana Sremska Mitrovica, Svetog Save 19, 22000 Sremska Mitrovica, SERBIA
*
trogloxen@gmail.com
Abstract
The Zasavica Nature Reserve study collection includes the Paleontological-Geological Section and
the Biological Section. About 50 specimens of minerals, rocks and fossils have been deposited in the
paleontological-petrological collection from the area of the reservoir and the surrounding area.The
paleontological part of the collection consists of a collection of quaternary vertebrates with parts of
the mammalian quaternary fauna skeletons, and here we have the mammoth atlas (Mammuthus sp.)
found in Crna bara (Jovaca); then a collection of invertebrate macrofauna with the remains of
Bivalvia, Gastropoda and other freshwater or marine invertebrates in limestone and other sediments
(silt, clay, etc.) and a paleobotanical collection consisting of parts of the tree found in silt and peat
and peat samples. The petrological part of the collection contains minerals and rocks found in alluvial
deposits or averaged fractions of deposits from sources on the Zasavica coast. The biological part of
the collection includes: Mycological collection of 111 liquid mushroom preparations; Botanical
collection with 2500-3000 specimens herbaceous material and 82 bottles and vials with liquid
preparations of plants and algae and Zoological collection in which we have a total of 113 samples of
64 species + 1 subspecies and include: Ichthyology collection with 34 samples in ethanol and one dry
preparation; Batrachological collection of ethanol from 28 samples in ethanol (9 from Caudata and
19 from Anura); Herpetological collection with 23 samples in ethanol and dry preparations (armor
and hairpieces); Ornithological collection of 8 prepared birds of 7 species; Mammological collection
of 20 exhibits (whole specimens and horned heads prepared), followed by skulls of small mammals,
rodents' nests and liquid preparations; Entomological collection and collection of other invertebrates
with 10 entomological boxes and about 300 vials and vials with liquid sample preparations in ethanol
and dry preparations. The collection so far contains the only specimens found so far in the reserve in
the past 23 years, namely those of fish: Neogobius fluviatilis, Gobio albipinnatum and Barbus
peloponesus; from amphibians Rana temporaria and from reptiles black (melano) specimen of the
species Vipera berus bosniensis.
Keywords: Natural History Collection, Zasavica Reserve
INTRODUCTION
The purpose of forming a natural collection is to serve the present and future interest of
research, protection and presentation to a wider range of stakeholders. Collecting material for
collections can be done by various ways. One way is to donate an item or an entire assembly.
The exhibits can be purchased through purchase, exchange or field research. Any material to
be included in the collection must be recorded in the inventory book with all necessary basic
and additional information. The material thus processed is stored either in a depot usually
inaccessible to visitors and used for scientific research or placed in collections for display in
an exhibition space [1].
128
An important segment in the scientific work of each protected area is to study natural
history collections, which represent significant scientific, historical and archival material of
the area. It preserves significant and valuable scientific material that proves the presence of
certain species and populations in the area, and from a historical point of view it is significant
because it also preserves species that have disappeared in the meantime or are rarely
encountered in the field. It is a significant material for various comparative analyzes,
evolutionary, morpho-anatomical and genetic studies on species and populations. In addition
to the scientific value of the collection, they also have an educational role for both visitors and
young professionals and scholars. All preparations in any collection in order to be
scientifically valid must have the following information: name (Latin) species, date of
collection, locality, habitat, legator and who has determined and prepared the specimen, and
of the additional data such as the method of preparation, the dimensions of the preparation,
ect. [2].
There are two methods of preparation in natural collections: dry and liquid preparations.
By dry preparation we mean all specimens that are dehydrated, pressed, stuffed specimens
(animals), osteological material (skeletal and skull parts), dermo preparations, etc. Liquid
preparations are specimens immersed in a certain substance (ethanol, formalin, glycerin, etc.)
to be preserved and thus stored in adequate containers [2].
The Zasavica Nature Reserve Study Collection Fund covers the period from 1996 to 2019
and has the following parts: Paleontological-geological part and biological part, which
includes: Mycological, Botanical and Zoological Collection, which include: Ichthyological,
Batrachological, Herpetological, Ornithological, Mammological, Entomological and other
invertebrate collections. The reserve collection includes dry and liquid preparations.
This paper deals with vertebrate artifacts in more detail in the study's natural collection of
reserves by groups, as this is the most central part of the collection so far.

The methodology consists in listing the exhibits and their basic data, which are later sorted
by systematic affiliation. For herbarium, algological and paleontological material and
collections related to the invertebrate fauna, only the total number of specimens has been
given, because a large part of the material has not yet been determined. Part of the material
stored in the collection is dry preparations specimens (herbarium, dermo and osteological
material, prepared (stuffed) animals (birds, mammals), entomological material, fruits, galls,
shells, nests of birds or insects, etc.), while a considerable proportion are liquid preparations
most often in ethanol (specimens of fish, amphibians, reptiles, smaller mammals (rodents,
cockroaches, bats) and most of the invertebrate fauna samples). Preparation of all but stuffed
animals is done by our expert associate, while the preparation of birds and mammals is done
by our professional preparer at the Provincial Institute for Nature Conservation in Novi Sad.

For the past 23 years, the following material has been deposited in the reserve's natural
history collection:
129
Paleontological-petrological collection: includes found paleontological and geological

material (minerals and rocks) in the area of the reservoir and in the immediate vicinity. A total
of about 50 specimens have been deposited in this collection. The paleontological part of the
collection can be divided into three parts: the collection of quaternary vertebrates, the
collection of invertebrate macrofauna and the paleobotanical collection. The collection of
quaternary vertebrates consists of parts of the mammalian quaternary fauna skeletons, and this
part of the collection has one exhibit, which is the mammoth atlas (Mammuthus sp.) found
during the gravel excavation at the Black Bar near Jovaca. By looking at certain parameters
and comparing the measured values of the length and width of the atlas, the obtained value is
1.7 to 1.8, which is between the species Mammuthus primigenius (Blumenbach) and
Mammuthus trogontherii Pohlig. with Mammuthus sp. The collection of invertebrate
macrofauna consists of the remains of shellfish (Bivalvia), snails (Gastropoda) and other
freshwater or marine invertebrates in limestone and other sediments (silt, clay, etc.), and in
this collection there are about a dozen pieces of limestone and other material with remains of
marina or freshwater fauna. The paleobotanical collection consists of parts of a tree found in
silt and peat and peat samples. The petrological part of the collection contains found pieces of
minerals and rocks (sedimentary, metamorphic and magmatic) in the alluvial deposition of the
Sava or Drina during field work (digging) or as a result of hydroerosion. This collection also
contains one box with averaged fractions of alluvial deposit from a single source on the
Zasavica coast.
Mycological collection - a total of 111 specimens of liquid mushroom preparations in
ethanol have been deposited.
Botanical Collection - consists of collected herbarium material of pressed plants, fruits,
twigs with buds, algae and lichen samples, etc. The collection contains between 2500-3000
excipients of herbarium material and 82 bottles and vials with liquid preparations of samples
of plants and algae in ethanol.
Zoological Collection - Includes collected complete material related to the reserve fauna.
The zoological collection can be divided into two major sections: the invertebrate collection,
which includes the Entomological Collection and the collection of other invertebrates, and the
vertebrate collection.
A total of 300 vials and vials containing liquid sample preparations in ethanol have been
deposited in the invertebrate collection and one smaller part is the dry preparation, i.e.
samples in boxes (cocoons, plant damage, gals, litters, etc.). Also, 10 entomological boxes
containes the collected entomological material (insect fauna) from the reserve area.
The vertebrate collection includes: Ichthyological, Batrachological, Herpetological,
Ornithological and Mammological collections.
A total of 106 specimens of liquid and dry preparations have been deposited in the
vertebrate collection.
Review of the spine collection (vertebrate)
Below will be analyzed and commented on the collection of vertebrates, which is the best
processed and arranged, in the brackets [] the number of specimens in the collection is given.
130
Ichthyological collection
The collection has a total of 34 samples in ethanol and one dry head preparation. The
collection includes exhibits of 19 species of fish.
Review of ichthyological collection: 1) Umbra krameri: Banovo Polje, Trebljevine,
26.07.1997 and 26.07.1998, Leg./Det. Stanković. M., [by 1]; 2) Scardinius erithrophthalmus:
Zasavica II, Valjevac, 13.05.2004 and 11.07.2000, Leg/Det.: Stanković. M., [by 1]; 3) Cobitis
elongatea [checkup. Cobitis taenia]: Banovo Polje, well, 26.07.2007, Leg: Stanković. M.,
Det: Sekulić. N., [by 1]; 4) Cobitis taenia: Salaš Noćajski, Sadžak, 13.07.2011, Leg.
Stanković. M., Det. Simić.V., [by 1]; 5) Abramis sapa: Zasavica II, Valjevac, 20.07.2007,
Leg. Stanković. M., Det. Sekulić. N., [1]; 6) Misgurnus fossilis: Radenković, Batar,
20.06.2005, Leg./Det. Stanković. M., [1]; 7) Carassius carassius: Ravnje, Prekopac,
22.06.2004, Leg. Stanković. M., Det. Simić. V., [1]; 8) Barbus peloponesus: Radenković,
Batar, 03.05.2004, Leg. Stanković. M., Det. Simić. V., [1]; 9) Ictalurus nebulosus: Zasavica
II, Valjevac, 07.07.2007, Leg./Det. Stanković. M., [1]; Zasavica I, Šumareva ćup., 2010,
Leg./Det. Stanković. M., [10 juv.]; 10) Lepomis gibosus: Zasavica II, Valjevac, 20.07.2007,
Leg./Det. Stanković. M., [1]; 11) Silurus vulgaris: Zasavica I, Šumareva ćup., 14.06.2007,
Leg./Det. Stanković. M., [1]; 12) Rutilus rutilus: Zasavica II, Valjevac, 20.07.2007, Leg.
Stanković. M., Det. Simić. V., [1]; Zasavica I, Šumareva ćup., 03.05.2003, Leg. Stanković.
M., Det. Simić. V., [1]; Radenković, Vrbovac, 20.07.2007, Leg. Stanković. M., Det. Simić.V.,
[1]; 13) Pseudorasbora parva: Zasavica II, Valjevac, 27.09.2007, 21.07.2007, 20.07. 2007,
Leg. Stanković. M., Det. Simić. V., [by 1]; 14) Abramis brama: Noćaj, Preseka, 04.05.2006,
Zasavica II, Valjevac, 20.07.2008, Zasavica II,Valjevac, 13.05.2007, Leg. Stanković. M., Det.
Simić. V., [by 1]; 15) Gobio albipinnatus: Radenković, Batar, 20.09.2002, Leg. Stanković.
M., Det. Simić. V., [1]; 16) Esox lucius: Zasavica I, Šumareva ćup., 18.05.2005, Zasavica II,
Valjevac, 30.05.2006, Leg./Det. Stanković. M., [1]; 17) Carassius auratus: Noćaj, Preseka,
05.05.2005, [3]; Zasavica II, Valjevac, 20.07.2002, Leg. Stanković. M., Det. Simić. V., [1];
18) Perca fluviatilis: Noćaj, Preseka, 19.03.2006, Zasavica I, Šumareva ćup., 08.04.2005,
Zasavica II, Valjevac, 21.07.2007, [by 1]; Banovo Polje, izvori, 26.07.2007, [1 juv.]; 19)
Neogobius fluviatilis: Zasavica II, Valjevac, 05.07.2008., Leg. Stanković. M., Det. Simić.V.,
[1].
It is important to mention that for the three species of fish in the collection the only data for
the reserve in the past 23 years are: Neogobius fluviatilis, found in 2008 in a watercourse on
Valjevo; Gobio albipinnatum, found in 2002 in Batar and Barbus peloponesus, found in 2004
in Batar.
Batrachological collection
The collection has a total of 28 samples in ethanol, of which 9 are from Caudata and 19
from Anura. In 9 samples of Caudat there are three species, two from the genus Triturus and
one species from the genus Salamandra, while in 19 samples from the Anura there are 10
species. All specimens are stored as a liquid preparation in ethanol.
Review of the Batrachological Collection: Caudata: 1) Salamandra salamandra: Ravnje,
Prekopac, 11.08.1997, Leg./Det. Stanković. M., [1]; Crna bara, Jovača, 27.04.1996, Leg./Det.
Stanković. M., [1 juv]; 2) Triturus vulgaris: Radenković, Vrbovac., 18.06.1998, Zasavica I,
131
Valjevac, 21.07.1997, Ravnje, Široka bara, 06.08.2006, Leg./Det. Stanković. M., [by 1
larva]; Radenković, Batar, 31.03.2000, Radenković, Pačija bara, 22.12.1997, Leg./Det.
Stanković. M., [by 1 juv.]; Ravnje, Prekopac, 07.05.1997, Leg./Det. Stanković. M., [1];
3)Triturus dobrogicus: Ravnje, Prekopac, 10.09.1997, Leg./Det. Stanković. M., [1]; Anura: 1)
Rana ridibunda: Salaš Noćajski, Sadžak, 22.08.1997, Mačv. Mitrovica, Modran, 20.07.1996,
Leg./Det. Stanković. M, [by 1]; 2) Rana temporaria: Radenko vić, Batar, 17.09.2005,
Leg./Det. Stanković. M., [1]; 3) Bufo viridis: Noćaj, Preseka, 25.05.1998, Salaš Noćajski,
canal, 14.04.1998, Leg./Det. Stanković. M., [by 1]; 4) Bufo bufo: Banovo Polje, Panjevine,
25.08.1998, [1 ad.]; Radenković, Batar, 04.11.2005, [1 ad.], 5) Pelobates fuscus: Radenković,
Vrbovac, 25.06.2000, Radenković, Gajića ćup., 30.03.2005, Banovo Polje, Batar,
23.04.2003, [ by 1]; Ravnje, Široka bara 16.07.2010, larvae (tadpoles); Zasavica I, run over,
01.08.2010, [1 juv]; 6) Rana dalmatina: Crna bara, Jovača, 13.05.1997, Leg./Det. Stanković.
M., [1]; 7) Bombina bombina: Salaš Noćajski, Ostrovac, 07.02. 2008.; Crna bara, Jovača,
03.08.2006, Leg./Det. Stanković. M., [by 1]; 8) Rana esc.complex: Zasavica II, Valjevac,
20.07.1996, Leg./ Det. Stanković. M., [1]; 9) Rana lessona: Salaš Noćajski, Sadžak,
03.08.1996, Leg./Det. Stanković.M., [1]; 10) Hyla arborea: Radenković, Batar, 29.07.1998,
Leg./Det. Stanković. M., [1 juv]; Ravnje, 13.07.1998, Leg./Det. Stanković. M., [1].
One specimen of the species Rana temporaria found in Batar (Radenković) in 2005 is also
kept in the Batrachological collection, and it is the only specimen found so far in the reserve.
From the Caudat, the collection contains only two specimens of the Salamandra salamandra
species found in the reserve found in the forests around Jovaca near Crne Bara.
Herpetological collection
The collection has a total of 23 samples in ethanol and dry preparations (armor), of a total
of 10 reptile species. Ordo Testudines: Out of 23 samples in a collection of 8 samples, it
belongs to the Testudines ordo within three types. The collection contains found armor, parts
of armor or whole turtle specimens as dry preparations and their eggs in ethanol. The
collection contains pieces of armor of the allochthonous species Pseudemys scripta elegans
for the time being the only finding in the reserve.
Review of the testudines collection: 1) Emys orbicularis: Noćaj, Preseka, 07.08.2000,
Leg./Det. Stanković. M., [1 oocit]; Zasavica I, Valjevac, 14.05.2008, Leg./Det. Stanković. M.,
[1 juv]; Noćaj, Preseka, 07.08.2009, Leg./Det. Stanković. M., [2 armors]; Mačvan. Mitrovica,
Modran, 23.05.2000, Leg./Det. Stanković. M., [1. ad]; Noćaj, Preseka, 27.07.2008, Leg./Det.
Stanković. M., [1 turtle armor]; 2) Testudo hermanni: Banovo Polje, Kupalište, 28.07.1999,
Leg./Det. Stanković. M., [1 juv]; Ravnje, Staniševac, 08.08.2008, Leg./Det. Stanković. M., [1
turtle armor]; 3) Pseudemys scripta elegans: Zasavica II,Valjevac, 31.07.2008, Leg. Grujić,
D., Det. Stanković, M., [parts of the armor].
Ordo Sauridae: out of a total of 23 specimens in a collection of 6 specimens belong to the
Sauridae order within three species. In addition to whole ethanol-stored specimens, the
collection also stores dried scum found in the field.
Review of the Sauridae collection: 1) Podarcis muralis: Zasavica II, Turske livade,
10.12.2006, Leg./Det. Stanković. M., [1. ad]; Zasavica II, Turske livade, 18.04.2004,
Leg./Det. Stanković. M., [1. ad]; 2) Lacerta viridis: Salaš Noćajski, Sadžak, 20.07.1996, [1
132
juv]; Lacerta sp.: Ravnje, Široka bara, 06.08.2006, Leg./Det. Stanković. M., [1 juv]; 3)
Lacerta agilis: Crna bara, Jovača, 09.06.1996, Leg./Det. Stanković. M., [1 svlak]; Salaš
Noćajski, Sadžak, 20.07.1996, Leg./Det. Stanković. M., [2. ad].
Ordo Serpentes: of the total of 23 specimens in the collection of 9 specimens belong to the
Serpentes order within three species and one intraspecific form. All specimens are stored as a
liquid preparation in ethanol. Special segments of this collection are snake hairs that are
stored in clear thin PVC boxes.
Review of the Serpentes collection: 1) Natrix natrix persa: Banovo Polje, Ribnjača bara,
13.02.1997, Leg./Det. Stanković. M., [1. ad]; Banovo Polje, Trebljevine, 28.08.2008,
Leg./Det. Stanković. M., [1. juv]; 2) Natrix natrix: Radenković, Batar, 29.09.2000, Leg./Det.
Stanković. M., [1]; Zasavica I, Valjevac, 20.07.1996, Leg./Det. Stanković. M., [1]; Salaš
Noćajski, Sadžak, 06.07.1996, Leg./Det. Stanković. M., [1. ad]; 3) Vipera berus bosniensis
melano: Radenković, Batar, 26.08.2005, Leg./Det. Stanković. M., [1. ad]; 4) Elaphe
longissimus: Mač. Mitrovica, Modran (Bogaz), 25.01.1998, Leg./Det. Stanković. M., [1. ad];
Zasavica II, Turske livade, 12.06.2011, Leg./Det. Stanković. M., [oocit]; Banovo Polje,
Trebljevine, 07.07.2004, Leg./Det. Stanković. M., [snake old skin].
The herpetological collection also preserves one black (melano) specimen of the species
Vipera berus bosniensis found in Batar (Radenković) in 2005, and it is the only specimen
found so far in the reserve.
Ornithological collection
The collection has a total of 8 specimens of prepared birds within 7 species. Please note
that all specimens of birds in the collection were found dead in the wild except in one instance
when the specimen was seized by hunter-gatherer hunters for illegal hunting of predators and
donated to us for collection as it comes from the reserve area. There are also several
specimens of bird nests in the collection.
Review of ornithological collections: 1) Phalacrocorax pygmeus: Salaš Noćajski,
05.01.2002, Leg. Nedić. Z., Det. Stanković. M., [1. ad]; Zasavica I, 16.09.2006, Leg. Simić.
S., Det. Stanković. M., [1. ad]; 2) Anas plathyrrhinchos: Zasavica II, Valjevac, 2002, Leg.
Papić. S., Det. Stanković. M., [1.♂ad]; 3) Gavia arctica: Zasavica II, 05.02.2007, Leg. Simić.
S., Det. Stanković. M., [1.♂ad]; 4) Recurvirostra avosetta: Zasavica II, Valjevac, 2008,
Leg./Det. Stanković. M. [1. ad]; 5) Accipiter nisus: Salaš Noćajski, Sadžak., 19.12.1998, Leg.
Papić. S., Det. Stanković. M., [1. ad]; 6) Phaesanus colchicus: Salaš Noćajski, Sadžak-
Ostrovac, 13.12.1998, Leg. Papić. S., Det. Stanković. M., [1. ad]; 7) Strix aluco: Salaš
Noćajski, Sadžak, 2000, Leg. Papić. S., Det. Stanković. M., [1. ad].
Mammological collection
It possesses a total of 20 specimens of prepared mammals within 16 species. In addition to
the prepared whole specimens, the collection includes the preparation of horned heads,
rodents' nests and skulls of small mammals and several specimens in ethanol as liquid
preparations (Erinaceus europaeus, Apodemus agrarius, Sorex araneus, Microtus arvalis,
Talpa europaea and Nyctalus noctua). Material that is only a year old has been received as a
gift and entered the year the copy was presented to us. All specimens that we have collected
133
and after preparation are in the collection were found dead in the wild or killed on the road
(e.g. Castor fiber).
Review mammological collections: 1) Castor fiber: Zasavica, 22.03.2008, Leg. Papić. S.,
Det. Stanković. M., [1. ad]; 2) Rattus norvegicus: Mačv. Mitrovica, Modran, 2002, Leg./Det.
Stanković. M., [1. ad-present]; 3) Ondatra zibethica: Zasavica I, Šumareva ćup, 15.04.2002,
Leg. Simić. S., Det. Stanković. M., [1. ad]; 4) Erinaceus europaeus: Zasavica II, Turske
livade, 12.08.2000, Leg./Det. Stanković. M., [1. ad]; Ravnje, Staniševac, 27.07.2004, Leg.
Stanković. M., Det. Paunović, M., [skull]; 5) Micromys minutus: Ravnje, Bostanište,
24.07.2007, Leg./Det. Stanković. M.; Radenković, Poljansko, 24.07.2007, Leg./Det.
Stanković. M., [∑=2 nests]; 6) Martes martes: Mačvan. Mitrovica, 15.12.1998, Leg./Det.
Stanković. M., [1. ad]; Noćaj, 07.01.2004, Leg. Stanković. M., Det. Paunović, M., [♀skull];
7) Sciurus vulgaris: Noćaj, Preseka, 2002, Leg./Det. Stanković. M., [1. ad-present]; 8) Felis
silvestris: Ravnje, 2005, Leg./Det. Stanković. M., [1. ad] (seized from hunters); 9) Capreolus
capreolus: Noćaj, 1997, Leg. Papić. S., Det. Stanković. M., [1 head, present]; 10) Apodemus
agrarius: Banovo Polje, Panjevine, 11.04.2005, Leg. Stanković. M., Det. Paunović, M., [1.
ad]; 11) Lutra lutra: Ravnje, 25.10.2005, Leg./Det. Stanković. M., [1. ad]; Zasavica I, 2006,
Leg./Det. Stanković. M., [1. ad-present]; 12) Meles meles: Salaš Noćajski 03.01.2002,
Leg./Det. Stanković. M., [1. ad]; 13) Sorex araneus: Radenković, Batar, 29.08.2000,
Leg./Det. Stanković. M., [1. ad]; 14) Microtus arvalis: Zasavica II, Turske livade, 04.08.2004,
Leg. Stanković. M., Det. Paunović, M., [1. ad]; 15) Talpa europaea: Ravnje, Bostanište,
23.07.1998, Leg./Det. Stanković. M., [1. ad]; 16) Nyctalus noctua: Radenković, Vrbovac,
08.07.1998, Leg. Stanković. M., Det. Paunović. M., [1. ad].
By analyzing the natural collection of the vertebrates of the Zasavica Reserve, we see that
all classes of vertebrates are represented.
CONCLUSION
The Zasavica Nature Reserve Study Collection includes the Paleontological-Geological
Section and the Biological Section. For the past 23 years, the following material has been
deposited in the reserve's natural history collection. A total of 50 specimens of minerals, rocks
and fossils have been deposited in the paleontological-petrological collection from the area of
the reservoir and the immediate environment. The paleontological part of the collection
includes a collection of quaternary vertebrates composed of parts of the skeletons of
mammals of the quaternary fauna, and here we have one exhibit, namely the mammoth atlas
(Mammuthus sp.) Found in Black Bar near Jovaca, then a collection of invertebrate
macrofauna consisting of the remains of shellfish shells (Bivalvia), snails (Gastropoda) and
other freshwater or marine invertebrates in limestone and other sediments (silt, clay, etc.) and
a paleobotanical collection consisting of parts of trees found in silt and peat and peat samples.
While the petrological part of the collection contains pieces of minerals and rocks found in
the alluvial deposit of the Sava or Drina or the average fraction of deposits from sources on
the Zasavica coast. The biological part of the collection includes: Mycological collection with
a total of 111 specimens of liquid preparations of fungi; Botanical collection with about 2500-
3000 exotic herbaceous material and 82 bottles and vials with liquid preparations of plants
and algae and the Zoological collection. In the zoological collection, we have a total of 113
134
samples with 64 species + 1 subspecies and include: ichthyological collection with a total of
34 samples in ethanol and one dry head preparation. For the three fish species in the
collection, these are the only data for the reserve in the past 23 years (Neogobius fluviatilis,
Gobio albipinnatum and Barbus peloponesus). A collection of ethanol from a total of 28
specimens of ethanol (9 are from the Caudata order and 19 from the Anura order) where the
only specimen found so far is found in the Rana temporaria species in the reserve.
Herpetological collection with a total of 23 samples in ethanol and dry preparations (armor),
and the only black (melano) specimen of the species Vipera berus bosniensis found so far is
kept in the collection. The ornithological collection consists of a total of 8 specimens of
prepared birds within 7 species, and the mammological collection has a total of 20 exhibits
(whole specimens prepared and head with horns), followed by small mammal skulls, rodent
nests and liquid preparations. The entomological collection has 10 entomological boxes
containing the collected entomological material, as well as a collection of other invertebrates
where about 300 vials and vials with liquid sample preparations in ethanol have been
deposited and one smaller part are dry preparations i.e. samples in boxes.
REFERENCES
[1] I. Maroević, Uvod u muzeologiju, Zavod za informacijske studije, Zagreb (1993).
[2] Available on the following link: https://hr.wikipedia.org/wiki/Muzejska_gra%C4%91a
135
SUITABILITY OF PROCEDURAL CALIBRATION STANDARDS AFTER LONG-
TERM STORAGE FOR PESTICIDE ANALYSIS IN APPLE PEEL
Darko Anđelković1, Milica Branković2*, Gordana Kocić3

1
2
3
*
Abstract
An ever-present problem in the pesticide residue analysis - the matrix effect, can lead to the
misleading results. Procedure-matched standards which compensate both for the matrix effect and the
recovery are one of the best options for the matrix effect overcoming. Since procedural standard
preparation is often time consuming, its storage for a prolonged usage can be valuable. For how long
procedural standards can be stored was evaluated by monitoring the main parameters of the apple
peel-matched calibration graphs for 5 pesticides over 57 days. The preparation procedure itself
consisted of a liquid-liquid and solid-phase extraction, common steps in sample preparation
procedures. Limited storage stability of pyrimethanil determined the storage period of less than 9
days.
Keywords: apple peel, procedural standards, GC-MS, storage
INTRODUCTION
When analyzing complex matrices such are fruits or vegetables, the matrix effect appears
as a certain problem in the domain of quantitative analysis. Abundant matrix compounds can
affect analyte response in two ways. The response enhancement effect, characteristic for gas-
chromatographic analysis, was originally described by Erney et al. [1]. Matrix compounds
from sample extracts block the active sites, primarily in the GC injector, thus leading to the
lesser analyte adsorption and consequently to the signal enhancement and vice-versa, the
growth of the new active sites number by gradual accumulation of non-volatile matrix
compounds in the GC inlet and front part of the chromatographic column could decrease the
analyte response as matrix – induced diminishment effect [2]. Therefore, the matrix effect can
lead to the misleading results in pesticide residue analysis, both in quantitation or validation
procedures and must be in some way overcome. Several approaches are nowadays frequently
applied, such as the use of analyte protectants [3], matrix matched [4] or standard addition
calibration method [5] or even the combination of matrix matching and multiple isotopically
labeled internal standards [6].
Since the matrix effect is matrix-type dependent, the reliable approach of analyte
quantitation should be the matrix-matching. Between the procedure-matched (pre-extraction
fortified standards) and matrix-matched standards (post-extraction fortified standards), the
136
usage of procedure-matched standards is more useful since it represents the straightest method
of quantitation, simultaneously compensating for the recovery and for the matrix effect.
Although this is the straightest method it is not the quickest one. Along with the positive
features, the time-consuming preparation stands as the major negative feature. Thus, an
adequate storage of the standards for the prolonged usage may be an alternative. The aim of
this study was to evaluate the long-term conservation degree of procedural standards of
several pesticides in apple peel as an example of complex matrix.

Chemicals
High purity pesticide standards of trifloxystrobin, bifenthrin and boscalid were obtained
from Sigma-Aldrich® (Germany). High purity pesticide standards of pyrimethanil and
cyprodinil were obtained from AccuStandard® (USA). High purity dibutyl adipate (DBA),
used as internal standard (IS), was purchased from Sigma-Aldrich Chemie® (Germany).
HPLC grade ethanol, HPLC grade hexane and HPLC grade methanol were purchased from
Fisher Scientific (USA). SELECTRA® (octadecyl, bulk form) was purchased from UCT
(USA). Florisil® (60-100 mesh) was purchased from LGC Promochem (Germany).
Stock solutions preparation
Primary pesticides stock solutions of 1,000.00 µg mL-1 were made of high purity pesticide
standards in ethanol. Secondary stock solutions of various pesticide concentration (single-
pesticide solutions) were prepared in ethanol by diluting the primary stock solutions.
Secondary stock solutions of various pesticide concentration (multi-pesticide solutions) were
prepared in ethanol by mixing and diluting the primary stock solutions. Primary DBA stock
solution of 1,000.00 µg mL-1 was prepared in ethanol; solutions of lower concentration were
prepared in hexane, by diluting the primary stock solution. All solutions were stored in freezer
at –15 °C.
Procedural standards preparation
[1] Fortification procedure: Apples of the Granny Smith variety were randomly chosen at
the open-air market (JP “Tržnica”, city of Niš, Serbia). One-kilogram sample was peeled. Peel
was homogenized by blending after which six 10 g-portions were weighted. Each portion was
mixed with 20 mL of water and additionally blended. The resulting mixture was transferred to
a glass container and fortified with 5-pesticide mixture solution (multi-pesticide solution).
The resulting concentration levels were: 0.000 mg kg-1 – blank procedural standard, 0.100,
0.200, 0.300, 0.400 and 0.500 mg kg-1.
[2] Extraction procedure: After homogenization by shaking, mixtures were left to
equilibrate for an hour and then subjected to a liquid-liquid extraction with two 10 mL-
portions of hexane.
[3] Clean-up procedure: Ten milliliters of the obtained hexane extract were subjected to
the SC, SE/LTP procedure, as detailed in Andelković et al. [7] in order to remove waxes.
Afterwards, partially cleaned-up extract was subjected to a SPE procedure in order to remove
pigments. The SPE cartridge was filled with 500 mg of C18, then with 500 mg of Florisil ®
and at last with another 500 mg of C18, thus creating a three-layered form. Prior to sample
137
extract loading, the column was conditioned with 3 mL of methanol. Then, 1 mL of

previously obtained methanol extract was loaded. The elution of analytes was performed with
2 mL of methanol, while the pigmentation was retained on the C18 part of the column. The
obtained eluate was evaporated to dryness, re-dissolved in 0,5 mL of DBA hexane solution (1
µgmL-1) and subjected to GC-MS analysis. Between each data acquisition standards were
kept in refrigerator at 4 °C in closed 2-mL GC glass vials.
Instruments
In sample preparation procedure, following appliances were used: balance KERN KB
2000-2N, Germany (acc. ± 0.01 g); food processor TEFAL 0.9L BL142A, centrifuge Thermo
Scientific Jouan C4i and TurboVap® LV evaporator, Zymark USA, Manifold SPE system
Waters®, USA.
GC-MS analysis
The gas chromatographic analysis was performed on Agilent 6890 gas chromatograph
equipped with 5973 Mass Selective Detector (MSD) and 7683 autosampler and SGE
25QC2/BPX5 0.25 capillary column (25 m×0.22 mm×0.25 µm, non-polar). The mass spectra
were recorded under an electron ionization (EI) voltage of 70 eV. The gas chromatograph was
operated in the splitless injection mode (purge time 1 min). The oven temperature was
programmed from 90 °C (hold time 0 min) to 280 °C (4 min) at 20°C min-1 rate; post run:
300°C (2 min). Helium was the carrier gas with constant flow rate of 1.0 mLmin-1. The target
compounds were identified and confirmed at scan mode (m/z 50–400) and analysed at
selected ion monitoring (SIM) mode with confirmation ions as given in Table 1. Both data
acquisition and processing were accomplished by Agilent MSD ChemStation® D.02.00.275
software.
Table 1 Properties and qualification parameters of tested pesticides (quantifier ion is given in bold)
Pesticide Class Structure MRLa, Molecular Log Retention Characteristic
mg kg mass Kow time, min ions, m/z
-1
Pyrimethanil Fungicide Anilinopyrimidine 15.00 199.25 2.84 6.79 198b

Cyprodinil Fungicide Anilinopyrimidine 2.00 225.28 3.59 7.95 224b
Trifloxystrobin Fungicide Strobilurin 0.70 408.37 4.50 9.06 116, 131, 145
Bifenthrin Insecticide Pyrethroid ester 0.01 422.86 6.00 9.61 181, 166, 165
Boscalid Fungicide Pyridine- 2.00 343.20 2.96 12.08 140, 342, 112
carboxamide
a
Maximum residual level (the highest level of a pesticide residue that is legally tolerated in or on food or
feed when pesticides are applied correctly (Good Agricultural Practice)); b Besides ions specified in the
table, EI ionization of pesticide molecules do not give other specific fragments.

Internal standard overview
Internal standard was added to each calibration standard in the last part of the standard
preparation procedure, and not prior to each data acquisition. This implies that possible
variation in IS signal might be both the outcome of the instrument drift and/or the storage. IS
signal variation as a function of storage time and instrument sequence is given in Figure 1.
138
Within-sequence variation in IS signal during the first data acquisition was about 2%. This
variation is also low after 9 days of storage (about 5%), after which it increases (24-32%),
mainly due to the different IS signal in blank sample (Figure 1, label 0). The percentage of
within-standard IS variation ranged between 8.87% for 0.400 mg kg-1 procedural standard
(label 0.4) to 24.60% for blank procedural standard (label 0). Based on the overall IS
variation, its stability can be considered as good.
Figure 1 Variation in internal standard signal within each sequence and within each standard
Calibration graphs
Evaluation of pyrimethanil calibration plots (Figure 2) and residual plots (not presented in
the paper) suggests that between the signals and the concentration of freshly prepared
standards and standards after 9 day of storage exists good linearity. Calibration plot
parameters assessed from standards after longer period of storage are quite altered. Both
lower slope and intercept values were observed, with no signal-to-concentration correlation
(Figure 2). Lower signal was measured for the same standard over period, suggesting the
decomposition of the pesticide original form. Comparison of 1st day and 9th day acquisition
plots indicate that although the signal-to-concentration correlation is still good after 9 days of
storage, the graphs would not give comparable quantitation result, owing to the clearly
distinct both the slope and the intercept. Thus, for the quantitation purposes of pyrimethanil in
apple peel, freshly prepared procedural standards should be used, or the longevity of
pyrimethanil standards should be additionally investigated and confirmed for periods <9 days.
The similar conclusion can be made either for cyprodinil plots (Figure 2), with the note
that calibration based on the same standards is also appropriate after 9 days of storage, since
the parameters are not altered (Table 2) and linearity is preserved. After that period
significantly lower signals were measured over the full concentration range, indicating certain
changes in the pesticide original form. Trifloxystrobin procedural standards, on the contrary,
preserved good signal-to-concentration correlation over the whole concentration range and
period of storage (Figure 2). The correlation coefficients were always higher than 0.95.
Similar was observed for boscalid calibration plots, where correlation coefficients ranged
from 0.9666 to 0.9899 indicating well-preserved correlation after storage (Table 2).
139
Figure 2 Procedure-matched calibration plots for pyrimethanil, cyprodinil, trifloxystrobin and

boscalid; relative analyte signal was calculated as absolute signal / IS signal
Table 2 Parameters of the procedure-matched calibration graphs for five pesticides in the 0.00 – 0.50
mg kg-1 concentration range
Correlation
Analyte Time range Slope Intercept
coefficient
1st day acquisition – fresh
5.26 0.81 0.9273
standards
Acquisition after 9 days 14.23 0.63 0.9788
Pyrimethanil
Acquisition after 57 days 4.39 -0.03 0.1420
7.57 0.79 0.9807
standards
Cyprodinil
8.95 0.10 0.9731
standards
Trifloxystrobin
4.70 0.05 0.9117
standards
Bifenthrin
140
Table 2 continued
1st day acquisition – fresh 5.90 -0.06 0.9791
standards
Boscalid
When compared to other plots, bifenthrin calibration plots (Figure 3) showed somewhat
weaker signal-to-concentration correlation from the beginning of storage, but the initial
correlation was linear. Stronger correlation and similar slope and intercept values were
maintained until the 9th day of storage, after which alteration was observed (Table 2). The
correlation coefficient ranged from 0.9117 at the beginning to 0.8485 after 57 days of storage.
Figure 3 Procedure-matched calibration plots for bifenthrin
CONCLUSION
Freshly prepared 5-pesticide mixture procedural standards showed good linear signal-to-
concentration correlation, ranging from 0.9117 for bifenthrin to 0.9807 for cyprodinil. Similar
calibration plot parameters i.e. slope and intercept, as well excellent correlation coefficient,
were preserved even after almost two months of trifloxystrobin and boscalid procedural
standards storage. Bifenthrin procedural standards showed slightly weaker linear correlation
than other 4 pesticides and slow decrease in slope until 30th day of storage with preserved
correlation. Pyrimethanil and cyprodinil procedural standards are suitable freshly prepared
and until 9 days of storage, respectively.
Regarding the feasibility of simultaneous analysis as a desirable feature, the overall
conclusion is that mixed procedural standards are suitable for quantitation only up to 9 days
of storage or even less, due to the limited storage stability of pyrimethanil.
ACKNOWLEDGEMENT
University of Niš.
141
REFERENCES
[1] D.R. Erney, A.M. Gillespie, D.M. Gilvydis, J. Chrom. A; 638 (1) (1993) 57–63.
[2] L. Silvestro, I. Tarcomnicu, S. Rizea Savu, Tandem Mass Spectrometry - Molecular
Characterization, IntechOpen, London, (2013), p.3, ISBN: 978-953-51-1136-8.
[3] Y. Li, X. Chen, C. Fan, et al., J .Chrom. A; 1266 (2012) 131–142.
[4] S. de Sousa Freitas, F.M. Lancas, J. Sep. Sci; 32 (2009) 3698–3705.
[5] G. Frenich, J.L. Martínez Vidal, J.L. Fernández Moreno, et al., J. Chrom. A; 1216 (2009)
4798–4808.
[6] T. Tsuchiyama, M. Katsuhara, M. Nakajima, J. Chrom. A; 1524 (2017) 233–245.
[7] D. Andelkovic, M. Brankovic, G. Kocic, et al., Biomed. Chrom; 34 (1) (2020) 4720.
142
LABORATORY SCALED EVALUATION OF SORPTION BEHAVIOR FOR FIVE
PESTICIDES IN APPLE PEEL: EFFECT OF CONTACT TIME
Darko Anđelković1, Milica Branković2*, Gordana Kocić3

1
2
3
*
Abstract
Apple fruit is frequently exposed to pesticide treatment, especially in the latest stages of apples
production. When a pesticide gets the fruit, its interaction with the cuticle and the cuticular waxes
starts via absorption mechanisms. Sorption behavior, that ultimately depends on the pesticide and the
peel waxes characteristics, tends to affect the fate of the pesticide as well as its persistence in the fruit.
This laboratory scaled study was designed to determine the residue levels of four fungicides and one
insecticide in apple peel after immersion in solution of commercial pesticides for different periods of
time. The study revealed that the amount of the fungicides and the insecticide in peel increases
linearly and exponentially, respectively.
Keywords: fruit, sorption, fungicides, insecticides
INTRODUCTION
Apple fruit is frequently exposed to pesticide treatment, especially in the latest stages of
the apples production. The first point of contact of pesticide molecule and fruit is the peel, the
fruits natural barrier. Peel is considered to have an ability to accumulate most of the applied
pesticides. The principal reason for this consideration is the cuticle and its structure and
composition.
Cuticle represents an extracellular coating comprising a polymeric matrix of cutin and
soluble cuticular waxes. The waxy part is mainly consisted of C16–C18 chain compounds i.e.
saturated and unsaturated dihydroxy hexadecenoic, trihydroxy and epoxy hydroxy
octadecanoic acids and a triterpenoid-rich cuticular wax mixture [1].
When a pesticide gets the fruit, its interaction with the cuticle and the cuticular waxes
starts, via absorption mechanisms. A study dealing with the effectiveness of washing agents
in the removal of surface and internalized pesticide residues from apples revealed pesticides
sorption phases [2]. Namely, after applying a pesticide solution to the apple surface, pesticide
was firstly absorbed onto the surface of epicuticular wax and then diffused into the wax and
cuticle. Equilibrium of the pesticide on the epicuticular wax and the pesticide in the wax and
cuticle is established when the amounts of pesticides in wax and cuticle no longer increase
and upon reaching the equilibrium, pesticides begin to penetrate the living cells below,
making this fraction of the pesticide permanently retained.
143
Although there is a range of factors such as the pesticide formulation applied, the applying
conditions etc., absorption processes and their magnitude ultimately depend on the pesticide
and the peel waxes characteristics. This includes the polarity characteristics of pesticides and
its mode of action (penetrating, non-penetrating), the maturity stage of apple fruit, the growth
season and even the apple variety. For sure, sorption behavior tends to affect the fate of the
pesticide as well as its persistence in the fruit.
This study was designed to determine the residue levels of four fungicides and one
insecticide in apple peel after immersion in commercial pesticides solution for different
periods of time and thus to assess if the pesticides sorption process is time dependent.

Chemicals
High purity pesticide standards of trifloxystrobin, bifenthrin and boscalid were obtained
from Sigma-Aldrich® (Germany). High purity pesticide standards of pyrimethanil and
cyprodinil were obtained from AccuStandard® (USA). High purity dibutyl adipate (DBA),
used as internal standard (IS), was purchased from Sigma-Aldrich Chemie® (Germany).
HPLC grade ethanol, HPLC grade hexane and HPLC grade methanol were purchased from
Fisher Scientific (USA). SELECTRA® (octadecyl, bulk form) was purchased from UCT
(USA). Florisil® (60-100 mesh) was purchased from LGC Promochem (Germany).
The following commercial formulations of pesticides were used: Botrystock® -
pyrimethanil (Stockton Crop Protection AG, Swizerland), Cormax® – cyprodinil (Shanghai
Mio, China), Bosco® – boscalid (Ningbo Synagrochem, China), Zato 50 WG® –
trifloxystrobin (Bayer AG, Germany) and Talstar 10 EC® – bifenthrin (FMC Corporation,
USA).
Stock solutions preparation
Primary pesticides stock solutions of 1,000.00 µg mL-1 were made of high purity pesticide
standards in ethanol. Secondary stock solutions of various pesticide concentration (single-
pesticide solutions) were prepared in ethanol by diluting the primary stock solutions. Primary
DBA stock solution of 1,000.00 µg mL-1 was prepared in ethanol; solutions of lower
concentration were prepared in hexane, by diluting primary stock solution. All solutions were
stored in freezer at –15°C. The stock solution of commercial pesticide formulations,
containing 100.00 µg mL-1 of each of five pesticides was prepared prior to experiment set-up
by dissolving commercial formulations in distilled water.
Experiment set-up
Apples of the Granny Smith variety, similar in shape, mass and maturity stage, were
chosen at the open-air market (JP “Tržnica”, city of Niš, Serbia). The average mass of 15
apple units used in this study was 153.64±8.89 g. Apples were cleaned from any visible
dirtiness by wiping. Pesticides sorption was studied by soaking each apple unit in 300 mL of
aqueous solution fortified with five pesticides with final concentration of 1.00 mg L-1, in a
500 mL glass beaker. The submersion period was 0.50, 1.50, 4.00, 5.50 and 7.50 minutes.
Each submersion was performed in triplicates. Immediately after submersion has finished, the
144
excess of immersion solution was removed from apple surface by 2-3 times short immersion
in tap water and wiping, after which apples were peeled.
Analysis: The complete peel mass obtained from apple unit was homogenized by blending
after which a 10 g-sub portion was weighted for analysis. Each portion was mixed with 20
mL of water and additionally blended. The resulting mixture was transferred to a glass
container and subjected to liquid-liquid extraction with two 10 mL-portions of hexane.
Clean-up procedure: Ten millilitres of the obtained hexane extract were subjected to the
SC, SE/LTP procedure, as detailed in Andelković et al. [3] in order to remove waxes.
Afterwards, partially cleaned-up extract was subjected to a SPE procedure in order to remove
pigments. The SPE cartridge was filled with 500 mg of C18, then with 500 mg of Florisil®
and at last with another 500 mg of C18, thus creating a three-layered form. Prior to sample
extract loading, the column was conditioned with 3 mL of methanol. Then, 1 mL of
previously obtained methanol extract was loaded. The elution of analytes was performed with
2 mL of methanol, while the pigmentation was retained on the C18 part of the column. The
obtained eluate was evaporated to dryness, re-dissolved in 0.50 mL of DBA hexane solution
(1 µg mL-1) and subjected to GC-MS analysis.
Note: In order to check for the possible migration of pesticides during the immersion
period, beside peel, the first layer of flesh (approx. 1 mm) was peeled and analysed. Although
there are no waxes in flesh, flesh samples were prepared according to the same procedure due
to the comparability of the results.
Quantitation: For the quantitation purposes procedure-matched standards representing the
mixture of five pesticides were prepared in the following analytical range: 0.000 – 0.050 –
0.100 – 0.200 – 0.300 – 0.350 – 0.400 – 0.500 – 0.600 – 0.700 mg per kg of apple peel and
0.000 – 0.010 – 0.030 – 0.050 – 0.075 – 0.100 – 0.200 mg per kg of apple flesh. Calibration
plots for peel (linear calibration range) at the end included following levels: pyrimethanil and
cyprodinil (0.00, 0.10, 0.30, 0.35, 0.40, 0.50 and 0.70 mgkg-1), trifloxystrobin (analytical
range), bifenthrin (0.000, 0.050, 0.100, 0.350, 0.400, 0.500, 0.600 and 0.700 mg kg-1) and
boscalid (0.000, 0.050, 0.100, 0.200, 0.350, 0.400, 0.500 and 0.700 mg kg-1).
Instruments
In sample preparation procedure, following appliances were used: balance KERN KB
2000-2N, Germany (acc. ± 0.01 g); food processor TEFAL 0.9L BL142A; Manifold SPE
system Waters®, USA; centrifuge Thermo Scientific Jouan C4i and TurboVap® LV
evaporator, Zymark USA.
GC-MS analysis
The gas chromatographic analysis was performed on Agilent 6890 gas chromatograph
equipped with 5973 Mass Selective Detector (MSD) and 7683 autosampler and SGE
25QC2/BPX5 0.25 capillary column (25 m×0.22 mm×0.25 µm, non-polar). The mass spectra
were recorded under an electron ionization (EI) voltage of 70 eV. The gas chromatograph was
operated in the splitless injection mode (purge time 1 min). The oven temperature was
programmed from 90°C (hold time 0 min) to 280°C (4 min) at 20°C min-1 rate; post run:
300°C (2 min). Helium was the carrier gas with constant flow rate of 1.0 mL min -1. The target
compounds were identified and confirmed at scan mode (m/z 50–400) and analyzed at
145
selected ion monitoring (SIM) mode with confirmation ions as given in Table 1. Both data
software.
Table 1 Properties and qualification parameters of tested pesticides (quantifier ion is given in bold)
MRLa, Molecular Log Retention Characteristic
Pesticide Class Structure
mg kg-1 mass Kow time, min ions, m/z
Pyrimethanil Fungicide Anilinopyrimidine 15.00 199.25 2.84 6.79 198b
Cyprodinil Fungicide Anilinopyrimidine 2.00 225.28 3.59 7.95 224b
Trifloxystrobin Fungicide Strobilurin 0.70 408.37 4.50 9.06 116, 131, 145
Bifenthrin Insecticide Pyrethroid ester 0.01 422.86 6.00 9.61 181, 166, 165
Pyridine-
Boscalid Fungicide 2.00 343.20 2.96 12.08 140, 342, 112
carboxamide
a
Maximum residual level (the highest level of a pesticide residue that is legally tolerated in or on food or feed
when pesticides are applied correctly (Good Agricultural Practice)); b Besides ions specified in the table, EI
ionization of pesticide molecules does not give other specific fragments.

Amount of tested pesticides in the first layer of flesh was for all intervals of immersion
below the limit of quantitation of the method. The amount of pyrimethanil and cyprodinil in
apple peel ranges from 0.087 and 0.045 after immersion for 0.50 min, to 0.393 and 0.378 mg
kg-1 after immersion for 7.50 min, respectively (Table 2). The highest tendency for sorption to
apple peel was observed for bifenthrin (3.686 mg kg-1 after 7.50 min of immersion), while
boscalid showed the lowest tendency, not being detected in peel after 0.50 min and reached
only 0.094 mg kg-1 after 7.50 min of immersion. Linear in-peel amount vs. immersion time
correlation can be observed for all pesticides, with exception of bifenthrin for which it is
exponential (Figure 1).
Figure 1 Relationship between pesticide solution-apple contact time and detected amount of pesticide
Considering the average peel mass of the three immersion period replicates and the
pesticide concentration in 300 mL immersion solution (1 mg L-1 each), the pesticide
146
concentration in peel (mg kg-1) in case of a 100% sorption was calculated; theoretical
maximum of each pesticide concentration in peel would be: 19.75 mg kg-1, 21.30 mg kg-1,
21.79 mg kg-1, 18.83 mg kg-1 and 19.00 mg kg-1 in apple units submerged for 0.50, 1.50, 4.00,
5.50 and 7.50 min, respectively. Thus, the sorption percentage for each pesticide over the
period of 7.50 minutes can be calculated (Table 2). The correlation between the immersion
period and the percentage of sorption was evidenced. For pyrimethanil, cyprodinil,
trifloxystrobin and boscalid linear correlation was observed with the correlation coefficient of
0.9974, 0.9762, 0.9755 and 0.8628, respectively. For bifenthrin exponential correlation was
evidenced (R2=0.9709).
Table 2 Pesticides residues and sorption percentage in apple peel (n=3) after being in contact with 1
mg L-1 pesticides solution during different time intervals
Time,
Pesticide: Pyrimethanil Cyprodinil Trifloxystrobin Bifenthrin Boscalid
min
mg kg-1 (RSD, %) 0.087 (32.35) 0.045 (24.80) 0.017 (27.16) 0.058 (15.75) n.d.
0.50
% of sorption 0.44 0.23 0.09 0.29 n.a.
mg kg-1 (RSD, %) 0.128 (31.09) 0.143 (18.76) 0.028 (7.01) 0.204 (15.25) 0.022 (32.18)
1.50
% of sorption 0.60 0.67 0.13 0.96 0.10
mg kg-1 (RSD, %) 0.278 (35.68) 0.278 (18.83) 0.088 (29.64) 0.903 (26.67) 0.076 (17.49)
4.00
% of sorption 1.28 1.28 0.41 4.15 0.35
mg kg-1 (RSD, %) 0.297 (32.08) 0.325 (26.69) 0.084 (44.25) 1.720 (23.72) 0.046 (25.85)
5.50
% of sorption 1.58 1.73 0.45 9.13 0.25
mg kg-1 (RSD, %) 0.393 (21.54) 0.378 (13.13) 0.113 (23.64) 3.686 (8.69) 0.094 (1.23)
7.50
% of sorption 2.07 1.99 0.59 19.39 0.49
CONCLUSION
Apple peel sorption experiments for four fungicides and one insecticide show that sorption
process leads to a linear increase of the fungicides amount in peel, with decreasing sorption
rate in following order: pyrimethanil, cyprodinil > trifloxystrobin > boscalid. Sorption process
for the insecticide bifenthrin leads to an exponential increase of the amount of this pesticide in
apple peel. The sorption percentage confirms the decreasing sorption tendency in following
order: bifenthrin > pyrimethanil, cyprodinil > trifloxystrobin > boscalid. Pesticides amount in
flesh, as determined by the first layer analysis, was below the method limit of quantitation.
ACKNOWLEDGEMENT
University of Niš.
REFERENCES
[1] J. Leide, A.X. de Souza, I. Papp, et al., Sci. Hortic.-Amsterdam; 229 (2018) 137–147.
[2] T. Yang, J. Doherty, B. Zhao, et al., J. Agric. Food Chem; 65 (44) (2017).
[3] D. Andelkovic, M. Brankovic, G. Kocic, et al., Biomed. Chrom; 34 (1) (2020) 4720.
147
THE MIGRATION OF DEHP FROM PLASTIC PACKAGING INTO DAIRY
PRODUCTS WITH DIFFERENT FAT CONTENT
Tatjana Anđelković1, Danica Bogdanović1*, Ivana Kostić1, Darko Anđelković1,

Gordana Kocić2
1
University of Niš, Faculty of Science and Matematics, Department of Chemistry,
2
*
Abstract
Objective of this study was to determine the effect of fat content of dairy products on the migration of
di-(2-ethylhexyl) phthalate (DEHP) from plastic packaging into different dairy products. Migration of
DEHP from plastic packaging into three dairy recipients with different fat content was observed:
infant formula, whey powder and water under the influence of increased temperature. Amount of
leached DEHP from plastic packaging into different recipients was determined by liquid-liquid
extraction followed by gas chromatography-mass spectrometry (GC/MS).The ion of base peak m/z 149
for DEHP was selected for the screening studies. The acquisition was performed at the selected ion
monitoring mode (SIM). The mass-selective detector (MSD) response for GC/MS DEHP calibration
standards was linear between 0.25 and 2.50 µg mL–1. The study demonstrated an increase of the
amount of migrated DEHP from packaging material into dairy product with higher percentage of fat.
The mass of migrated DEHP was the highest in the sample of infant formula, followed by whey
powder and water. Also, the results show that longer exposure to high temperature results in reaching
the plateau on the graph Mass of migrated DEHP vs time, which means that further exposure to high
temperature does not result in increase of DEHP leaching.
Keywords: DEHP migration, dairy products, fat content, plastic packaging, GC/MS
INTRODUCTION
Phthalates, known as dialkyl or alkyl aryl esters of 1,2-benzenedicarboxylic acid, are a type
of chemical compounds used to soften plastics, making plastics more suitable for a wider
range of uses. Plastics treated with such plasticizers are softer and more flexible, with a
suitable odour and colour. As such, plastics are used to manufacture medical equipment,
children's toys, food packaging and other different plastic packaging. However, the phthalates
are not chemically bonded to the polymer but are only impregnated in the polymer, making
phthalates more accessible to the environment (phthalates can easily migrate to their
environment - food, drink, air, soil, etc.).In this way, human health can be affected by
phthalates, so the European Food Safety Authority (EFSA) had set the tolerable daily intake
(TDI) for the most commonly used phthalate - DEHP and amounts 0.05 mg kg–1 body weight
of adult human day–1 [1]. Various studies have shown that DEHP exposure may induce
reproductive toxicity, liver damage, and carcinogenesis in humans [2]. Given that DEHP
148
affects human health, and that DEHP is easily leached into food from plastic packaging
materials, it is of great importance to determine the concentration of DEHP in the investigated
matrices as well as to test the impact of fat content to a DEHP migration.
Determination of DEHP can be performed using different techniques, depending on the
investigated matrix. Gas chromatography coupled with mass spectrometry (GC/MS) is the
most used technique for DEHP determination [3].
In this experiment, the migration of DEHP from plastic packaging materials of known
percentages of DEHP was done under the influence of increased temperature, while dairy
products with different fat content were used as the receiving matrix for the leached DEHP.
The quantification of leached DEHP from plastic packaging into different dairy products was
performed by GC/MS. In this way, the impact of fat content of dairy products on migration
of DEHP from plastic packaging was determined.

Reagents and materials
HPLC grade n-hexane was purchased from Sigma–Aldrich (St. Louis, MO, USA). Di(2-
ethylhexyl) phthalate (DEHP) was purchased, in the highest available purity, from Sigma–
Aldrich (St. Louis, MO, USA). Dibutyladipate (DBA) was purchased from Fluka (Buchs,
Switzerland) and used as an internal standard. Water from a Milli-Q system (Millipore,
Bedford, MA, USA) was used. Dialysis bag (Baxter, USA) was used. Whey powder and
infant formula were purchased from commercial manufacturers offered at the Serbian market.
All stock, intermediate and working solutions were prepared in n-hexane. The stock
solutions of DEHP and DBA were prepared at a concentration of 1.0 mg mL-1. The stock
standard was diluted stepwise with n-hexane to prepare working solutions of DEHP. The
calibration standard series was obtained with DEHP in the concentration range of 0.25, 0.50,
1.00, 1.50 and 2.50 µg mL-1 with DBA as the internal standard, at a concentration of 1 µg mL-
1
. The calibration curve was linear in the range from 0.25 to 2.5 µg mL-1 with a correlation
coefficient higher than 0.99. The linear dynamic range was broader and covered the range
from 2.50 to 50 µg mL-1.
GC-MS technique
Gas chromatographic analysis was performed by gas chromatograph 6890 (Hewlett-
Packard, USA) equipped with a mass selective detector (MSD) 5973 (Hewlett-Packard, USA)
and Autosampler 7683 (Agilent, USA) and a DB-5 MS capillary column (30 m × 250 mm ×
0.25 mm) (Agilent, USA). The gas chromatograph was operated in the split less injection
mode. The oven temperature was programmed from initial temperature 60 °C (hold time 1
min) to 220 °C (hold time 1 min) at a rate of 20 °C min-1and then to 280 °C (hold time 4 min)
at a rate of 5 °C min-1. Helium was the carrier gas (flow rate of 1.0 mL min-1) and the inlet
temperature was 250 °C. The operating temperature of the MSD was 280 °C with the electron
impact ionization (EI) voltage of 70 eV. The dwell time was 100 ms. The MSD was used in
the single ion-monitoring mode (SIM), the quantification ion wasm/z 149 for DEHP and ion
m/z 185 was chosen as representative ion of DBA. Analyte response was normalized to DBA
as internal standard. The identification and quantification of target compound was based on
149
the relative retention time, the presence of target ion and its relative abundance. Both data
software.
Sample preparation
In the migration experiment, recipients for migrated DEHP from plastic packaging
materials under the influence of temperature were infant formula, whey powder and water.
Dairy products (infant formula and whey powder) were non-polar and had different fat
content, unlike water which was polar and without fat, and it was taken for comparison. Fat
content for infant formula and whey powder were 22.8 and 2 %, respectively.
Whey powder (65 g) and infant formula (45 g) were dissolved in 1 L of water from a Milli-
Q system, respectively, according to the producer instruction. Fresh samples were always
prepared immediately before analysis.
The dialysis bag was used as a plastic packaging material with high phthalate content. This
reliable source of DEHP which contains about 35.8 % of DEHP compared to the total weight
was used to examine DEHP migration [4]. The measured pieces of 1 cm2 of dialysis bag were
covered with 35 mL of dairy samples (infant formula and whey powder) and water.
Migration experiment and extraction procedure
The conditions of a migration experiment were set up to determine the effects of exposure
time and temperature to DEHP migration into dairy products: dairy products with plastic
packaging materials were heated up to 60 °C for up to 60 min, with repetition of cooling and
heating processes with the total heating time up to 60 hours.
Dairy samples with 1 cm2 of dialysis bag were vigorously stirred and heated to a
temperature up to 60 °C, for 60 min. After cooling the samples at room temperature and
filtering, 20 mL of n-hexane, as effective extraction agent[5], was added to the samples.
Extracts were manually shake for 15 minutes followed by extraction inthe ultrasonic bath for
30 minutes. After clarification of blurred extracts, the n-hexane layers were separated and
concentrated to the volume of 1 mL. DBA was added to concentrated n-hexane extracts such
that its concentration in each sample was 1 µg mL-1.
Pieces of dialysis bag, were subjected to repeated migration tests into dairy products,
providing total heating time of 60 hours. The test was performed until the plateau was reached
on the curve m = f (t), where m is mass of the migrated DEHP and t time of exposure.
Blank samples (dairy products without plastic pieces from dialysis bag) were treated in the
same way as the dairy samples with plastic pieces from dialysis bag. The laboratory
contamination was thus monitored.
All experiments were performed in triplicate and quantification on GC/MS was repeated
twice.
Glassware control
In order to minimize the contamination by phthalates from the laboratory, only glassware
equipment was used. All glassware was washed with soap, tap water and ultrapure water, then
washed with acetone and n-hexane and dried at 200 °C in the oven for 4 hours [6].
150

The chromatogram of a standard solution of DEHP and DBA, given in Figure 1, shows
good separation of DEHP and DBA occurred within a running time of 20 minand retention
times for DBA and DEHP were 9.990 and 18.426 min, respectively. The calibration curve
was linear in the range from 0.25 to 2.5 µg mL-1 with correlation coefficient of calibration
curve higher than 0.990.
Figure 1 GC/MS chromatogram of a standard solution of DEHP and DBA in a concentration of 2.5
µg mL-1 and 1.00 µg mL-1, respectively
Figure 2 shows the graphs of the mass of the migrated DEHP as the function of exposure
time to increased temperature for three types of dairy products. The graphs show a linear
increase of the mass of migrated DEHP over time under the influence of temperature, until the
plateau is reached. Plateau indicates that after the maximum migration of DEHP has been
reached DEHP no longer migrates into the food receiving matrices under the influence of
increased temperature. Maximal amount of migrated DEHP, to water as recipient, is reached
after 2500 min. The time required to achieve maximum DEHP migration into whey powder
and infant formula were2950 and 3000 minutes, respectively.
151
Figure 2 The influence of temperature on the migration of DEHP in a) water, b) whey powder, c)
infant formula
The total migrated amount of DEHP follows the order: infant formula (601.29 µg), whey
powder (311.83 µg) and water (135.67 µg), which is in correlation with the time of reaching
plateau and with fat content of receiving matrix.
Figure 3 shows two regions in the mass vs. time graphs. Graph (a) shows the dependence of
the mass of the migrated DEHP relative to the total exposure time of the samples to increased
temperature and graph (b) shows the dependence of the mass of migrated DEHP in the first
450 min of exposure. The second graph shows higher slope of curve of migrated DEHP over
time and curve is almost linear. During this period of 450 min about 30 % of total amount of
migrated DEHP migrated into recipients. Unlike this rapid migration in the first 450 min, the
migration in the remaining exposure time is slower, and slope of curve of migrated DEHP
over time was smaller then of the above noted.
Figure 3 Mass of the migrated DEHP under the influence of temperature a) in a time period of
3500 min and b) in a time period of 450 min
The aim of this migration experiment was to determine the total mass of the migrated
DEHP from plastic packaging materials into dairy products after repeated migration, related
to temperature. The effects of temperature and fat content of dairy products on DEHP
leaching are presented in Table 1.The results show that the highest mass of migrated DEHP
was determined in the dairy product with the highest percentage of fat, which was expected,
since DEHP is a non-polar molecule and is more soluble in non-polar media such as the infant
formula with 22 % of fat. Water as a polar medium was not a suitable recipient for migrated
152
DEHP, while whey powder was second recipient for DEHP due to a fat content of 2 %.In all
three cases, the percentage of DEHP leaching was low and ranged from to 0.02-0.12 %
relative to the mass of DEHP in plastic materials.
Table 1 Migration of DEHP influenced by temperature and fat content of food receiving matrix
Percentage of
Food receiving Mass of dialysis Mass of DEHP in Maximal amount of
migrated DEHP
matrix bag (g) dialysis bag (g)[4] migrated DEHP (µg)
(%)
Water 1.7410 0.6233 135.67±1.23 0.02
Whey powder 1.6113 0.5768 311.83±1.40 0.05
Infant formula 1.4560 0.5212 601.29±2.73 0.12
CONCLUSION
Migration of DEHP from plastic packaging materials to dairy products depends on
exposure temperature, exposure time and fat content of dairy product. Obtained data showed
the following: amount of migrated DEHP decreases by following order infant formula > whey
powder > water. In this order the fat content also decreases, which indicates that the highest
migration is for dairy product with highest fat content. Results indicate that increasing
temperature increases the migration of phthalates into diary matrices. Thus, during period of
450 min about 30 % of total amount of DEHP migrated into recipients, while the migration in
the remaining exposure time is slower.
ACKNOWLEDGEMENT
of the Republic of Serbia and was performed as a part of Project TR 31060. This investigation was
done under agreement 451-03-68/2020-14/200124.
REFERENCES
[1] European Food Safety Authority, EFSA J; 243(2005) 1.
[2] S. Benjamin, E. Masai, N. Kamimura, et al., J. Haz. Mat; 340 (2017) 360–383.
[3] C. Sablayrolles, M. Montréjaud-Vignoles, D. Benanou, et al., J. Chrom. A; 1072 (2005)
233–242.
[4] I. Kostić, T. Anđelković, D. Anđelković, et al., Bulg. Chem. Commun; 49 (2) (2017) 360–
365.
[5] D. Milojković, D. Anđelković, G. Kocić, et al., J. Serb. Chem. Soc; 80 (8) (2015) 983–
996.
[6] A. Fankhauser-Noti, K. Grob, Anal. Chim. Acta; 582 (2) (2007) 353–360.
153
OPTIMIZATION AND APPLICATION OF LIGNOCELLULOSIC-Al2O3
BIOSORBENT FOR COPPER IONS REMOVAL FROM WATER
Nena Velinov1*, Milica Petrović1, Miljana Radović Vučić1, Miloš Kostić1,

Jelena Mitrović1, Danijela Bojić1, Aleksandar Bojić1
1
*
nena.velinov@yahoo.com
Abstract
The chemically modified lignocellulosic biomass with an inorganic oxide (Al 2O3) was tested as a new
sorbent for the removal of copper (Cu (II)) ions from aqueous solution in batch conditions. As a
lignocellulosic base material woodchips from an oak tree (Quercus rubra) were used. In order to
define optimal conditions for sorption of Cu (II) ions from water by lignocellulosic-Al2O3 hybrid (LC-
Al2O3), effects of initial pH, sorbent dosage and initial Cu(II) ions concentration, were studied. The
increase in the solution pH from 1.0 to 6.0 led to an increase of removal efficiency of Cu (II) ions. The
highest removal efficiency of Cu (II) ions was observed at pH 6 reached 99.08%. The increase of
biosorbent dose from 0.5 to 8.0 g dm-3 led to an increase of removal efficiency of Cu (II) ions. Optimal
sorbent dosage was 2.0 g dm-3. With the increase of initial Cu (II) ions concentration, the removal
efficiency decrease. In addition to the high removal efficiency, LC-Al2O3 biosorbent possesses other
benefits, like mechanical stability, ease of synthesis, cost-effectiveness, biocompatibility and
environmental-friendliness, which all makes it a promising material for the removal of heavy metal
ions from water.
Keywords: optimization, biosorption, removal, copper, wastewater treatment
INTRODUCTION
Water bodies can be polluted by a wide variety of substances and the largest source of it
are small and big industries. One of the most basic environmental pollutants discharged to
water or wastewaters are heavy metals which may originate from wastewater of many
industries, such as batteries, tanneries, electrical, electroplating, mining, refining ores,
fertilizers, pesticides, etc. [1,2]. Heavy metals can pose a risk to the human and environmental
health due to their hazardous effects, persistency and accumulation tendency causing damage
to many parts of human bodies, even at very low concentrations [3,4]. Therefore, the removal
of heavy metals from aqueous solutions is of extreme importance. Numerous processes and
technologies have been used for heavy metal removal, such as: precipitation, ion exchange,
membrane filtration, electroplating [1]. Among them, biosorption, using inactive and dead
biomasses as sorbents, has emerged as a promising technique as compared to other methods
of wastewater treatment in terms of cost, the simplicity of design and operation, availability,
effectiveness, insensitivity to toxic substances and potential metal recovery [5].
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In this paper, application of a chemically modified lignocellulosic biomass with a small

amount of Al2O3 (LC-Al2O3) for removal of copper (Cu (II)) ions from water was studied. As
a lignocellulosic base material woodchips from an oak tree (Quercus robur) were used.
Woodchips were generated from wood industries, particularly from furniture manufacturing,
so in that manner reusing this kind of material we can reduce waste and increase reuse/recycle
options. In order to investigate principal operational process parameters effects of pH,
temperature, sorbent dose and Cu (II) ions concentration on the sorption process were
examined.

The experiments have been performed using a woodchips residue generated from an oak
tree (Quercus robur), which were fractionated by size and washed with deionized water. Ten
grams of the biomass was acid treated (0.3 M HNO3) to remove bio-accumulated metals, then
alkali treated (1 M NaOH) in the period of 60 min. After that the material was mixed with
solution of 1g of Al(NO3)3 × 9H2O dissolved in 100 cm3 of deionized water and the
suspension was stirred for 0.5 h at 25.0 ± 0.5°C. After that the solution was evaporated. The
obtained material was washed with deionized water, and treated by trimethylamine, then
washed with deionized water until neutral pH and dried at 55 ± 1ºC for 5h. This material was
abbreviated as LC-Al2O3.
Working model solutions of Cu (II) ions was prepared by the appropriate dilution of the
stock solutions (1.0000 g dm-3). The pH of the solutions was adjusted with 0.1/0.01 mol dm-3
NaOH/HNO3 solutions pH-metrically (Orion Star A214, Thermo Fisher Scientific, USA). All
experiments were performed at 25.0 ± 0.2°C. The aliquots of the solution were taken before
the sorption started, and after particular periods of time. The concentrations of Cu (II) ions in
the solution were determined by an atomic adsorption spectrometer Analyst AA 300 (Perkin
Elmer, USA).
The removal efficiency (RE) of Cu (II) ions by biosorbent was calculated using the
equation (1):
c0  c t
RE(%)  x100 (1)
c0
where c0 and ct are the initial and final Cu (II) ions concentrations in the solution (mg dm–3).
All experiments were performed in triplicate. Average values ± SD (error bars) are
presented in all graphs. All parameters were evaluated with the non-linear regression method
by means of Origin Pro 2016 software (Origin Lab Corporation, USA).

Effects of initial pH
The removal of Cu (II) ions by LC-Al2O3 biosorbent is highly affected by the pH value of
the solution. The experiments were studied by varying initial pH value from 1.0 up to 6.0,
while other parameters were kept constant (initial metal concentration 20.0 mg dm-3, sorbent
dose 2.0 g dm-3, temperature 25.0 ± 0.2ºC). Results show that an increase in the solution pH
155
from 2.0 to 6.0 led to an increase in the removal efficiency of Cu (II) ions from 35.05 to
99.08% (Figure 1).
Figure 1 Effect of pH on the Cu (II) ions removal with LC-Al2O3. Initial Cu (II) ions concentration
20.0 mg dm-3, sorbent dose 2.0 g dm-3, temperature 25.0 ± 0.2ºC
Therefore, when the pH decreased, concentrations of protons increased and competition in

binding the active sites on the surface of biosorbent, between the H+ and metal ions started.
Protonated active sites were incapable of binding metal ions, leading to free ions remaining in
the solution. With the increase in pH, the overall surface on LC-Al2O3 became negative and
sorption was increased and the competing effect of hydronium ions decreased. Dominant
species of copper in the pH range 3–5 are Cu2+ and CuOH+, while the copper at above 6.3
occurs as insoluble Cu(OH)2, so above pH 6.0, insoluble copper hydroxide starts precipitating
from the solution and experiments could not be done [6,7]. From the obtained results, it can
be concluded that the optimal pH value is 6.0 and this pH value was also used for all further
experiments.
Effect of temperature
The temperature of the solution plays an important role in the sorption process. Increasing
the temperature is known to cause an increase in the rate of diffusion of the sorbate molecules
across the external boundary layer and in the internal pores of the sorbent, owing to the
decrease in the viscosity of the solution. In that manner, changing the temperature will change
the rate of the sorption [8]. The experiments were done at different temperatures: 10.0, 20.0,
35.0 and 50.0 °C, while the other parameters were kept constant (initial pH 6.0, initial
pollutant concentration 20.0 mg dm−3 and sorbent dose 2.0 g dm−3). Results show that an
increase in the solution temperature from 10.0 to 50.0 °C led to an increase in the removal
efficiency of Cu (II) ions from 84.12 to 99.9%, indicating the process to be endothermic in
nature (Figure 2).
156
Figure 2 Effect of temperature on the Cu (II) ions removal with LC-Al2O3. Initial pH 6.0, initial Cu
(II) ions concentration 20.0 mg dm-3, sorbent dose 2.0 g dm-3
Such influence of temperature may be a result of expected increase in the diffusion of Cu

(II) ions in the water environment [8].
Effect of biosorbent dose
The removal efficiency of Cu (II) ions by LC-Al2O3 biosorbent significantly depends on
amount of the biosorbent due to active surface area of the biosorbent and of available binding
sites for Cu (II) ions. The effect of sorbent dose on the removal efficiency of pollutants by
LC-Al2O3 was investigated in the range from 0.5 to 8.0 g dm−3, while other parameters were
kept constant (initial pH 6.0, initial pollutant concentration 20.0 mg dm−3 and temperature
25.0 ± 0.2 °C). Results show that an increase in the biosorbent dose from 0.5 to 8.0 g dm−3 led
to an increase in the removal efficiency of Cu (II) ions from 34.05 to 99.8% (Figure 3).
Figure 3 Effect of biosorbent dose on the Cu (II) ions removal with LC-Al2O3. Initial pH 6.0, initial
Cu (II) ions concentration 20.0 mg dm-3, temperature 25.0 ± 0.2ºC
157
Removal efficiency of Cu (II) ions increased quickly from 34.05 to 98.21% with an
increase in the sorbent dose from 0.5 to 2.0 g dm−3, because of the increased active surface
area of the biosorbent and the number of available binding sites for pollutants. Further
increase in the sorbent dose to 4.0 g dm−3 slightly enhanced removal efficiency to 99.1%. The
removal efficiency was without change at the sorbent doses of 6.0–8.0 g dm−3. A negligible
change in the removal efficiency at a biosorbent dosage higher than 2.0 g dm−3 may be
attributed to the presence of the excess of active centres for pollutants binding on the
biosorbent surface, with regard to the amount of Cu (II) ions initial concentration [9].
Therefore, a value of 2.0 g dm−3 was considered as the optimal biosorbent dose of LC-Al2O3
for removal of Cu (II) ions used in all other experiments.
Effect of initial Cu(II) ions concentration
Effects of initial Cu (II) ions concentration on the removal efficiency by LC-Al2O3 was
investigated in the range from 5.0 to 100.0 mg dm−3, while other parameters were kept
constant (initial pH 6.0, sorbent dose 2.0 g dm−3 and temperature 25.0 ± 0.2 °C). Results show
that an increase in initial Cu (II) ions concentration from 5.0 to 100.0 mg dm−3 led to an
decreased in the removal efficiency of Cu (II) ions (Figure 4).
Figure 4 Effect of initial Cu (II) ions concentration on the removal with LC-Al2O3. Initial pH 6.0,
sorbent dose 2.0 g dm-3, temperature 25.0 ± 0.2ºC
With an increase in initial Cu (II) ions concentration, removal efficiency decreased. For
initial concentrations of Cu (II) ions from 5.0 to 20.0 mg dm−3, the removal efficiency was
very high (99.11–98.21%). With further increase in concentrations to 50.0 mg dm−3, the
removal efficiency slowly decreased. With the increase in the initial Cu (II) ions
concentration up to 100.0 mg dm−3, removal efficiency decreased, reaching a value of
31.38%. In the case of a lower concentration range (5.0, 10.0 and 20.0 mg dm−3), the ratio of
initial number of sorbate molecules to the available sorption sites is low, and the biosorption
becomes independent of initial concentration, which enabled the 99% ions uptake. At higher
investigated concentrations (up to 100.0 mg dm−3), a certain amount of molecules is left
158
unsorbed in the solution due to a saturation of the limited available binding sites in the
biomass [9,10].
CONCLUSION
A new material based on the chemical modification of lignocellulosic biomass with Al2O3
was synthesized in order to improve ability of starting biomass to remove heavy metal ions,
such as Cu (II) ions. The initial pH strongly affects the sorption of Cu (II) ions onto LC-
Al2O3. The optimal pH value for Cu (II) ions removal is 5 with very high removal efficiency
(99.08%). It can be assumed that the main binding mechanism is ion exchange. The effect of
temperature shows that the biosorption process for Cu (II) ions was endothermic in nature.
The extent Cu (II) ions removal is directly related to the concentration of LC-Al2O3 in the
suspension, with an optimal biosorbent dose of 2.0 g dm-3. With the increase of initial metal
ions concentration, the removal efficiency decrease. In addition to the high removal
efficiency, LC-Al2O3 possesses other benefits, like mechanical stability, ease of synthesis,
cost-effectiveness, biocompatibility and environmental-friendliness, which all makes it a
promising material for the removal of heavy metal ions from water.
ACKNOWLEDGEMENT
The authors would like to acknowledge financial support from the Ministry of Education, Science
and Technological Development of the Republic of Serbia (Agreement No 451-03-68/2020-
14/200124).
REFERENCES
[1] K. Banerjee, S.T. Ramesh, P.V. Nidheesh, et al., Iranica J. Energy Environ; 3 (2012) 143–
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[2] Q. Manzoor, R. Nadeem, M. Iqbal, et al., Bioresour. Technol; 132 (2013) 446–452.
[3] P.S. Kumar, S. Ramalingam, V. Sathyaselvabala, et al., Korean J. Chem. Eng; 29 (2012)
756–768.
[4] A.B.P. Marin, M.I. Aguilar, J.F. Ortuno, et al., J. Chem. Technol. Biotechnol; 85 (2010)
1310–1318.
[5] T.V. Nguyen, S. Vigneswaran, H.H. Ngo, et al., J. Haz. Mat; 182 (2010) 723–729.
[6] M. Akbari, A. Hallajisani, A.R. Keshtkar, et al., J. Environ. Chem. Eng; 3 (2015) 140–
149.
[7] T. Todorciuc, L. Bulgariu, I.V. Popa, Cell Chem. Technol; 49 (2015) 439–447.
[8] H. Javadian, M.T. Angaji, M. Naushad, J. Ind. Eng. Chem; 20 (2014) 3890–3900.
[9] B. Tural, E. Ertaş, B. Enez, et al., J. Environ. Chem. Eng; 5 (2017) 4795–4802.
[10] F. Kallel, F. Bouaziz, F. Chaari, et al., Process Saf. Environ. Prot; 102 (2016) 30–43.
159
REACTIVE DYE CONTAMINATED WATER TREATED BY PHOTO DRIVEN
ADVANCED OXIDATION PROCESSES
Miljana Radović Vučić1, Nena Velinov1*, Milica Petrović1, Slobodan Najdanović1,

Jelena Mitrović1, Danijela Bojić1, Aleksandar Bojić1
1
University of Niš, Department of Chemistry, Faculty of Science and Mathematics,
*
Abstract
Reactive dyes are extensively used in the last years due to superior performance. This study examines,
for the first time, heterogeneous advanced oxidation processes TiO2/UV/KBrO3, TiO2/UV/(NH4)2S2O8
and TiO2/UV/H2O2 for the purpose of decolorization of anthraquinone dye Reactive Blue 19 (RB 19).
Decolorization is very fast for TiO2/UV/H2O2 (87.79%), becomes even faster for TiO2/UV/KBrO3
(96.38%), after 10 min. On the other hand for TiO2/UV/(NH4)2S2O8 process, complete dye
decolorization was achieved in less than 10 min. In addition, experiments performed in three different
matrixes were compared. In the surface water and dyebath effluent water, the removal efficiency of RB
19 was lower than that in the deionized water because of the interference of complex constituents in
the surface water and effluent.
Keywords: AOPs, reactive blue 19, reactive dye, photocatalysis, electron acceptors
INTRODUCTION
Synthetic dyes are widely used in textile, cosmetics, printing, drug and food processing
industries. Anthraquinone dyes represented the second most used class of commercial dyes
after azo-compounds and are mainly used for dyeing wool, polyamide and leather. Dyes
present in wastewater are of particular environmental concern since they not only give an
undesirable color to the waters but also in some cases are themselves harmful compounds and
can originate dangerous by-products through oxidation, hydrolysis, or other chemical
reactions taking place in the waste phase [1]. A wide range of methods has been developed
for the removal of synthetic dyes from natural and wastewaters to decrease their impact on the
environment.
The main problem of heterogeneous photocatalysis is the undesired electron-hole pair
recombination. This is the step in which the major energy-wasting occurs. This further leads
to low quantum yield. These could be achieved by using electron acceptors or hole scavengers
[2].
To the best of our knowledge, the study of photocatalytic decolorization of anthraquinone
dye Reactive Blue 19 (RB 19) using heterogeneous advanced oxidation processes
TiO2/UV/KBrO3, TiO2/UV/H2O2 and TiO2/UV/(NH4)2S2O8 has not been reported in the
literature. The performance of these processes in terms of decolorization efficiency was
compared. In addition, experiments performed in three different matrixes (lab deionized
160
water, surface water collected from the Nišava River and dyebath effluent water from a local
cotton dyeing) were compared.

Reagents
The anthraquinone reactive dye C.I. Reactive Blue 19 (RB 19) (Mw = 626.55 g mol–1) was
obtained from Sigma-Aldrich (USA) and used without any purification. The hydrogen
peroxide (H2O2) solution (30.0%), potassium bromate (KBrO3) and ammonium persulfate
((NH4)2S2O8) were of analytical grade and purchased from Merck (Germany). TiO2-P25 was
received from Degussa (Frankfurt, Germany). TiO2-P25 contains anatase 80.0 and rutile 20.0
with the mean particle size of 30.0 nm and BET surface area of 50.0 m2 g–1.
Photoreactor
Photochemical experiments were carried out in a batch photoreactor handmade in our
laboratory. The UV lamps were turned on 10 min before performing each experiment. The
intensity of UV radiation was measured by UV radiometer Solarmeter model 8.0 UVC
(Solartech, USA). The total UV intensity was controlled by turning on different numbers of
UV lamps and the maximum intensity was 1950 μW cm–2 (with all ten UV lamps on) at the
distance of 220 mm, from working solution surface.
Procedures
A stock solution of RB 19 was made by dissolving 1.0 g dye in 1000.0 cm 3 of deionized
water. Working solutions were prepared freshly, before irradiation, by diluting the stock to the
desired concentration with deionized water. The pH of solutions was adjusted by addition of
NaOH or HCl (0.1/0.01 mol dm–3) with pH/ISE meter (Orion Star A214, Thermo scientific,
USA). The suspensions of dye and TiO2 were magnetically stirred in dark for 30 min to attain
adsorption-desorption equilibrium between dye and TiO2, and then the dye solutions are
treated in the UV reactor.
During irradiation, the solution was magnetically stirred (Are, Velp Scientifica, Italy) in a
constant rate and temperature was maintained at 25 ± 0.5ºC by thermostating. At required
time intervals, 4.0 cm3 of samples were withdrawn, centrifuged (3000 o min–1, 15 min) and
filtered through a 0.20 μm regenerated cellulose membrane filter (Agilent Technologies,
Germany) to separate the catalyst. Absorbance at 592 nm was measured using a UV-vis
spectrophotometer Shimadzu UV-1800 PC (Shimadzu, Japan) to determine the degree of
decolorization of the solution. To ensure the accuracy, reliability, and reproducibility of the
collected data, all experiments were carried out in triplicate, and mean values are recorded.
OriginPro 2016 (OriginLab Corporation) software was used for statistical analysis and
calculation of the data.

The preliminary experiments were carried out in order to investigate the effect of UV
radiation only, TiO2 without UV radiation, electron acceptors (KBrO3, H2O2 and (NH4)2S2O8)
without UV radiation and UV irradiation in the presence of TiO2 and electron acceptors. The
161
solution of RB 19 dye (initial dye concentration was 50.0 mg dm–3) was irradiated in the time
period of 180 min to examine the effect of UV light radiation alone and there was no
observable decrease of the residual dye concentration. It indicated that the direct photolysis of
RB 19 dye by UV irradiation was slow. Experiments with only electron acceptors were done
in the time period of 180 min in dark. The dye removal efficiency, in that case, was also
negligible. No decolorization was observed for the dye solution with TiO2 without UV
radiation (Figure 1).
In order to optimize the process, a comparison was made between the three heterogeneous
oxidation processes after 10 minutes of treatment under given conditions. The initial electron
acceptors concentrations in these experiments were 30.0 mmol dm–3, and the amount of TiO2
was 1.0 g dm–3. In the case of photocatalytic decolorization, S2O82– is the most effective for
the photodecolorization of RB 19 among the additives studied in this paper. The
decolorization efficiency of RB 19 are in the following order TiO2/UV/(NH4)2S2O8 (100%) >
TiO2/UV/KBrO3 (96.38%) > TiO2/UV/H2O2 (87.79%).
Figure 1 Effect of UV light, TiO2, electron acceptors, TiO2/UV/KBrO3, TiO2/UV/H2O2 and

TiO2/UV/(NH4)2S2O8 processes on decolorization of RB 19. [RB19]0 = 50.0 mg dm–3,
TiO2 = 1.0 g dm–3, [KBrO3]0 = 30.0 mmol dm–3, [H2O2]0 = 30.0 mmol dm–3, [(NH4)2S2O8]0 = 30.0
mmol dm–3, initial pH was 7.0, UV radiation intensity was 1950 μW cm–2, temperature was 25 ± 0.5ºC
Electron acceptors such as hydrogen peroxide, potassium bromate and ammonium

persulfate were added into the solution in order to enhance the decolorization [3–5]. All the
additives showed a beneficial effect on the decolorization of the dye, whereas S2O82– have
been found to enhance the decolorization of pollutant remarkably. The efficiency of
TiO2/UV/H2O2 process is comparable to TiO2/UV/KBrO3 process. TiO2-based photocatalysts
also offer the advantages of high physical and chemical stability, low cost, easy availability,
low toxicity, and excellent photoactivity [6].
162
In order to confirm the behavior of RB 19 decolorization by TiO2/UV/KBrO3,

TiO2/UV/H2O2 and TiO2/UV/(NH4)2S2O8 processes in different practical water samples under
best conditions, we chose three kinds of water samples as experimental matrixes: (1) Lab
deionized water (DW) as the simulation wastewater treatment effluent, (2) surface water (SW)
collected from the Nišava River (pH 7.2, Ca+ = 79 mg dm–3, Mg+ = 21 mg dm–3, Na+ = 13.42
mg dm–3, Cl– = 69 mg dm–3, SO42– = 35 mg dm–3, HCO3– = 240 mg dm–3), and (3) dyebath
effluent water (DEW) collected from a local cotton dyeing. Dyebath effluent contained 0.050
g dm–3 of dye RB 19. Assisting chemicals were also present in reactive dyebath effluent: 40 g
dm–3 NaCl (electrolyte, aggregation of dye onto fabric), 13 g dm–3 Na2CO3 (pH buffer), 0.51
g dm–3 NaOH (produces covalent bonds between dyestuff and fabric), 0.79 g dm–3 acetic acid
(neutralization), 0.50 g dm–3 alkylphenol polyglycol ether (detergent, washing out of unfixed
dyestuff). For preparing a model effluent, dyebath effluent wastewater was diluted to get a
new solution with 50.0 mg dm–3 of RB 19. RB 19 was spiked in surface water after the water
samples filtration with the initial concentration 50 mg dm–3. Figure 2 shows the removal
efficiency of RB 19 obtained by TiO2/UV/KBrO3, TiO2/UV/H2O2 and TiO2/UV/(NH4)2S2O8
processes. Each process was carried out in all three matrixes: DW, SW and DEW.
Figure 2 The removal of RB 19 by different oxidation processes: TiO2/UV/KBrO3 (pH = 7.0, [RB19]0
= 50.0 mg dm–3, TiO2 = 1.0 g dm–3, [KBrO3] 0 = 30.0 mmol dm–3, UV intensity 1950 μW cm–2),
TiO2/UV/H2O2 (pH= 7.0, [RB19] 0 = 50.0 mg dm–3, TiO2 = 1.0 g dm–3, [H2O2]0 = 30.0 mmol dm–3, UV
intensity 1950 μW cm–2) and TiO2/UV/(NH4)2S2O8 (pH= 7.0, [RB19]0 = 50.0 mg dm–3,
TiO2 = 1.0 g dm–3, [(NH4)2S2O8]0 =30.0 mmol dm–3, UV intensity 1950 μW cm–2)
As shown in Figure 2, in the surface water and dyebath effluent the removal efficiency of
RB 19 was lower than that in the deionized water because of the interference of complex
constituents in the surface water and dyebath effluent.
163
CONCLUSION
The decolorization of the Reactive Blue 19 solutions examined strongly depends on the
electron acceptors. From the economical point of view, the TiO2/UV/(NH4)2S2O8 process
emerges as the most attractive oxidation system for reactive dye effluents in terms of
complete decolorization (100.00% in less than 10 min) very closely followed by the
TiO2/UV/KBrO3 process (96.44% after 10 min) and TiO2/UV/H2O2 process (87.79% after 10
min). All three oxidation processes were carried out in three matrixes (lab deionized water,
surface water collected from the Nišava River and dyebath effluent water from a local cotton
dyeing). In the surface water and dyebath effluent, the removal efficiency of Reactive Blue 19
was lower than that in the deionized water because of the interference of complex constituents
in the surface water and dyebath effluent.
ACKNOWLEDGEMENT
14/200124).
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[2] L. Wei, C. Shifu, Z. Wei et al., J. Haz. Mat; 164 (1) (2009) 154–160.
[3] I. Poulios, I. Tsachpinis, J. Chem. Technol. Biotechnol; 74 (4) (1999) 349–357.
[4] C. K. Gratzel, M. Jirousek, M. Gratzel, J. Mol. Catal; 60 (3) (1990) 375–387.
[5] L. Sanchez, J. Peral and X. Domenech, Appl. Cat. B Environ; 19 (1) (1998) 59–65.
[6] S. Banerjee, S.C. Pillai, P. Falaras, et al., J. Phys. Chem. Lett; 5 (15) (2014) 2543–2554.
164
A NOVEL STAINLESS STEEL/Bi2O3 ELECTRODE FOR ELECTROCHEMICAL
DEGRADATION OF TEXTILE DYE
Milica Petrović1, Nena Velinov1*, Miljana Radović Vučić1, Slobodan Najdanović1,

Miloš Kostić1, Jelena Mitrović1, Aleksandar Bojić1
1
University of Niš, Faculty of Sciences and Mathematics, Višegradska 33, 18000 Niš,
SERBIA
*
Abstract
Stainless steel/Bi2O3 electrode was synthesized by galvanostatic electrodeposition on stainless steel
substrate and calcination at 500°C. Characterization by SEM, EDX, XRD and TGA revealed that the
anode surface was fully covered with pure α-Bi2O3, which formed inhomogeneous coat. This electrode
was used for electrochemical degradation of a textile dye Reactive Orange 4 (RO 4) in the presence of
H2O2. The optimization of decolorization parameters (applied current density, H2O2 and Na2SO4
concentration) was done.
Keywords: stainless steel/Bi2O3, dye, degradation, parameters
INTRODUCTION
Wastewater originating from textile and other industries contain synthetic organic dyes,
which presents a serious environmental problem, due to high resistance of those dyes towards
standard physico-chemical removal procedures. Electrochemical degradation of textile dyes
has many advantages, such as high efficiency, environmental compatibility, versatility and
safety. Electrochemical oxidation of the dyes is usually accomplished by hydroxyl radical
•OH, a strong oxidant, electrogenerated by water decomposition at the anode, which can lead
to a complete mineralization of a dye. The anodic material is very important; certain materials
based on metal oxide coats make very good anodes, due to their high surface area and
excellent mechanical and chemical resistance even at high current densities [1,2].
Electrochemical stability and catalysis behaviour makes Bi2O3 an interesting material for the
application in electrochemical oxidation of various organic pollutants [3,4]. In this work,
stainless steel/Bi2O3 electrode was synthesized by galvanostatic electrodeposition on stainless
steel substrate, followed by calcination, and used as anode for electrochemical degradation of
the textile dye Reactive Orange 4.

The electrode was prepared by electrodeposition from 0.3 mol dm-3 Bi (III) solution in 1 M
HNO3 at constant current density of 10 mA cm-2 during 120 minutes at 20 ± 0.5°C in the two
electrode cell with a stainless steel sheet as a substrate (cathode) and a Pt sheet as auxillary
electrode (anode). All electrochemical experiments were performed using Amel 510 DC
165
potentiostat (Materials Mates, Italy) controlled by VoltaScope software package. After the
deposition, the stainless steel sheet covered with deposited coat was washed with water, dried
at 50°C for 12 h, calcined at 500°C for 90 minutes in a furnace in the air and used as anode
for electrochemical degradation of RO 4. It was examined by SEM, EDX (Hitachi SU8030),
XRD (Siemens D500) and TGA (Q5000, TA Instruments, USA). Dye degradation was done
under galvanostatic conditions in one compartment two-electrode cell, with synthesized anode
and Pt sheet as the cathode. The working dye solutions were prepared by diluting the stock
solutions, which were prepared by dissolving the required amount of powdered dye in
deionized water. The required amount of H2O2 and Na2SO4 were added to the working dye
solutions. Dye concentrations were determined spectrophotometrically (UV-1650 PC,
Shimadzu, Japan) at 497 nm.

Characterization of the electrode
XRD pattern of the synthesized electrode shows a series of sharp, narrow diffraction peaks
with characteristic 2θ values at: 27.4°, 33.3° and 46.3°, corresponding to (120), (200) and
(041) reflection, respectively, of a highly crystalline monoclinic α-Bi2O3 at the stainless steel
surface (Figure 1). No trace of any other Bi2O3 phase was detected.
Figure 1 XRD pattern of the obtained electrode
Electrode surface is mostly composed of oval and worm-like particles, with some of them
closely packed, most of them seemingly sintered, forming the larger aggregates (Figure 2).
The particles of undefined shapes and different sizes are also spotted in places, as well as the
large pores and holes with different shapes and sizes between particles and particle
aggregates. Though the surface does not seem very compact, it is mechanically stable.
166
Figure 2 Surface morphology of the synthesized stainless steel/Bi2O3 electrode
EDX shows that weight ratios of Bi and O on the surface are 88.05% and 11.95%,
respectively, close to their theoretical weight ratios in Bi2O3 of 89.70% and 10.30%,
respectively, meaning that the coat posses little higher O-content. It might be adsorbed
oxygen or moisture as well.
The obtained Bi2O3 coat was peeled of the surface and heated from room temperature to
600 °C at a heating rate of 10°C /minute (Figure 3). No significant change of its weight was
observed within the given temperature interval, indicating its chemical stability under these
conditions. Total weight loss was 1.97% and it might be attributed to a slight loss of oxygen.
Figure 3 TG data for deposited Bi2O3
167
Dye degradation
RO 4 does not react with H2O2. Its sorption on stainless steel/Bi2O3 anode is negligible. Its
electrochemical degradation without H2O2 is slow. In the presence of H2O2, fast
electrochemical decolorization under the applied electric current at the stainless steel/Bi2O3
anode is observed.
The applied current density (j) affects the dye degradation rate (Figure 4). Total
decolorization was achieved at all of the applied current densities, but decolorization time
decreases with the increase of j. That decease is more notable for the lower j values; the
increase of j from 40 mA cm-2 to 50 mA cm-2 dos not bring any significant decrease in
decolorization time, meaning that the process has reached its limit current density, so it was
assumed that the optimal current density for the process was 40 mA cm-2.
Figure 4 Effect of current density on the decolorization time of RO 4 at stainless steel/Bi2O3 anode
(c0dye = 0.08 mmol dm-3, c0 (H2O2) = 10 mmol dm-3, c0 (Na2SO4) = 10 mmol dm-3)
Initial H2O2 concentration has a significant effect on the decolorization time (Figure 5),
since it is a source of •OH radical, which is generated by decomposition of H2O2 at the anode
at high potential. And which oxidizes the dye. Decolorization time decreases as the H2O2
concentration increases up to 10 mmol dm-3, as expected. However, an increase of the H2O2
concentration up to 20 mmol dm-3 causes a slight increase of the decolorization time. The
reason is probably the loss of some •OH radicals due to the scavenging effect, which occurs at
relatively high H2O2 concentration; when electrogenerated •OH radicals start to react with the
excess H2O2 and produce hydroperoxyl radicals, HO2•, which are much les reactive than •OH
radicals [5]. Thus, the process is the most efficient with 10 mmol dm-3 H2O2, which is
assumed to be the optimal H2O2 concentration.
168
Figure 5 Effect of H2O2 initial concentration on the decolorization time of RO 4 at stainless

steel/Bi2O3 anode (c0dye = 0.08 mmol dm-3, j =40 mA cm-2, c0 (Na2SO4) = 10 mmol dm-3)
Na2SO4, which is added to the dye solutions in order to increase electrical conductivity,
also affects the decolorization time as well (Figure 6). As the Na2SO4 concentration increases
from 1 to 10 mmol dm-3, the dye decolorization time decreases, but when its concentration
increased from 10 to 20 mmol dm-3, decolorization time increased compared to that in the
presence of 10 mmol dm-3 Na2SO4, i.e., decolorization efficacy decreases. This decrease
occurred because SO42- anions are also able to react with the electrogenerated •OH radicals,
and competition between the dye and the SO42- anions with the respect to •OH radicals may
occur as well [5]. Thus, the optimal Na2SO4 concentration in the investigated system is
assumed to be 10 mmol dm-3.
Figure 6 Effect of Na2SO4 initial concentration on the decolorization time of RO 4 at stainless

steel/Bi2O3 anode (c0dye = 0.08 mmol dm-3, j =40 mA cm-2, c0 (H2O2) = 10 mmol dm-3)
169
CONCLUSION
Stainless steel/Bi2O3 electrode was synthesized by galvanostatic electrodeposition on
stainless steel from Bi (III) acidic solution, fallowed by calcination at 500°C. The anode
surface was covered with inhomogeneous, mechanically stable coat of pure α-Bi2O3. The
obtained Bi2O3 was chemically stable to the heating up to 500°C. The synthesized electrode
was used as the anode for electrochemical oxidative degradation of textile dye RO 4.
Decolorization time decreases as the current density and concentration of H2O2 and Na2SO4
increase, but only up to certain value of each of these parameters; decolorization time is the
lowest for the current density of 40 mA cm-2 and H2O2 and Na2SO4 concentrations of 10
mmol dm-3. These values are taken as the optimal ones, with which the complete
decolorization proceeds in about 35 minutes. Increase of current density above 40 mA cm-2
does not significantly affect the decolorization time, and increase of H2O2 and Na2SO4
concentrations above 10 mmol dm-3 causes the increase of decolorization time.
ACKNOWLEDGEMENT
14/200124).
REFERENCES
[1] C.A. Martínez-Huitle, E. Brillas, Appl. Catal. B; 87 (2009) 105–145.
[2] J.L. Nava, M.A. Quiroz, C.A. Martínez-Huitle, J. Mex. Chem. Soc; 52 (2008) 249–255.
[3] Y. Wu, Y. Chaing, C. Huang, et al., Dyes Pigm; 98 (2013) 25–30.
[4] M. Zidan, T.W. Tee, A.L.H. Abdullah, et al., Int. J. Electrochem. Sci; 6 (2011) 289–300.
[5] J. Mitrović, M. Radović, et al., J. Serb. Chem. Soc; 77 (2012) 465–481.
170
ISOTHERMAL TITRATION CALORIMETRY STUDY OF As(III) BINDING TO
HUMIC ACIDS
Đuro Čokeša1*, Mirjana Marković1, Maja Gajić-Kvaščev1, Branka Kaluđerović1,

Svjetlana Radmanović2, Snežana Šerbula3
1
University of Belgrade, Vinča Institute of Nuclear Sciences,
Chemical Dynamics Laboratory, P.O. Box 522, 11001 Belgrade, SERBIA
2
University of Belgrade, Faculty of Agriculture, Nemanjina 6, 11080 Belgrade, SERBIA
3
*
cokesadj@vinca.rs
Abstract
Part of Cu post flotation tailings of Copper Mine Bor were reclaimed by reconstructing the topsoil
with arable soils and revegetation in 1991. Humic acids were isolated from these Technosols and
binding of arsenic present at high concentration, to selected humic acid was studied by Isothermal
Titration Calorimetry (ITC). Same binding experiment was performed with the standard IHSS soil
humic acid and results obtained were compared. From the results presented in this study it can be
concluded that ITC technique can be successfully used to get quantitative insight into interaction
energies between metal ions and soil humic acids. Humic acids investigated are of different type and
origin having various characteristics, influencing so differences in As(III) binding. Row ITC data
obtained can be used to determine thermodynamic parameters associated to the As(III)-humic acid
complexation process applying relevant theoretical models. Theoretical treatment applied could even
distinguish various humic acid reactive groups. Additionally, to explain results obtained using chosen
theoretical MNIS model and calculate thermodynamic parameters pointing to nature of binding
process, additional pH-metric (potentiometric) titration must be performed. As at the location studied
arsenic as very toxic metal is present at extremely high concentrations influencing environment
contamination, this study is of great environmental significance.
Keywords: Cu Post Flotation Tailings; Technosol Humic Acids; As(III) Binding; Isothermal
Titration Microcalorimertry
INTRODUCTION
One of the largest mines in Serbia is the Copper Mining and Smelting Combine Bor.
Besides other mine wastes, post-flotation tailings (PFT) dumps as a result of copper ore
processing were formed. The PFT dump "Polje 2" was definitively abandoned in 1987. In
addition to degradation of large land areas, these mine wastes are sources of pollution to the
surrounding environment. In order to restore the function of a portion of PFT dumps,
reclamation measures were implemented. In 1991, an area of about 16 ha was reclaimed by
reconstructing the topsoil with natural arable soil, an average depth of 40 cm. The soil was
taken from the southern part of the town of Bor where the residential area expanded. One part
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of the reclaimed area was planted with grass and the other with trees. Previous investigations
of reclaimed PFT 20 years after remediation [1] have shown that A horizon (about 45 cm
deep) was formed on the soil surface by reclamation process, mixing of natural arable soils
with tailings. Most of these soils are characterized by degraded structure, low humus content,
predominantly low pH, high As and Cu concentrations, and low soil microbial activity.
According to WRB 2007 [2], these soils are classified as RSG Technosols.
Humic substances (HSs) are the most important organic components present in water, soil,
and sediments and have significant environmental functions. They are recognized for their
role in controlling both the fate of environmental pollutants and the biogeochemistry of
organic C in the global ecosystem [3]. Humic substances affect the soil and water properties
through their participation in dynamic processes where their constituent molecules interact
with other molecules or ions (complexation/decomplexation), solid surfaces
(adsorption/desorption), and among themselves (aggregation/deaggregation) [4]. Their roles
in removal of heavy metals from soil and water, inhibition of free radicals formation by metal
catalysis, reduction, and stabilization of metal nanoparticles are among the most important
[5].
To get quantitative insight into interaction energies between As(III) ion and humic acids
and to determine thermodynamic parameters associated to the metal-humic acid complexation
process, Isothermal Titration Calorimetry technique was used [6,7].

Humic acid samples
Two various humic acids were investigated in this study. The first (T1HA) was isolated
from soil sample taken at a 0-25 cm depth [8,9] from the A horizon of Technosols (T) on
reclaimed Cu PFT "Polje 2", Bor - Serbia. Selected T1 soil sample was classified as a silt
loam. T1HA was isolated from soil using a modified IHSS method (HA gel was dried at
35°C, powdered, and sieved using a 0.05-mm sieve) [10]. Results obtained for Technosol
humic acid (T1 HA) were compared to well characterized standard IHSS humic acid isolated
from Elliott Soil (ESHA), which is silt loam, silty clay loam or loam, moderately acid to
neutral [11].
Stock humic acid suspensions of T1HA and ESHA (2 g/l) were prepared in 0.01 M KOH
and stored at 4oC. Working HA suspensions (0.8 g/l) were prepared before each titration by
mixing stock suspensions and 0.1 M KNO3 solution (1:1.5). Initial pH of working HA
suspensions was adjusted to 5.
Preparation of As(III) solutions
As(III) solutions were prepared using sodiumhydroxoarsenate (III) (NaAsO2) (Merck) in
0.1 M KNO3. Two concentrations were used in titration experiments: 5 and 10 mmol As/l.
Isothermal Titration Calorimetry
Termal events were monitored by the Thermal Activity Monitor (227, LKB Bromma,
Sweden) using a perfussion cell (227-401/402, Sweden) as measuring device. Titrations were
performed using Radiometer Automatic Titrator (ABU 80, Denmark). Prior to titration
172
experiments, measuring cell of the perfussion system was filled with 2.5 ml of HA
suspension, thermally equilibrated in four steps and calibrated (10 µW range) using both static
and dynamic calibration procedure. Working temperature was 298.15K. Titration experiments
started after the stable base line was obtained.
Titrant (As(III) solution) was added in 30 µl portions at every 20 minutes for experiments
investigating binding at various pH values, and at every 30 minutes in experiments comparing
As(III)-HA binding for two humic acids studied. Titration speed was 50 µl/min in both cases.
For each titration, the output signal, power (μW) versus time (min), was recorded by the TAM
assistant software and thermograms were obtained. Software used for titration control and
data acquisition, as well as software for termogram peak area determination, was developed in
the laboratory.

ITC thermograms representing heat changes upon As(III) complexation with ESHA and
T1HA at different pH values are presented in Figures 1 to 6.
ESHA: pH5
As: 5 mM; 30 µl
10.0
5.0
µW
0.0
6 66 126 186 246 306 366 426 486
min
-5.0
-10.0
Figure 1 Reaction heat change of binding ESHA and As(III) at pH5
Figure 2 Reaction heat change of binding ESHA and As(III) at pH6
173
Figure 3 Reaction heat change of binding T1HA and As(III) at pH4
174
From results presented in Figures 1-6 revealing positive sign of heat effects, it is obvious
that binding of As(III) to both humic acids studied is exothermic process. Each thermogram peak
represents one titrant injection. Peak areas represent heat evolved for the given titrant
injection. Based on the peak area calculated for each single injection, cumulative heat reaction
and As(III) concentration for every injection was calculated and their dependence is presented
in Figure 7.
Figure 7 Cumulative reaction heat versus As(III) concentration for T1HA and ESHA at various pH values
It is obvious from Figure 7 that heat changes are highest at pH5, but more pronounced for
ESHA. At pH higher than 5 are much lower for both humic acids studied and do not differ
significantly. Additionally, it can be seen that heat change values for T1HA are significantly
lower at pH4 than at pH5. At higher As(III) concentration (10 mM) (Fig.ure 8) difference in
heat effects changes are more pronounced in comparison to lower concentration (Figure 7).
As for lower As(III) concentration, heat effects are more pronounced for ESHA at higher
concentration.
175
Figure 8 Cumulative reaction heat versus As(III) concentration for T1HA and ESHA at pH5
CONCLUSION
From the results presented it can be concluded that ITC technique can be successfully used
to get quantitative insight into interaction energies between metal ions and soil humic acids.
Nevertheless, it is evident that optimisation of ITC measuring parameters is necessary to
improve measurement uncertainty. Humic acids investigated are of different type and origin
having various characteristics, influencing so differences in As(III) binding. Row ITC data
obtained can be used to determine thermodynamic parameters associated to the metal-humic
acid complexation process applying relevant theoretical models. Theoretical treatment applied
could even distinguish various humic acid reactive groups. Additionally, to explain results
obtained using chosen theoretical MNIS model and calculate thermodynamic parameters
pointing to nature of binding process, additional pH-metric (potentiometric) titration must be
performed.
As at the location studied arsenic as very toxic metal is present at extremely high
concentrations influencing environment contamination, future investigations will be focused
to investigation of As binding to humic acids.
ACKNOWLEDGEMENT
This study was financially supported by the Ministry of Education, Science and Technological
Development of the Republic of Serbia (projects No: 37006 and 45012).
REFERENCES
[1] J. Lilić, S. Cupać, B. Lalević, et al., J. Soil Sci. Plant. Nutr; 14 (2014) 161–170.
[2] IUSS Working Group WRB (2007) World reference base for soil resources 2006, first
update 2007. World Soil Resources Reports No. 103. FAO, Rome.
[3] A. Piccolo, Advances in Agronomy; 75 (2002) 57–134.
[4] M. Avena, K. Wilkinson, Environ. Sci. Technol; 36 (2002) 5100–5105.
176
[5] B.A.G. De Melo, F.L. Motta, M.H.A. Santana, Mater. Sci. Eng. C; 62 (2016) 967–974.
doi: 10.1016/j.msec.2015.12.001.
[6] F. Loosli, L. Vitorazi, J.F. Berret, et al., Environ. Sci.: Nano; 2 (2015) 541–551. doi:
10.1039/c5en00139krsc.li/.
[7] J. Xu, L.K. Koopal, L. Fang, et al., Environ. Sci. Technol; 52 (2018) 4099−4107. doi:
10.1021/acs.est.7b06281.
[8] M. Carter, Soil sampling and methods of analysis, Lewis Publishers, Boca Raton (1993)
ISBN: 0-87371-861-5.
[9] FAO (2006) Guidelines for soil description, Fourth edition, Food and agriculture
organization of the United Nations, Rome.
[10] R.S. Swift, Organic matter characterization. In: D.L. Sparks, et al., Eds., Methods of soil
analysis, Part 3, Chemical methods, Soil Sci. Soc. Am. Book Series: 5. Soil Sci. Soc. Am.
Madison, (1996), Available on the following link: http://humic-substances.org/isolation-of-
ihss-soil-fulvic-and-humic-acids/
[11] USDA-NRCS 2015 Elliott Series, Available on the following link: https://soilseries.sc.
egov.usda.gov/OSD_Docs /E/ELLIOTT.html
177
DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHs)
CONTENT IN FOOD AND HEY IN PLJEVLJA MUNICIPALITY, MONTENEGRO
Miljan Bigović1*, Slađana Krivokapić1, Ivana Milašević2, Nevena Cupara1,2,

Dijana Đurović2
1
University of Montenegro, Faculty of Natural Science and Mathematics,
Džordža Vašingtona bb, 81000 Podgorica, MONTENEGRO
2
MONTENEGRO
*
miljan@ucg.ac.me
Abstract
This paper aimed to investigate the content of polycyclic aromatic hydrocarbons (PAHs) in three types
of food (cheese, apples, potatoes) in municipality Pljevlja, north part of Montenegro. We also
examined the content of these substances in hay, as a representative of livestock feed. All four types of
samples were taken from locations: Thermal power plant (TE Pljevlja) and Zinc and lead mine (Šuplja
stijena, Montenegro). The analysis examined the presence and concentration of fourteen polycyclic
aromatic hydrocarbons. The obtained results showed the following: almost all samples contained
naphthalene and acenaphtene (most were found in samples near the Thermal power plant), and the
highest concentration of benzo[a]pyrene was found in the potato sample also at the site around the
Thermal power plant.
Keywords: PAHs, food, contamination, thermal plant, mine
INTRODUCTION
Polycyclic aromatic hydrocarbons (PAHs) are highly teratogenic, persistent carcinogens
and they are widespread in the environment. They can occur either during biological
processes or through human activities. Natural sources of PAHs are forest or brush fires,
volcanic activity, hydrothermal processes and anthropogenic sources are car emissions or
cigarette smoke, thermal processing of food (roasting, frying, grilling), drying or smoking
food. They are strongly adsorbed to the organic fraction of soils and therefore they do not
usually penetrate deeper in soil layers. Once they reach the soil, the PAHs there remain
because they are, as very non-polar, insoluble in water, and thus cannot be further mobilized
through the soil. After deposition in the soil, they can further accumulate in plants, and
through the food chain they can reach the human body. Determination of PAHs content in
food is very important especially in terms of food safety and health reasons. Food can be
contaminated by PAHs from environmental sources and from the way of preparing food in the
household. In 2007, the European Food Safety Authority (EFSA) proposes benzo[a]pyrene as
a good indicator of food pollution of PAHs [1]. The European Commission set maximum
levels for benzo[a]pyrene and PAHs in 2011. According to this legislation, maximum level of
benzo[a]pyrene in food is 6.0 μg/kg, and sum of PAHs is 35.0 μg/kg [2]. Based on the results
178
of analyses of over 10,000 samples, EFSA reported this kind of exposure distribution to these
substances by foods [3]. Thus, dietary exposure to PAHs from vegetables and nuts is 14%,
fruits 5 % and cheese 1 %. The maximum exposure is from seafood products (19%) and meat
products (12%).
In this paper we have examined the presence and concentration of fourteen polycyclic
aromatic hydrocarbons which are shown in table 1. According to International Agency for
Research on Cancer (IARC), all substances are classified in four groups: 1 – carcinogenic to
humans; 2A-probably carcinogenic to humans; 2B – possibly carcinogenic to humans, 3 – not
carcinogenic to humans [4].
Table 1 PAHs, their structures, psysical constants and carcinogenicity

M Carcinogenicity
Name Abbreviation
(g/mol) group (IARC)
Naphtalene1 NPH 128 2B
Acenaphtalene ACY 152 N.A.
Fluorene FLR 166 3
Phenanthrene PHE 178 3
Anthracene ANT 178 3
Fluoranhtene FA 202 3
Pyrene PYR 202 3
Benzo[a]anthracene BaA 228 2B
Chrysene CHR 228 2B
Benzo[b]fluoranthene BbFA 252 2B
Benzo[k]fluoranthene BkFA 252 2B
Benzo[a]pyrene BaP 252 1
Dibenzo[ah]anthracene DBahA 278 2A
Benzo[ghi]perylene BghiP 276 3
N.A. – not available

Materials and Sampling
Samples were taken from agricultural households near Pljevlja in period September-
November 2019. The households are located near two sources of pollution, Thermal power
plant (TE Pljevlja) and Zinc and lead mine (Šuplja stijena, Montenegro). Samples 1, 2, 3, 4, 6,
7 and 11 are located near Thermal power plant. Sample 5 is located between Thermal power
1
According to a number of authors, naphthalene is not considered a typical PAH but is rather labelled as
“specific PAH“. However, since it is a significant environmental pollutant and belongs to the group of potentially
carcinogenic agents, and it can cause the breakdown of red blood cells, naphtalene is included in the group of the
most commonly analyzed PAHs.
179
plant and surface Coal mine. Samples 8, 9 and 10 were collected from households near Zinc
and lead mine. Apples and potatoes were sampled directly from the indicated locations. The
hay was taken from the agricultural households where it was located, but it was mowed and
dried to the specified sites. The cheese was obtained from cows that consumed hay, which
was mowed at the indicated sites and as such was sampled.
For PAHs analysis samples were homogenized in blender, weighed (2g for cheese and hay;
10g for apples and potato) and prepared by QuEChERS method [5]. In first part of
preparation 10 ml of distilled water was added for cheese and hay samples, homogenized by
vortex (this step is not necessary for apple and potato samples). For sample extraction
QuEChERS 1 was used (4 g anhydrous magnesium sulphate; 1 g of sodium chloride; 1 g
trisodium citrate dihydrate; 0.5 g disodium hydrogen citrate sesquihydrate). For clean up step
QuEChERS 2 was used (900 mg anhydrous magnesium sulphate; 150 mg PSA; 15mg GCB).
After preparation samples were analysed by High-Performance Liquid Chromatography
(HPLC) with fluorescence detector.

Total contents for the PAHs measured in this study are listed below. Figure 1 and 2 show a
diagram of PAHs ratio concentrations in potato and apple samples, respectively: FLR, ANT,
FA, PYR, BaA, CHR, BkFA, DBahA and BghiP were below the detection limits of the
instrument for potato samples.
As observed from the measurement results presented in the Figure 1, acenaphtalene (ACY)
was present in potato samples from all 11 locations. The highest concentration of this PAH is
at location 5, between the Thermal power plant and Coal mine, as well as at location 11, in
the vicinity of the Pljevlja Thermal power plant. No carcinogenicity group was assigned to
this hydrocarbon. Slightly elevated naphthalene concentrations were found at locations 4 and
8. It is similar with concentration of benzo[b]fluoranthene (BbFA) at location 6. However, we
found a worryingly high concentration of benzo[a]pyrene in the potato sample at site 6
(Thermal power plant surrounding). Based the EU Regulations, the maximum allowable
concentration of this PAH is 6 μg/kg. Also note that this compound belongs to class 1
carcinogenic agents (table 1) [4] and considered as environmental indicator for PAHs
contamination.
According to EU regulation No 835/2011 [2], maximum levels of PAHs in food was
calculated from the sum of the concentrations of PAHs. The range of these concentrations,
depending on the type of food, is 10.0 - 35.0 μg/kg. An increased concentration of the sum of
the PAHs was found in the potato sample at location number 6 and it was 8.39 µg/kg, but it is
still significantly lower than the upper limit. The lowest concentration of total PAHs was
found in the sample from the site 1. PHE, ANT, PYR, BbFA, BkFA and DBahA were below
the detection limits of the instrument.
Higher concentrations of naphthalene (NPH) were found in the examined apple samples in
the vicinity of the Thermal power plant compared to the potato samples taken from the same
locations, Figure 2. However, except for the sample from sites 1 and 2, these concentrations
are relatively low. Acenaphtalene (ACY) was found in samples from almost all sites, but its
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concentration is highest at site 3. Benzo[a]anthracene (BaA) was found in moderate

concentrations at all locations around the Zinc and lead mines, as well as at most locations
around the Thermal power plant while concentrations of benzo[a]pyrene are quite low in most
locations. The highest concentration of total PAHs was found in the sample from the locality
1 and it was 7.35 µg/kg, and the lowest in the sample from the site 11 (both sites are in the
vicinity of the Thermal power plant).
Figure 1 Comparison of PAHs concentrations in potato samples from different sites
Figure 2 Comparison of PAHs concentrations in apple samples from different sites
In Figure 3 and 4 are shown PAHs concentrations in cheese and hay samples on different
locations, respectively. According to EU regulation No 835/2011 [4], the maximum allowed
concentration of PAHs in milk and milk products is 1.0 μg/kg. The highest concentration of
naphthalene (NPH) was measured in the cheese sample number 4, while acenaphtalene (ACY)
181
was present in increased (and unallowed) concentrations in almost all remaining samples
tested. The concentration of total found PAHs is highest in the cheese sample from location
number 4 (2.45 µg/kg) while in other samples it is lower, but still higher than maximum
allowed concentrations from the point of view of food safety. Based on these analyses and
according to this regulation we conclude that only cheese from location 3 is safe for human
consumption. All remaining analysed PAHs were below the limit of detection.
In order to examine the impact of cows' food consumption on transporting PAHs into the
products derived from these cows, we examined PAH contents in the hay, at the locations
where the cows were fed and collected the same hay. The relationships between the
concentrations of the measured substances are presented graphically in Figure 4.
Figure 3 Comparison of PAH concentrations in cheese samples from different sites
Figure 4 Comparison of PAH concentrations in hay samples from different sites

182
ANT, PYR, BaA, BbFA, BkFA, BaP, DBahA and BghiP were below the limit of detection.
Here again, the concentration of naphthalene is highest in the sample from locality number 4
but also from locality number 11. Acenaphtalene (ACY) was found in all samples at relatively
high concentrations, given that it is food for livestock. Fluoranhtene (FA) was found in
enlarged concentration in sample number 9. The concentration of total found PAHs is highest
in the hay sample from location number 9 and the lowest in sample number 2.
CONCLUSION
The results of our investigation have shown that the pollutants are transported by air to
plants for human consumption. In most cases, according to the analysis of total PAHs in the
tested food, we can conclude that a greater amount of these compounds are emitted from the
Thermal power plant than from the Zinc and lead mines.
We could not find a direct dependence of the concentration of PAHs in cheese relative to
their concentration in the hay sample consumed by the cows. Analysing the content of PAH in
the cheese, we have shown that these pollutants can be incorporated into the food chain in a
non-metabolized form. Based on the content of individual or even total PAHs in the samples
obtained from the indicated locations, we can estimate the degree of pollution of both the food
itself and the environment.
ACKNOWLEDGEMENT
This work was supported by the Montenegrin Ministry of Science under grant no. 01-779/2.
REFERENCES
[1] Findings of the EFSA Data Collection on Polycyclic Aromatic Hydrocarbons in Food,
EFSA Journal, 5 (9) (2007), Available on the following link: https://efsa.onlinelibrary.wiley.
com/doi/abs/10.2903/j.efsa.2007.33r
[2] European Union, Commission Regulation (EU) No 835/2011, Official Journal of
European Union L214/5 (2011).
[3] European Food Safety Authority, EFSA J. 724 (2008) 1–114.
[4] IARC monographs on the identification of carcinogenic hazards to humans, Available on
the following link: https://monographs.iarc.fr/agents-classified-by-the-iarc/
[5] T.-T. Tran-Lam, Y. H. Dao, L. K. T. Nguyen, et al., Foods, 7(12), 201 (2018) 1–16.
183
CORROSION BEHAVIOUR OF ZA27 AND ZA27/EGGSHELL COMPOSITE IN
SCOTCH BONNET PEPPER FLUID
Adeleke Victor Adedayo1,2*

1
Department of Materials Science and Engineering, Obafemi Awolowo University, Ile-Ife,
NIGERIA
2
LDepartment of Metallurgical Engineering, Kwara State Polytechnic, Ilorin, NIGERIA
*
a.v.adedayo@gmail.com
Abstract
This study investigated the corrosion behavior of ZA27 and ZA27/Eggshell Composite in pepper
fluids. The objective of the study is to know the corrosion behavior such as corrosion rates, corrosion
potentials and pitting potentials of ZA27 and ZA27/Eggshell composite in pepper fluids. ZA27 and
ZA27/Eggshell composites were prepared in the laboratory. The prepared alloy and composite were
then tested for corrosion behavior in pepper fluids by potentiodynamic method. The result of the study
showed that corrosion behavior of ZA27 and ZA27/Eggshell composite is dependent on the particular
pepper fluid environment.
Keywords: metal matrix composites, ZA27, eggshell, particulate reinforcement
INTRODUCTION
The term “corrosion” is generally applied to a reaction involving oxygen. However, in the
world of chemistry, the term “Oxidation” does not only apply to a reaction with oxygen. An
element is “Oxidized as opposed to being “reduced”, when it gives up electrons and to form a
compound. For example, sodium converts to sodium chloride in the presence of chlorine in
what is referred to as an “Oxidative” reaction [1]. The importance of corrosion is widespread,
and goes beyond huge financial loss due to engineering material loss. Corrosion control
treatment is necessary to reduce the leaching of biologically toxic metals such as lead and
cadmium [2]. Corrosion control treatment also affects consumers’ perceptions of the quality
of drinks by reducing metallic tastes, water color and odors [2]. Hence, the need for corrosion
studies for better understanding of corrosion.
Zinc-Aluminum (ZA) alloys are alloys with Zinc as the base metal, with higher
concentrations of Aluminum when compared to traditional Zinc alloys. These alloys have
proven themselves in a wide variety of demanding applications. They are alloy materials that
offer designers and casting specifiers viable, cost-effective alternatives for their component
requirements. Specifically, compared to Aluminum, the Zinc-Aluminum alloys are harder and
stronger, machine more easily, have superior pressure tightness, and have substantially better
wear and bearing characteristics. The alloys 8 and 12 are not subject to incentive sparking.
The alloys become viable choices when Aluminum is inadequate.
While many studies have reported investigations on ZA27 alloy [3–5], only Adedayo and
Abdulsalam [6] and Adedayo [7] have published research efforts to characterize
184
ZA27/Eggshell composite. The work of Adedayo and Abdusalam [6] dwelled on engineering
management of chicken eggshell for improvement of properties of ZA27 alloy. In their work,
20% of 600 microns particles of eggshell were added to ZA27 through casting. The result of
their study showed that strength of ZA27 alloy is improved with addition of 20% of eggshell.
In this present work, the corrosion responses of ZA27 and ZA27/Eggshell composite in
pepper fluids are being studied. Although, peppers are important food spice, only scanty
technical information is available on industrial processing of pepper, and on effect of
processing equipment materials on the pepper paste. There are no information on chemical
characteristics of ZA27 and ZA27/Eggshell composite in pepper fluids. Hence the need for
this present study to provide useful information for engineering management of pepper
processing plants. The study will equally provide vital information useful for evaluating
implication of food contact of ZA27 and ZA27/Eggshell composite.

The study materials are ZA27 and ZA27/Eggshell composite rods produced in the
laboratory by melting ZA27 alloy. A volume of about 850ml of the molten alloy was bailed
out, and 170 ml of prepared eggshell sieved to 600 microns was added to the molten alloy and
stirred vigorously. Previous researches published have used particulate sizes of a few microns,
however current trend is exploring particulate sizes between 100 to 850 microns [5–7]. The
mixture was in sand mold into rods with 15mm diameter and 200mm in length. A control
sample which had no eggshell content was also prepared.
The electrochemical responses of ZA27 alloy and ZA27/eggshell composite in pepper fluid
were evaluated by potentiodynamic method. The pepper fluid was obtained from scotch
bonnet pepper, by squeezing the fluid out of the pepper fruits ground to paste by a blender.
The ZA27 and ZA27/Eggshell composite samples used for the potentiodynamic analysis were
metallographically prepared and polished. The polished samples were then mounted in
Bakelite with connected flexible conducting wires for potentiodynamics analysis. The
prepared samples were made the working electrodes, and the counter electrode is platinum.
The reference electrode is Ag/AgCl. A scan rate of ~ 1mv/s was used with open circuit
potential (OCP) for 600s. The polarization curve was studied with potentiostat equipped with
VERSASTAT 4 software. The entire electrochemical test were performed at room-
temperature.

The results of the electrochemical corrosion of the test samples by potentiodynamic
method are presented as potentiodynamic polarization curves in the Figures 1 and 2, while
Table 1 presents corrosion rates and potentials of ZA27 and composite in the pepper fluid.
Figures 1a and 2a present the potentiodynamic polarization curve of the specimens in the
pepper fluid while Figures 1b and 2b show the microstructures of the samples after they were
exposed to pepper fluid through potentiodynamic analysis.
185
Potential (V)
Log of Currents (A/cm-2)
Figure 1a Polarization curve of ZA27 in Scotch bonnet Pepper fluid
800 µm
Figure 1b Microstructure of ZA27 exposed to Scotch Bonnet Pepper fluid through potentiodynamic
test
Potential (V)
Figure 2a Polarization curve of ZA27-Eggshall composite in Scotch bonnet pepper fluid
186
800 µm
Figure 2b Microstructure of ZA27- Eggshell composite exposed to Scotch Bonnet Pepper fluid
through potentiodynamic test
Table 1 Corrosion rates and potentials of ZA27 and composite in pepper fluids
Sample Ecorr Corrosion Rate
ZA27 -1.005 V 1.872 mmpy
ZA27/Eggshell -0.543149 V 2.34·10-5 mmpy
In Figure 1a, the potentiodynamic polarization curve of ZA27 in Scotch Bonnet fluid is
presented. The polarization curve has both anodic and cathodic domains [3]. The cathodic
domain includes potentials below the corrosion potential (Ecorr), where current density
determined by the cathodic reaction shows a continuous increase in the current density of the
cathodic branch as the potential decreases [4]. The polarization curve is significantly active
corrosion behavior, where current density increased with applied voltage. Corrosion potential
for this system of pepper fluid and ZA27 is -1.005V and corrosion rate is 1.872 mmpy. The
microstructure of the ZA27 sample immersed in scotch bonnet presented in Figure 1b
revealed the presence of some intergranular corrosion, which suggests the susceptibility of
ZA27 alloy to intergranular corrosion in scotch bonnet. In Figure 2a, the polarization curve of
ZA27/Eggshell composite in Scotch Bonnet Pepper fluid is presented. The Ecorr for the system
is – 0.543149 V, and the corrosion rate is 2.34 ·10-5 mmpy. The curve is active, but weakly
passivating with some pitting potentials at about -0.45 mV. Presence of pits is confirmed in
the microstructure of the sample presented in Figure 2b. Comparing the performance of ZA27
and ZA27/Eggshell in the pepper fluid, it is evident that the ZA27/Eggshell composite show
lower corrosion rates and therefore exhibit better corrosion resistance. This suggests that
introducing eggshell into ZA27 alloy to improve corrosion resistance should be encouraged.
CONCLUSION
ZA27 alloy generally exhibits good corrosion resistance in pepper fluids. However,
comparing the performance of ZA27 and ZA27/Eggshell in the pepper fluid, it is evident that
the ZA27/Eggshell composite show lower corrosion rates and therefore exhibit better
corrosion resistance. This suggests that introducing eggshell into ZA27 alloy to improve
187
corrosion resistance should be encouraged. The use of ZA27 as a material for producing
grinders in processing pepper fruits to paste is recommended. The use of eggshell particles as
reinforcement composite particulates in ZA27 alloy materials for producing pepper grinding
product is also recommended.
REFERENCES
[1] K. Loughrey (2018) Answer to: What is corrosion on Quora, Available on the following
link: https://www.quora.com/What-is-corrosion
[2] S. Randall, Importance of corrosion control; NSF Municipal Water Matters, June (2017)
10–11.
[3] E. Blasco-Tamarit, D.M. Garcia-Garcia, J. Garcia Anton, Corrosi. Sci; 53 (2) (2011) 784–
795.
[4] M. Saadawy, Kinetics of Pitting Dissolution of Austenitic Stainless Steel 304 in Sodium
Chloride Solution, International Scholarly Research Network ISRN Corrosion, (2012) 1–5,
doi:10.5402/2012/916367.
[5] E. Barnard, L. Hager, J. Lichter, et al., MMC Hammer design review, MIT (2004).
[6] A.V. Adedayo, Y.N. Abdusalam, IJMREM; 2 (5) (2018) 108–112.
[7] A.V. Adedayo, East African Scholars J. Eng. Computer Sci; 2 (5) (2019) 149–152.
188
CORROSION BEHAVIOUR OF ZA27 AND ZA27/EGGSHELL COMPOSITE IN
SIMULATED SEA WATER
Adeleke Victor Adedayo1,2*

1
Department of Materials Science and Engineering, Obafemi Awolowo University, Ile-Ife,
NIGERIA
2
LDepartment of Metallurgical Engineering, Kwara State Polytechnic, Ilorin, NIGERIA
*
a.v.adedayo@gmail.com
Abstract
This study investigated the corrosion behavior of ZA27 and ZA27/Eggshell Composite in simulated
sea water. The objective of the study is to know the behavior, corrosion rates, corrosion potentials and
pitting potentials of ZA27 and ZA27/Eggshell composite in simulated sea water. ZA27 and
ZA27/Eggshell composites were prepared in the laboratory, the prepared alloy and composite were
then tested for corrosion behavior in simulated sea water by potentiodynamic method. The result of
the study showed that ZA27/Eggshell composite had better corrosion resistance; therefore the choice
of ZA27/Eggshell composite is preferred for sea water or simulated sea water environment.
Keywords: Metal matrix composites, ZA27, eggshell, particulate reinforcement, Zinc
INTRODUCTION
Zinc Aluminium (ZA) alloys are a new family of zinc casting alloys that have been found
useful in a wide variety of demanding applications. The most common alloys available in this
family are the alloys designated as ZA8, ZA12 and ZA27. The alloys are designated 8, 12,
and 27 to indicate their approximate aluminium content. Both tensile strength and
compressive strength of the alloy have been studied elaborately. These ZA alloys are not
subject to incentive sparking, and they become viable choices when Aluminum is inadequate
[1].
Although some studies have been carried out to investigate the corrosion behaviours of
alloys and effects of particulate reinforcement on properties of alloys [2–4], however, the
literature has reported only Adedayo and Abdulsalam [5] and Adedayo [6] to studied and
characterize ZA27/Eggshell composite. The investigations made by Adedayo and Abdusalam,
[5] focused on managing chicken eggshell to improve engineering properties of ZA27 alloy.
The study showed that 20% of 600 microns particles of eggshell added to ZA27 through
casting improved strength of ZA27 alloy.
In this particular study, the corrosion responses of ZA27 and ZA27/Eggshell composite in
simulated sea water are being studied. Only scanty technical information is available on
effects of eggshell as particulate reinforce in alloys on corrosion behavior of alloys in Sea
water. There are no information on chemical characteristics of ZA27/Eggshell composite in
Sea water. Hence the need for this present study to provide useful information for engineering
application of ZA27 in marine environment.
189

The study materials are ZA27 and ZA27/Eggshell composite rods produced by melting
zinc scrap with 27% Aluminum metals obtained from Aluminum cables. About 3 Kg of Zinc
metal scrap was melted in a lift-out crucible furnace, after which about 0.82 Kg of Aluminum
was dissolved in the molten zinc metal. A volume of about 850 ml of the molten alloy was
bailed out, and 170 ml of prepared eggshell sieved to 600 microns was added to the molten
alloy and stirred vigorously. Previous researches published have used particulate sizes of a
few microns, however current trend is exploring particulate sizes between 100 to 850 microns
[4-6].The mixture of molten metal alloy and eggshell produced was then quickly poured into
a prepared sand mold and cast into rods with 15mm diameter and 200 mm in length. A control
sample which had no eggshell content was also prepared by casting in sand molds. Produced
cast rods were then machined on a lathe machine into test pieces of 10 mm diameter and 10
mm length. High Speed Steel (hss) cutting tool was used, with a cutting speed of 305
revolutions per minute. Micrometer screw gauge and vernier callipers were used for
measuring the dimensions of the machined samples. The electrochemical responses of ZA27
alloy and ZA27/eggshell composite in simulated sea water were evaluated by
potentiodynamic method. The ZA27 and ZA27/Eggshell composite samples used for the
potentiodynamic test were metallographically prepared by grinding successively with
abrasive papers of 60p, 120p and 220p before they were polished. The polished samples were
then mounted in Bakelite with connected flexible conducting wires before they were
immersed in simulated sea water for potentiodynamics test. The prepared samples were made
the working electrodes, and the counter electrode is platinum. The reference electrode is
Ag/AgCl. A scan rate of ~ 1mv/s was used with open circuit potential (OCP) for 600s. The
polarization curve was studied with potentiostat equipped with VERSASTAT 4 software. The
entire electrochemical test were performed at room-temperature.

The results of the electrochemical corrosion of the test samples by potentiodynamic
method are presented as potentiodynamic polarization curves in Figures 1 and 2, while Table
1 presents corrosion potentials and rates of ZA27 and ZA27/Eggshell composites in simulated
sea water.
In Figure 1a, the polarization curve of ZA27 in simulated sea water is presented. The
polarization curve has both cathodic and anodic branches [2]. The cathodic domain includes
potentials below the corrosion potential (Ecorr), where current density determined by the
cathodic reaction shows a continuous increase in the current density of the cathodic branch as
the potential decreases [3]. The anodic branch shows a spontaneously passive behavior with
few pitting potentials. The micrograph of the sample presented in Figure 1b revealed few pits
randomly distributed in the micrograph, confirming presence of pits as indicated by the
polarization curve of Figure 1a. The micrograph also reveals areas of white patches which are
adhesions to the surface of the sample as a result of immersion of the sample in simulated sea
water for potentiodynamic test. The corrosion potential for the system is -11.868 mV and the
corrosion rate is 7.2655e-07 mmpy.
190
a) b)
Potential (V)
Figure 1 a) Polarization curves of ZA27 in simulated sea water; b) Microstructure of ZA27 in

Simulated sea water
a) b)
Potential (V)
Figure 2 a) Polarization curves of ZA27/Eggshell composite in simulated sea water;

b) Microstructure of ZA27/Eggshell composite in simulated sea water
In Figure 2a, the polarization curve of ZA27/Eggshell composite in simulated sea water is
presented. The polarization curve has both anodic and cathodic branches. The anodic branch
shows a spontaneously passive corrosion behavior. The micrograph of the sample is presented
in Figure 2b. The Ecorr for the system is -339.925 mV and the corrosion rate is 5.6874e-08
mmpy.
Table 1 Corrosion potentials and rates of ZA27 and ZA27/Eggshell composites in simulated sea water
Sample Corrosion potential Corrosion rates
ZA27 in Simulated sea water -0.011868 V 7.2685·10-7 mmpy
ZA27/Eggshell in Simulated sea water -0.339925 V 5. ·10-8 mmpy
191
CONCLUSION
The study has shown that ZA27 alloy material has good corrosion resistant property.
Introducing eggshell into the matrix improves the corrosion resistance ability of the alloy
material in sea water/Simulated sea water environment. ZA27/Eggshell composite had
improved corrosion resistance, therefore the choice of ZA27/Eggshell composite is preferred
for sea water or simulated sea water environment.
REFERENCES
[1] Total material, (2002) Zinc-Aluminum Foundry Alloys, Available on the following link:
https://www.totalmateria.com/page.aspx?ID=CheckArticle&site=ktn&NM=46
[2] E. Blasco-Tamarit, D.M. Garcia-Garcia, J. Garcia Anton, Corros. Sci; 53 (2) (2011) 784–
795.
[3] M. Saadawy, International Scholarly Research Network ISRN Corrosion; (2012) 1–5,
doi:10.5402/2012/916367.
[4] E. Barnard, L. Hager, J. Lichter, et al., (2004) MMC Hammer design review, MIT.
[5] A.V. Adedayo, Y.N. Abdusalam, IJMER; 2 (5) (2018) 108–112.
[6] A.V. Adedayo, East African Scholars J. Eng. Comput. Sci; 2 (5) (2019) 149–152.
192
MODIFIED FLY ASH AS A NEW ADSORBENT FOR Cu2+ REMOVAL FROM
AQUATIC SOLUTIONS
Milena Tadić1, Irena Nikolić1, Danica Laković1, Dijana Đurović2*, Nevena Cupara2,3
1
University of Montenegro, Faculty of Metallurgy and Technology, Džorža Vašingtona bb,
2
MONTENEGRO
3
University of Montenegro Faculty of Natural Science of Montenegro, Džorža Vašingtona bb,
*
dijana.djurovic@ijzcg.me
Abstract
Given the fact that copper is the one of the metals of great industrial application, there are numerous
opportunities for environmental pollution with this metal. Considering the importance of water for
human health, today a special attention is paid to the removal of copper ions from wastewater before
being discharged into environment. The aim of this paper was to investigate the fly ash, the waste
material from coal fired power station as adsorbent for Cu2+ removal from aquatic solution. Fly ash,
supplied from coal fired power station Pljevlja in Montenegro, was modified by alkali activation
process and used for the adsorption test. The paper emphasizes the influence of solid / liquid ratio, pH
of solution, initial copper concentration in solution and temperature on the removal efficiency of Cu 2+
from aquatic solution. It has been shown that increase the pH in the range of 3-5, initial concentration
from 20-100 ppm and solid/liquid ratio from 0.4-0.8 lead to the increase of copper removal efficiency
from aquatic solution. Moreover the increase of temperature from 20-45 C is favorable from the
stand point of Cu2+ removal from solutions.
Keywords: copper, fly ash, adsorption, aquatic solution
INTRODUCTION
The copper is one of the essential micronutrient influencing a different metabolic process
in a human body, but when it exceeds some limits the copper exposes the toxic effect on the
human health. Long term copper intake leads to nose, mouth and eyes irritation and causes
stomach diseases and ultimately can lead to fatal liver and kidney damage. Chronic copper
poisoning leads to Wilson's disease [1]. So the World Health Organization set the value of
0.05 mg L-1 as the maximally allowed Cu concentration in a drinking water [2].
The water contamination by Cu is a result of different anthropological activity (metal
processing, mine industry, agriculture etc.). Due to the rapid industrialization there is a
potential dangerous of water contamination by Cu. So, a great attention is paid to the
wastewater treatment before being discharged in the environment.
There are numerous methods for a Cu removal from wastewater [3] but adsorption is
recognized as a relatively cheap and easy feasible method for a metal removal from
193
wastewater. The active carbon is mainly in a use as a commercial adsorbent but in pass
decade the numerous by-product from industrial sector are proposed as a possible adsorbent
for a heavy metals removal from wastewater.
Thus the aim of this study was to investigate the use of fly ash (the by-product of coal
combustion in coal fired power stations) as novel low-cost adsorbent for Cu2+ removal from
aquatic solution.

Fly ash supplied from coal fired power station Pljevlja in Montenegro was used for
adsorbent preparation. Its chemical composition is given in the Table 1.
Table 1 Chemical composition of fly ash

Component %
SiO2 49.45
Fe2O3 5.23
Al2O3 21.77
TiO 0.66
CaO 13.34
Na2O 0.46
ZnO 4.510-3
MgO 1.29
MnO 0.02
P2O5 0.24
K2O 1.40
Loss of ignition 4.35
Fly ash modified by alkali activation was used as a sorbent for adsorption tests. Alkali
activation was carried out by mixing of fly ash with alkali activator in a solid to liquid ratio of
1.2 to 1. The mixture of 10 M NaOH and commercial water glass (commercial Na silicate
solution: Na2O = 8.5%, SiO2 = 28.5%, density of 1.39 kg/m3) was used as an alkali activator.
These two solutions were mixed in a mass ratio of 1.5. The paste obtained by mixing of fly
ash and alkali activator was casted in a closed plastic mould and cured for 48 h at 65° C. After
that time, the samples were allowed to cool, removed from moulds and left to stay for
additional 28 days at ambient temperature before being powdered to the size below 63 µm.
Such prepared sorbent was washed with distilled water until the neutral pH value was
obtained. Subsequently, the wet adsorbents were dried at 105°C. A set of adsorption tests was
performed in a batch conditions at 25, 35 and 45 C by mixing sorbent with solution
containing 20-120 mg L-1 of Cu2+ ions at pH between 3 and 5 and solid to liquid ratio of 0.4-
0.8 for a period of 60 min. All the experiments were carried out in triplicate and the average
values of the results are taken into account. Copper sulfate pentahydrate (CuSO45H2O) and
deionized water were used for the preparation of copper containing solution.
194
Upon completion of adsorption tests, the solutions were filtered and analyzed for the
concentration of Cu2+ by using inductively coupled plasma optical emission spectrometry
(ICP-OES). Removal efficiency of Cu2+ ions (RE) from aquatic solutions was determined
using equations Eq.1.
(Co  Ct )
RE   100;% (1)
Co
where Co and Ct are initial and final concentrations of Cu2+ in solutions.

Influence of pH of solution
The results of investigation of pH of solution on the removal efficiency of Cu2+ from
aquatic solution are given in the Figure 1. It is evident that increase of pH of solution from 3
to 5 lead to the increase of removal efficiency from 38.8% to 74. 3% e.g. the higher removal
efficiency was achieved in slightly acid solution than in a strong acid solution. This can be
explained by the competition of Cu2+ and H+ ions to adsorb on the active site of sorbent. The
increase of pH of solution lead to the decrease of H+ ions concentration and increase the
concentration of Cu2+ ions adsorbed [4]. Since the maximal removal efficiency was achieved
at the pH of 5, this pH value was chosen as an optimal for further experiment.
Figure 1 Influence of pH of solution on the efficiency of Cu2+ removal from aquatic solutions
Influence of initial solution concentration and sorbent dosage

Investigation of the influence of initial Cu2+ concentration on the efficiency of Cu2+
removal from aquatic solution was carried out in the range of 20-120 mg L-1 and the results
are given in the Figure 2a. The removal efficiency of Cu2+ ions from aquatic solution
increases from 39.7% to 74.3% with the increase of initial Cu2+ concentration from 20 to 100
mg L-1. Further increase of initial metal concentration in the solution up to 120 mg L-1 did not
195
changed the removal efficiency considerably ant thus the value of initial Cu2+ concentration
was chosen as an optimal for the rest of experiments. The increase of metal removal
efficiency with the increase of initial metal concentration in a solution can be explained by the
increase of amount of Cu ions adsorbed on the available active site on the adsorbent surface.
At the initial Cu concentration of 100 mg L-1, all available active sites on the sorbent surface
were occupied, so the further increase of initial concentration to the value of 120 mg L-1 had
no influence on the removal efficiency of Cu2+ ions from solution.
Since the availability of active sites on the sorbent surface depend on the amount of
sorbent used for the adsorption tests, the influence of sorbent dosage on the metal removal
efficiency was investigated in the range of solid to liquid ratio of 0.4 to 0.8 and the results are
given in the Figure 2b. The results indicate that increase of adsorbent dosage in investigated
range lead to the increase of removal efficiency from 44.2% (at solid to liquid ratio of 0.4) to
74.3 % (at solid to liquid ratio of 0.8).
Figure 2 a) Influence of initial solution concentration and b) sorbent dosage on the efficiency of Cu2+
removal from aquatic solutions
Influence of time and temperature

Figure 3 presents the results obtained by the investigation of time and temperature of
adsorption test. The results obtained have shown that the adsorption of Cu2+ on the fly ash
based adsorbent occur in a relatively short time and the maximal removal efficiency was
achieved after 10 min and practically did not changed with the further prolongation of
adsorption process. This means that equilibrium of Cu2+ adsorption was achieved within the
first 10 min. Since the adsorption process involves a several steps including the diffusion of
metal ions to the sorbent surface, influence of temperature of adsorption was needed to be
investigated. The results obtained indicate theta increase of temperature from 25 to 45 C is
favorable for the adsorption of Cu2+ process.
The removal efficiency was increased from 61.4% at 20 C to 74.3% at 45 C after 10 min
of test which can be explained by the increase of diffusion of metal ions to the sorbent surface
[5].
196
Figure 3 Influence of time and temperature on the efficiency of Cu2+ removal from aquatic solutions
CONCLUSION
Based on the results obtained in this study the following conclusions can be drown:
 The removal efficiency of Cu2+ ions from aquatic solutions increase in the pH range of 3-
5.
 Increase of initial metal concentration in the range of 20-100 mg L-1 and sorbent dosage
in the range of 0.4-0.8g L-1 lead to the increase of Cu2+ ions removal efficiency.
 Cu2+ adsorption on fly ash modified by alkali activation is a relatively fast process and
equilibrium was achieved within 10 min.
 The metal removal efficiency increases with the increase of temperature in the range of
25-45 C.
ACKNOWLEDGEMENT
This work was supported by the Montenegrin Ministry of Science under grant No. 01-779/2.
REFERENCES
[1] C.A. Flemming, J.T. Trevors, Water Air Soil Pollut; 44 (1989) 143–158.
[2] WHO, World Health Organization International (1971): Standards for Drinking Water,
WHO, Geneva, 1971.
[3] S.A. Al-Saydeha, H. Muftah, S.J. Zaidi, J. Ind. Eng. Chem; 56 (2017) 35–44.
[4] C.C. Femina, P.S. Kumar, A. Saravanan, et al., J. Environ. Chem. Eng; 5 (2017) 2782–
2799.
[5] W. Peng, H. Li, Y. Liu, et al., J. Mol. Liq; 230 (2017) 496–504.
197
HYDROTHERMAL CARBONIZATION–GREEN PROCESS FOR CARBON
MATERIAL PREPARATION
Branka Kaluđerović1*, Đuro Čokeša1, Mirjana Marković1, Višeslava Rajković1,

Milesa Srećković2
1
University of Belgrade, Vinča Institute of Nuclear Sciences, Mike Petrovića Alasa 12-14,
11351 Vinča, SERBIA
2
University of Belgrade, Faculty of Electrical Engineering, Bulevar Kralja Aleksandra 73,
*
branka@vin.bg.ac.rs
Abstract
A hydrothermal carbonization process of simple sugar or low value biomass–plane tree seed, can be
transformed into an efficient form of carbonaceous material. Elemental analysis of the obtained
samples suggests that the hydrothermal carbonization is useful technique for making carbon-rich
substances. Low porous carbonaceous materials were produced by means of the hydrothermal
carbonization of fructose at 140 and plane tree seed at temperatures in the 200–260°C range. The
materials so formed from fructose are composed of agglomerates of carbonaceous microspheres (size
~2–5 μm), as evidenced by SEM. The combination of the results of the elemental analysis with that
obtained by infrared spectroscopic technique has allowed us to assume that the material surface
possesses oxygen functionality groups (i.e. hydroxyl, carbonyl, carboxylic…).
Keywords: hydrothermal carbonization process, fructose, plane tree seed, carbonaceous
material
INTRODUCTION
Green chemistry, also called sustainable chemistry, has been focused on the designing of
products and processes that minimize or eliminate the use and generation of hazardous
substances and on the environmental impact of chemistry. The main principles that cover such
concepts are: the use of renewable material feedstock and energy sources, the design
technological approaches for preventing pollution, the use of safe, environmentally friendly
substances, including solvents, whenever possible, the design of energy efficient processes,
avoiding the production of waste, etc. [1].
Carbon materials can be made with a wide range of structures, compositions and
properties, depending on the nature of the organic precursor and process parameters [2–5]. So,
carbon has a wide variety of allotropes, from crystalline (diamond and graphite) to amorphous
(carbon black, active carbon, glassy carbon, etc.) as well as the nanostructured forms of
crystalline carbon (fullerenes, nanotubes, nanodiamond, and graphene) [6,7].
Hydrothermal carbonization (HTC) process is a technique to turn simple sugars or waste
biomass as renewable material into black soil, peat, brown carbon and carbonaceous
198
materials, all in water [8–10]. This thermal treatment is under autogenous pressure at
temperatures in the 150–350°C range [11].
HTC of low value biomass is a tool for the sequestration of atmospheric CO2. Biomass is
the biggest carbon converter, with the highest efficiency to bind CO2 from the atmosphere.
This is due to microbial decomposition of biomass that liberates exactly the amount of CO 2
formerly bound in the plant material [12].
Carbon materials obtained by HTC can be made with a wide range of carbon
nanostructured and nanaporous properties that provides attractive opportunities for various
applications: environmental protection, energy-storage and conversion, in catalysis, for
sensor, etc. Due to these properties there are various applications in green chemistry. In that
sense, HTC can be seen as much more than just a technique for making carbon-rich
substances.

All samples have been prepared by hydrothermal carbonization of different precursors
varying the row material and process parameters.
Fructose and plane tree seed were used as a raw material for carbonaceous material
preparation. Fructose (analytical purity, Centrohem, Stara Pazova, Serbia), was dissolved in
0.1 M HNO3 solution (40 mL) to form 0.5 M (F1), 1 M (F2) and 3 M (F3) fructose solution.
Collected plane tree fruits were cut open to take the inside seed that consist from bristles and
achene. The seed was washed than dried in an oven and finally milled in coffee mill. Plane
tree seed (2 g: PTS1 and PTS4, or 5 g: PTS2 and PTS3) were dispersed in about 50 ml of
water. All samples were mixed with magnetic stirrer at room temperature for about 15 min.
These solutions or mixtures were put in a reactor and closed. After that reactor was sealed
and placed in the dryer and then temperature is adjusted at various temperatures (t) from 140
to 260oC and maintained () from 3 to 70 hours. The samples are marked depending on the
process parameters, as follows: F1, F2 and F3: t=140oC, 3 h; PTS1: t=260oC,5.5 h;
PTS2: t=260oC, 19 h; PTS3: t=260oC, 25 h, and PTS4: t=200oC, 70 h.
After hydrothermal carbonization, the precipitate was collected by filtration and then
washed repeatedly with distilled water and ethanol. Samples denoted with F were carbonized
in tube oven up to 800oC under an inert atmosphere. After carbonization samples were labeled
as FC.
The resulting samples were characterized by, nitrogen adsorption/desorption isotherms
measurements, (EA) elemental analysis by Vario EL III analyser, (XRD) analysis, scanning
electron (SEM) and Fourier transform infrared spectroscopy (FTIR).

The percentages of carbon retained in the final solid product obtained by elemental
analysis are listed in Table 1. As should be seen, after HTC all samples show increase in
carbon content. For the samples obtained from the fructose drastic increase in carbon content
as well as and for specific surface area (S) can be seen after carbonization process.
199
It can be seen that, depending on the operational conditions, the carbon present in the PTS
retained in the hydrochar products is in the 55–60 wt.% range.
Table 1 Chemical elemental analysis and surface area for samples obtained by HTC
Sample C (wt.%) O (wt.%) H (wt.%) N (wt.%) S (m2/g)
Fructose 40 53 7 - -
F1 60.61 34.91 4.48
F2 60.64 34.86 4.50 - 103
F3 59.87 35.55 4.58 - 48
F3C 91.51 7.65 0.43 - 173
PTS 45.82 47.85 4.63 1.70 -
PTS1 55.06 41.58 2.75 0.61 -
PTS2 54.70 40.17 0.92 0.92 -
PTS3 59.73 34.87 4.89 0.51 -
PTS4 57.46 34.46 6.44 1.64 -
Figure 1, shows results of the XRD analysis of the PTS samples. As can be seen the all
sample has amorphous structure.
a) b)
1000
700
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600
800
500
600
Arb jed
400
Arb jed
400 300
200
200
100
0 0
10 20 30 40 50
10 20 30 40 50
o
o 2 ( )
 ( )
c) d)
1600
700
1-10/12/10 4-29/03/10
1400
600
1200
500
1000
Arb jed
400
Arb jed
800
300
200 600
100 400
0 200
5 10 15 20 25 30 35 40 45 50 5 10 15 20 25 30 35 40 45
o
2 ( )
o
2 ( )
Figure 1 XRD analysis of the PTS samples a) PTS1; b) PTS2; c) PTS3; d) PTS4
SEM analysis shows that the microspheres formed during HTC process of fructose persists
and after carbonization process (Figure 2).
Figure 3 shows results of the of FTIR analysis. There are some present some functional
groups on the surface of the samples, and they are very similar for both samples.
200
Comparing results from EA analysis (Table 1) with results of FTIR (Figure 3) it become
obvious presence of oxygen.
a) bar=10 m b) bar=10 m
Figure 2 SEM micrographs of sample F3 a) before carbonization; b) after carbonization
a) F2 b) PTS
Figure 3 FTIR analysis of samples obtained by HTC from a) Fructose; b) plane tree seed
CONCLUSION
Hydrothermal carbonization process is efficient and green process for making carbon reach
substances from simple sugar and biowaste material such as plane tree seed. Simple sugar like
fructose can change to hydrochar at low temperature such as 140oC. It is quite natural that the
carbonization process increases carbon content and improves porosity in this material.
Presence of oxygen functional groups on the surface of materials after HTC process is
confirmed by FTIR analysis.
ACKNOWLEDGEMENT
the Republic of Serbia for financial support (III 45005).
REFERENCES
[1] P.T. Anastas, J.C. Warner, Green chemistry: theory and practice. Oxford University Press,
Oxford (1998), ISBN: 9780198502340.
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(2003), 28, p. 41–228, ISBN: 9780824709877.
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Carbon Science and Technology, 1st ed.; Publisher: Elsevier Science, Oxford, UK (2003),
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[8] M.-M. Titirici, R.J. White, C. Falcoa, et al., Energy Environ. Sci; 5 (2012) 6796–6822.
[9] M.-M. Titirici, M. Antonietti, N. Baccile, Green Chem; 10 (2007) 1204–1212.
[10] A.T. Mursito, T. Hirajima, K. Sasaki, Fuel; 89 (2010) 635–641.
[11] M. Sevilla, A.B. Fuertes, Carbon; 47 (2009) 2281–2289.
[12] M.-M. Titirici, A. Thomas, M. Antonietti, New J. Chem; 31 (2007) 787–789.
202
THE APPLICATION OF PENCIL GRAPHITE ELECTRODE IN
ELECTROANALYSIS
Žaklina Tasić1*, Ana Simonović1, Marija Petrović Mihajlović1, Milan Radovanović1,

Milan Antonijević1
1
*
ztasic@tfbor.bg.ac.rs
Abstract
Different methods including ultraviolet (UV) spectroscopy, liquid chromatography, capillary
electrophoresis and electrochemical methods are used to analyze the target compounds in various
mediums. In comparison with others, electrochemical methods are more sensitive, simpler and faster
and have been widely used for determination of electroactive compounds. In recent years, graphite
pencil electrodes as working electrodes have been used in the analysis of inorganic and organic
compounds. This working electrode is available, cost effective and has good reproducibility and
sensitivity for low concentration of analyte. Additionally, graphite pencil electrodes are easy to
modify. The surface of graphite pencil electrode could be improved by using modifiers or
electrochemical pretreatment.
Keywords: electrochemical methods, pencil graphite electrode, modified pencil graphite
electrode, electrochemical pretreatment
INTRODUCTION
Electrochemical methods are widely used in various areas including corrosion processes,
adsorption processes on surfaces, reaction mechanisms, kinetics of electron transfer processes
and for determination of compounds in different mediums [1–4]. In comparison to the
ultraviolet (UV) spectroscopy, liquid chromatography and capillary electrophoresis,
electrochemical methods are simpler, more economical, faster and more sensitive to reach the
lower limit of detection [5].
The most common methods used in electroanalytics are cyclic voltammetry, differential
pulse voltammetry, square wave voltammetry and adsorptive stripping voltammetry.
Voltammetry is an electrochemical method in which different working electrodes are used
including glassy carbon electrode (GCE), carbon paste electrode (CPE), platinum, graphite
pencil electrode (GPE) and boron doped diamond electrode (BDDE) in order to determine
target compound [6,7].
APPLICATION OF GRAPHITE PENCIL ELECTRODE

Graphite pencil electrode belongs to the graphitic electrodes and has properties such as
good conductivity, high surface area, cost effectiveness and easily availability [8]. It is a
nanocomposite containing graphite as the main component and clay. The content of these
203
compounds determines hardness of graphite pencil. As the content of graphite is greater, the
pencil is softer [9].
Some researcher groups reported that graphite pencil electrodes have better properties than
other carbon-based electrodes. In the paper by Gowda et al. [10] was observed that GPE has
larger surface area (0.255 cm2) than CPE (0.0951 cm2). Thus, GPE was successfully used for
determination of paclitaxel without any preconcentration. Furthermore, Dilgin et al. [11]
compared the properties of GPE and GCE for determination of acyclovir in Britton-Robinson
buffer at pH 4. Based on the obtained cyclic volatmmograms, the peak current was
significantly improved when GPE was used in comparison to the GCE. This behaviour can be
attributed to the presence of clay that generates a porous structure and a high specific surface
area of the pencil graphite [12].
Tavares et al. [13] investigated the influence of the softness of graphite on voltammetric
response by cyclic voltammetry in a K4[Fe(CN)6] solution. They observed that harder
graphite shows higher peak current than softer graphite. This behaviour could be explained by
the presence of polarized chemical groups in softer graphite. Additionally, greater sensitivity
and reproducibility is found for harder graphite pencil electrodes. Also, Skrzypczyńska et al.
[9] investigated the effects of the hardness of graphite pencil electrode on the voltammetric
signal of pentachlorphenol. In this research 2B, 5B and 8B pencil graphites were used. The
sensitivity of the electrodes was correlated with the hardness of the pencil graphites and
follows the order: 2B < 5B < 8B. Limit of detection of used electrodes was 0.277 mmol/L,
0.189 mmol/L and 0.098 mmol/L for 2B, 5B and 8B, respectively.
The pencil graphite electrode was investigated for determination of different compounds in
pharmaceuticals and certain results are summarized in Table 1.
Table 1 The electroanalytical application of pencil graphite electrode in pharmaceuticals

Experimental
Compound Technique LODe Reference
conditions
Mcllvaine buffer f [14]
Acetaminophen CVa /
(pH 6)
Britton- [15]
Acetylsalicylic b
SWV Robinson buffer 167 ng/mL
acid
(pH 1.81)
Vitamin B6 2.81 µg/L [16]
DPVc 0.2 M NaOH
Vitamin B1 5.34 µg/L
Phosphate [17]
Paclitaxel DPVc 0.00246 µg/L
buffer
Britton- [18]
c
Niclosamide DPV Robinson buffer 0.015 µg/L
(pH 7)
Britton- [19]
c
Eugenol DPV Robinson buffer 0.085 µg/L
(pH 2)
204
Table 1 continued
Britton- [11]
c
Acyclovir DPV Robinson buffer 0.3 µg/L
(pH 4)
CVa Phosphate [20]
Chlorpromazine 0.003 µg/L
DPVc buffer (pH 7)
Britton- [21]
Nalbuphine c
DPV Robinson buffer 6.38 µmol/L
Hydrochloride
(pH 6)
Britton- [22]
d
Itraconazole As-DPV Robinson buffer 9.1 ng/L
(pH 2)
a
CV – cyclic voltammetry; b SWV – square wave voltammetry; c DPV – differential pulse voltammetry;
d
As-DPV – anodic stripping differential pulse voltammetry; e LOD – limit of detection; f / – no data.
Based on the results shown in Table 1, it can be said that the graphite pen electrode has
been successfully applied to determine the pharmaceutical compounds under different
conditions.
PRETREATMENT OF GRAPHITE PENCIL ELECTRODE

Graphite pencil electrodes are easy to modify in order to enhance their sensitivity [23]. The
surface of graphite pencil electrode could be improved by using modifiers or electrochemical
pretreatment. During electrochemical pretreatment some functional groups containing oxygen
such as carboxylic, carbonyl or phenolic could be formed on the surface. Because of that, the
current response of the analyte is enhanced. Electrochemical pretreatment of electrode surface
is suitable because it is very simple and less time-consuming than treatment with some
complex material [8].
Ozcan and Sahin [24] investigated the possibility of application of electrochemically
treated GPE to determine uric acid in urine and blood serum. The GPE was treated in the
mixture of lithium perchlorate and sodium carbonate solutions. They reported that the mixture
of LiClO4 and Na2CO3 showed synergistic effect on the electrochemical treatment of GPE
that led to the higher response of uric acid. According to the obtained results, it was
concluded that electrochemically treated GPE could be applied in determination of uric acid
in biological samples. Further, Alipour et al. [25] electrochemically treated pencil graphite
electrode in phosphate buffer solution at 1.80V for five minutes. Such prepared electrode was
used for determination of morphine. Electrochemically treated GPE showed well defined two
anodic peaks at about 0.35 V and 0.8 V respectively in comparison to only one peak at 0.5 V
with untreated GPE. The detection limit of morphine in biological samples with
electrochemically treated GPE was 0.26 µM.
Koyun and Sahin [26] in their research used modified pencil graphite electrode with
poly(L-cysteine) for determination of Sunset Yellow in food and beverage samples.
205
Figure 1 Cyclic voltammograms of phosphate buffer solution (0.1 M, pH 7) containing 1 mM Sunset

Yellow at the bare PGE and modified PGE, scan rate 100 mV/s [26]
The obtained results using cyclic voltammetry (Figure 1) reveals that peak current of
Sunset Yellow is enhanced on modified GPE in comparison on bare GPE. Also, the surface
morphology obtained by scanning electron microscopy (SEM) (Figure 2) indicates that
modified GPE has rough surface and sphere-like structures in comparison to the bare GPE. It
is assumed that the polymerization of L-cycteine on the GPE is occurred and the rough
surface is responsible for the improved electrochemical behaviour.
Figure 2 Scanning electron microscopy micrographs of the a) bare GPE and b) modified GPE [26]
Pattar and Nandibewoor [27] used polyaniline and polypyrrole as modifiers for graphite
pencil electrode. Such prepared electrode was used for detection of 2-thiouracil in
pharmaceuticals and human biological fluids. According to the obtained results, the electro-
oxidation of 2-thiouracil was irreversible, diffusion controlled process. By comparing the
intensity of peak current on a cyclic voltammogram for bare graphite pencil electrode and
206
modified ones, it is observed that the peak intensity is enhanced using modified electrodes. It
is presumed that modified electrodes have larger surface area than bare graphite electrode.
CONCLUSION
The applicability of electrochemical methods is diverse. They can be used in investigation
of corrosion processes, reaction mechanisms and kinetics of electron transfer processes as
well as for the determination of compounds in different medium. Among the various
electrodes used in these methods, pencil graphite electrode stands out due to its sensitivity,
conductivity and easy availability. The pencil graphite electrode was used in determining of
various compounds such as metal ions, phenolic and pharmaceutical compounds. The
hardness of the pencil graphite electrodes has effect on the voltammetric response.
Additionally, the graphite pencil electrodes are easy to modify. Therefore, the research groups
performed electrochemical treatment of the pencil graphite electrodes or treated them using
some modifiers. Based on the obtained results, it is concluded that the analyte peak current on
the modified GPE is enhanced in comparison to the bare GPE.
ACKNOWLEDGEMENT
REFERENCES
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doi:10.1038/s41598-019-52635-2.
[2] M.B. Petrović Mihajlović, M.B. Radovanović, Ž.Z. Tasić, et al., J. Mol. Liq; 225 (2017)
127–136.
[3] Ž.Z. Tasić, M.B. Petrović Mihajlović, M.B. Radovanović, et al., J. Mol. Liq; 265 (2018)
687–692.
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and Management 1–2 (2014) 8–13.
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[8] A.-N. Kawde, N. Baig, M. Sajid, RSC Adv; 6 (2016) 91325.
[9] K. Skrzypczyńska, K.Kuśmierek, A. Świątkowski, et al., Int. J. Electrochem. Sci; 13
(2018) 88–100.
[10] J. I. Gowda, S. T. Nandibewoor, Electrochim. Acta; 116 (2014) 326–333.
[11] D. G. Dilgin, S. Karakaya, Mat. Sci. Eng. C; 63 (2016) 570–576.
207
[12] I.G. David, D.-E. Popa, M. Buleandra, J. Anal. Methods Chem; 2017 (2017),
doi:10.1155/2017/1905968.
[13] P.H.C.P. Tavares, P.J.S. Barbeira, J. Appl. Electrochem; 38 (2008) 827–832.
[14] P. Masawat, S. Liawruangrath, Y. Vaneesorn, et al., Talanta 58 (6) (2002) 1221–1234.
[15] V. Supalkova, J. Petrek, L. Havel, et al., Sensors; 6 (11) (2006) 1483–1497.
[16] I.G. David, M. Florea, O.G. Cracea, et al., Chem. Pap; 69 (7) (2015) 901–910.
[17] J.I. Gowda, S.T. Nandibewoor, Electrochim. Acta; 116 (2014) 326–333.
[18] E. Dede, O. Saglam, Y. Dilgin, Electrochim. Acta; 127 (2014) 20–26.
[19] O. Saglam, D.G. Dilgin, B. Ertek, et al., Mat. Sci. Eng. C; 60 (2016) 156–162.
[20] H.T. Purushothama, Y.A. Nayaka, M.M. Vinay, et al., Journal of Science: Advanced
Materials and Devices; 3 (2018) 161–166.
[21] H.M. Elqudaby, H.A.M. Hendawy, E.R. Souaya, et al., Int. J. Electrochem; 2016 (2016)
doi:10.1155/2016/8621234.
[22] A. Shalaby, W.S. Hassan, H.A.M. Hendawy, et al., J. Electroanal. Chem; 763 (2016) 51–
62.
[23] I.G. David, I.A. Badea, G.L. Radu, Turk. J. Chem; 37 (2013) 91–100.
[24] A. Ozcan, Y. Sahin, Biosens. Bioelectron; 25 (2010) 2497–2502.
[25] E. Alipour, S. Gasemlou, Anal. Methods; 4 (2012) 2962–2969.
[26] O. Koyun, Y. Sahin, Int. J. Electrochem. Sci; 13 (2018) 159–174.
[27] V.P. Pattar, S.T. Nandibewoor, Sensor Actuat. A-Phy; 250 (2016) 40–47.
208
RECOVERY OF METALS FROM SPENT LITHIUM ION BATTERIES
Ivan Đorđević1*, Snežana Milić1, Dragana Medić1, Maja Nujkić1,

Aleksandra Papludis1
1
*
idjordjevic@tfbor.bg.ac.rs
Abstract
With the development of portable electric appliances and electric vehicles, there came a rise in the
production of lithium-ion batteries, and, consequently, an increase in the number of spent batteries.
Recycling of spent batteries, from the point of view of the environmental protection, economy and
health, is inevitable. Due to the high content of valuable and polluting metals such as Cu, Co, Li, Ni,
Mn, etc. it is necessary to do metal valorization when many methods can be applied. The most widely
used methods are: solvent extraction, chemical precipitation, and various electrochemical processes.
However, in recent times, work has been done on the development of new and more efficient methods
and technologies for the separation of metals from used batteries. Such methods would have great
merit for minimal environmental pollution.
Keywords: Lithium-ion batteries, valorisation, recycling
INTRODUCTION
The essential division of batteries can arrange them into two fundamental classifications:
primary batteries and secondary batteries. Lithium-ion batteries (LIBs) are categorized as
secondary batteries. LIBs are composed of: cathode, anode, electrolyte and separator. Pure
carbon is utilized as the anode whereas the cathode material is made out of LiMeO2 (Me =
Co, Ni, Mn, Fe ...) and, lastly, lithium salts are dissolved in the electrolyte solution. LIBs also
contain various organic solvents such as: ethylene carbonate (EC), dimethyl carbonate
(DMC), propylene carbonate (PC), diethyl carbonate (DEC) and ethylmethyl carbonate
(EMC) [1–3].
In 2000, the global LIB production reached 500 million units and practically 4.6 billion in
2010 [4]. In 2014, however, the production of the LIBs in China has come to 5,287 billion
units [3].
The general reusing process incorporates two essential categories: physical and chemical
procedures. Physical procedures can be frequently linked with the pre-treatment forms, for
example, pounding, sieving and the separation of materials to remove the cathode materials
from the case, collector and anode active materials. On the other hand, the chemical
procedures can be summed up as pyrometallurgy, biometallurgy and hydrometallurgy.
Pyrometallurgical forms are regularly joined by high gas emissions and have high energy
consumption, so they require rigid air filtration measures and costly gear investments. By
utilizing these procedures, nickel, cobalt, and copper can be recuperated adequately, while
lithium and aluminium can be lost in the slag [5]. In any case, pre-treatment of utilized LIBs
209
is not required in such procedures, and their higher energy consumption, high equipment
investment, and natural contamination can impede their application. The biometallurgy
procedure brings numerous advantages, for example, high productivity, minimal effort and
the utilization of a simple apparatus. The long treatment time frame and the troublesome
incubation of microbes limit the popularization of this procedure. Consequently, the most well
established process is the hydrometallurgy. The hydrometallurgy procedure frequently began
with the acid leaching, utilizing the diluted H2SO4, HNO3, HCl, or even mixed acid to
dissolve the cathode material.
PRETREATMENT OF Li–ION BATTERIES

As indicated by Figure 1, three basic routes are in the recycling process. Route 1 represents
reusing or recuperation process, which consists of pre-treatment (sometimes the discharging
process is also regarded as a pretreatment process), pyrometallurgical process, and
hydrometallurgical process. Route 2 is the fixing procedure. Route 3 presents the reusing
procedure, which is mainly based on reusing Cu, Al foil, and plastic that could be
straightforwardly reused after disassembling the elements. The accomplishment of the Route
3 relies upon the productivity of the disassembly procedure to a great extent. As for route 2,
the advantage of it is shorting the recycling route to decrease the loss of valuable metals or
materials and increase the profile of technologies. Moreover, the strategies for reuse and
fixing are frequently disregarded even though these procedures could be extremely
advantageous and reasonable in terms of expenses because of their short and effective flows.
Figure 1 General flow sheet of spent LIB treatment processes [5]
Spent LIBs generally contain 5%–20% cobalt (Co), 5%–10% nickel (Ni), 5%–7% lithium
(Li), 5%–10% different metals (copper (Cu), aluminium (Al), iron (Fe), etc., 15% natural
mixtures, and 7% plastic [6].
210
Pyrometallurgical process
The pyrometallurgical procedure is one part of the extractive metallurgies that is
implemented in order to remove minerals and concentrates with thermal treatment through
physical and synthetic changes that enhance the recuperation of valuable metals.
Pyrometallurgical techniques have been generally researched in retrieving Zn, Ni, Cd, and
other significant metals from used Zn−Mn dry batteries or Ni−Cd batteries. Generally
speaking, smelt slags were utilized in pyrometallurgical strategies to isolate metals in which
some metals end up in the slag and target metals transform into alloy.
When conducting a typical pyrometallurgical process, Li will end up in the slag stage,
which must be additionally removed. Carbothermal reduction methods as a pyrometallurgical
method to recycle Li and other metals have received attention in recent years. In this
procedure, the blended utilized LIBs can be transformed to metal oxide, pure metal, or lithium
carbonate. In one stage, lithium carbonate is filtered by water, while the graphite in the
draining slag consumes and leaves metal oxide as the last residue. In the following step, pure
metal, graphite, and lithium carbonate are additionally isolated by wet magnetic separation. In
any case, the pyrometallurgical advances are also currently facing difficulties in reducing
energy consumption and meeting the rigorous requirements for the treatment equipment.
Biometallurgical process
Bioleaching is a rising interdisciplinary procedure that incorporates biology, chemistry and
metallurgy. The success of the biometallurgical procedure basically relies upon the capacity
of microorganisms to transform the insoluble strong compounds into dissolvable and
extractable structures.
Hydrometallurgical process
The hydrometallurgical technique is widely used to recover significant metals from spent
LIBs. In the beginning, Co and Li are dissolved by acid leaching or biological leaching. At
that point metals in the solution can be recouped by means of a chemical or an
electrochemical deposition. Co and Li can likewise be isolated by organic solvent extraction,
and afterwards be recovered by electrolysis or chemical precipitation. It has numerous
advantages when compared to the pyrometallurgical procedure, for example, because of high
extraction effectiveness, low energy consumption, minimal dangerous gas discharge, and low
expenses. It has a tremendous potential and can therefore be widely used in the industrial
realization. In any case, little flexibility for the removal of crude materials can be a real
challenge.
Leaching
In order for the spent LIBs to be reused, the cathode materials are usually dissolved in
leaching reagents followed by separation and extraction as the fundamental stages, which are
just like other metallurgical procedures. In the development phases of the research, inorganic
acid reagents, for example, HCl, HNO3, and H2SO4 were generally utilized as leaching agents
and demonstrated to be plausible and effective, but they likewise had a few downsides. The
chemical reaction (1) of utilizing HCl can be described as:
211
8HCl + 2LiCoO2 → 2CoCl2 + Cl2↑ + 2LiCl + 5H2O (1)
The leaching efficiency of Co without reductants follows the order of HCl>HNO3≈H2SO4.

The generally high reducibility level of HCl predominantly adds to this diverse leaching
performance. In this manner, the leaching efficiency of most reagents would be unsatisfying
unless H2O2 or different reductants are included. The mechanism for the decrease response
can be described as (taking LiCoO2 for instance) following reaction (2):
3H2SO4 + 2LiCoO2 + 2H2O2 → Li2SO4 + 5H2O + 3/2O2↑ + 2CoSO4 (2)
With increasing in reductant concentrations, the leaching efficiency and reaction rate
would first increase accordingly and then reach a plateau at which leaching efficiency and
reaction rate would not vary appreciably.
RECOVERY OF METALS FROM LEACHATE

The leachate that can be obtained upon acid leaching generally contains many metal ions.
One of the fundamental focuses for the reusing procedure is to get pure metal or metal
compounds. In any case, the coexistence of different metal ions in the leachate will
unavoidably smother the reusing of pure metal or metal compounds. Likewise, the overlap of
the pH range for the precipitation of various metals makes the endeavour to obtain pure
metals from a single step precipitation insufficient. Consequently, the leaching solution must
be subjected to various stages of separation and extraction, e.g., solvent extraction, selective
precipitation, and an electrochemical method to accomplish acceptable degrees of purity.
Solvent Extraction
Solvent extraction is otherwise known as a liquid−liquid extraction technique that
incorporates the diverse relative solubility’s of compounds in two immiscible fluids to isolate
them from one another. Despite the fact that it is facing the difficulties in isolating compounds
with similar functional groups, it stays well-grounded and is broadly applied in the extraction
of tungsten and molybdenum, copper from minerals, nuclear reprocessing, and the production
of fine organic compounds.
In one study, Kang et al. [7] proposed a procedure that includes acid leaching,
precipitation, and extraction that yielded an estimated 92% of Co recouped. In this proposed
procedure, subsequent to leaching with 2M H2SO4 and 6 vol.% H2O2, Co is specifically
separated from the purified aqueous phase through equilibrating with 50% saponified 0.4M
Cyanex 272 at an equilibrium pH~6. Therefore, following the removal of the stacked organic
stage with 2M H2SO4, a solution of 96 g/L Co remains after the procedure, from which pure
pigment−grade cobalt sulphate can be recovered by utilizing evaporation/recrystallization.
Nayl et al. [8] extracted and isolated Mn(II), Co(II), Ni(II) and Li(I) from the leach liquor
in used LIBs. Precipitates of Mn(II), Co(II), Ni(II) and Li(I) with more than 99% of purity
could be acquired under the researched conditions (20% Acorga M5640 in kerosene with
agitation for 5 min at 30°C at an equal stage proportion of unity).
212
Solvent extraction can provide metals with high levels of purity and efficiency, and is
generally conducted at room temperature within a short timeframe. Nonetheless, this
procedure likewise has a few downsides, for example, complex activities and significant
expenses for solvents. Therefore, future research efforts should be focused on the
improvement of economical solvents as well as the cyclic use of solvents.
Selective precipitation
The selective precipitation is a single chemical procedure that has been widely researched
and applied in separating metals from complex systems of compounds. At times, it is difficult
to precipitate just a single ion from the solution.
There is an overlap between stable areas of Co(OH)2 and Ni(OH)2, and it is so enormous to
the point that Ni2+ and Co2+ are likely to be co−precipitated by means of a neutralization
reaction. However, the stable areas of Ni2+ and Co(OH)3 have a significantly smaller overlap.
Hence, one potential methodology is to transform Co2+ to Co3+ to accomplish a selective
precipitation of Co3+ in this small area. This procedure was demonstrated to be possible and
effecti e by ouli et al. [9]. With NaClO as the oxidant, the recovery efficiencies of Co and
Ni were both almost 100%. The reaction mechanism can be expressed as following reactions
(3,4):
Co2+ + ClO- + 2H3O+ → 2Co3+ + Cl- + 3H2O (3)
Co3+ + 6OH- → Co2O3 + 3H2O (4)
Kim et al. [10] researched a hydrothermal re˗lithiation strategy utilizing a concentrated

LiOH solution at 200°C with no scraping methods to recover LCO cathodes and their results
indicated that in spite of the fact that the acquired and recovered LCO had some
electrochemically inactive polluting impurities, it was still able to accomplish a starting
discharge capacity of 144.0 mAh/g and a capacity retention of 92.2% after 40 cycles.
Electrochemical method
In comparison to other hydrometallurgical procedures for reusing metals from spent LIBs,
the electrochemical method can yield the cobalt compound of the highest level of purity since
it does not include different substances and hence avoids the introduction of other impurities
in the system.
Myoung et al. [11] applied an electrochemical deposition and a suitable thermal treatment
to extract cobalt oxide from Co (III) of waste LiCoO2 cathodes. Under relevant pH conditions,
island˗shaped cobalt hydroxide is precipitated in the titanium substrate and the thermal
treatment of the cobalt hydroxide brings about the creation of cobalt oxide.
Freitas et al. [12] recovered cobalt from spent LIBs by utilizing electrochemical techniques
and initiate a series of discussions about the electrochemical deposition of cobalt, the
difference in pH value in the electrochemical reaction and the impact of pH on the
development of crystals.
213
CONCLUSION
The general reusing of spent LIBs includes methodical engineering comprising of a source
control, a handling control, and a treatment. By increasing ecological awareness, a great deal
of consideration will be given to the improvement of green and basic reusing strategies.
Moreover, in the long run, the essential way for the spent LIBs to be reused lies in the choice
of recently developed materials, for example, cathodes, anodes, and electrolytes, just as well
as battery designs. Therefore, efforts must be focused on the use of abundant and nontoxic
materials so that whatever developments are made will not create new environmental
problems. With simpler battery designs facilitating better treatment of spent LIBs.
ACKNOWLEDGEMENT
REFERENCES
[1] Y. Yu, B. Chen, K. Huang, et al., Int. J. Environ. Res. Public Health; 11 (3) (2014) 3185–
3198.
[2] A. Manthiram, ACS Cent. Sci; 3 (10) (2017) 1063–1069.
[3] H. Yao, G. Xi, Y. Fenga, RSC Advances; 6 (22) (2016) 17947–17954.
[4] L. Li, J.B. Dunn, X.X. Zhang, et al., J. Power Sources; 233 (2013) 180–189.
[5] W. Lv, Z. Wang, H. Cao, et al., ACS Sustainable Chem. Eng; 6 (2018) 1504–1521.
[6] J. Ordoñez, E.J. Gago, A. Girard, Renew. Sustain. Energ. Rev; 60 (2016) 195–205.
[7] J. Kang, G. Senanayake, J. Sohn, et al., Hydromet; 100 (2010) 168–171.
[8] A.A. Nayl, M. M. Hamed, S.E. Rizk, J. Taiwan Inst. Chem. Eng; (2015) 1–7.
[9] M. Joulie, R. Laucournet, E. Billy, J. Power Sources; 247 (2014) 551–555.
[10] D.S. Kim, J.S. Sohn, C.K. Lee, et al., J. Power Sources; 132 (2004) 145–149.
[11] J. Myoung, Y. Jung, J. Lee, et al., J. Power Sources; 112 (2002) 639–642.
[12] M.B.J.G. Freitas, V.G. Celante, M.K. Pietre, J. Power Sources; 195 (2010) 3309–3315.
214
APPLICATION OF SIMULATION METHODS AND ANALYSIS OF THE
INFLUENCE OF PRECIPITATION REGIME ON TURBIDITY OF KARST
AQUIFER: A CASE STUDY OF KARST ZLOT’S SPRING (BOR, SERBIA)
Marina Pešić1, Snežana Milić2*, Maja Nujkić2, Dragana Medić2, Sonja Stanković2
1
JKP “Vodvod” Bor, R.J. Čoče 16, 19210 Bor, SERBIA
2
*
smilic@tfbor.bg.ac.rs
Abstract
Water resources from karst aquifers are becoming more and more important sources of fresh and
quality drinking water. Efflux and the quality of karst aquifers depends mostly of the pluviographic
regime, as well as on the regime of surface water that sink. For these reasons, it is necessary to
monitor the quality parameters of karst aquifers, but the pluviographic regime of the area should also
be observed. Monitoring of the spring is basic for establishing an adequate simulation model. Long-
term monitoring of those parameters enables the application of simulation models through
dependence between quantity precipitation and characteristic parameters of water quality.
Establishment of a simulation model for dependence between precipitation, water level and turbidity,
will make the management of the water system in the city of Bor more secure. Based on the weather
forecast, the occurence time of turbidity on the source will be known, which will allow timely response
and disconnection of the source from the water supply system.
Keywords: karst aquifers, water quality, turbidity, regression models
INTRODUCTION
Karst aquifers have a special importance in the water supply because the water resources of
this area require minimal processing in order to obtain good quality drinking water [1]. The
biggest problem with karst aquifers is the decrease or increase in water levels during long
periods without rain or long rainy periods. The response of karst aquifers to precipitation is
often rapid, and the change in certain parameters of quantity and quality is sudden (ie.
leakage, groundwater level, turbidity, total number of bacteria, suspended sediment). If the
anthropogenic factor is not present on a basin that drains a particular well, the flow regime
and the quality of karst aquifers depend on the pluviographic regime and the regimes of
formed surface sinking streams. On the other hand, the regimes of formed surface sinking
streams that nourish the karst are also conditioned by the pluviographic regime of the given
area. Under the influence of precipitation the karst groundwater begins to move extremely
fast, causing the surrounding terrain to flush out and the formation of turbid water consisting
of suspended and colloidal particles.
The karst aquifer is characterized by a turbidity in water that occurs abruptly, rarely
exceeding 20 Nephelometric Turbidity Units (NTUs) and rapidly decreasing to 2 -3 NTUs.
Turbidity 2 -3 NTU can be detain in the water for up to ten days, and such water is already
hygienically defective water, to which a certain technological procedure must be applied.
215
Quality and safe management with wells, in the water supply process, includes knowledge of
the input parameters that cause turbidity, such as the size of the dispersed particles, the
amount of precipitation, the ambient temperature and the water temperature, the number and
thickness of the aquifer layers through which the groundwater passes to the springs [2].
The aim of this paper will be to point out the importance of monitoring parameters of water
quality at the spring, and to present the results of the conducted analyzes, as well as the results
of simulation models on the waters of karst Zlot`s spring which are used for water supply in
the city of Bor. A characteristic of the Zlot`s spring is that after a period of sudden snow or
intense rainfall occurs turbid water. The turbidity at the Zlot`s spring reaches values up to 20
NTU. Spring water quickly and abruptly turbid to higher NTU values, decreases rapidly to 1-
2 NTU values, but takes days or weeks to fall below 1 NTU. The subject of this paper will be
based on the prediction of increased water turbidity depending on precipitation. The
application of simulation methods can predict the effects of precipitation, as the bigest factor,
on the occurrence of turbidity of spring water [3]. Establishing an adequate simulation model
during water system management will be more accurate. Based on the forecast, the occurrence
time of turbidity at the spring will be known, which will allow timely response and exclusion
of the spring from the water supply system.

Study Area
The study area is the Zlot`s spring located in the basin of river Beljevina, 11 km southwest
of Bor. The Zlot`s spring consists of 4 captive sources: Gaura Mare, Gaura Mika, Rnić and
Mejlanović. The flow regime of captive springs and the river itself is extremely complex. The
flow regime is primarily influenced by the geological and hydrogeological diversity of the
river basin.
Climatic data used in the research were taken from the database of the Republic
Hydrometeorological Service of Serbia [4]. Data of daily precipitation was taken from the
nearest meteorological station Crni Vrh. The flow and water level of the river Beljevina is
measured at the station "Seliste", which was built a decade ago by the Republic
Hydrometeorological Service of Serbia. The water level of the river Beljevina is recorded at
the same time every day.
Methods of Analysis
Continuous monitoring of turbidity at Zlot`s spring was started in 2010. For this purpose,
Portable Turbidimeter (Eutech TN 100) was used to measure turbidity in raw water samples.
A samples of raw water were taken every two hours. According to The Official Gazette on the
Hygienic Safety of Drinking Water [5], the maximum permissible turbidity value is 1 NTU.
When the turbidity was higher than 1 NTU, sample for measurement of the turbidity was
taken by the hour. Water samples were analyzed from each captured spring individually.
Samples with higher turbidity than 1 NTU are excluded from the water supply system.
Turbidity was determined immediately after sampling, so that three turbidity measurements
were made on the basis of one sample, and a mean value was adopted for the reference value
of turbidity for the investigeted sample.
216

Regression models were used for simulation of parameters for quality of karst aquifer
water such as turbidity, precipitation and water level. Autoregression (AR), cross-regression
(CR) and autocross-regression (ACR) models were used to simulate turbidity at the karst
source. The AR model was applied to obtain the correlation coefficient of the measured and
calculated turbidity values, applying equation (1) [6]:
TDSi=a+b1.TDSi-1+b2.TDSi-2+ b2.TDSi-2 + +b10.TDSi-10 (1)
where TDSi is water turbidity at time “i”, the independently variable TDSi-1, TDSi-2, .TDSi-k,
were analyzed parameter of water turbidity for 1, 2, ... k days and a, b are the parameters of
the model.
Figure 1 Correlation coefficient obtained by autoregressive method depending on the time shift
expressed in days
The correlations between the observed and calculated TDS values using equation (1) are
given in Figure 1 and Table 1.
Table 1 Correlation coefficients obtained by regression method

Time shift (day) TDS-TDS TDS-P TDS-H
1 0.779109 0.366334 0.637869
2 0.780128 0.423894 0.678277
3 0.781625 0.447547 0.71283
4 0.781628 0.459245 0.728664
5 0.781875 0.464304 0.742501
6 0.783336 0.464355 0.751948
7 0.783529 0.464401 0.753945
8 0.785223 0.464427 0.755461
9 0.785227 0.464501 0.756107
10 0.786202 0.464541 0.757202
*
P – precipitation, H-water level
217
CR model for simulation of turbidity obtained via measured amount of precipitation was
based on following equation [6]:
TDSi=a+b1.Pi-1+b2.Pi-2+…+b10.Pi-10 (2)
where the dependent variable TDSi in time "i" and the known independent variable amount of
precipitation Pi-1, Pi-2, ... Pi-k, for 1, 2, .. .k days.
The correlation between TDS and P using equation (2) is given in Table 1 and Figure 2.
Figure 2 Correlation coefficient obtained by cross-regression method depending on the time shift
expressed in days
From Figure 2 it can be concluded that the inclusion of 4 or 5 independently variables (in
this case precipitation with a shift of up to 5 days) is sufficient. Subsequently, the inclusion of
independent variables does not increase the quality of the regression equation, that is, we do
not get any better simulations by including new variables. This can be proved by the
regression equation, which will most likely show that they are insignificant in the equation, so
they should not be included in the equation (more than 5 terms).
The simulation of turbidity at the expense of the water level of the river Beljevina is
performed according to the same principle as for precipitation, using the following equation
[6]:
TDSi=a+b1.Hi-1+b2.Hi-2+…+b10.Hi-10 (3)
where: H is water level.

From Figure 4 it is concluded that the inclusion of 5 or 6 independent variables (in this
case the water level with a shift of up to 6 days) is sufficient.
218
Figure 3 Correlation coefficient obtained by cross-regression method depending on the time shift
expressed in days
Based on the above, an equation with 6 displacements is set, considering that there is a
dependence for these displacements. The turbidity of the Zlot`s spring is simulated using
known independent variables such as precipitation, water levels and turbidity registered in the
given profile of the previous days. Based on the presented results, the following equation of
multiple linear regression was formed:
TDSi = a + b1.TDSi-1 + b2.Pi-1 + b3.Pi-2 + b4.Pi-3 + b5.Pi-4 + b6.Hi-1 (4)
where are: TDSi and TDSi-1 turbidity of the Zlot`s spring at the moment "i" and "i-1", then Pi-
1, Pi-2, Pi-3, Pi-4, daily precipitation amounts recorded at the meteorological station Crni Vrh in
at the time i -1, i -2, i -3 i i-4 and Hi-1 is water level of the river Beljevina in the profile of
Selište at the moment i-1. Parameters a, b1, b2, b3, b4, b5 and b6 are dimensionless parameters
of the above equation, which are obtained by the method of least squares and whose values
are presented in Table 2.
Table 2 Multiple linear regression coefficients

a b1 b2 b3 b4 b5 b6
-0.63678 0.63380 0.07620 -0.00986 -0.00626 -0.00640 0.01841
Using the values of the obtained parameters, the calculation of the turbidity value can be
done on the basis of the observed values of precipitation, water level and turbidity of the
Zlot`s spring. The previous analysis of the influence of precipitation on the water level of the
river Beljevina in the Selište profile, as well as on the turbidity of the waters of the captured
springs of the Zlot`s spring, indicates the fact that there is a good correlation between
precipitation and the considered variables.
CONCLUSION
The defined equation of multiple linear regression enables the prediction of turbidity
values in a certain moment at the Zlot`s spring, based on previously measured values of
219
precipitation, water level and turbidity. In this way, opportunities are created for the
management of the company for the distribution of drinking water to realize its strategic plan,
to deliver hygienically safe drinking water, in sufficient quantity, at any time through a set of
preventive procedures.
From an ethical point of view, the significance of this work is also very important. Water
with increased turbidity contains a certain type of bacteria that can cause gastroenteritis. On
the other hand, since turbidity entails an increased concentration of organic and inorganic
substances, it is necessary to maintain a higher concentration of residual disinfectant in water,
in this case chlorine, which increases the possibility of trihalomethane formation in the
reaction of residual chlorine and present natural organic matter. It is very important to know
that trihalomethanes are carcinogenic and extremely harmful to human health.
REFERENCES
[1] M. Pešić, V. Ristić Vakanjac, B. Vakanjac, et al., Proceedings of the XXIII International
Conference Ecological Truth, 17-20 June 2015, Kopaonik, Serbia (2015) 583–589.
[2] M. Pešić, V. Ristić Vakanjac, B. Vakanjac, et al., Доклади на Българската академия на
науките, Comptes rendus de l’Académie bulgare des Sciences 9 (69) (2016) 1183–1194.
[3] M. Pešić, S.Milić, M.Nujkić, et al., Water Air Soil Poll; 231 (3) (2020) 1–12.
[4] Republic Hydrometeorological Service of Serbia – RHMS.
[5] Pravilnik o higijenskoj ispravnosti vode za piće, Sl. list SRJ, br. 42/98 i 44/99,40/03,28/19
(in Serbian).
[6] N. Krešić, Z. Stevanović, Groundwater hydrology of springs: engineering, theory,
management and sustainability, Amsterdam, Boston, Butterworth Heinemann (2010) 573.
220
DISPOSAL OF FLYING ASH FROM THERMAL POWER PLANTS
Nataša Đorđević1*, Slavica Mihajlović1, Aleksandra Patarić1

1
Institute for Technology of Nuclear and Other Mineral Raw Materials,
Franchet dÈsperey 86, 11000 Belgrade, SERBIA
*
n.djordjevic@itnms.ac.rs
Abstract
The problem of fly ash as a by-product of thermal power plants is an actual issue. This ash is
extremely hazardous to the environment. It contains particles of extremely small diameter that are
easily carried by the wind, and have many toxic elements and heavy metals. The scattered particles
reach the water and soil, thus causing environmental contamination. Multiple solutions have been
offered to remedy this serious problem, which relates not only to the environment (land, air and water)
but also significantly affects the health of people living close to the thermal power plants. Remediation
of ultra-fine particles spread by aeolian erosion reduces the potential for water and soil
contamination as well as crops used by the population for nutrition, and thus for acute and chronic
diseases found to be caused by fly ash pollution. The use of elemental sulfur, which is a secondary
product of the oil refining process, in order to bind fly ash, manages waste, thus solving two
environmental problems.
Keywords: environment, fly ash, heavy metals, solid waste, risk, pollutants, contamination,
waste management, protection.
INTRODUCTION
Now days, it is virtually impossible to imagine a life without electricity. The primary
energy sources used in power generation are coal, oil, natural gas and fossil fuels. When low-
calorie coal types are used in the production of electricity, many environmental pollutants are
produced as a result of their combustion. Their combustion produces solid waste as well as
harmful gases that lead to significant pollution of water, land and air. One of the biggest
problems facing both employees in thermal power plants and, even more importantly, people
living near the thermal power plant is fly ash [1].
In most existing thermal power plant installations, ash that has not reacted in the coal
combustion process is carried to special landfills where it is deposited. At the exit of the
thermal power plant, ash is soaking with water. At the landfill, the water level should be
constantly above the ash level to prevent ash spreading [2]. To make an ash watering system
more effective, it must be constant, adapted to the weather conditions. Water has to be applied
over a larger area than the surface of the ejected ash. This requires a large amount of water,
which significantly complicates the ash moistening process without being a permanent
solution [3]. In practice, adequate wetting is practically impossible to achieve because the
quantities of ash that emerge from the thermal power plant daily are extremely high. Data
show that about 35 million tons of coal, mainly lignite, is used in power plants in Serbia
221
annually [4,5]. This type of coal has a lower heat output of 6000-8000 kJ/kg, average
moisture content of 45-53% and ash of 10-23%. Daily consumption of coal is from 17000 to
19000 tons per unit of power plant ("Nikola Tesla" thermal power plant, Obrenovac),
whereby a significant amount of ash remains by burning coal in thermal power plants,
producing every kilowatt of electricity. The landfills where ash is deposited have a total area
of approximately 1639 hectares. Between 1974 and today, between 250 and 300 million tons
of ash and slag have been disposed. Ash is one of the most common pollutants in the
workplace and the environment, polluting land, water and air.

In this study, the possibility of using elemental sulfur to bond fly ash was investigated. To
be used for this purpose, it is necessary to modify the elemental sulfur, which is a secondary
product of the oil refining process, with dicyclopentadiene to a chain crystal structure. The
process of homogenization and binding of ultrafine ash particles with sulfur would be carried
out in the reactor at temperatures of 150ºC to 170ºC by injecting sulfur in an amount of 15%
to 22% with intensive mixing of the components. As the ash leaving the thermal power plant
is already at the high temperature required for the sulfur agro-metering process, no additional
heating of the system is necessary. The ash is fed to the corresponding reactor with a rotary
mixer at the exit point from the existing plant. At these temperatures, elemental sulfur enters
the molten state boundary, and plays the role of filler and binder. The ash particles get coated,
and increase the dimensions and weight. Analyzes show that the particle content of less than
63 μm decreases from 17.5% to 7% (with 15% sulfur added) and 1% (with 22% sulfur
added). During the cooling process of the obtained product (after homogenization and
agglomeration), a product is obtained that can be deposited much more easily into the landfill
without additional use of the wetting system used so far to prevent the fly ash from scattering.
The resulting ash-sulfur agglomerate cannot be dispersed by the wind due to the size and
weight of the particles. Sulfur that coats the ash prevents heavy metals from leaching from the
ash and thus reduces water and soil pollution. This procedure is a permanent solution to the
problem of the deposition of ash from thermal power plants, and the problem of
environmental pollution also.

The bonding of ultra-fine ash particles with elemental sulfur solves three current problems.
This implies a drastic reduction in the amount of fly ash spread by aerosol erosion over the
wider area of the thermal power plant. This has a direct impact on reducing the respiratory
diseases of the surrounding population, as well as reducing pollution of water and land on
which food crops are cultivated. Reducing the intake of heavy metals into the body would
significantly reduce the number of patients with malignant diseases. Statistics show that over
50% of the population has respiratory problems, and that almost 2/3 of school and preschool
children have similar problems, which can be directly linked to the impact of ash dump. In
addition to the complex effects of air pollution factors, other food and drinking factors are
also important, as the areas around power plants are mostly populated by agrarian
222
populations, and many households use both drinking water and the food they produce at these
locations. Considering the statistical data on the number of patients with respiratory diseases
in these regions, environmental pollution in the ash dumps reaches the level of ecological
catastrophe. Chemical analysis of ash reveals the presence of heavy metals (Zn, Cr, Cd, Sr,
Pb, Co, and Ni) that through the diet indirectly enter the human body and increase the number
of cancerous diseases. Remediation of fly ash has therefore become a burning problem from
an environmental point of view.
Figure 1 SEM micrographs original fly ash
Using sulfur, which is a co-product in the oil refining process, reduces the sulfur landfill,
which without that threatens to become a serious environmental problem. Elemental sulfur is
a product of oil refining process and a result of desulphurisation of the resulting petroleum
products. It is a ballast material and also threatens to become a serious environmental
problem. In the future, the amount of sulfur obtained and deposited in this way will be
increasing with us, with the tightening of domestic regulations on the sulfur content of
petroleum products and the approximation of those regulations to EU norms. In recent years,
the world has been intensively working on finding effective ways to rationally consume
rapidly increasing amounts of elemental secondary sulfur. This technological solution enables
the use of elemental sulfur, which is a by-product of the petroleum refining process, as a
binder of fly ash particles of less than 63 μm and reduces the amount of these ultrafine
particles from 17.5% to 1%. This would allow its permanent binding to soil and thus
suppressing aeolian erosion of deposited ash. Implementing suitable technical solutions
shown in this article, it could effectively solve both environmental problems in one place.
223
Figure 2 SEM of a sample of fly ash bound with sulfur
CONCLUSION
Repairing fly ash problems by bonding to elemental sulfur, it is not necessary to make
drastic changes to the existing equipment within the thermal power plant. As the ash
temperature at the outlet of the reactor is at the appropriate level required for the sulfur
bonding process, it is sufficient to associate the outlet system with a mixer in which to
agglomerate. Some solutions even require sintering of the material, which requires the
investment of large material assets and new facilities. After sulfur-coated agglomeration, the
resulting product is transported to already existing by-products landfills. It is not necessary to
use water used in large quantities for the purpose of wetting fine ash particles, which thus far
prevents the ash from spreading around the environment and affects the pollution of
surrounding soil and water due to the presence of heavy metals in the ash. By wetting system,
it would be necessary to ensure that the water level is always above the ash level, which is
difficult to achieve under current conditions. Ash binding to sulfur completely replaces the
use of water, which significantly reduces material investment, as a problem of summer high
temperatures. Elemental sulfur that would be used as a binder for ash agglomeration is
available without investment because it is a secondary product in the oil refining industry, and
as such is a disposal problem, so this technological solution would practically solve the
problem of its disposal as well. Ash after agglomeration can still be used in the construction
industry and in the road construction process.
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[1] V. Vidojković, N. Đorđević, T. Boljanac, et al., Hem. Ind; 60 (5–6) (2006) 144–147.
[2] L. Gray, K. J. Champagne, Y. Soong, et al., International Ash Utilization Symposium,
Center for Applied Energy Research, University of Kentucky, (1999) Paper #6.
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[5] B.G. Kutchko, A.G. Kim, Fuel; 85 (17–18) (2006) 2537–2544.
224
EFFECTS OF ALLELOPATHY ON THE SPREAD OF INVASIVE SPECIES Aster
Lanceolatus WILLD. COMPLEX
Marija Nešić1*, Dragica Obratov-Petković1, Ivana Bjedov1, Dragana Skočajić1

1
University of Belgrade, Faculty of Forestry, Kneza Višeslava 1, 11000 Belgrade, SERBIA
*
marija.nesic@sfb.bg.ac.rs
Abstract
Aster lanceolatus Willd. complex is an invasive plant in many European countries. There are several
traits that may contribute to the invasiveness success of this species. One of them could be the
presence of allelopathic compounds in soil. Therefore, this study set out to assess the allelopathic
potential of the topsoil from A. lanceolatus growing sites on bioassay species (Lactuca sativa L.).
Four localities were selected, and the soil sandwich method was applied. Percentage of seed
germination, length of radicles and hypocotyls of bioassay species were recorded. The soil collected
from the invaded sites significantly inhibited the germination of L. sativa seeds on three localities.
However, the soil from invaded sites promoted elongation of the hypocotyl. Similarly, radicle growth
was significantly promoted in treatments with soil from the invaded sites on one locality. From the
present study, it can be concluded that allelochemicals are present in the soil infested with this plant
and that allelopathy could be an important mechanism that promotes the spread of A. lanceolatus.
Further research is needed to investigate types of allelochemicals present in the A. lanceolatus tissue
and the mechanisms of their influences.
Keywords: Aster lanceolatus Willd. complex, invasive plants, allelopathy, bioassay
INTRODUCTION
Invasive plants reduce species richness, change habitat and ecosystem functioning,
affecting ecosystem services and human well-being [1,2]. Unremitting climate changes affect
the plants and the ones that will survive will be those that are capable to evolve or to quickly
adapt to changes, migrate and colonize areas that suit them better. Invasive plants have these
abilities and it is reasonable to anticipate that they will pose an even greater threat to
biodiversity and economy [3].
Aster lanceolatus Willd. complex is a herbaceous perennial, native to North America. This
species is considered invasive in many European countries and in many Lists of invasive
species it is marked as highly invasive. Previous research showed that A. lanceolatus has the
ability to influence soil properties [4,5]. It usually grows in the pioneer communities of
variable floristic composition [6]. In Serbia, A. lanceolatus has become the dominant plant on
wet habitats and in some urban areas, reducing floristic species diversity [7]. Its spread is
conditioned by species biology and reinforced by climate change, anthropogenic impacts and
competitive interrelationships [8].
A great number of studies examined which traits are especially important in terms of
climate change and invasion successes and try to predict how invasive species will behave in
225
new conditions. Responses of plants to global changes will be species-specific, with potential
influences on community structure [9]. Also, much of the current literature on plant invasion
pays particular attention to competition for limited resources and the release of
allelochemicals as two main mechanisms contributing to invasion success [10].
Allelochemicals can be excreted into the soil as exudates from living plants or by plant
residues and they can inhibit seed germination and plant growth [11,12]. The chemical
composition of plant residue, especially the content of secondary metabolites affects the soil
organisms and has an important role in the mineralization and absorption of soil nutrients by
plants [13]. Biochemical changes in soil may be the result of allelopathic impacts of invasive
plants on natural vegetation and by replacing natural vegetation, and by changing species
composition, invasive plants alter soil properties and form mono-stands [14–16].
It is noticed that plants exposed to increased CO2 have increased concentration of
carbohydrates, which induced an increase in the concentration of secondary compounds in the
leaves which are potential allelopathic substances and thus hinder the allelopathic potential of
species [17]. Changes in temperature, precipitation, and climatic variability will presumably
have an indirect influence on allelopathy by altering rates of decomposition [18].
It is of great importance to determent traits that contribute to the spread and the formation
of dense, monospecific stands of A. lanceolatus. Laboratory bioassays can be used to assess
the impact of allelochemicals and to eliminate the various interferences through the controlled
conditions in which the research takes place [19]. The purpose of this study is to evaluate the
allelopathic effect of the topsoil from A. lanceolatus growing sites on bioassay species.

To compare the allelopathic potential of topsoil from invaded and adjacent uninvaded plots
on receptor plants, four localities were selected: Beočin, Beška, Kumodraž, and Sremski
Karlovci. At each site, several 1 m2 plots were selected in invaded patches and adjacent
uninvaded patches with native vegetation. In each plot, five soil samples 10 x 10 cm, at a
depth of 10 cm were collected. Roots and rhizomes were removed from the soil. These five
soil samples were air-dried, sieved (< 2 mm) and 200 g of each sample were mixed up to a
single sample for each plot.
Lettuce (Lactuca sativa L.) seeds were used as the receptor plant in the bioassay. This
plant was selected because it has rapid germination and high sensitivity to bioactive
substances [20].
Soil sandwich method was applied to compare the allelopathic potential of the soil in
invaded and uninvaded sites. Into 9 cm Petri dishes, containing 3 g of soil, 5 ml of agar
(0.75%), cooled at 42 oC, was added [21,22]. After solidification, 3.2 ml of agar was added to
the soil-agar layer. 15 L. sativa seeds were sown in one Petri dish at 20 ºC (±2) and a 16h
photoperiod was applied. Treatments were replicated three times with soil from invaded and
three times with soil from uninvaded sites. Percentage of seed germination, length of radicles
and hypocotyls of bioassay species were recorded after 3 days.
For all investigated parameters, one-way analysis of variance (ANOVA) followed by
Fisher's LSD test (P < 0.05) was applied. Germination percentage values were arcsine
226
transformed before being subjected to a one-way analysis of variance. All statistical analyses
were carried out using STATGRAPHICS Centurion XVI (Statpoint Technologies, Inc.,
Warrenton, VA, USA).

Plants that through the production of secondary metabolites have a negative impact on
other plants are considered allelopathic [23]. Bioassays can be used to identify the presence of
phytotoxic compounds in plant tissue or soil. Comparison of topsoil of invaded and adjacent
uninvaded plots with native vegetation will show the impact of invasive plants on some soil
properties [24,25]. Also, comparing growth parameters of bioassay species in soil in which
the donor plant has been grown in the same soil where the plant has not been grown can
indicate the presents of allelochemicals [26].
Except for volatile compounds, most compounds produced by the plants are likely to flow
into the soil [27]. According to some authors, soil-free bioassays carried out under controlled
conditions, such as Petri dishes, probably overestimate the effect of allelopathy since the soil
can significantly neutralize the effects of secondary metabolites [13,26]. To prove the
existence of the allelopathic compounds, it is important to evaluate the plant growth activity
of soils. Also, agar usage in bioassays provides the transfer of water-soluble chemicals from
soil to bioassay species [28].
The soil collected from the invaded sites on all localities significantly inhibited the
germination of L. sativa seeds, except in treatment with soil from locality Beška (Figure 1).
The highest reduction was noticed in treatment with soil from invaded sites from locality
Sremski Karlovci.
Figure 1 L. sativa germination percentage in soil bioassay. Bars represent means ± SE. Asterisk
above the bars indicates a significant difference among invaded and uninvaded sites on a given
locality at p<0.005
The soil from invaded sites promoted elongation of the hypocotyl (Figure 2). Although
hypocotyl length was higher in treatment with soil from invaded sites on the other three
localities, those differences were statistically significant only at locality Kumodraž. Soil
collected from invaded sites on locality Beška significantly promoted radicle growth (Figure
3). Radicle elongation was noticed in the treatment with soil from invaded sites on locality
Sremski Karlovci but without significant differences. The length of radicle decreased in
treatment with soil from invaded patches on the other two localities, but without significance
(Figure 3).
227
Figure 2 Hypocotyl growth of L. sativa in soil bioassay. Bars represent means ± SE. Asterisk above
the bars indicates a significant difference among invaded and uninvaded sites on a given locality at
p<0.005
Figure 3 Radicle growth of L. sativa in soil bioassay. Bars represent means ± SE. Asterisk above the
bars indicates a significant difference among invaded and uninvaded sites on a given locality at
p<0.005
In accordance with the present results, previous studie [29] have demonstrated that
aqueous extracts obtained from different vegetative organs of A. lanceolatus have an
inhibitory effect on seed germination and seedling growth of the test species. Inhibition of
seed germination of test species in soil bioassay may be the result of allelochemical stress and
is a confirmation that the secondary metabolites produced by A. lanceolatus are released and
accumulated in the soil beneath [30]. Cell division and elongation which are essential for
growth are known to be inhibited by allelochemicals [31].
Community composition can be changed by the influence of allelopathic plants [26,27]. It
is anticipated that plants will produce greater levels of chemicals under a changing
environment which will affect the way plants interact with one another through the processes
of competition and allelopathy [9]. It has been suggested that a low concentration of some
allelochemicals can inhibit the development of some species, while in higher concentration
they may have a stimulative effect on the growth of other species [32]. Initially, these
substances can have little impact on community vegetation, but they can have long- term
effects [26]. Moreover, over time these substances could increase their concentration in soil
[26], and thus their impact on adjacent plants. A. lanceolatus is herbaceous perennial and
these plants release exudates into the soil over several growing seasons. The results of this
study could explain the invasive success and the existence of monodominant stands of this
invasive species.
228
Even though allelopathic inhibition is a separate process from the competition, allelopathic
plants can take advantage of this process by excluding other potential competitors [30].
However, separating allelopathy and competition can be difficult since these processes can
influence each other [26]. Many phytotoxic compounds were extracted and isolated from
plants and their residues [28]. Dias et al. [33] found that aromatic water of A. lanceolatus
inhibited germination and hypocotyl growth of L. sativa. Non-native species with allelopathic
substances become more competitive in new communities compared to native plants which
are vulnerable to new allelochemicals. Asteretum lanceolati community in Serbia is
characterized by the presents of a large number of invasive species [7]. The results of this
research provide further support for the hypothesis that A. lanceolatus inhibit the development
of indigenous flora, which creates empty space on the site and causes increased nutrient
availability that triggers an increase in the number of invasive species in the community.
CONCLUSION
From the present study, it can be concluded that allelochemicals are present in the soil
infested with this plant. Components of an ecosystem are closely interlinked and factors that
change one component often have an indirect impact on the other. Responses of plants to
global changes will be species-specific, potentially shifting plant community structure.
Results of this study showed that soil collected from sites infested with A. lanceolatus
inhibited the germination of L. sativa seeds, while it promoted elongation of hypocotyl and
radicle of test species. Therefore, the results of this study should be confirmed and
supplemented by additional experiments in natural conditions to determine the exact role of
allelochemicals in the spread of this invasive species. Also, further research will investigate
the types of allelochemicals present in the A. lanceolatus tissue as well as the mechanisms of
the influences of these compounds.
ACKNOWLEDGEMENT
This paper was realized as a part of the project "Studying climate change and its influence on the
environment: impacts, adaptation and mitigation" (43007) financed by the Ministry of Education and
Science of the Republic of Serbia within the framework of integrated and interdisciplinary research
for the period 2011-2020.
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[2] P. Pyšek, D.M. Richardson, Annu Rev Env Resour; 35 (1) (2010) 25–55.
[3] M. Nešić, D. Obratov-Petković, I. Bjedov, et al., Proceedings of International Scientific
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[5] M. Nešić, D. Obratov-Petković, I. Bjedov, et al., Proceedings of XXI International
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230
CHANGES IN THE DISTRIBUTION OF Vaccinium L. GENUS IN RELATION TO
THE SOIL ACIDIFICATION SCENARIO
Ivana Bjedov1*, Dragica Obratov-Petković1, Marija Nešić1, Snežana Belanović-Simić1,

Jelena Beloica1
1
University of Belgrade, Faculty of Forestry, Kneza Višeslava 1, 11030 Belgrade, SERBIA
*
ivana.bjedov@sfb.bg.ac.rs
Abstract
In the hilly and mountainous regions on the territory of Serbia, three species of Vaccinium genus are
described: V. myrtillus, V. uliginosum and V. vitis-idaea. As these species present one of the most
important biological and economic resources of every country, conservation of their population is
very important. Soil acidification is one of the major threats to floristic diversity. In this paper the
possible changes in the cover of the Vaccinium species at selected localities, in relation to the
scenario of soil acidification, is presented. The investigations are performed in selected mountainous
and hilly regions of Serbia: Stara planina Mt., Kopaonik Mt., Vlasina, Kamena Gora and Divčibare.
In order to investigate the cover changes of selected species VSD model was used. In addition to
changes in cover of Vaccinium species, the changes of cover of the most common characteristic
species were also observed. Based on obtained results, it could conclude that soli acidification will
not condition decreasing of Vaccinium sp. populations at investigated localities.
Keywords: Vaccinium sp., VSD model, distribution prediction
INTRODUCTION
The species of the Vaccinium genus include deciduous or evergreen shrubs which belong
to Ericaceae family. They are widespread in the mountainous regions of central Europe and
in the boreal and sub-arctic regions of northern Europe, particularly on the ground floor of
coniferous forests. In the hilly and mountainous regions on the territory of Serbia, three
species of this genus are described: V. myrtillus, V. uliginosum and V. vitis-idaea. These
species are one of the most important biological and economic resources of every country.
Namely, Vaccinium species are medicinal plants and their berries are edible and in many
countries they are traditionally harvested. Harvesting is very popular in the poor countries, as
well as, in developed countries such as Finland, Sweden, Norway as well as Russia [1].
Finland, Sweden, Norway and Russia are the countries where the fruits of V. myrtillus and V.
vitis-idaea are harvested in largest quantities, relative to other species [1–3]. In many
countries harvesting of Vaccinium species is unsustainable. The unsustainable harvesting is
one of the threats to Vaccinium species conservation. Also, soil acidification presents one of
the major threats to floristic diversity. Soil acidification is a natural process that can either be
accelerated by certain human activities [4]. This process caused reduction of the soil pH that
is conditioned by nitrogen, sulfur or carbon deposition. Soil acidification affects decrease of
231
floristic diversity. Some investigations [5,6] point out that nitrogen and sulphur deposition in
the soil causes changes in populations of Vaccinium sp.
In accordance with the importance of Vaccinium sp. conservation in Serbia, the goal of
this investigation was determined. The main aim of this paper was to determine the possible
changes in the cover of the Vaccinium species at selected localities, in relation to the scenario
of soil acidification, using the VSD model. Obtained results could be useful for future
monitoring and harvesting of Vaccinium species.

Phytocoenological investigations
In order to predict the possible changes of the species cover at the selected localities
(Table 1), analysis of certain plant communities were done. Phyotcoenological investigation
has been performed in period from 2009 to 2012. For the analysis, those plant communities in
which Vaccinium sp. have high presence degree were chosen.
Table 1 Selected species at the studied localities for the VSD model
Localities GPS Species
coordinates
Kopren N 43°19´56.88˝ Vaccinium myrtillus, V. vitis-idaea, Erica carnea, Juniperus
(Mt Stara E 22°47´48.43˝ communis, Luzula multiflora, Thymus sp.
planina)
Srebrnac N 43°18´59.04˝ Vaccinium myrtillus, V. uliginosum, Juniperus communis,
(Mt Kopaonik) E 20°50´06.19˝ Calamogrostis arundinacea, Nardus stricta, Thymus sp.
Kamena Gora N 43°17´15.01˝ Picea abies, Luzula sylvatica, Oxalis acetosella, Vaccinium
E 19°33´53.88˝ myrtillus
Divčibare N 44°07´49.12˝ Pinus nigra, P. sylvestris, Erica carnea, Daphne blagayana,
E 20°00´55.42˝ Vaccinium myrtillus, Avenella flexuosa
Vlasina N 42°47'40.20" Bruckenthalia spiculifolia, Vaccinium myrtillus, V. vitis-
E 22°22'50.70" idaea, V. uliginosum, Avenella flexuosa, Calamogrostis
arundinacea
VSD/Veg model
The VSD (Very Simple Dynamic Soil Acidification Model) model was applied to analyze
the acidification process at selected localities. This model is used in order to calculate critical
sulfur (S) and nitrogen (N) loads in ecosystems [7].
In order to simulate the spread of certain plant species, within selected habitats over time,
based on the input data on abiotic factors (climate and edaphic factors), Veg-model was used.
Veg-model is incorporated into the VSD model. The model then calculates the relative
surface of the studied habitat that the certain species could occupy, depending on its ability to
survive under appropriate habitat conditions. For the simulation of plant species spread, the
model does not include a complete list of species found in the area, but includes the
edificators and the most common characteristic species. The model performs the simulation
232
of species spread based on the ecological characteristics of the species and the change in
abiotic factors which occurs during the selected time [8].
The localities encompassed by this investigation are presented in the Table 1. Also, the
Table 1 shows species selected by Veg-model.

Anthropogenic acid deposition–induced soil acidification is one of the major threats to
biodiversity, ecosystem functioning and services [9]. As already mentioned, soil acidification
implies a decreasing of the soil pH value.
By the VSD model, for the given conditions, for each locality, the trend of the ratio of pH
and C/N (carbon to nitrogen ratio) was analyzed for the period from 1960 to 2100, in the soil
layer up to 20 cm. Also, for each locality, species that occur with the highest cover in
phytocenoses were isolated in order to analyze changes in the cover of these species, and
especially species of the genus Vaccinium, in the community over time.
Nordin et al. [5] found that under certain conditions, related to soil load with nitrogen,
population of Vaccinium myrtilus и V. vitus-idaea would be reduced. At the other hand,
Coudun and Gégout [6] concluded that cover of Vaccinium myrtilus could be increased up 50
%, when the environmental conditions are such that the pH value of the soil is <4, the C/N
ratio is > 30 and the air temperature is <6°C. So, depending on the change in pH and C/N in
the soil, changes in the structure of the plant community may occur over time.
At Divčibare, the model has been monitored the changes in the cover of the following
species: Pinus nigra, P. sylvestris, Erica carnea, Daphne blagayana, Avenella flexuosa and
Vaccinium myrtillus. It can be observed that the model does not predict changes in cover for
Vaccinium myrtillus and Erica carnea. For the other species monitored in the model,
significant changes in coverage occurred between 1960 and 2004 (Figure 1).
Figure 1 Chages of characteristics species cover over time at Divčibare
From 2010 to 2100 the cover of Daphne blagayana and Avenella flexuosa will increase,
while the cover of Pinus nigra, P. sylvestris and Abies alba will decrease. However, these
changes are not significant (Figure 1).
233
The cover of Picea abies, Luzula sylvatica, Oxalis acetosella, and Vaccinium myrtillus has
been monitored at Kamena Gora. Figure 2 shows that by 2010 the cover of Oxalis acetosella
is changing, increasing and decreasing, but compared to 1960 the cover of this species in
2010 is smaller. From 2010 until the target year, its cover will remain unchanged. The cover
of Picea abies and Luzula sylvatica species has been increasing from 2002, with a more
pronounced increase in Luzula sylvatica. The cover of Vaccinium myrtillus grows from 2005.
Figure 2 Chages of characteristics species cover over time at Kamena Gora
At Srebrnac (Mt Kopaonik) V. myrtillus, V. uliginosum, Juniperus communis,

Calamagrostis arundinacea, Nardus stricta and Thymus sp. have been monitored (Figure 3).
Figure 3 Chages of characteristics species cover over time at Srebrnac (Mt Kopaonik)
The largest changes in species cover are recorded for the species Calamagrostis
arundinacea whose cover declines sharply from 2003 to 2025, followed by a slight declining
of cover to the target year. The cover of Nardus stricta oscillates between 1975 and 2015,
after which it will remain stable until 2100. From 2005 to 2015 cover of the species Thymus
sp. declines, and after that period it remain unchanged until the target year. Changes in the
cover of V. myrtillus and Juniperus communis have the same trend. Their cover increases
gradually from 2000 to 2035, and further, by 2100 it will be stable. However, the model does
not predict any changes for V. uliginosum at this locality (Figure 3).
234
By VSD model, the cover of Bruckenthalia spiculifolia, Vaccinium myrtillus, V. vitis-

idaea, V. uliginosum, Avenella flecuosa and Calamagrostis arundinacea has been monitored
at Vlasina (Figure 4).
Figure 4 Chages of characteristics species cover over time at Vlasina
The model does not register cover changes for V. vitis-idaea, V. uliginosum and Erica
carnea. The trend of changing Calamogrostis arundinacea cover at Vlasina is the same as at
Srebrnac (Mt Kopaonik). The coverage of Avenella flecuosa decreased between 1976 and
2003. Furthermore, cover this species remains stable over time. The model predicts an
increase of Vaccinium myrtillus cover from 2000 to 2015, followed by a stable period.
At Kopren (Mt Stara planina) the changes of the cover of following species has been
monitored: V. myrtillus, V. vitis-idaea, Bruckenthalia spiculifolia, Juniperus communis,
Luzula multiflora and Thymus sp. (Figure 5). According to the model the cover of Thymus sp.
will decline sharply from 2003 to 2020, and after it will gradually stabilize. From 2004, the
cover of Vaccinium myrtillus and Juniperus communis increase by 2030 for V. myrtillus,
respectively until 2090 for Juniperus communis, and after that period stabilization will begin
(Figure 5).
Figure 5 Chages of characteristics species cover over time at Kopren (Mt Stara planina)
235
CONCLUSION
VSD model does not detect changes of cover in Vaccinium uliginosum and V. vitis-idaea
at studied localities. Also, the VSD model does not predict change of V. myrtillus cover at
Divčibare. At other localities, the model predicts the increasing abundance of V. myrtillus.
This change is most pronounced at Kopren (Mt Stara planina). Based on obtained results it
could be concluded that soli acidification will not condition decreasing of Vaccinium sp.
populations.
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[4] N.S. Bolan, D. Curtin, D.C. Adriano, Encyclopedia of Soils in the Environment, Elsevier
Ltd., New York (2005) p.11, ISBN: 978-0-12-348530-4.
[5] A. Nordin, J. Strengbom, J. Witzell, et al., Ambio; 34 (2005) 20–24.
[6] Ch. Coudun, J.C. Gégout, J. Veg. Sci; 18 (2007) 517–524.
[7] M. Posch, G.J. Reinds, Environ. Modell. Softw; 24 (2008) 329–340.
[8] S. Belyazid, D. Kurz, H. Sverdrup, et al., CCE Status Report, Developing a method for
estimating critical loads of nitrogen deposition under a changing climate, based on
biological indicators (2009).
[9] D. Chen, Z. Lan, X. Bai, et al., J. Ecol; 101 (5) (2013) 1322–1334.
236
ADSORPTION OF METHYLENE BLUE FROM AQUEOUS SOLUTION USING
ACTIVATED CARBON PREPARED FROM HAZELNUT SHELL
Veselin Bežanović1*, Mladenka Novaković1, Miodrag Živančev1, Dušan Milovanović1,

Dragan Adamović1
1
University of Novi Sad, Faculty of Technical Sciences in Novi Sad, Department of
Environmental Engineering and Occupational, Safety and Health, Trg Dositeja Obradovića 6,
21000 Novi Sad, SERBIA
*
veselinbezanovic@uns.ac.rs
Abstract
The discharge of colored wastewater from different industries into natural streams has caused many
significant problems such as increasing the toxicity and chemical oxygen demand (COD). In addition
to all the contaminants found in industrial wastewater, dyes are the most undesirable for toxicological
and aesthetic reasons. This work describes the adsorption process of one of the most dominant dye in
textile and paper industry, methylene blue (MB) from aqueous solutions with activated carbon
prepared from hazelnut shell (HSAC). In Serbia hazelnut shells represent an agricultural waste that is
generated during the production of hazelnuts and in most cases it’s not used for any purpose, usually
just disposed on landfill or burned in furnaces. The adsorption process is generally known as effective
and complementary to conventional treatments in the removal of dyes compounds. Adsorption studies
were performed on powdered HSAC, in ambient temperature, on pH value between 2–9 and with
different masses of adsorbent (50 – 1500 mg). The results show that HSAC can be applied in the
process of adsorption for the purpose of removing MB from aqueous solution.
Keywords: methylene blue, adsorption, activated carbon, pH value
INTRODUCTION
The visual pollution has a significant impact on residential and tourist areas and it is
related to different sources with negative effects on the living environment. Industrial
pollution and production are synchronously connected and in developing countries with less
environmental regulations with weaker environmental standards, can turn them “pollution
havens” for developed countries [1]. Wastewater production has substantially increased due to
rapid industrial development, which is ultimately responsible for the degradation of water
quality [2].
Dyes are the first indicator of pollutants in wastewater and they are used in many industries
such as, paper, carpets, plastics, cosmetics, graphic and textiles in order to color their products
and can be classified as natural and synthetic which are complex organic molecules having
groups such as azo, carbonyl, methine, nitro, quinoid, etc [3]. Large amounts of complex dye
wastewaters are generated as a result of use of too much water during coloring processes,
particularly in textile industry [4].
The discharge of colored wastewater from these industries into natural streams has caused
many significant problems such as increasing the toxicity and chemical oxygen demand
237
(COD) of the effluent, and also reducing light penetration, which has a derogatory effect on
photosynthetic phenomena [5].
Most of the dyes are resistant to photo-oxidation and non-biodegradable in nature and
some of conventional treatment methods such as biological and coagulation/flocculation are
generally unsuccessful for the removal of wastewater containing dyes [6]. There are
advantages and disadvantages of various methods of dye removal from wastewaters, many
physicochemical methods have been tested, but only process of adsorption is considered to be
superior to other techniques and it has fascinated the researchers owing to its accuracy, easy
operation, insensitivity to toxic substances and ability to treat concentrated colored solution
[2,5].
Activated carbons (AC), both granular and powdered, have demonstrated higher adsorbing
effects and it is one of the most important general purpose adsorbents in the adsorption
technique because of its high adsorption capacity, large surface area and high surface
reactivity [7]. Therefore, large numbers of studies have been focused on the production of low
cost AC from various plant-based waste materials such as sugar beet molasses, rice husk,
hazelnut husk and apricot stone [8–10] and the prepared ACs have been used for the removal
of various metal ions or coloring agents from aqueous solutions.
Hazelnut shell (HS) represent a low cost agricultural waste that is generated during
hazelnut production, not used for any purpose and generally disposed of by burning in open
air in threshing area. Since HS is obtained in large amounts (around 4000 tons per annum in
Serbia) and has no economic value, it is thought to be an appropriate source for AC
production.
In this study HS agro-based waste material, was used as adsorbent for the removal of
methylene blue (MB) from an aqueous solution. Methylene blue was selected as a model
compound in order to evaluate the capacity of HS for the removal of dyes from aqueous
solutions. During adsorption studies of MB performed by the batch method, effects of three
variables; pH values and agitation time, were investigated.

Chemicals and instruments
Methylene blue was chosen for this study because of its known strong adsorption onto
solids. Methylene blue (CI = 52015; chemical formula: C16H18ClN3S; molecular weight =
319.86 g/mol; maximum wavelength = 662 nm) supplied by Merck was used as adsorbate and
was not purified prior to use.
An accurately weighted amount of MB was dissolved in deionised water to prepare 1000
mg/L as stock solution, while the working solution was prepared by diluting this solution to
the required initial concentrations. The MB concentration evaluation was carried out using
UV–visible spectrophotometer (model DR 5000 HACH Lange) at a wavelength of 431 nm.
The removal percentage of MB was calculated using the following relationship (1):
(1)
238
where Co (mg/L) and Ct (mg/L) are the dye concentration at initial and after time t
respectively. The entire experiment was conducted in Accredited Laboratory for the
monitoring of living and working environment at Department of Environmental Engineering
and Occupational Health and Safety, Faculty of Technical Sciences, University of Novi Sad,
Serbia.
Materials
Hazelnut (Corylus avellana L.; the variety is Tonda Istriana) shells (Figure 1) were
supplied from the north part of Serbia, Autonomous Province of Vojvodina. Fresh hazelnut
shells were washed several times with distilled water to remove surface impurities, dried at
100 0C overnight, crushed by a hammer mill and simultaneously carbonized and activated in
microwave oven for 25 minutes.
Afterwards, the granular activated carbon was washed two times with distilled water, dried
at 100 0C for 12 h. Dried shells were grinded and sieved to get a powdered hazelnut shell
activated carbon (HSAC) and stored in a desiccator.
Figure 1 Hazelnut shells before and after carbonized and activated in microwave oven
Methods
For adsorption experiments, 50 mL of dye solution of known initial concentration, in
erlenmeyer flasks was agitated on stirrer (model Heidolph Unimax 1010) with a certain
amount of adsorbent at desired pH values at room temperature, with speed of 140 RPM for 20
minutes.
pH value of MB solution was 6.0 and during experiments it was adjusted with 0.1 N HCl
or 0.1 N NH3OH and measured by using Multi 340i pH-meter with a combined pH electrode.
The pH-meter was standardized with NBS buffers before every set of measurement.

Effect of adsorbent dosage
In order to determine the effects of the adsorbent dosage on MB adsorption efficiency on
low cost alternative activated carbon, different amounts (50, 100, 100, 200, 400, 600, 1000
and 1500) mg of HSAC was mixed with 50 mL of MB solution, initial concentration of 10
mg/l for 30 minutes.
By increasing the amount of adsorbent, adsorption capacity significantly increased. The
removal percentage increased rapidly and further addition has not significantly affected the
239
MB removal percentage. Therefore, 400 mg of adsorbent was selected for subsequent work
(Figure 2).
Figure 2 Mass adsorbent effect on the adsorption of MB onto HSAC (T = 25oC, Co = 10 mg/L, V = 50
mL, contact time = 30 min, pH value ≈5.3)
Figure 2 shows that on the mass of adsorbents, 400 mg, the efficiency of MB removal is
about 97%, with a mass of 1000 mg, efficiency is higher than 98%. With higher dosage of
adsorbent, efficiency in the removal of 10 mg/l of MB is 99%.
Effect of solution pH value
After determination of the effects of the adsorbent dosage on MB adsorption efficiency on
low cost alternative activated carbon HSAC, using different amounts of adsorbent, it was
found that 400 mg is ideal mass for this study and with it was approached to determine a
favorable pH value. As it is known, the solution pH has a dominant impact on ions sorption.
Figure 3 shows the effect of the solution pH on the adsorption of MB on the HSAC.
The initial MB solution with a concentration of 10 mg/l has the pH value 6.0 and after
adding 50 mg of adsorbent in volume sample of 50 ml, pH value was 5.5. The influence of pH
values was analyzed at different f points (2, 3, 4, 5, 7, 8, 9) using 0.1 N HCl or 0.1 N NH3OH.
On lower pH values and acidic environment, efficiency of MB removal is lower than in
alkaline environment.
Figure 3 shows medium deviations in efficiency of removal MB by HSAC, on lower pH
values. The small reduction of the MB adsorption in the acidic solutions could be attributed to
the neutralization of free OH groups on the surface of HSAC by bonding with H+ from HCl
used for pH adjustment.
Accordingly, since it was found that the highest biosorption efficiency was obtained at pH
5.3, further experiments should be prepared under the same pH condition, respectively, in the
future experiments there is not necessary to adjust the pH value of the MB solution, using
HSAC.
240
Figure 3 pH value effect on the adsorption of MB onto HSAC C (T = 25oC, Co = 10 mg/L, V = 50 mL,
contact time = 30 min)
CONCLUSION
The conducted study and presented results demonstrate that it is possible to use HSAC, an
agro-based waste biomaterial as a highly efficient adsorbent for the removal of methylene
blue from water solutions. The obtained results show that the efficiency of HSAC, for the
removal of methylene blue, a non-degradable cationic dye, from aqueous solutions, depends
more on the adsorbent amount and not so much of pH value of the dye solution.
HSAC shows excellent abilities in the adsorption process at almost all pH values and the
most important data is that during experiments, it is not required to change the pH value of
solution, for the cause, efficiency of MB removal on pH value 5.3 is higher than 97%. This
study demonstrated that the HSAC could be used as an effective adsorbent for the treatment
of wastewater containing MB.
ACKNOWLEDGEMENT
This study was financially supported by the Project III 46009, „Improvement and development of
hygienic and technological procedures in the production of food stuffs of animal origin in order to
obtain quality and safe products that are competitive on the world market” by Ministry of Education,
Science and Technological development of the Republic of Serbia.
REFERENCES
[1] B.R. Copeland, M. Taylor M, J. Econ. Lit; 42 (2004) 7–71.
[2] G. Deepak, C.B. Majumdera, et al., J. Environ. Chem. Eng; 7 (2019) 103365.
[3] R. Christie, Colour Chemistry The Royal Society of Chemistry, Cambridge, 2001.
[4] G. Karacetin, S. Sivrikaya, M. Imamoglu, J Anal. Appl. Pyrol; 110 (2014) 270–276.
[5] Y. Bulut, H. Aydın, Desalination; 194 (2006) 259–267.
[6] S.C.R. Santos, V.J.P. Vilar, R.A.R. Boaventura, J. Haz. Mat; 153 (2008) 999–1008.
[7] Y. Satyawali, M. Balaksishnan, Bioresour. Technol; 98 (2008) 2629–2635.
241
[8] F. Aci, M. Nebioglu, M. Arslan, et al., Fresenius Environ. Bull; 17 (2008) 997–1001.
[9] C. Ozer C, M. Imamoglu, Y. Turhan, et al., Toxicol. Environ. Chem; 94 (2012) 1283–
1293.
[10] C. Sentorun-Shalaby, M.G. Ucak-Astarlioglu, L. Artok, et al., Microporous Mesoporous
Mater; 88 (2006) 126–134.
242
CONTRIBUTION OF WASTE MANAGEMENT SECTOR IN NOVI SAD TO
CLIMATE CHANGE
Miodrag Živančev1*, Dušan Milovanović1, Veselin Bežanović1, Mladenka Novaković1,

Maja Petrović1, Dejan Ubavin1
1
University of Novi Sad, Faculty of Technical Sciences, Trg Dositeja Obradovića 6,
21000 Novi Sad, SERBIA
*
miodragzivancev@uns.ac.rs
Abstract
Waste management system represents the third most important anthropogenic source of emissions of
methane, which is considered as primary driver of climate change. This sector produces emissions of
methane, carbon dioxide and black carbon, as the main source of particulate matter in the air. Novi
Sad, as the second largest city of Serbia, generates significant amounts of municipal solid waste,
consisting of more than 50% of biodegradable fraction, which is disposed on landfill without any pre-
treatment, and represents the main cause of total greenhouse gas (GHG) emissions (expressed in
metric tons CO2 equivalent). This paper represents the modelling data for GHG emissions from waste
management sector in the city of Novi Sad. The modelling results cover the emissions from all parts of
waste management system including: collection and transportation, waste handling at the landfill,
waste biodegradation processes and open burning.
Keywords: Waste management, GHG emissions, methane, climate change
INTRODUCTION
Waste management system represents the third most important anthropogenic source of
emissions of methane, which is considered as primary driver of climate change. This sector
produces emissions of methane, carbon dioxide and black carbon, as the main source of
particulate matter in the air. Novi Sad is the second largest city in Serbia, with a population of
approximately 340,000 as of 2014 [1]. Novi Sad and the municipalities of Backa Palanka,
Backi Petrovac, Beocin, Zabalj, Srbobran, Temerin, Vrbas, and Becej form the South Backa
Waste Management Region (SBWMR) [2]. The SBWMR has a combined population of
approximately 600,000 and encompasses approximately 3,000 square kilometers (km2).
General information about SBWMR is presented in Table 1.
The nine municipalities in the SBWMR produce approximately 214,000 tons per annum
(tpa) of solid waste. Nearly half of the solid waste generated in the region is organic. Overall,
the region produces approximately 65,500 tpa of food waste and 34,500 tpa of garden waste.
The Novi Sad commercial sector (hotels, restaurants, and cafeterias) produces 805 tpa of
organic waste from approximately 730 facilities. In addition, the city’s schools produce 283
tpa in food waste. Overall, these large-scale generators produce about 1,100 tpa of organic
waste, primarily food waste, representing about 3 percent of the total organic waste produced
in Novi Sad [3].
243
Landfilling is primary waste management practice in all municipalities. In addition,

recycling is present, but only in certain municipalities and in small percentages. In the city of
Novi Sad there is source separation in the downtown, where system with “two underground
containers” points (one for recyclables and one for residues) is introduced [4]. From other
member municipalities, Bački Petrovac demonstrated some progress in source separation,
using plastic bags approach. Relatively greater amounts of recyclable materials are separated
within the waste separation line in Novi Sad. Since the input material for the separation line is
mostly “low-quality” separated dry recyclables waste stream, the percentage of sorted
materials is not high, and does not exceed 10%. Also, the capacity of the current plant is
insufficient, and only about 10-15% of the total MSW generated in Novi Sad can be
processed [5,6].
Therefore, all biodegradable waste is deposited on landfills without any pretreatment and
without controlled emissions of GHG, which poses significant environmental risk. The aim of
this paper is to estimate total emissions of methane and black carbon from waste management
sector of SBWMR, in order to facilitate decision making regarding mitigation of climate
change effects.
Table 1 General information about SBWMR [1,7]

Total
kg/ Garden Food Rural
Total MSW organic
capita/ waste waste population
population (tpa) waste
day (tpa) (tpa) (%)
(tpa)
Serbia 7,164,132
Autonomous
province (AP) of 1,912,095
Vojvodina
Novi Sad 346,163 1.07 135,194 18,075 40,788 58,863 15
Becej 36,663 0.94 12,579 2,533 4,139 6,672 37
Beocin 15,551 0.94 5,336 713 1,610 2,323 52
Backa Palanka 54,631 0.94 18,744 4,658 6,127 10,785 50
Backi Petrovac 13,222 0.86 4,150 838 1,144 1,982 52
Temerin 28,244 0.94 9,691 1,952 3,188 5,140 10
Zabalj 25,873 0.86 8,122 1,641 2,239 3,880 64
Srbobran 16,073 0.94 5,515 1,114 1,520 2,634 26
Vrbas 41,378 0.94 14,197 2,859 4,671 7,530 42
SBWMR 577,798 1.01 213,526 34,384 65,426 99,810 26
EXPERIMENTAL
As part of the research conducted for the purposes of this project, the calculation of
baseline GHG emissions is based on implementation of the SWEET tool developed by Abt
Associates and SCS Engineers for the US EPA and Climate and Clean Air Coalition (CCAC).
SWEET assists stakeholders in estimating emissions and comparing the emissions
reduction benefits of different waste management scenarios. The tool can be used to inform
244
MSW management decision-making and priority setting and allows cities to benchmark and
project their emissions over time [8].
The tool assists users in determining first-order city-level estimates of annual emissions of
methane, black carbon, and other pollutants (e.g., carbon dioxide) from various sources
including:
 Waste collection and transportation;
 Waste burning (including open burning and fires at landfills and dumpsites);
 Landfills and dumpsites;
 Waste handling equipment (e.g., forklifts, bulldozers);
 Organic waste management facilities (e.g., composting facilities);
 Waste combustion equipment (e.g., waste-to-energy facilities).
Emissions are expressed in metric tons CO2 equivalent [8].
Except for landfills and dumpsites, the tool generates annual emissions using annual
activity data and process-specific emissions factors. For landfills and dumpsites, the tool uses
disposal site data to calculate annual methane emissions into the future (i.e., to 2050) using a
methodology developed by the US EPA for the Colombia Landfill Gas model [8].
SWEET is designed to provide estimates of waste sector SLCP emissions for cities
throughout the world, and to evaluate the effects of alternative waste management strategies
on those emissions. Although SWEET uses state-of-the-industry assumptions and calculation
methods, the emissions estimates should be considered as approximate and not a substitute for
detailed technical analyses and feasibility assessments [8]. Sources of potential model
inaccuracies and uncertainties include the following:
 Uncertain emissions factors, particularly for waste burning and landfill methane;
 Uncertain estimates of waste decay rates and methane generation, collection, and
 oxidation rates at disposal sites;
 Limits to the complexity of user inputs, which were made to allow the model to be
user-friendly and to limit model sensitivity to lack of data or data error;
 Limits to detailed accounting of site-specific factors influencing emissions.

In order to assess the current state of greenhouse gas emissions using the model described
in the previous chapter, it is necessary to define the input parameters that include the
following information:
 Population covered by the waste collection system;
 Climate conditions;
 Waste generation data;
 Composition of waste;
 Waste quantities treated by alternative methods (composting, AD, incineration,
recycling);
 Number and type of waste collection vehicle;
 Data on uncontrolled incineration of waste (landfill fires and open-air burning);
245
 Number and type of waste handling machinery at the landfill;

 Landfill information.
The emission results are shown in the Tables 2, and show the emissions of individual
greenhouse gas (CH4, CO2), as well as particulate matter (PM2.5, PM10) resulting from the
black carbon emission.
Table 2 Total annual emissions of selected GHG and particulate matters (tons per year)
Year CH4 CO2 PM2.5 PM10
2019 134.804 8.021 29 14
2020 136.318 8.101 29 14
2021 137.838 8.182 30 15
2022 139.363 8.264 30 15
2023 140.895 8.347 30 15
2024 142.434 8.430 31 15
2025 143.981 8.514 31 15
2026 145.537 8.599 31 15
2027 147.103 8.685 31 15
2028 148.678 8.772 32 16
2029 150.263 8.860 32 16
2030 151.859 8.949 32 16
2031 153.467 9.038 33 16
2032 155.086 9.128 33 16
2033 156.717 9.220 33 16
2034 158.361 9.312 34 17
2035 160.017 9.405 34 17
2036 161.687 9.499 34 17
2037 163.370 9.594 35 17
2038 165.067 9.690 35 17
2039 166.778 9.787 35 17
2040 168.504 9.885 36 18
2041 170.244 9.984 36 18
2042 171.999 10.084 37 18
2043 173.770 10.184 37 18
2044 175.556 10.286 37 18
2045 177.358 10.389 38 19
2046 179.177 10.493 38 19
2047 181.011 10.598 38 19
2048 182.862 10.704 39 19
2049 184.730 10.811 39 19
2050 186.615 10.919 40 19
246
Figure 1 Total CO2, NOx, CH4, organic carbon, black carbon trends
Since the baseline waste management scenario in Novi Sad does not imply the treatment of
organic waste, total emissions from this sector have a constant growth (Figure 1). In the
situation that no improvements of the organic waste management system will occur in the
given period, total emissions from this sector are projected to increase by 40% in 2050,
compared to the current year.
CONCLUSION
The research was conducted to consider the impact of waste management system in
SBWMR on greenhouse gas emissions. Without any changes to waste management practice,
emissions will constantly increase and will reach over 200 000 tons of CO2 equivalent in
2050.
Considering the requirements of the Landfill Directive regarding the reduction of
biodegradable waste landfill disposal that should successively reach 65% reductions from the
reference year, it turned out that the current system could not result in meeting this objective.
Therefore, in order to reach the biodegradable waste diversion goals, the decision makers
within SWMBR will need to start implementing solutions for treatment of biodegradable
waste, which include source separation and various treatment options for separately collected
organic waste (food waste and green waste).
ACKNOWLEDGEMENT
The presented research is partly financed by Provincial Secretariat for Higher Education and
Scientific Research, Autonomous Province of Vojvodina, within project No. 114-451-2249.
247
REFERENCES
[1] Statistical Office of the Republic of Serbia, Opštine i regioni u Srbiji, ISSN/ISBN 2217-
7981 (in Serbian) (2018).
[2] The national waste management strategy for the period 2010-2019 ("Official Gazette of
RS” no. 29/2010).
[3] Utvrđivanje količine i morfološkog sastava otpada iz komercijalnih objekata u Novom
Sadu u cilju definisanja odgovarajućeg sistema za upravljanje komercijalnim tokom otpada
na lokalnom nivou, Fakultet tehničkih nauka, Novi Sad, 2018 (in Serbian).
[4] М. Živančev, Challenges in development of waste collection systems in emerging
countries, 2016 ISWA-SWIS Winter School Proceedings, ISBN-13:978-0-9976542-0-2.
[5] M. Živančev, B. Batinic, S. Vujovic, et al., Proceedings of the 4th International
Conference on Sustainable Solid Waste Management, 23–25 June, Limassol, Cyprus
(2016).
[6] D. Milovanović, M. Živančev, S. Hossain, et al., Proceedings of the 8th PSU-UNS
International Conference on Engineering and Technology (ICET-2017), 8–10 June, Novi
Sad, Serbia (2017).
[7] Faculty of Technical Sciences, Novi Sad, Report on quantities and morphological
composition of waste in 9 representative municipalities in Serbia, 2015.
[8] Solid Waste Emissions Estimation Tool (SWEET) version 3.0, Available on the following
link: https://www.ccacoalition.org/en/resources/solid-waste-emissions-estimation-tool-
sweet-version-30
248
OPINIONS AND ATTITUDES OF THE CITIZENS OF NIS ON COMMUNITY
NOISE
Ljiljana Stosic1*, Dusica Stojanovic1, Konstansa Lazarevic2

1
University of Nis, Faculty of Medicine Nis, Bulevar Dr. Zorana Đinđića 81, 18000 Niš,
SERBIA
2
State University of Novi Pazar, Department of Biomedical sciences
*
ljstosic@live.com
Abstract
Community noise is considered a very important environmental factor, due to its harmful effect and
increasing exposure. The aim of the study was to assess opinions and attitudes of the citizens of Nis on
community noise. A cross-sectional questionnaire survey was performed on 911 adult residents, of
whom 388 were men (42.6%) and 523 women (57.4%). Based on noise measurements, parts of the city
are divided into a noisy zone (for the daily Leq level ≥ 55 dB A and the night Leq ≥ 45 dB A) and the
quiet zone (the daily Leq level ≤ 55 dB A and the night Leq ≤ 45 dB A). The survey used an original
questionnaire, adapted to local conditions and requirements, created on the basis of a questionnaire
already used in similar surveys. The results showed that the citizens from noisy area ranked noise as
the most important risk factor in the 21.20% response, while the same number in quiet streets was
2.5% (χ2=192.32; p<0.001). The most significant sources of noise for the respondents of both groups
were traffic and street works, and the least significant sources of industry and building installations.
Respondents to the noisy zone kept windows open for shorter periods of time, more often stating that
they would change their apartment due to noise and have worse inter-neighbour relationships.
Keywords: community noise, exposure, population, opinions, attitudes
INTRODUCTION
Due to its detrimental effect and increasing exposure, community noise is considered a
very important environmental factor [1]. Long-term noise exposure has a major impact on
health and quality of life. In addition to affecting different systems and organs, noise can
cause numerous behavioral and social effects that are often complex and indirect. These
effects include changing everyday patterns of behavior, changes in social behavior
(aggression, hostility, non-hatred), mood swings [2]. Although it is assumed that humans can
adapt to noise in their environment, epidemiological studies in residents around noisy roads
show that community noise also affects behavior. People living in noisy environments attach
special importance to noise, ready to take various measures to protect them from noise, from
closing windows facing noisy streets and avoiding going out to streets to filing lawsuits with
authorities and changing their place of residence [3]. The aim of this paper was to determine
the opinions and attitudes of the citizens of Nis on community noise.
249

Traffic noise was measured at six sites in the centre of Nis, of which three were in the city,
s busiest streets and three in quiet side streets. Measurements were done with a „Brüel &
Kjær“ noise level analyzer type 4426. The total number of samples was 9000, with a period of
sampling 0.1 s in a fast dynamic range during three day-time (09.00 h to 12.00 h, 13.00 h to
16.00 h and 17.00 h to 20.00 h) and two night-time intervals (22.00 h to 01.00 h and 02.00 h
to 05.00 h). Streets with day Leq ≥ 55 dB (A) and night Leq ≥45 dB (A) were regarded as
noisy and those with day Leq ≤ 55 dB (A) and night Leq ≤ 45 dB (A) were regarded as quiet,
in accordiance with WHO recommendations and Serbian regulation on noise in residential
areas. This study was designed as a cross-sectional questionnaire survey. A total of 3000
questionnaires were distributed to residents of three busy streets and three quiet side streets,
who served as control. The number of distributed questionnaires corresponded to the number
of adult dwellers in each flat. The residents were asked to fill out the questionnaires by the
next day, when these were collected. The criteria for inclusion of persons in the research were
age between 18 and 80 years and the period of residence in the given apartment is not shorter
than a year. The exclusion criteria were exposure to noise at work and hearing loss. Of 3000
distributed questionnaires, 1063 were completed (35.4 %), but applying exclusion criteria, the
study included 911 participants, of whom 388 (42.6 %) were men and 523 (57.4 %) women.
463 participants lived in noisy streets and 448 participants in quiet streets. All statistical
analyzes were performed using a standard data processing program such as Excel and the
SPSS version 16 software package.

Noise measurements showed that the average night Leq was significantly higher in noisy
streets than in quiet streets, as well as average day Leq (Table 1).
Table 1 Characteristics of noise of the investigated areas in Nis

Measurement
Noisy area Quiet area p-value
parameters
Leq (dB(A)) day 64.33±2.18 49.62±2.31 < 0.05
Leq (dB(A)) night 61.33±2.31 43±3.46 < 0.05
A comparison of demographic data between the groups showed that noisy area residents
were four years older on average, enjoyed fewer square metres of flat area per tenant, and
fewer of them had only elementary school education than quiet area residents. The average
daily holding time of open windows facing the street during the summer period of the year
was statistically significantly shorter for the respondents in the noisy zone. When asked if
they would change the apartment because of the noise, over a third of the respondents from
the noisy zone and four times fewer respondents from the control zone answered in the
affirmative. In the noisy zone respondents, dissatisfaction with their family life, material
status and comfort of their apartment was significantly more frequent. Of the total number of
250
respondents, seven reported complaints to the authorities about traffic noise. No statistically
significant difference was found between the studied groups (Table 2).
Table 2 Basic demographic data of examinees

Noisy area Quiet area
Variables p-value
(N=463) (N=448)
Age (years) X ±SD 45.0±16.3 41.7±13.6 <0.01*
Males (%) 44.1 41.1 >0.05#
Apartment size (m2 per
63.3±18.3 77.7±30.2 <0.01$
tenant)
Period of residence (years),
17.9±13.0 17.9±11.6 >0.05$
X ±SD
Daily time spent in
14.4±3.4 14.4±3.4 >0.05*
aprtment (h)
Education (%)
Elementary 1.9 4.9 <0.05#
Secondary 59.8 58.3
Higher 10.8 13.4
University 27.4 23.4
Keeping windows open
8.2±6.4 12.8±7.9 <0.001$
during the day (h)
Very dissatisfied with
5.0 2.5 <0.05#
family life (%)
Very dissatisfied with
8.7 4.0 <0.05#
material status (%)
Very dissatisfied with the
comfort of the apartment 19.0 8.0 <0.001#
(%)
The desire to change an
35.4 8.5 <0.001#
apartment (%)
Noise complaint (%) 1.1 0.4 >0.05#
*Student,s t-test, #Pearson,s χ2 test, $Mann-Whitney U-test
The study showed that the respondents from noisy streets ranked noise as the most
important risk factor in the 21.20% response, while the number in quiet streets was 2.5%.
The residents from noisy area ranked noise as least important in the 13.0% response, while
the number in quiet area was 41.1 % (Table 3).
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Table 3 Rank by importance of different environmental factors

Environmmental factors
Rank
Radioactive
of Air pollution Waste matter Noise Water pollution
radiation
importance
Noisy Quiet Noisy Quiet Noisy Quiet Noisy Quiet Noisy Quiet
147 144 52 75 98 11 74 83 92 135
1.
(31.7%) (32.1%) (11.2%) (16.7%) (21.2%) (2.5%) (16.0%) (18.5%) (19.9%) (30.1%)
141 106 71 108 128 44 100 149 26 42
2.
(30.5%) (23.7%) (15.3%) (24.1%) (27.6%) (9.8%) (21.6%) (33.3%) (5.6%) (9.4%)
96 120 158 139 107 83 74 69 27 38
3.
(20.7%) (26.8%) (34.1%) (31.0%) (23.1%) (18.5%) (16.0%) (15.4%) (5.8%) (8.5%)
48 59 127 89 70 126 169 111 48 62
4.
(10.4%) (13.2%) (27.4%) (19.9%) (15.1%) (28.1%) (36.5%) (24.8%) (10.4%) (13.8%)
31 19 55 37 60 184 46 36 270 171
5.
(6.7%) (4.2%) (11.9%) (8.3%) (13.0%) (41.1%) (9.9%) (8.0%) (58.3%) (38.2%)
χ2=11.42 and χ2=22.99 and χ2=192.32 and χ2=23.33 and χ2=37.54 and
p=0.02 p<0.001 p<0.001 p<0.001 p<0.001
The most significant sources of noise were traffic and street works, and the least significant
sources of noise were industry and building installations (Figure 1).
Figure 1 Rank by importance of the different sources of noise
In the noisy zone, almost a third of respondents rated their relations with their neighbors as
bad or very bad, while this percentage was significantly lower in the quiet zone respondents.
The distribution of respondents according to the nature of their relations with their neighbors
differed significantly between the groups studied (χ2 =16.86 and p=0.001).
DISCUSSION
Our study found respondents who lived in the noisy zone were ten times more likely to cite
noise as the most significant adverse environmental factor than those who lived in the quiet
zone. Noise was rated as the least harmful factor in the noisy zone in 13.0% of responses, and
in the quiet zone three times more.
Results similar to ours were obtained by researchers in Hong Kong, where 17% of
respondents between the ages of 15 and 69 rated noise as the most important adverse
environmental factor [3], as well as a survey in Belgrade (22.9%) [4]. The most significant
252
sources of noise were traffic and street works, and the least significant sources of noise were
industry and installations in the building, which coincides with the research of Belgrade
authors, where traffic noise was the most significant source for almost 60% of respondents,
and street work in one fifth of respondents [4]. Traffic and neighborhood noise were most
important for the Copenhagen respondents [5], as well as for the respondents from the eight
major European cities included in the large LARES study [6]. On the other hand, a group of
Macedonian authors obtained different results. The most significant source of noise in their
study among respondents from Skopje was site noise (34%), followed by traffic (24%) [7].
The authors from Slovakia found that the respondents were most disturbed by the noise of fun
events [8]. The different results of these studies only confirm the fact that the sources of
community noise are numerous, and it is often the case that studies do not all capture and
fully capture them. In a Canadian study, respondents were offered eighteen different sources
of noise in the questionnaire, and 25% of respondents indicated some new sources of noise to
which they attach particular importance. For this reason, future research should well identify
all potential sources of noise that could have a negative impact on the exposed population [9].
In any case, no matter what the source of the noise from the outside, one of the measures to
protect it from its stressful action is certainly to close the window in the warmer months.
People living in noisy areas are more likely to close their windows facing the street, which
our research confirmed.
The average daily holding time of open windows facing the street during the warmer
period of the year was twice shorter in the noisy zone compared to the quiet and the Belgrade
survey [2]. The population opts for this compulsory measure of protection only with
extremely high noise interference, as natural ventilation contributes to the improvement of the
microclimatic conditions in the dwelling. When the windows are closed, the temperature and
humidity of the air in the room increases, which is conducive to the propagation of bacteria
and mold. In addition, such conditions on the premises lead to occupant fatigue, decreased
concentration and increased susceptibility to infections.
Our research showed that over a third of the total number of subjects in the noisy zone
would change their apartment due to noise, while a significantly smaller number of subjects in
the control zone would be for this ultimate measure of noise protection. Similar results were
found in a survey in Belgrade in which 50% of respondents from the noisy zone were ready to
change their place of residence, which is, in fact, the ultimate measure of protection against
noise disturbance [2]. Of the total number of respondents, less than 1% complained to the
authorities about traffic noise. No statistically significant difference was found between the
studied groups. Given the high levels of noise the respondents were exposed to, the small
number of them who tried to solve the problem in this way is quite surprising. However,
earlier studies have also shown that the number of noise complaints is not a reliable indicator
of the extent of population interference, nor is it significantly positively correlated with
communal noise levels [3]. Such passive behavior of the respondents is probably due to the
population's assessment that the ability of local authorities to solve the noise problem is very
limited. Living in a noisy environment probably influenced that, in this study, in the noisy
zone respondents, compared to the quiet zone respondents, they were statistically significantly
more likely to be dissatisfied with their family life, material status and the comfort of their
253
apartment. Also, a large number of respondents from the noisy zone rated their relations with
their neighbors as bad and very bad.
CONCLUSION
Living in a noisy environment caused a significantly higher number of respondents from
the noisy zone to consider noise as the most significant adverse environmental factor. The
most significant sources of noise for the respondents of both groups were traffic and street
works, and the least significant sources of industry and building installations. Respondents to
the noisy zone kept windows open for a short period of time, more often stating that they
would change their apartment because of the noise and have worse inter-neighbor
relationships.
REFERENCES
[1] M. Hadži-Nikolova, D. Mirakovski, N. Doneva, et al., J. Environ. Prot. Ecol; 19 (1)
(2018) 173–185.
[2] B. Jakovljević, G. Belojević, Saobraćajna buka i mentalno zdravlje, Medicinski fakultet
Univerziteta u Beogradu, Beograd (1998).
[3] C.L. Wong, W. Chau, L.W. Wong, Noise Health; 4 (65) (2002) 69.
[4] B. Jakovljević, K. Paunović, K. Belojević, Environ. Int; 35 (3) (2009) 552–6.
[5] R. Persson, J. Bjork, J. Ardo, et al., Int. Arch. Occup. Environ. Health; 81 (2) (2007) 179–
191.
[6] H. Niemann, C. Maschke, WHO LARES, Final report, Noise effects and morbidity, WHO
2004.
[7] G. Ristovska, D. Gjorgev, E. Stikova, et al., Journal of Medical Sciences; 2 (2009) 255–
60.
[8] L. Sobotova, J. Jurkovicova, Z. Stefanikova, et al., Bratisl. Lek. Listy; 107 (5) (2006)
214–6.
[9] D.S. Michaud, S.E. Keith, D. Mcurchy, J. Acoust. Soc. Am; 123 (2) (2008) 784–92.
254
PHYSICAL-CHEMICAL CHARACTERISTICS OF SM "VELIKI CRLJENI" COAL
AND ITS EFFECT ON THE ENVIRONMENT
Zoranka Malešević1*, Rada Krgović2, Mirjana Jovović3

1
Academy of Professional Studies, Sumadija, Josifa Pančića 11, 34300 Arandjelovac,
SERBIA
2
SM Kolubara, Svetog Save 1, 11550 Lazarevac, SERBIA
3
Faculty of Agriculture, University of East Sarajevo, Vuka Karadžića 30,
71123 East Sarajevo, BOSNIA AND HERZEGOVINA
*
zorankamalesevic@msn.com
Abstract
The aim of this work is to determine the quality of coal in the Kolubara basin, more precisely in the
"Veliki Crljeni" mine, which started its operations in 2007. The research comes down to determining
the chemical composition, elemental and technical analysis of coal. Significant differences are
represented in terms of the geochemical characteristics of coal, the chemical composition, the content
of macroelements, the content of heavy metals and other microelements, both in their vertical profile
of the main coal layer distribution so as laterally. The results show the differences are particularly
pronounced in the contents of some elements, e.g. chromium, manganese, vanadium, arsenic, etc. The
environmental impact of coal mining is also briefly overviewed.
Keywords: coal, microelements, macroelements, environment
INTRODUCTION
Coal is a widely available, inexpensive, affordable and reliable source of energy. The
geopolitical distribution of the world's reserves is in a much better position than the
distribution of oil and gas. Europe's lignite production is still competitive with coal imports,
but the economic reserves of major European producers are exhaustive. Efforts to more
efficiently and thoroughly exploit coal reserves will reduce the EU's overall energy
dependency and as a result, coal in Europe will remain the primary energy source by 2030 [1].
Characteristics of coal
In genetic terms, coal can be humus, derived from the remnants of higher terrestrial plants
or sapropellous which originates mainly from lower plants, primarily algae. Coal is almost
never pure in the earth's crust; various matter is mixed with a coal substance that reduces its
energy (ballast) or pollutes the environment. When decomposed by aerobic conditions, coal
loses about 80% of its organic matter, and only 20% remains and participates in synthesis.
The elemental composition of the organic mass of coal is characterized by a predominance of
carbon (from 65% in brown coals to 98% in anthracite) and a lower amount of oxygen (from
30% to 1%) and hydrogen (from 6% to 1%) [2]. Kolubara coal is mostly xylitic and earth-bar,
woody structured and with significant content of fusite. Fusite is often mineralized, because
its structural openings are filled with clay matter and pyrite. Characteristics of trench coal as a
255
fuel are not the most favorable because, due to the higher content of moisture and minerals,
uneven granulation and composition, and therefore low thermal power. Its use is limited to the
immediate vicinity of the site. By technological or chemical processing, coal is therefore
brought to such a state that it can completely replace the fuels used in high-temperature
technological processes, as well as in direct combustion for electricity and heat production
[3].
There are two ways to express the composition of coal; by technical analysis, where
moisture, volatiles, carbon and ash are determined or by elemental analysis, which determines
the chemical composition, content of macronutrients, heavy metals and other microelements.
Elemental analysis also allows the thermal value of some coal to be calculated, and the
composition of the relays can to be determined [4].
Kolubara basin
The Kolubara basin is one of the largest lignite basins in the Republic of Serbia, located
south of Belgrade. It began to be exploited around 1910. The first thermal power plant was
built in 1936 within the basin, more precisely in Veliki Crljen. The Kolubara part of the basin
covers over 600 km2 of surface. There are excavation fields A, B, C, D, as well as the mines
of Vreoci, Veliki Crljeni, Kolubara, Kosmaj, Baroševac Tamnava etc [5].
Figure 1 Surface mines in the area of SM „Kolubara”

Coal samples for analysis were taken from the wells of the main coal seam in the „Veliki
Crljeni“ field, more precisely in the Q0/ Qqr-120 well located in the western part of the field
where the exploitable part extends between the eastern boundary of the SM „Tamnava-
Istočno Polje“ and the Belgrade- Bar railway line.
A major coal seam is drilled in the well in the depth range from 8.90 m to 26,10 m. The
profile was tested with 4 samples, representing vertical intervals from 0.60 m to 5.00 m.
During sampling, all cores from the exploratory well had a natural moisture content of the
reservoir because they have an impact on the determination of coal quality.
In the first part of the work, the samples were dried at room temperature, ground and
pulverized. The content of coarse, hygroscopic moisture, ash content and thermal power were
determined. Technical tests were performed in the laboratory of MB Kolubara, using the
standard methods [6].
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In the second part of the paper, macro and microelements in coal are analyzed. All
analyzes were done by X-ray fluorescence spectroscopy, using the device ARL Optimix
(Thermo Electron Corporation, USA). This method has also been recognized by the American
Geological Society for Coal Analysis (“Methods for sampling and inorganic analysis of
coal”, U.S. Geological Survey Bulletin 1823). Due to very low concentrations, some
microelements were determined by atomic absorption spectrophotometry (AAS): Hg, Cd, Th,
U, Se, Be, Co, As.

Coal samples taken from the well represent the entire interval of the punctured layer in the
well. The results of the coal analysis of the main coal seam in the "Polje Veliki Crnjani" in the
well Qo / Qqr-120 are given in the form of tables.
Table 1 Technical analysis of the coal of the main coal layer in the "Polju Veliki Crnjani"
Samples 1 2 3 4 Medium
Depth (m) 8.90–13.90 13.90–18.50 19.50–24.50 24.50–25.10 value
Moisture % 60.80 58.20 59.30 53.80 58.03
Ash % 5.60 6.50 5.10 9.00 6.55
GTE (кЈ/кg) 8890 9203 9450 10207 9438
DTE (кЈ/кg) 7064 7436 7658 8542 7675
Δ=DТЕ-GТЕ (кЈ/кg) 1826 1767 1802 1665 1765
The moisture content of coal in the vertical profile of the coal layer shows a trend of
declining from the highest to the lowest level, and the ash content shows the opposite trend -
it’s increasing in the profile of the layer from top to bottom GTE and DTE in the vertical
profile of the coal bed progressively increase from the highest to the lowest part and they are
opposite to the trend of changing moisture content (negative correlation). Free moisture, ash
and sulfur are not desirable constituents of fuel [7,8].
From this, as well as from a number of other analyzed geological coal wells and the
corresponding measured trench coal, discrepancies between geological measurements and
measurements during exploitation can be observed. The cause of such phenomena is the
secondary presence of tailings and this analysis once again confirmed the dependence of the
decline in coal quality and its pollution by the presence of tailings [9].
The forthcoming coal exploitation in this basin has to be viewed through increasingly
complex geological conditions, primarily through the increasingly complex geological
structure of the coal layers, which are built with an intensive participation of overburden
layers with a thickness of more than 1 m. This, in exploitation terms, automatically means an
increased participation of "bad lots" coal.
Macro and microelements in coal
The chemical composition of coal, that is, the content of macroelements in coal, in the well
profile Qo / Qqr-120 is shown in Table 2.
257
The most abundant component is SiO2 (3.26 - 22.65%), and in the lowest part of the coal
bed profile it grows fairly progressively and then decreases significantly.
Table 2 Chemical composition-content of macronutrients in the coal in the „Polju Veliki Crljeni“
Depth (m) 8.90–13.90 13.90–18.50 19.50–24.50 24.50–26.10 value
SiO2 11.6 22.65 10.42 3.26 11.98
TiO2 0.14 0.11 0.25 0.01 0.13
Al2O3 3.93 5.12 2.87 1.24 3.29
Fe2O3 1.47 1.31 2.48 1.33 1.65
MgO 0.18 0.20 0.14 0.11 0.16
CaO 2.65 1.43 1.66 3.30 2.26
K2O 0.40 0.70 0.23 0.07 0.35
P2O5 0.01 ˂0.01 0.01 0.01 0.01
S 1.09 0.945 2.207 1.602 1.460
If the highest interval of the layer is excluded, the aluminum content shows the same trend
of down enrichment as for silicon (Figure 2).
a) b)
Figure 2 Change of trace elements concentration with dept
The contents of S, Fe2O3 and CaO correlate very well and they are in smaller quantities in
the higher part compared to the lower part. The concentrations of MgO, K 2O, TiO2 and P2O5
are low in all samples [10].
The contents of heavy metals and other microelements in the profile of the Qo / Qqr-120
well are shown in Table 3. The values of the microelements by depth show a parabolic
arrangement for all elements except Ni and Zn which show linear dependence with respect to
depth. Most elements (As, V, Zr, Hg, Pb) have maximum values at 19.50-24.50 m, except
Mn, Ni and Zn which have the highest values at 24.50-25.10 m [11].
Mercury, chromium and manganese, although occurring in low concentrations, pose a
threat to the environment [12]. All elements except the Mn, Ni and Zn have minimum values
at the greatest depth. If the results in depth are viewed solely through minerals, uneven
granulation and composition, then the changes in microelements in depth should be constant
growth curves (except for Pb) [13].
258
Table 3 Content of heavy metals and other trace elements in coal in the “Polje Veliki Crljeni”
Depth (m) 8.90–13.90 13.90–18.50 19.50–24.50 24.50–25.10 value
As 55 45 65 45 53
Ba 175 160 170 55 140
Cr 1070 4540 850 195 1664
Cu 85 90 75 65 79
Mn 225 95 85 430 209
Ni 25 20 30 35 28
Sr 95 55 50 45 61
V 35 30 85 20 43
W ˂1 ˂1 ˂1 ˂1 ˂1
Zn 65 60 75 80 70
Zr 8 6 9 7 8
Hg 0.31 0.32 0.28 0.27 0.30
Cd ˂ 0.1 ˂ 0.1 ˂ 0.1 ˂ 0.1 ˂ 0.1
Pb 48 44 39 38 42
Th ˂1 ˂1 ˂1 ˂1 ˂1
U ˂ 10 ˂ 10 ˂ 10 ˂ 10 ˂ 10
Se ˂ 0.1 ˂ 0.1 ˂ 0.1 ˂ 0.1 ˂ 0.1
Be ˂ 0.1 ˂ 0.1 ˂ 0.1 ˂ 0.1 ˂ 0.1
Co 7 12 5 9 8
Cl 200 200 200 300 225
The mechanism responsible for such distribution is petrographic composition, degree of

carbonization and deposition.
Sources of harmful substances in various operations in environmental wells
Many years of massive coal exploitation created large quantities of tailings that were
landfilled in inappropriate locations. In addition to the depletion of natural resources and
pollution of water, air and soil, this fact has also led to significant destruction and degradation
of land. Landfills in Serbia are estimated to have between 1.4 and 1.7 billion tonnes of
overburden tailings and about 700 million tonnes of flotation and separation tailings.
About 40,000 acres of land have been degraded by surface mines and tailings dumps in
large mining basins. Recultivation covered less than 20% of the degraded land area [14,15].
Considering the technology of coal mining on surface mines, sources of harmful substances or
environmental hazards may be considered [16].
CONCLUSION
The results of testing of Kolubara coal in the coal field "Polje Veliki Crljeni", in terms of
its ability to produce products of the highest calorific value through preparation and
processing, indicated that this coal is characterized by the highest ash and coke content, and
the lowest GTE and DTE values. In addition to the high percentage of moisture, a larger
amount of inorganic matter is present in some samples.
259
The chemical composition of coal is dominated by Al, Si, Ca, and Fe, and there are also
significant amounts of S. At higher concentrations there are B, Cr and Mn, St and Cl, and
slightly less Cu, Zn, Pb, As, Ni, and others. Exactly these elements, with a change in pH, can
become mobile and bioavailable. Their concentration can increase which leads to human
health hazards and environmental pollution.
REFERENCES
[1] N. Ćalić, Lj. Andrić, Rudarstvo i održivi razvoj u Srbiji, I Međunarodni simpozijum
Rudarstvo 2010, Zbornik radova str.1-9. Tara, (2010) (in Serbian).
[2] T. Larry, Coal as substance in Coal Geology, 2nd edition, Wiley-Blackwell, (2013).
[3] S. Srinivasachar, J.J. Helble, A.A. Boni, et al., Prog. Energy Combust. Sci; 16 (4) (1990)
293–302.
[4] S.V. Vassilev, K. Kitano, Sh. Takeda, et al., Fuel Process. Technol; (45) (1995) 27–51.
[5] V. Bogdanović, Z. Ilić, D. Polomčić, Izbor ograničenja i otvaranja površinskog kopa
Južno Polje u Kolubarskom ugljenosnom basenu, Kolubara projekt, Lazarevac, (2007) (in
Serbian).
[6] R. Milosavljević, Metode ispitivanja mineralnih sirovina u pripremi mineralnih sirovina,
Rudarsko-geološki fakultet, Beograd, (1994) (in Serbian).
[7] F. Goodarzi, Fuel; (85) (2006) 273–280.
[8] M. Ivković, Đ. Đukanović, D. Đukanović, „Istraživanje ranga uticaja prirodno-geoloških
uslova na izbor sistema podzemnog otkopavanja ugljenih slojeva u Srbiji”, Rudarski
radovi; 3 (2012) 49–55 (in Serbian).
[9] M. Ahmaruzzaman, Prog. Energy Combust. Sci; (2010) 327–363.
[10] Studija modeliranja mineralnih transformacija i raspodele mikroelemenata u lignitskim
basenima EPS-a, Institut za opštu i fizičku hemiju Beograd, (2010) (in Serbian).
[11] V.C. Pandey, J.S. Singh, R.P. Singh, et al., Arsenic hazards in coal fly ash and its fate in
Indian scenario, Resour. Conserv. Recy; 55 (2011) 819–835.
[12] Z. Wei, G. Wu, R. Su, et al., Environ. Toxicol. Chem; 30 (9) (2011) 1997–2003.
[13] M. Životić, D. Stojiljković, V.A. Jovović, et al., Hem. Ind; 66 (3) (2012) 403–412 (in
Serbian).
[14] S. Đukičin, J. Đorđević, J. Milanković, Acta geographica Slovenica; 54 (1) (2014).
[15] R. Krgović, Mobilizacija i biodostupnost makro i mikro elemenata iz pepela
Termoelektrane "Kolubara", Hemijski fakultet Univerziteta u Beogradu, Beograd, (2015)
(in Serbian).
[16] Grupa autora: Plan upravljanja otpadom (2017–2020), Ogranak RB Kolubara,
Organizaciona celina Kolubara-Prerada, „Kolubara-Projekt“ Lazarevac, (2017) (in
Serbian).
260
IMPLEMENTATION OF QUALITY CONTROL ON SAMPLED SOIL WITH TRIP
AND FIELD BLANK
Daniela Urošević1*, Zorica Sovrlić1, Ivan Svrkota1, Miomir Mikić1, Renata Kovačević1,
Mirjana Šteharnik1
1
Mining and Metallurgy Institute Bor, Zeleni Bulevar 35, 19210 Bor, SERBIA
*
daniela.urosevic@irmbor.co.rs
Abstract
The quality control of the sampled soil is monitored by Trip and Field Blanks according to the ISO
18400-106:2017 standard. Except these blanks, before terrain sampling, it is necessary to form so
called Zero Blank, which is analyzed element by element, and on which soil samples are to be
analyzed. Returning from the terrain, Trip and Field Blanks are to be analyzed as well. Soil sampling
was conducted on the following places: Kostolac, Prahovo and Coka Korugu. After every sampling on
this place the quality control was implemented by Field and Trip Blank, as well as by duplicated
control samples. Soil sampling on this terrain was carried out every three months. Samples were
tested on Cu (ppm) and presented on R-control maps, that also implicate on the absence of the cross
contamination in the process of sampling, transport, preparation of the chemical analysis. All this is
confirmed by the analysis results which are below the detection limit and alert limit.
Keywords: soil sampling, quality control, Field and Trip blanks, R- control maps
INTRODUCTION
Soil is a complex heterogeneous matrix composed of mineral and organic solid matter,
liquid and gaseous components and living organisms. It presents the important part of the
urban ecosystem which directly or indirectly has impact on life quality and people’s health.
Industrial and urban development of human society among many advantages and benefits,
results in environmental pollution and soil pollution as well. So, it is of the great importance
to do the soil control and analysis more frequently.
Sampling is the beginning and the basis, on which depends the accuracy of the output
results of chemical analysis of sampled soil. Mining and Metallurgy Institute has established
procedures and standards for quality control.
For the blank forming can be taken any kind of soil, only thing to be known is the zero
chemical soil composition so called zero blank. After soil sampling, the chemical composition
of trip and field blanks are compared with the chemical composition of the zero blank.
If there are no significant deviations between the blanks and the zero blank, it can be
concluded that no cross contamination occurred during the sampling and transport, which
guarantees the accuracy of soil sampled chemical analysis [1].
261
SAMPLING QUALITY CONTROL

Sampling quality control has 3 main goals: Monitoring and detecting errors which may
occur in the process of sampling, sampling error control and to present the sampling
variability [2].
Precondition for accuracy and reproducibility of analytical results is sampling quality
control that includes the following:
- Representativeness of the sampled material;
- Prevention of contamination during the terrain sampling, transport to the laboratory,
storage and preservation of samples and preparation for chemical analysis.
Inadequate sampling can lead to the unexpected effects, for example, to the change of
chemical composition of samples, which can bring into question the accuracy of chemical
analysis inputs. In order to prevent the unwanted effects, in the Mining and Metallurgy
Institute laboratory, the quality control is done by:
- Using field and trip blanks;
- Taking double control samples by each sampling in order to check sampling precision.
They provide information which ideally rejects all mistakes of possible sources of
contamination, sampling inconsistency and check of applied analytical technics.
ZERO FIELDS AND TRIP BLANKS

For blank forming can be used soil of different chemical and physical characteristics. It is
recommended to use unpolluted areas. Parameters on which zero, trip and field blanks are
analyzed must be known before the coming on the terrain, they must be the same as the
parameters where the sampled soil is to be analyzed [2–4].
Trip blanks are used to detect prospective mutual contamination of blanks during the
transport and are also used to confirm or eliminate possible cross contaminations of samples.
The sample must go through the entire process, from transport to the laboratory, preparation
on the ring mill and chemical analysis.
Trip blank is analyzed on chemical elements, on which the soil samples will be analyzed,
before going to the terrain. The sample must go through the entire process, from the field
sampling, transport to the laboratory, preparation on the ring mill and chemical analysis. This
way confirms or eliminates possible inconsistency in entire process, considering transport
than preparation and chemical analysis at the end.
Comparative analysis of field and trip blanks with zero blanks, determines possible
contamination of sampled soil, proper sampling method with previously established sampling
plan or excludes the possibility for negative outputs.
CHEMICAL ANALYSIS AND SAMPLE PREPARATION

All samples including, control samples, field and trip blanks are transported to the
laboratory for preparation and are stored according to the ISO18400 Soil quality-sampling-
part105: Packaging, transport, storage and preservation of samples standard [4,5].
262
Preparation includes the following steps: sample drying at 40ºC, or on the air, exemption
of representative samples for particle size analysis by aerometric, exemption of representative
samples for chemical analysis and grinding the sample in the ring mill on the particle of 85-
90% -75 μ. The prepared soil samples, in ring mill, are dissolved in the automatized system
for digestion "Vulcan-Questron Technologies", with the addition of 3 different acids (HCl,
HNO3 and HClO4) and the process of digestion is done in Teflon container on the temperature
of 200ºC.
Measured soil amount is 0.25 g and after the dissolving, the samples are moved to the
normal container and the final volume of the dissolved sample was 25 mL. The prepared
samples are further tested for copper content by ICP MS method.
An Agilent SPS 4 autosampler was used to deliver the samples. Standard Ni-cones were
used. The operating conditions are shown below.
Multi-element standard solution for ICP MS, concentration 10 µg/ml, Calibration
Standard#2, Ultra Scientific (Al, As, Ba, Be, Bi, Cd, Ca, Ce, Cr, Co, Cu, Ga, In, Fe, Pb, Li,
Mg, Mn, Ni, K, Rb, Se, Na, Sr, Tl, U, V, Zn) was used to prepare the external calibration
curve (from 1 to 200 µg/L). All solutions were prepared using Milli-Q® water (18 MΩ∙cm-1).
To prevent contamination, all glassware and plasticware were acid-washed before use.
All the blanks undergo the same way of preparation, and are analyzed with all samples on
the same element after coming from terrain. Exceptions are zero blanks whose composition
must be known before going on the terrain. For each location are formed zero, trip and field
blanks.
RESULT AND DISCUSION

Soil sampling is conducted according to the criteria which is applied in the Republic of
Serbia, and are in accordance with standard norms [5–8].
In Tables 1, 2 and 3 are presented rezults of analyzed blanks for the given sampling
periods. Results of analyzed control samples are presented in Table 4 and Table 5 presents
limits of R-chart, on the basic calculated values of relative range.
According to the values of relative range, the control limits of R-chart are calculated for
control samples, central lines, warning limits, detection limits, and presented on R-charts.
From R-charts can be clearly seen that there is no outliery-the values that bounced off from
the calculated limits [1,8].
Looking at the results of chemical analysis on copper for indicated period we can come to
possitive constatation , according to the cross contamination during the transport, preparation
and chemical analysis at the end, which leads to the conclusion that the sample contamination
during the entire process is excluded and any inconsistency in the entire process from
sampling to the the preparation and chemical analysis did not occur.
By comparative analyse of the sample, trip and fild blanks, zero blank we come to the
minimal deviations, which can be regarded as negligible.
263
Table 1 Comparative chemical analysis zero blank with field and transport blank, Cu content (ppm) -
mean of two measurements, sampling site of Čoka Korugu
Month of sampling
January March Jun September December
Sample name
Zero blank 34.0 33.9 33.6 33.6 34.0
Trip blank 34.4 34.3 34.5 34.7 34.4
Field blank 34.1 34.2 34.1 34.3 34.1
mean of two measurements, sampling site of Kostolac
Month of sampling
Sample name
Zero blank 44.7 44.6 44.7 45.0 44.9
Trip blank 45.0 45.1 44.2 44.7 44.0
Field blank 44.4 45.0 44.0 45.4 45.5
mean of two measurements, sampling site of Prahovo
Month of sampling
Sample of name
Zero blank 51.5 51.8 51.8 51.0 51.6
Trip blank 49.9 51.2 49.6 50.0 50.5
Field blank 50.0 52.2 49.9 50.5 51.5
Table 4 Chemical analysis of control samples on Cu content (ppm), sampling sites of Čoka Korugu
Kostolac, Prahovo
Month of sampling
Sample of name
KK1ČK 52.9 53.2 54.0 53.4 53.5
KK2ČK 51.7 52.2 51.8 53.0 51.3
KK1K 64.3 65.2 63.6 65.1 64.5
KK2K 64.7 65.3 64.1 66.5 65.7
KK1P 70.0 71,1 68,9 71.3 73.5
KK2P 71.6 73.3 70.0 69.2 73.8
264
Table 5 Results of R-chart , CL- center line, CL, WL alert limit, and AL detection limits, ppm
Month of sampling January March Jun December
September
Sample of name CL WL AL CL WL AL CL WL AL CL WL AL CL WL AL
KK1ČK 0.22 0.552535 0.718901 0.22 0.552535 0.718901 0.22 0.552535 0.718901 0.22 0.552535 0.718901 0.22 0.552535 0.718901
KK2ČK 0.18 0.452074 0.588191 0.18 0.452074 0.588191 0.18 0.452074 0.588191 0.18 0.452074 0.588191 0.18 0.452074 0.588191
KK1K 0.24 0.602766 0.784255 0.24 0.602766 0.784255 0.24 0.602766 0.784255 0.24 0.602766 0.784255 0.24 0.602766 0.784255
KK2K 0.22 0.552535 0.718901 0.22 0.552535 0.718901 0.22 0.552535 0.718901 0.22 0.552535 0.718901 0.22 0.552535 0.718901
KK1P 0.21 0.505625 0.662143 0.21 0.505625 0.662143 0.21 0.505625 0.662143 0.21 0.505625 0.662143 0.21 0.505625 0.662143
KK2P 0.3 0.753457 0.980319 0.3 0.753457 0.980319 0.3 0.753457 0.980319 0.3 0.753457 0.980319 0.3 0.753457 0.980319
R - control chart
0,7189007090,7189007090,7189007090,7189007090,718900709 R - control chart
0,588191 0,588191 0,588191 0,588191 0,588191
0,5525354610,5525354610,5525354610,5525354610,552535461
WL-Alert limit
0,452074 0,452074 0,452074 0,452074WL-Alert limit
0,452074
Cu, ppm
Cu, ppm
0,3 0,3
0,22
0,2 0,22 0,22 0,22 0,22
CL-Central
0,2 line 0,2
0,18 0,2
0,18 0,2
0,18 0,18
CL-Central
0,2
0,18
line
0,1 0,1
JANUARY MARCH JUNE SEPTEMBER DECEMBER JANUARY MARCH JUNE SEPTEMBER DECEMBER
month month
Figure 1 R chart of control sample KK1ČK Figure 2 R chart of control sample KK2ČK
265
Figure 3 R chart of control sample KK1K Figure 4 R chart of control sample KK2K
R - control chart R - control chart

0.980319149 0.980319149 0.980319149 0.980319149 0.980319149
0.653546099 0.653546099 0.653546099 0.653546099 0.653546099
0.753457447 0.753457447 0.753457447 0.753457447 0.753457447

0.502304965 0.502304965 0.502304965 0.502304965 0.502304965
WL-Alert limit WL-Alert limit
Cu, ppm
Cu, ppm
0.5
0.3 0.3 0.4
0.22 0.22 0.22 0.22
CL-Central
0.22
line 0.3 0.3 0.3 0.3 CL-Central
0.3 line
0.2
0.1 0.1
0
JANUARY MARCH JUNE SEPTEMBER DECEMBER JANUARY MARCH JUNE SEPTEMBER DECEMBER
month month
Figure 5 R chart of control sample KK1P Figure 6 R chart of control sample KK2P
266
CONCLUSION
On the locations Coka Korugu, Kostolac i Prahovo, the soil sampling was done every 3
months according to the standards norm. Results of the analyzed parameter, copper, on the
sampled soil are not part of this work, for justified reasons, except the copper content in
blanks and control samples. The sampling and sampler control was done in laboratory in two
ways:
- with field and transport blanks;
- and with taking control samples in duplicate.
Results of chemical analysis of control samples are presented on R-maps. R-control map is
made of the range of two measurements and of the difference in results of two measurements.
The value of the arithmetical range is used as a central line (CL). Standard deviation is used
for calculation of control limits where the Al is limit of action and WL is warning limit.
Results from the R-control map present that all the results of analyzed parameters on
blanks and control samples, go into range of measuring and are acceptable, and can be used
for further statistic data, as well as the quality of sampling and measurements in specific
period of time.
The double samples are used for monitoring the sampling quality and precision of
analytical laboratory processes. Field and trip blanks illustrate the effects of managing the
samples, they reveal the contaminations such as dust and atmospheric precipitation.
Examining and analyzing result from the Tables 1, 2 and 3 we can conclude that the
deviation values of field and trip blanks are minor in comparison to the zero blank. The entire
process of sampling, transport, to the preparation and analyze of the samples is conducted in
adequate and accurate way relying on previously mentioned standards, relevant legislation
and examining methods.
The conclusion is that the adequately conducted quality control on soil sampling on the
terrain results in high accuracy of chemical analysis outputs. R-control charts of field,
transport and zero blanks, because of the limited number of pages, were not presented in this
work [8,9].
ACKNOWLEDGEMENT
the Republic of Serbia for financial support TR 33023 and 34005.
REFERENCES
[1] Standard ISO/IEC 17025, Opšti zahtevi za kompetentnost laboratorija za ispitivanje i
laboratorija za etaloniranje, decembar 2017 (In Serbian).
[2] Standard ISO 18400 Soil quality – Sampling – Part 101: Framework for the preparation
and application of a sampling plan, 2017.
[3] Standard ISO 18400 Soil quality – Sampling – Part 102: Selection and application of
sampling techniques, 2017.
[4] Standard ISO 18400 Soil quality – Sampling – Part 104: Strategies, 2018.
267
[5] Standard ISO 18400 Soil quality – Sampling – Part105: Packaging, transport, storage and
preservation of samples standard, 2017.
[6] Standard ISO 18400 Soil quality – Sampling – Part 106: Quality control and quality
assurance, 2017.
[7] Zakon o zaštiti zemljišta ("SG RS", broj 112, decembar 2015.) (In Serbian).
[8] Uredba o graničnim vrednostima zagađujućih, štetnih i opasnih materija u zemljištu
(Službeni glasnik RS, broj 30/2018) i Uredba o programu sistemskog praćenja kvaliteta
zemljišta, indikatorima za ocenu rizika od degradacije zemljišta i metodologije za izradu
remedijacionih programa ("Službeni glasnik RS" br. 73/2019) (In Serbian).
[9] Uzorkovanje, validacija procesa i vrednovanje merne nesigurnosti, jul 2019 (In Serbian).
268
ENERGY, RENEWABLE ENERGY SOURCES, POTENTIALS AND
APPLICATIONS
Miomir Mikić1*, Daniela Urošević1, Nikola Stanić1, Milenko Jovanović1, Sanja Petrović1
1
Mining and Metallurgy Institute Bor, Zeleni Bulevar 35, 19210 Bor, SERBIA
*
miomir.mikic@irmbor.co.rs
Abstract
The need for the use of renewable energy sources has surfaced over the past several decades since
alarming data has been released on the effects of greenhouse gases emitted by combustion of fossil
fuels. Renewable energy sources include the energy of watercourses, wind, solar energy, biomass and
geothermal energy. The use of renewable energy sources is imposed as a very acceptable option in
providing energy for the future and for stopping further environmental degradation.
Keywords: renewable energy sources, energy, environmental
INTRODUCTION
While energy is at the heart of economic and social development, its production,
transportation and use are the cause of a wide range of major environmental problems at the
local, national and global levels. The demand for energy, mostly met with fossil fuels
(particularly oil and coal), has increased steadily during recent years, with an average growth
in demand of roughly 2% per year in the 1990s. Demand is expected to continue growing,
especially in developing countries, as access to energy plays a critical role in alleviating
poverty through rural job creation, education, improved health and living conditions.
The energy systems developed so far to meet this demand are clearly unsustainable, as they
lead directly or indirectly to health-damaging levels of air pollution, acidification of
ecosystems, land and water contamination, loss of biodiversity, and global warming.
ENERGY
Energy is closely linked to economic development and to environmental quality. It is
central to the world economy, providing the power needed for industrial production,
transportation and (increasingly) agriculture.
Energy is a major contributor to health, wellbeing and productivity, making possible the
existence of services that include heating, lighting and refrigeration. The energy chain
delivering these services starts with the collection or extraction of a primary energy source –
for example, coal – which may be transformed into another form of energy such as electricity,
transported or transmitted to the point of use, and finally used to power a piece of equipment
such as a heater, lamp or motor. Figure 1 shows an energy chain, using coal as an example.
Primary energy sources include fossil fuels (coal, oil, natural gas) and renewable sources
such as biomass (wood, other plant sources, dung), hydropower, solar power, wind power,
269
tidal power and geothermal energy. A small but significant proportion of the world’s
electrical energy is also provided by nuclear power. The ways in which these primary sources
are extracted, transformed, delivered and used have enormous environmental impacts at local
and global levels. They also have both positive and negative effects on human health.
Figure 1 Energy chain: from extraction to energy services
RENEWABLE ENERGY SOURCES, POTENTIALS AND APPLICATIONS IN

SERBIA
The need to use renewable energy sources has emerged over the past few decades as
alarming data on the effects of greenhouse gas emissions from fossil fuel combustion have
been published. This has led to climate change in the world, which is primarily reflected in
the increase in average temperature, ie global warming. Climate disturbances have not
bypassed Serbia either - temperatures have been rising since the early 1980s, and due to
climate disturbances, dry and warm summers can be expected, extreme weather changes,
temperature fluctuations, periods of unstable climate, occurrences such as floods and the city.
The EU has committed itself to reducing greenhouse gas emissions, including carbon dioxide,
by 20% from 1990, by 2020 to combat climate change, to increase the share of renewable
energy to 20% and to take measures energy efficiency achieves savings of 20%.
Serbia's energy profile is expressed through a brief description of the country's basic
macroeconomic indicators as well as an analysis of the energy sector. Serbia is a middle-
income country with great potential for rapid economic development, as the country is
endowed with natural and mineral resources and fertile and arable agricultural land. Serbia's
GDP declined dramatically during the 1990s. However, since 2000, GDP has grown steadily
and in 2006 it was almost 30% higher than in 2000. Strong economic progress has been made
270
since 2001, especially in expanding private sector participation in the economy.

Macroeconomic stability, which was quickly achieved in the early years of transition, has
largely been maintained. Serbia has a total dependency of 40%, and compared to the energy
dependency of other EU27 + countries, the country's energy dependence is considered
average [1].
The energy sector is a major polluter in Serbia, mainly due to the use of domestic lignite,
which burns with old equipment without adequate emission reduction technology. Indeed,
energy efficiency in Serbia is inefficient. In fact, it uses five times the amount of energy to
produce one unit of GDP compared to the EU average [2]. The carbon intensity in Serbia by
GDP is 6.8 times higher than the world average and 10.8 times the OECD average [3].
Transmission and distribution losses in 2008 were 2.79% and 14%, respectively [4]. In 2007,
the country's total primary energy consumption was 15.8 Mtoe (Table 1). The most significant
role in this amount is played by coal, which has a share of 49.8%, followed by oil and its
products (27%), natural gas (12.4%) and RES (10.8%), a share which is slightly reduced
compared to 2005 (41%) [5]. The current capacity of hydropower plants is 10,200 GVh / year,
while the potential capacity is estimated at 14,200 GVh / year. Energy production sectors
have had various problems in the past, including inadequate pricing of services, lack of
adequate maintenance and investment costs, lack of competition, over-employment and the
resulting large fiscal wastage of government resources [6]. As can be observed, with respect
to transmission and distribution systems (Table 1), Serbia suffers from transmission and
distribution losses, either due to catastrophes caused by war or due to system obsolescence.
Therefore, the main goal for Serbia is the need to reconstruct the transmission and distribution
system.
Table 1 Total energy data and economic profile

Indicator Serbia EU 27+
40,088.65
GDP/capital (2018) 5,992.28 (USD)
(USD)
12,589.50
GDP (2018) 41.42 (mil.USD)
(mil.USD)
Inflation (2018) 2% 1.1 %
Exchange rate (2020) 1.14 € for USD 1.3948
Population 7306,677 340.72 (mil.)
Production 9,751 31,736
Import (2019) 2,327.40 (mil.USD) 165,403 (mil.€)
Export (2019) 1,753.50 (mil.USD) 183,341(mil.€)
Reserves change 20.40 N/A
Transmission and distribution - Increased losses in transmission and
N/A
system status distribution of electricity
ENERGY RESOURCES AND POTENTIALS OF THE REPUBLIC OF SERBIA

Table 2 represents energy resources and potentials of the Republic of Serbia consist of
fossil, conventional (coal, oil and natural gas) and unconventional fuels (oil shale), as well as
renewable energy sources [7].
271
Table 2 Geological reserves of fossil fuels (million tonnes of oil equivalent (toe))
Energy resource Balance and off-balance Total geological
geological reserves reserves
Stone coal 2,77 4,02
Dark coal 37,7 45,17
Carbon black coal 134,25 193
Lignite 1583 (780*) 3,698
Oil 10,14 50
Natural gas 3,37 50
Oil shale - 398**
Stone coal 2,77 4,02
Dark coal 37,7 45,17
Carbon black coal 134,25 193
*witout Kosovo; **Kerogen-organic part of oil shale.
The total technically available potential of renewable energy in the Republic of Serbia
(Table 3) is estimated at 5.65 million toe per year. Of this potential, 1,054 million toe biomass
(mostly as firewood) and 909 thousand toe hydropower is already used [8].
Table 3 Total technically available potential of renewable energy sources

Type of RES Available technical Unused available Total available
potential used (million technical potential technical potential
toe/year) (million toe/year) (million toe/year)
BIOMASS 1,054 2,394 3,448
Agricultural biomass 0,033 1,637 1,67
Agricultural crop residues 0,033 0,99 1,023
Residues in fruit growing,
0,605 0,605
viticulture and fruit processing
Liquid manure 0,042 0,042
Wood (forest) biomass 1,021 0,509 1,53
Energy plantings NA
Biodegradable waste 0 0,248 0,248
Biodegradable municipal waste 0 0,205 0,205
Biodegradable waste (excluding
0 0,043 0,043
municipal waste)
HYDRO ENERGY 0,909 0,77 1,679
For installed capacity up to 10 MW 0,004 0,151 0,155
For installed capacity up to 10 MW
0,02 0,102 0,122
up to 30 MW
For installed capacity exceeding 30
0,885 0,517 1,402
MW
WIND ENERGY ≈0 0,103 0,103
THE ENERGY OF THE SUN ≈0 0,24 0,24
For the production of el. Energy ≈0 0,046 0,046
For the production of thermal
≈0 0,194 0,194
energy
GEOTERMALNA ≈0 0,1 0,18
For the production of el. Energy ≈0 ≈0 ≈0
For the production of thermal
0,005 0,175 0,18
energy
Total from all RES 1,968 3,682 5,65
272
THE RATE OF RENEWABLE ENERGY SOURCES IN SERBIA

In Serbia, most energy comes from coal, which is used most in addition to oil and natural
gas. Coal is the dominant raw material in electricity production. In Serbia, only hydro
potential and biomass are used to a greater extent than renewable sources. The production and
consumption of energy from renewable sources are also calculated according to EU
regulations for large hydropower plants, but those in the field of environmental protection are
not considered as ecological plants due to the adverse effects of the construction of dams on
the environment. In this context, without large hydro plants, the share of electricity from
renewable sources is very small.
Considering the current situation in Serbia, the lack of quantitative indicators in the
planned fields of application of renewable energy sources, as well as the need for much more
pronounced efforts to promote their use, must be emphasized [9]. The share of energy from
renewable sources in Serbia is around 6% (including large hydro power plants) and is
projected to remain stable in the coming period. The Energy Development Strategy by 2015
foresees that the share of new renewable sources (excluding large hydro power plants) in total
primary energy consumption should increase from 1.07 to 1.21% in 2015 (Table 4) [9].
Table 4 The share of energy from renewable sources in the total primary energy consumption,
according to the Energy Development Strategy, scenario of dynamic economic development [9]
2006 2009 2012 2015
Total primary consumption energy (in PJ) 615 647 715 753
Share of renewable energy sources
0.8 1.1 1.05 1.1
(no large hydro)
The share of energy generated in Serbia from renewable sources is small, and Table 4
shows the fact that its increased share is not foreseen until the end of 2015. Currently in
Serbia, only about 1% of energy is generated from alternative sources, which is negligible if
one considers the natural potentials and requirements of the Kyoto Protocol.
When it comes to establishing and raising the share of renewable energy in the country's
energy supply, Serbia's example is not positive. In order for a country to think at all about
promoting renewable energy, it needs to have these resources at its disposal. With a
renewable energy potential of 3.83 miltoe (tons of oil equivalent), Serbia is very much in line
with this requirement. What is missing is an adequate strategic plan for a much more
ambitious implementation of RES into the country's energy potential [8–10].
CONCLUSION
Serbia has considerable energy potential in renewable energy sources, but it has not been
sufficiently utilized. The use of energy from renewable sources is still in its infancy and in the
world, except in some developed countries, and the greatest challenge is the transition to
cleaner technologies while achieving economic viability.
273
In addition to the environmentally friendly, the use of renewable energy sources is also of
e o omi im ort e it can contribute to the reduction of fossil fuel imports, the
development of local industries and job creation, but also to savings for households.
ACKNOWLEDGEMENT
The work came from project number TR33021, which was funded by the Ministry of Science and
Technological Development of the Republic of Serbia. The authors are grateful to the Ministry of
Education, Science and Technological development of the Republic of Serbia for financial support.
REFERENCES
[1] Eurostat, Energy dependence, % of net imports in gross inland consumption (2009)
Available on the following link: http://epp.eurostat.ec.europa.eu/tgm/table.do?tab=table
&init=1&language=en&pcode=tgigs360&plugin=1S
[2] European Agency for Reconstruction, The energy sector in Serbia, European Union,
European Agency for Reconstruction, Serbia (2007).
[3] United Nations Economic Commission for Europe, Financing Energy Efficiency
Investments for Climate Change Mitigation. Regional Analysis of Policy Reforms to
Promote Energy Efficiency and Renewable Energy Investments (2010).
[4] Economic Commission for Europe. Committee on Environmental Policy, Environmental
Performance Reviews Republic of Serbia, Second Review, Environmental performance
reviews Series No.26. NewYork and Geneva: United Nations Publication (2007).
[5] Larive Serbia, Croatia, Serbia and Bosnia–Herzegovina – Renewable energy. Dutch
Ministry of Economic Affairs, EVD – The Agency of International Business and
Cooperation, The Netherlands (2009).
[6] J. Zenic Zeljkovic, Serbian experience in regulating the infrastructu reservices,
UNCTAD—United Nations Conference on Trade and Development, Geneva (2010).
[7] Kjoto Protokol uz Okvirnu konvenciju Ujedinjenih nacija o promeni klime (1997).
[8] S. Kol ković, „Hidro-energetski potencijal hidrosistema Dunav-Tisa-Du v“, Fakultet
teh ičkih uk , Novi S d, Srbij .
[9] Ministarstvo rudarstva i energetike Republike Srbije, Strategija razvoja energetike
Republike Srbije do 2025.godine sa projekcijama do 2030. godine (2015).
[10] Re ublik Srbij , Re ublički z vod z st tistiku, Ekobilten 2005-2006, ISSN 0354-3641,
Beograd, Srbija (2007).
274
APPLICATION AND PROPERTIES OF NATURAL FIBER-BASED
BIOCOMPOSITE MATERIALS – A REVIEW
Jovana Bošnjaković1*, Ivana Jelić1, Velimir Komadinić1

1
Institute Lola Ltd., K. V. 70a, 11030 Belgrade, SERBIA
*
jovana.bosnjakovic@li.rs
Abstract
Natural fiber-based biocomposite materials are increasingly present on the market primarily due to
their environmental, economic, and recyclable properties. Compared to man-made polymers, which
represent non-biodegradable materials derived from petroleum products, nowadays natural fiber-
based biocomposites are gaining more attention because of their performance. Biocomposites are a
group of materials consisting of matrix and reinforcement (fillers). Natural fibers, which usually have
a reinforcing role in biocomposite materials, are derived from biomass (e.g. kenaf, flax, hemp). Also,
the matrix can come from renewable sources. Biocomposite materials exhibit better properties than
conventional or biopolymer materials. Their use reduces the negative impact on the environment and
thus achieves greater sustainability. The increasing presence of these materials is mainly due to good
mechanical and thermal properties. For example, they play a very important role in the production of
many interior and exterior parts for cars, ships, aircraft. They are widely used in the household,
medicine, and pharmaceutical industry, etc.
Keywords: biomass, natural fiber, environment, material
INTRODUCTION
Composite materials are increasingly being developed and redesigned to produce materials
with improved properties [1]. Natural fiber-based materials have been used in recent years due
to their significant environmental and economic performance. The use of composites based on
natural fibers leads to the development of rural areas, increasing employment and thus
reducing the poverty rate, on the basis of which it can be conclude that they play a very
important role in socio-economic development, and overall sustainability.
Biocomposite materials represent composites in which at least one of the constituents is of
natural origin. Their properties depend on the matrix, the natural filler (reinforcement), the
fiber size, and the interconnection of the fiber and the matrix. These fibers could have a
natural or synthetic origin. The natural fibers represent an alternative to synthetic fibers (e.g.
carbon, glass), which represent reinforcements in polymeric materials. In the composite
industry, they are often referred to as plants fibers. Plants fibers are based on cellulose,
hemicellulose, and lignin, which can be obtained from the bark of wood, leaves, seeds, fruits,
and reeds. Biocomposite materials have the great advantage that they can be used in many
industries, such as the aerospace, automotive, and pharmaceutical, etc. [2].
275
PROPERTIES AND DIVISION OF NATURAL FIBERS

The properties of natural fibers are influenced by many factors, such as cultivation
location, the nature and age of the plant, and the method of extraction used. Advantages of
natural fibers, compared to synthetic fibers, are greater availability, renewability, short plant
growth period, cost-effectiveness, biodegradability, and recyclability, as well as lower energy
consumption, i.e. energy efficiency, and reduction of carbon dioxide emissions during
production. Several natural fibers derived from palm wood, banana, jute, wheat, sugarcane,
cotton, silk, coconut, bamboo represent effective stiffening of matrices [3]. Natural fiber
based composites can be used in various structures due to their high specific strength [4].
They are of great use in the design of spacecraft [5]. The use of natural fiber-based composite
materials has led to market growth. There are multiple divisions of natural fibers. Some of the
divisions are given in Figure 1 and Table 1.
Figure 1 shows the division according to the biological origin of the constituent parts,
where the composites can be classified into partly ecological and green. Green composites are
composites where all components are from renewable sources, thereby reducing carbon
dioxide emissions. While partially ecological, only one of the constituents comes from
renewable sources and the other comes from non-renewable sources (petroleum products) [1].
Natural fiber properties are affected by the size, number, shape, arrangement [6].
Figure 1 Type of natural fibre reinforcements [7]
The classification of natural fibers according to their origin and the world annual
production is shown in Table 1.
Table 1 Classification of natural fibers, origin, world annual production and cost [8]
Production
Fiber type (plant) Botanical name Origin
(103 ton)
Abaca Musa textilis Leaf 91

Saccharum
Bagasse Stem 102,000
officinarum L.
Musa uluguruensis
Banana Leaf 200
Warb.
276
Table 1 continued
Gigantochloa
Bamboo scortechinii Stem 10,000
Dendrocalamus apus
Coir Cocos nucifera L. Fruit 650
Cotton Gossypium spp. Seed 19,010
Flax Linum usitatissimum Stem 830
Hemp Cannabis sativa L. Stem 214

Corchorus capsularis,
Jute Stem 2850
Corchorus olitorius
Kapok Ceiba pentandra Seed 123
Phormium Phormium tenax Leaf -
Pineapple Ananas comosus Merr. Leaf -
Ramie Boehmeria nivea Gaud Stem 100
Sisal Agave sisalana Leaf 318.8
BIOPOLYMER MATRIX
The mechanical properties of biocomposite materials are influenced by a polymer matrix,
which can be thermoplastic or thermosetting. Polymers used in matrix production may be of
plant or animal origin, or synthetic (carbon-based) origin. Mechanical properties, chemical
resistance, stability, manufacturing process, in order to achieve biodegradability or
recyclability play a crucial role in the selection of polymeric material. The recycling
efficiency of a biopolymer matrix, at the end of its working life, depends primarily on the
nature of its elements. Thermocouple dies, on the one hand, are more used because they have
good thermal properties, high chemical resistance and excellent mechanical properties, while
on the other hand, they are very difficult to recycle, making it difficult to reuse (although
some studies indicate that they can be easily reused) [9]. Thermoplastic dies can be
comfortably melted, and they are also recyclable as opposed to thermosetting. The aim is to
adapt mechanical, chemical, and thermal properties to achieve a recyclability process [10,11].
APPLICATION OF NATURAL FIBER REINFORCED COMPOSITE MATERIALS

Industries, such as automotive, construction, aviation, aim to produce, whose products are
environmentally friendly and come from renewable sources [12–14]. The use of composite
materials based on natural fibers contributes to the employment of people in rural and less
developed areas, thereby achieving sustainable development. The aim is to reduce the poverty
rate, to develop new innovative ideas, to create sustainable cities and communities, to make
the process of production and consumption rational. Based on these facts, we can conclude
that they play a very large role in the socio-economic development of society. In the
production processes, the most common are the fibers based on the figure, which include
277
(jute, flax, hemp, and kenaf), leaf (abaca, sisal, and pineapple), seeds based on seeds (coconut,
and cotton), grass fibers, reeds ( wheat, maize, and rice), wood-based fibers, roots [14].
Some countries cultivate different types of fiber, while others import. In the European
automotive industry, flax and hemp, which are mainly grown, are the most used, while jute
and kenaf are imported from Bangladesh and India. Bananas are imported from the
Philippines, sisal from South Africa, the United States, and Brazil.
Biocomposite Materials in the Automotive Industry
The use of biocomposite materials in the automotive industry dates back to the 1940s when
the scientist Henry Ford produced the first cannabis-based parts [15]. Then in the 1950s, the
production of bodywork based on biocomposite materials for the German Trabant [15]. In the
automotive industry, by using natural fibers, mass reduction is achieved, leading to a
reduction in fuel consumption and carbon dioxide emissions into the atmosphere. Studies
show that the use of natural fibers in the automotive industry achieves cost reductions of
about 20% and weights of about 30% [15]. Natural fibers are made mainly of the interior of
the car, such as dashboards, doors, seat covers, while the use of exterior components is
limited. The interior parts of German cars, such as Mercedes, Volkswagen, Audi, and Ford,
are made of natural fibers. Figure 2 shows the process of manufacturing hemp doors.
Figure 2 Production of the door from hemp fibre [16]
In the German automotive industry, which is one of the largest manufacturers of natural
fiber-based parts, the matrix used in combination with these fibers is polypropylene (PP). It is
noted that on average, each car contains about 3.6 kg of natural fibers (e.g. wood, cotton, flax,
hemp, and kenaf). Flax fibers are used in the manufacture of brakes [17]. Their advantage is
that they reduce the coefficient of friction.
Application in other branches of industry
The use of biocomposite materials is also prevalent in sectors such as medicine, pharmacy,
packaging, household, and construction. The reason for their use in the mentioned areas is in
the lower economic costs, less weight.
For medical purposes, combinations of fibers, such as sisal/glass fibers or sisal/silk fibers,
are used to reduce the use of titanium, cobalt, chromium. By their use for orthopedic
278
purposes, internal and external fixations are achieved when a bone is fractured [18]. They are
also used in the construction of water tanks and chemicals [19,20].
Household items, such as garden furniture, chairs, floor coverings, are made of jute and
coconut fibers [21]. Kenaf fibers are used in construction because of their low cost and low
mass [22].
CONCLUSION
The aim of this paper was to present the properties and application of natural fiber-based
biocomposite materials, which achieve significant savings during the production process in
many industries. The use of these materials achieves economic, environmental, and energy
efficiency. Unlike synthetic fibers, natural fibers are more widespread, more recyclable, plant
growth periods are shorter, carbon dioxide emissions are lower. The nature of the matrix
affects the mechanical properties. It can be thermoplastic and thermosetting. Unlike
thermoplastics, thermosetting matrices have good thermal, mechanical properties and high
chemical resistance, but their disadvantage is that they are difficult to recycle, making it
difficult to reuse them. These materials are widely used in many industries, such as
automotive, construction, aviation, and many others. The largest use has been reported in the
automotive industry, primarily because of the reduction in car weight, costs, and
environmental impact. In the automotive industry, they are mainly used in the manufacture of
interior car parts. Also, they are very widely used in the manufacture of various items, such as
helmets, cases, mailboxes, garden furniture, floor coverings, panels, and various packaging
products, etc. Likewise, the use of composites based on natural fibers leads to the
development of rural areas, increasing employment and thus reducing the poverty rate, on the
basis of which it can be conclude that they play a very important role in socio-economic
development, and overall sustainability.
ACKNOWLEDGEMENT
This work was supported by the Ministry of Education, Science and Technological Development of
the Republic of Serbia.
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[1] B. Mitra, Def. Sci. J; 64 (3) (2014) 244–261.
[2] V. Fiore, A. Valenza, G. Di Bella, Compos. Sci. Technol; 71 (8) (2011) 1138–1144.
[3] I. Siva, J.T. Winowlin Jappes, B. Suresha, Polym. Compos; 33 (2012) 723–732.
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[5] A. Hassan, A.A. Salema, F.N. Ani, et al., Polym. Compos; 31 (2010) 2079–2101.
[6] M. Dicker, P. Duckworth, A. Baker, et al., Composites: Part A; 56 (2014) 280–289.
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279
[10] S. Pickering, Management, Recycling and Reuse of Waste Composites, (2010) 65–101.
[11] N. Reynolds, M. Pharaoh, Management, Recycling and Reuse of Waste Composites,
(2010) 3–19.
[12] F. AL-Oqla, S. Sapuan, J. Clean. Prod; 66 (2014) 347–354.
[13] V.L.P. Salazar, A.L. Leao, D.S. Rosa, et al., J. Polym. Environ; (2011) 677–688.
[14] O. Faruk, A.K. Bledzki, H.P. Fink, et al., Prog. Polym. Sci; 37 (11) (2012) 1552–1596.
[15] M.S. Huda, L.T. Drzal, D. Ray, et al., Properties and Performance of Natural-Fibre
Composites, Woodhead Publishing (2008), p. 576, ISBN: 978-1-84569-267-4.
[16] E. Pollitt, Automotive Composites, Available on the following link:
http://www.globalhemp.com/2011/02/automotive-composites.html
[17] Z. Fu, B. Suo, R. Yun, et al., J. Reinf. Plast. Compos; 31 (10) (2012) 681–689.
[18] D. Chandramohan, K. Marimuthu, Journal Science Research; 54 (2011) 384–406.
[19] K. John, S.V. Naidu, J. Reinf. Plast. Compos; 26 (4) (2007) 373–376.
[20] K. Raghu, P.N. Khanam, S.V. Naidu, J. Reinf. Plast. Compos; 29 (3) (2010) 343–345.
[21] K. Satyanarayana, J. Guimaraes, F. Wypych, Composites: Part A; 38 (2007) 1694–1709.
[22] S. Ozturk, J. Compos. Mater; 44 (2010) 2265–2288.
280
PLANET PRESERVATION THROUGH CLIMATE ACTIONS AND CREATING
QUALITY JOBS ONLY
Maja Radić1*, Sanel Ćemer2, Mehmed Avdagić2

1
Business Academy Novi Sad, Faculty of Economics and Engineering Management,
Novi Sad, REPUBLIC OF SERBIA
2
International University of Goražde, Faculty of Social Sciences, Goražde,
BOSNIA AND HERZEGOVINA
*
maja.radic84@gmail.com
Abstract
Climate changes are affecting all countries on all continents. It has a negative impact on
national economies and on people's lives, already creating additional costs for people,
communities and countries that will be even greater in the future. The whole world needs a
change in leadership and political direction that would move away from the neoliberal and
conservative models of the past, focusing on quality jobs for their populations, a healthy
environment, social security, and an economic cost-cutting inequality-solving model. The
status quo is not an option. A radical change is needed in order to build a project for the
future that everyone in the world can trust in. Creating quality jobs will remain a major
challenge for almost every economy even after 2019.
Keywords: climate change, planet, jobs
INTRODUCTION
Climate change is one of the most serious challenges our world faces with today. Our
planet is undergoing significant and accelerating climate change that has begun more than a
century ago. Most scientists agree that the planet is heating up faster than ever because of the
huge amount of greenhouse gases that are being pumped into the atmosphere as a result of
human actions. These include activities such as burning fossil fuels (coal, oil and gas), driving
cars, and cutting down forests.
Many of us have seen, and even experienced, the effects of climate change. It is not just
about the extreme weather conditions such as floods, droughts and hurricanes. Slower and less
noticeable changes in our climate could completely change the way we live. The good news is
that in December 2015 in Paris, 195 countries (literally the whole world) entered into a first
legally binding global agreement on combating climate change.
In the EU and around the world, governments, companies and individuals are already
trying to reduce the causes of climate change and adapt to the changes it brings. We all have a
role to play because climate change is a global problem that can affect us all. We share one
planet, and the changes we make in one place can affect other distant places as well. It could
be said that our behaviour leaves a lasting impression, like a footprint. Therefore, by our
281
actions and choices, each of us can undertake measures to leave smaller footprints and help
combat climate change.
Many changes are needed to preserve the planet. In order to continue to live, it is necessary
to ensure that we have and continue to have the basic resources needed for survival, such as
water, food and energy.
Being sustainable means taking care of the planet and living within the limits of what it can
provide to us. Waste prevention is becoming increasingly important as the global population
grows and we are slowly consuming our limited reserves of natural resources. Also, one of the
burning issues is to provide quality jobs only, all with a goal to preserve the planet [1].
PRESERVATION OF THE PLANET THROUGH CLIMATE ACTIONS

Climate actions in the fight against climate change
Without the further emission reductions policy, it is estimated that the average world
temperature could rise by 1.1ºC and 6.4ºC during this century. Human activities such as the
combustion of fossil fuels, deforestation and agriculture result in the production of carbon
dioxide (CO2), methane (CH4), nitrogen oxide (N2O) and fluorocarbon emissions. These
greenhouse gases retain the heat released from the Earth's surface and prevent its expansion
into space and thus causing the global warming [2].
As we have already stated, climate change affects all countries on all continents. It has a
negative impact on the national economies and people's lives, creating, even today, additional
costs that will be even greater in the future for people, communities and countries.
People are already experiencing the significant consequences of climate change, which
include the changes in weather patterns, rising sea levels and more extreme weather
conditions. The emissions of greenhouse gases, as a result of human activities, lead to climate
change that continues to increase. Today, they are at higher levels than ever in history.
Without any actions, the average temperature on the planet is predicted to rise during the 21st
century, which is likely to exceed 3 degrees Celsius.
The poorest and most vulnerable people are, unfortunately, the most affected. Today, many
affordable solutions are available to enable countries to move to cleaner and more resilient
economies. More and more people are turning to renewable energy sources and other
measures that reduce the emissions and contribute to adaptation efforts. Climate change is a
global challenge which does not recognize national boundaries. The emissions at one location
affect people in a wider environment.
This is an issue that requires solutions and coordination at the international level, and the
international cooperation which will assist developing countries and their advance towards a
low carbon economy. In order to address climate change, countries adopted a global
agreement in Paris in December 2015. The measures to reduce climate change need to be
integrated into national policies, strategies and plans. In addition, there is a need for improved
education, raising awareness, as well as human and institutional capacity to mitigate and
reduce the impact of climate change, from adaptation to early warning.
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Preserve and sustainably use the oceans, seas and marine resources for sustainable
development
The world oceans - their temperature, chemical composition, currents and life in them, are
very important for the global systems that make the Earth fit for a human life. Rain, drinking
water, weather conditions, climate, shores, a good portion of our food, and even the amount of
oxygen we breathe in, ultimately is given and controlled by the sea. Throughout history, the
oceans and seas were vital for commercial and transportation purposes. Therefore, a careful
management of this essential global resource is key to a sustainable future.
By the end of 2025, all types of pollution of marine resources, especially those coming
from the land, should be prevented or significantly reduced. By the end of 2020, a sustainable
management of marine and coastal ecosystems should be ensured; they should be protected
from all negative impacts, and actions should be taken to rebuild them to make the oceans
healthy and productive again [3].
The plan is to efficiently regulate the catch of fish and to end the excessive fishing as well
as the destructive fishing practices. Furthermore, the plan is to apply the management plans
prepared on a scientific basis in order to restore the stock of fish as soon as possible. On the
other hand, small professional fishermen should be provided with access to marine resources
and trade markets.
Sustainable use of terrestrial ecosystems
Forests cover 30 percent of the Earth's surface, and apart from being a source of food and
shelter, forests are the key to help fighting climate change and preserving biological diversity.
It is estimated that 13 million hectares of forest are lost annually. Deforestation and
desertification - caused by human activities and climate change - represent major challenges
for sustainable development and affect the lives and livelihoods of millions of people in the
fight against poverty. Efforts have been taken to improve forest management and to combat
desertification.
By the end of 2020, plans are being made to stop deforestation, restore destroyed forest
and significantly increase afforestation on a global scale. It is necessary to fight against
desertification, to restore degraded soil and to neutralize soil degradation.
By the end of 2020, the preservation, restoration and sustainable use of inland freshwater
ecosystems and their environment, in particular forests, wetlands, mountains and dried land,
should be ensured in accordance to commitments adopted through international agreements.
One of the goals is to undertake urgent and significant actions to reduce the degradation of
natural habitats, to stop the loss of biological diversity by the end of 2020, to protect
endangered species and to prevent their extinction. By the end of 2020, it is important to
integrate ecological values and biological diversity into national and local planning,
development processes and poverty reduction strategies. In order to achieve this goal, it is
necessary to mobilize and significantly increase financial resources from all sources to
conserve and sustainably use biological diversity of the ecosystems, sustainable forest
management and afforestation, fight against poaching and trade of protected species through
the increase of the capacity of the local communities.
283
Better jobs
In order to preserve the planet, we need better jobs, which need to be created in the future.
One example of better jobs is definitely cleaner industry.
Factories whose products we use and power plants that produce the electricity we need in
our households, schools, and offices, emit large amounts of CO2 and other greenhouse gases.
In order to reduce these emissions, the EU has designed the world's first and largest system
which limits the amount of greenhouse gases emitted and according to this system the
companies need to pay for the emission of the greenhouse gases that they release into the
atmosphere. The EU Emissions Trading System (EU ETS) was launched in 2005 and is the
key part of the EU's climate policy. It covers more than 11,000 power plants and industrial
plants and also includes the emissions from intra-EU flights [4].
The EU Emissions Trading System (EU ETS) sets limitations on the annual amount of
greenhouse gases that the companies can emit. The total amount decreases every year, and
since companies have to report their emissions we can be certain this system reduces the
pollution.
The more the companies emit greenhouse gases, the more they have to pay, so it is in their
interest to emit as little as possible, for example, by investing in cleaner technologies that emit
less CO2.
Today, there are similar systems around the world, such as in China, South Korea and
California. For sectors that are not covered by the EU Emissions Trading System, such as
transport, buildings, agriculture and waste, the responsibility for reducing greenhouse gas
emissions is shared by all EU countries by setting targets at national levels.
The support for new EU technologies helps to develop innovative low carbon technologies
through a special fund raised through the EU ETS. So far, around € 2.1 billion have been used
to support 38 renewable energy projects across Europe. Some of them are focused on
renewable energy sources, such as offshore wind farms, geothermal energy and biofuels, and
others on new technologies that capture carbon and store it underground.
The EU and its member states will continue to support research and development of low-
carbon related innovations through the Innovation Fund and the EU Framework Program for
Research. The key goal is to turn ideas associated with low carbon into practical solutions in
many areas of life. We can only imagine buildings and cars of the future with no carbon-rich
steel or cars that function as mobile batteries and contribute to the energy demands of
households!
On the other hand, underground carbon storage is a carbon capturing and storaging
technology that captures, stores and transports carbon dioxide emitted by power plants and
industrial installations to convenient underground storages.
This has a considerable potential for combating the climate change in Europe and around
the world, because underground, literally all carbon dioxide can be stored for hundreds, even
thousands of years. However, this technology is currently very expensive and in Europe there
are only two functional commercial projects. Therefore, the EU provides basic funding to
support carbon capture and storage projects and has created rules that ensure the application
of this technique in an environment - friendly manner [5].
284
Many people in the world are looking for new future interests and want to build a career
within the latest and most up-to-date technologies. Today, there are many jobs in the fields
such as renewable energy sources that have not existed ten years ago.
Some EU countries have even set up special training centres for the handling and
maintenance of offshore wind farms.
CONCLUSION
The Earth's climate has changed over time, gradually becoming warmer or colder over long
periods of time. There have been a dozen ice ages in the last millennium, with much warmer
periods in between. Those changes happened due to natural causes, such as the changes in the
degree of the planets, solar activities and sea currents. But the changes we witness today are
different - and we are responsible! By releasing more gases that have the ability to trap heat in
the atmosphere, we cause a very rapid rise of the Earth's temperature.
Climate change is caused by the increase in the Earth's temperature (global warming)
which is caused by the release of the unnaturally large amount of greenhouse gases into the
atmosphere. These additional greenhouse gases are mainly generated by the burning of fossil
fuels for the production of energy, as well as for other human activities, such as logging,
agriculture, livestock farming and chemical production. Certainly, one of the ways to preserve
the planet is to carry out many climate actions, at the global level, and to create high-quality
jobs only.
REFERENCES
[1] Available on the following link: https://sustаіnаbledevelopment.un.org/іndex.php?pаge=vіew&t
ype=400&nr=2013&menu=35
[2] Available on the following link: http://www.europаrl.europа.eu/fаctsheets/hr/sheet/72/borbа-
protіv-klіmаtskіh-promjenа
[3] European Commission, Our planet, our future – Fighting climate change together, European Union
publication office, Luxemburg, 2018, p.13.
[4] European Commission, Our planet, our future – Fighting climate change together, European Union
publication office, Luxemburg, 2018, p.15.
[5] V. Jelіć–Muck, Global Sustainable Development Goals by 2030, Reflection - Sustainable
Community Development, Zаgreb, 2015, p. 8.
285
PREVENTION OF CONTAMINATION OPEN WATERCOURSES FROM
EVACUATION MINE WATER FROM SURFACE MINE TURIJA
Senad Čergić1*, Hamid Husić1

1
Brown Coal Mines “Banovici”, 75290 Banovici, BOSNIA AND HERZEGOVINA
*
senadcergic@hotmail.com
Abstract
Evacuation water from surface mines into open watercourses is increasingly complex due to stricter
environmental regulations. Mine water pumped from the lowest points of a mine often contains a
certain amount of particulate matter that is stirred by the pumping itself and in the production
process. Before discharging water into an open watercourse, it is necessary to provide conditions for
their deposition, that is, the water meets the criteria prescribed by applicable legal solutions.
Keywords: mine water, evacuation, environment
INTRODUCTION
The Turija surface mine is spatially located on the former source the Turija River, which
has lost its main source by opening the mine. Following the disruption of hydrogeological
conditions, the occurrence of leachate as well as smaller sources that occasionally form and
disappear in the area are frequent [1].
As with most surface mines, one of the important segments its stable operation is the
adequate solution evacuation the resulting water in the crater the mine itself. Part of the water
is generated by atmospheric precipitation itself, while part the water occurs as groundwater.
Evacuation or pumping of water from a mine crater represents a complex process, especially
in today's time when legal solutions to environmental protection are increasingly stringent.
Depicting a catchment area gravitating to the surface mine Turija

The catchment area that gravitates toward the Turija surface mine consists the 6 catchment
areas presented in the following Table 1.
Table 1 Display of catchment areas [2]

Catchments area Area (m2) Water gravity direction
Area 1 615 000 North peripheral canal
Area 2 75 000 North peripheral canal
Area 3 890 000 The main water collector
Area 4 1 920 000 The main water collector
Area 5 2 450 000 Water collector on point 340
Area 6 850 000 Southern peripheral canal
TOTAL 6 800 000
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Figure 1 Catchments areas gravitating towards the mine Turija
According to the analysis the catchment areas (Figure 1), it is evident that the lowest mine
level are gravitated by the catchment areas 3 and 4 with a total area of 2810000 m2 or 2.81
km2, which is the highest burden on the inflow water into the mine crater. The waters from
the catchment area 1, 2 are poured into the northern circumferential canal, while the
catchment 5 is flows into the water collector on point 340 located outside the pit and pumped
separately into the control canal 2 [2].
Waters gravitating from the south flow into the concrete canal regulation 1 and drains
towards Ramičko lakes and further in the direction of the River Turija.
Location and dimensions of mine water treatment facilities
In order to more efficiently purify mine technological waters from surface mine Turija,
three sedimentary pools (Table 2) were constructed before the mine water was discharged into
the open recipient. The location, size and description of the pool are described in this chapter.
Table 2 Dimensions of sedimentation pools

Sedimentation pool
Poll 1 Poll 2 Poll 3 TOTAL
parameters
Length (m) 126 126 82
Width (m) 21 21 21
Height (m) 4 4 4
Over flow discharge height (m) 0.5 0.5 0.5
Height of water column (m) 3.5 3.5 3.5
Angle of the side of the poll (0) 60 60 60
The bright surface of the water (m2) 2 646 2 646 1 743 7 035
The volume of water in the poll (m3) 7 929 7 929 5 160 21 018
287
The basic parameters for the physical contamination water or the content of suspended
materials are: the volume of the suspended materials, the particle size, the deposition rate
(Table 3), and the amount of particles in the volume unit [6].
The size suspended materials will be set in the range of 0.2 mm (fine sand) up to 0.005 mm
(clay), for such quantities, the deposition rate was calculated by the formula [3]:
(1)
where: C – constant for a given type of material
Table 3 Tabular view of calculated deposition rates

Particle deposite rate (m/s)
Material
d=0.2 mm d= 0.1 mm d=0.05 mm d=0.01 mm d=0.005 mm
-2 -2 -3
Coal roof 8.7x10 2.18x10 5.45x10 2.18x10-4 5.45x10-5
-2 -2 -3
Coal 5.81x10 1.45x10 3.6x10 1.45x10-4 3.6x10-5
Lower level of coal 1.02x10-1 2.54x10-2 6.35x10-3 2.54x10-4 6.35x10-5
The characteristic parameter the sedimentation pool is the bright surface and is obtained by
the form:
(m2) (2)
where:
Q – digging capacity from the mine (m3/s)
Vt – particle deposition rate (m/s)
ηh – hydraulic sediment coefficient (0.7-0.9)
The lowest particle deposition rate is for coal, so for the particle velocity of coal particles
0.005 mm which is Vt = 3.6x10-5 m/s and maximum pumping capacity Q = 0.225 m3/s.
(3)
The total bright water surface is 7035 m2 and the volume water of 21018 m3 in displaced
sedimentation pool (Figure 2) is higher than the defined minimum dimensions and meets the
optimum water purification parameters.
The depth of the sedimentation pool is maximum 5 m, while the retention time the water in
the pool is at least 1/4 days and 6 hours, respectively, with a maximum capacity extraction
from the mine.
288
Figure 2 Construction of sedimentation pools
Quality control of mining water

In order to be sure the quality or composition mine water ejected from the mine crater, it is
obligatory to control them in accordance with the legal solutions in force in our country
(Table 4). Measurements process wastewater and sampling are performed at the connection
points technological collectors or at discharge points in order to monitor average and
maximum values.
In this connection, it should be stressed that solutions have been imposed that require
constant monitoring the quality mine water discharged into open watercourses, where
authorized companies and institutions perform quality controls on a monthly basis and
elaborate on realized or measured values.
Accordingly, since the mine is a large producer, it also discharges several thousand m 3 into
the watercourses and is obliged to monitor certain parameters every month.
Table 4 Number of binding measurements in relation to the amount of wastewater [4]

Waste water flow m3/day Number of tests per year
<5 1
5-20 2
20-50 4
50-100 6
100-500 8
>500 12
289
Measurement results
Considering that Banovići Mine belongs to the category of large consumers whose water
flow exceeds several 1000 m3 water, it is a legal obligation to carry out a detailed analysis of
water at a discharge point once a month by an authorized institution [5]. The Table 5 gives a
brief overview some the measured parameters obtained by measuring in 2019.
Table 5 Results of measurement parameters for 2019 year

Overall results of measurement and testing of basic parameters at measurement site E-1 In 2019
Name of pollutant RMU Banovići
Location PK TURIJA
Municipality and Canton Banovići, Tuzlanski kanton
Wastewater Recipient River Turija
The catchment area River Bosna
Name of the river areas The Sava River catchments
Sampling performed TQM d.o.o. Lukavac
Total suspended
PH value matter
Parameter Flow Temperature
mg/l
tested m3/day °C
Measured Limit Measured Limit
values values values values
JANUARY 3510 14.7 7.85 19
FEBRUARY 3904 11 7.2 32
MARCH 9774 12 6.95 28
APRIL 3160 12 7.5 30
MAY 3120.8 13 7.7 29
JUNE 2764.9 16 8.1 24
6.5-9 35
JULY 2240.3 20 8.3 29
AUGUST 1890.6 23.1 7.93 24
SEPTEMBER 1859.3 20.1 7.81 21
OKTOBER 1795.2 18 7.59 20
NOVEMBER 2140 11.7 7.66 27
DECEMBER 1994.2 12.4 7.46 31
AVERAGE 3179.44 15.33 7.85 26.16
CONCLUSION
Adequate treatment mine water has a major impact on the quality the water discharged into
open recipients.
The analysis the parameters presented in the preceding table in 2019 at the measuring point
E-1 outlet into the Turija River recipient give certain results that show us the extent to which
the mining work affected the quality of the water discharged from the mine crater.
The results show that the average flow per day at the measuring point E-1 is 3179.44
3
m /day, and it is directly dependent on the amount of rainfall and the amount water entering
the crater. The temperature of the discharge water is conditioned by the outside temperature
and ranged from 11-23.1 °C.
290
By analyzing water by pH, the results obtained did not exceed the permissible limit values
of (6.5-9).
Total suspended solids ranged from the E-1 limit values and averaged 23.16 mg/l
compared to the 35 mg/l limit. This parameter is particularly important because under
experimental conditions (artificially induced) the values of this parameter ranged up to several
hundred times greater than measured by this measurement. All this tells us that by an
adequate deposition process solid suspended particles, this is reduced to the limit to fit the
limit values.
It is of course important to point out that the auxiliary sedimentation pools (main and
auxiliary water reservoirs) located in the pits certainly have a significant influence on the
measured sizes because they have a function in front of the precipitator.
The analysis of the measured quantities leads to the conclusion that the water quality meets
the measured parameters. There is no exceeding of limit values, that is, the made
sedimentation pools fulfil their role, they are designed in accordance with the needs of the
surface mine Turija.
REFERENCES
[1] DOPUNSKI RUDARSKI PROJEKAT prve etape razvoja PK Turija RMU Banovići
projektno rješenje evakuacije i prečišćavanja vode iz kratera površinskog kopa Rudarski
institut Tuzla, Tuzla (2010).
[2] GLAVNI PROJEKAT regulacije rijeke Turije u sklopu povrinskog kopa“Turija“ Knjiga I,
II, III, Javno preduzeće za privrednu djelatnost d.d. Spreča Tuzla, Tuzla (2013).
[3] B.Tušar, Pročišćavanje otpadnih voda, Kigen d.o.o. i Geotehnički fakultet Sveučilišta u
Zagrebu, Zagreb (2009).
[4] Uredba o uslovima ispuštanja otpadnih voda u prirodne recipijente i sisteme javne
kanalizacije (Službene novine Federacije BiH, broj 101/15, 1/16, 101/18).
[5] Zakon o vodama (Službene novine Federacije BiH, broj 70/06).
[6] A. Štrkalj, Onečišćenje i zaštita voda, Metalurški fakultet u Sisku, Sisak (2014).
291
CROP’ CONTRIBUTION TO SEASONAL CARBON EXCHANGE IN TEMPERATE
CLIMATE OF CENTRAL LITHUANIA
Ligita Baležentienė1*
1
Vytautas Magnus University, Studentų 11, Akademija, LT-53361 Kaunas, LITHUANIA
*
ligita.balezentiene@vdu.lt
Abstract
This study comprised carbon exchange rate, specifically, emitted and absorbed CO2 fluxes closed
chamber method. For the evaluation of CO2 emissions in different agro-ecosystems the biomass and
leaf area index (LAI) at different plant growth stages have applied. The leaf area index significantly
affected (p = 0.04) the differences in absorbed atmospheric CO2 amounts during vegetation period.
The significant strong correlation (r = 0.6–0.7) has confirmed between soil respirational emissions
and LAI. Soil and crops respiration composed in average 21% and 16% of agroecosystem carbon
exchange, respectively. Generally, the total respirational emissions evidently have recovered by crop’
gross primary production (GPP) in all agroecosystems. As a result, the crops promoted reduction of
atmospheric CO2 content. The maximum mean GPP and NEP values were determined for ley and
maize due to the biggest LAI and yield removed from fields. These agro-ecosystems sank the maximum
atmospheric C rates, and consequently they potentially be considered the most sustainable items
between crops. Considering the data, crop rotations might be improved by right selection of cultivated
crops as well as their area in terms to mitigate their effect on environment and climate.
Keywords: CO2 fluxes, bio-parameters, environment, crops
INTRODUCTION
Agricultural areas cover considerable ranges of terrestrial land, near 12% in total and 30%
of Europe continent, and thus emitted significant rates of greenhouse gas (GHG) [1,2].
Agricultural contributes to the emissions ca. 12% of anthropogenic issues in total, and ca.
10% in EU countries. Soil management produces 4.94% of biospheric fluxes [4,5].
Nonetheless, soil sequestered over 53% of total carbon [6–8].
Amongst measured biospheric fluxes, gross primary production (GPP) exhibited the
atmospheric CO2 volumes photosynthetically assimilated by autotrophs in ecosystems [9].
Respiration of all organisms including plants represents the opposite process to
photosynthesis that emits carbon to atmosphere. Accumulated net carbon identified as net
ecosystem production (NEP) [10]. These parameters related to seasonal environmental
conditions and plant growth [11–13]. In addition, leaf area (LAI) also performed
photosynthesis and carbon assimilation [14,15]. Carbon fluxes between atmosphere, plant and
soil depend on certain crops, their rotational system, applied agro technology, longevity and
environment conditions of growth period [16,17]. Former studies revealed strong reliance
(r=0.7) between carbon emissions and temperature and precipitation [18]. Recent
conventional agro technologies mostly focused on commercial incomes but not on
environment protection including soil fertility, biodiversity, etc. Commercial purposes and
292
severe application of agro chemicals in conventional farming often approval over-exploitation

of environmental resources and thus leading to soil over-cropping and irreversibly changing
environment in ecosystems. Therefore, sustainable agro technologies of ecological farming,
crops and field technologies must be chosen [19].
In this research, the main aim was to analyse and compare the seasonal variation of soil
and plant respirational emissions, gross ecosystem production and net ecosystem production
during growth period in conventional agroecosystems of ley, winter wheat, maize, barley and
spring rapeseed. Crop parameters, i.e. density, leaf area index and yield were applied for
explicate the carbon fluxes.

Measurement object and location
Investigations of seasonal C exchange of conventional farming (CF) ley (L), winter wheat
(W), maize (M), spring rapeseed (R) and barley + ley undercrop (B) were carried out during
growth period in 2014–2016 at the Training Farm of Vytautas Magnus University (54°52' N,
23°49' E) (Table 1). The cropland soil types were Hapli-Epihypogleyic Luvisol, LVg-p-w-ha,
[20].
Table 1 Agroecosystem parameters

Agroecosystem Area, ha Mineral fertilisation
Ley (L) 22.86 Ammonium nitrate, 150 kg ha-1 (N 51 kg ha-1);
in 2nd yr. autumn - manure 50 t ha-1
Wheat (W) 13.7 NPK 8-20-30, 200 kg ha-1
Ammonium nitrate, 140 kg ha-1 (N 48 kg ha-1)
Rapeseed (R) 47.59 Ammonium sulphate, 300 kg ha-1 (N 63 kg ha-1)
Ammonium nitrate 100 kg ha-1 (N 34 kg ha-1)
Maize (M) 46.68 NPK 8-20-30. 280 kg ha-1
Ammonium sulphate, 300 kg ha-1 (N 63 kg ha-1)
Barley (B) 14.51 NPK 8-20-30, 200 kg ha-1
Crop rotation Ley 1-yr. + Ley 2-yr. + winter wheat + maize + spring rapeseed + barley with ley
undercrop
A 2-cut system was applied in ley (04 06 and 11 08 2014; 02 06 and 06 08 2015; 08 06 and
04 08 2016). Thecrop density (un. m-2), leaf surface area (cm2 m-2) were determined and leaf
area index (LAI, m2 m-2) was calculated in the plots of 0.25 m-2 (0.5 m x 0.5 m) in six
replications. Fresh plant biomass (FM, g m-2) and dry matter content (DM, g m-2) were
determined by the weighing method. Dry matter content was determined by drying plant
samples (80oC thermostat Tritec HANNOVER).
293
C exchange investigation
Agroecosystems’ seasonal C exchange was investigated by measuring the rate of gross
primary production (GPP, µmol m-2 s-1) and respiration emissions of soil and autotrophs (Rs+a,
µmol m-2 s-1) applying closed chamber method [22] using LCpro system (ADC Bioscientific
LTD) every 7–10 days with regard to plant growth stages (BBCH-scale) [21]. C exchange of
each agroecosystem was evaluated by net ecosystem production (NEP, µmol m -2s-1) [23]
which was calculated by the formula: NEP=GPP- Ra+s [24].
Meteorological conditions
Crops germination, growth, development, maturity and yield depended on meteorological
conditions. Crops growth has slowed down due to drought periods in the summer of 2014–
2016 (Table 2).
Table 2 Hydrothermal coefficients (HTK) of 2013–2016

Year /
03. 04. 05. 06. 07. 08. 09. 10. 11. Mean
Month
2013 2.81 1.62 4.15 2.86
2014 1.83 0.78 2.03 1.13 0.82 2.02 1.98 1.61 4.15 1.81
2015 3.21 2.15 1.30 0.35 1.34 0.11 1.32 1.96 3.46 1.68
2016 2.94 1.85 0.77 1.62 2.93 2.18 0.6 2.69 1.94
Statistical analysis
Standard deviation for LAI, FM, DM, Ra+s, GPP, NPP was determined with standard error
(mean ± SE). The correlation coefficient r between respiration emission, GPP, NEP and
environmental conditions, biometric parameters was determined.

Plant growth and C exchange parameters closely depended on meteorological (Figure 1)
and soil physical conditions. During vegetation period plant respiration (Ra) varied from 0.202
in March to 2.384 µmol m-2 s-1 in August. Soil respiration (Rs) ranged between 0.225 and
2.526 µmol m-2 s-1 and composed insignificant part in total C exchange. Strong negative
correlation determined between precipitation and Ra (r = -0.6) and Rs (r = -0.7). Though the
decrease of soil humidity due to climate change is recently referred [25], occurrence of
moisture surplus supressed aerobical respiration Rs in soil during spring or autumn seasons in
investigated agroecosystems.
Agreeing to Haboudane et al. [26], crop LAI also depends on environmental conditions
that determine seasonal intensity of physiological processes at different growth stages (Figure
2). The maximum LAI of maize exceeded LAI of L, W, R and B in average by 41%, 28%,
21% and 57%, respectively [27]. Maize belongs to C4 photosynthesis type plant [28], whereas
L, W, R and B are C3 type, therefore anatomic structure of leaves, size of chloroplasts
determined different photosynthesis intensity of these crops [29].
294
Figure 1 Soil (Rs), plant (Ra) and total (Rs+Ra) respirational emissions in conventional agroecosystems
during the vegetation period. Mean ± SE, p < 0.05
Assimilated atmospheric carbon in biomass was estimated by GPP parameter that strongly
depended on Ta (r = 0.7) and FM, DM and LAI (r = 0.8). Some researchers concluded that
environmental conditions and bio-parameters determined GPP and NEP variation [8,30]. In
our investigation, the NEP enlarged from 6.22 µmol m-2 s-1 to 10.09 µmol m-2 s-1 in spring,
and from 11.91 µmol m-2 s-1 to 18.06 µmol m-2 s-1 in summer season. Between the
agroecosystems, M and L assimilated the maximum rates of atmospheric CO2, which has
accumulated in their biomass (Figure 2), that has harvested and removed from the field.
Consequently, M and L can significantly sink atmospheric CO2, and contribute to climate
change mitigation.
Figure 2 Assimilated and sequestered carbon and LAI rates in agroecosystems of conventional crops
during vegetation period. Mean ± SE, p < 0.05
As exhibited the data of carbon exchange, the correct choice of the cultivated plant species
and appropriately changed areas might approve the aims of environmental sustainability in
agroenvironment. The data of this and previous studies take a significant value in order to
295
enhance of the alteration and areas of crop in rotational systems so that advance correct
mitigation strategies of climate change.
CONCLUSION
Photosynthetic surface and rates of assimilated atmospheric CO2 depended on bio-
parameters, specifically crop density and LAI in agro-ecosystems. Maize and ley developed
the highest CO2 assimilation capacity between crops. Therefore, the data revealed that
appropriate choice of plant species and alteration their area in rotational systems can enhance
assimilation of atmospheric CO2, increase agroenvironment sustainability and mitigate to
climate change.
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[1] S. Wood, K. Sebastian, S.J. Scherr, Pilot analysis of global ecosystems. International Food
Policy Research Institute and World Resources Institute, Washington (2000), ISBN: 1-
56973-457-7
[2] FAO 2003, FAO statistical databases, Available on the following link:
http://faostat.fao.org
[3] P. Smith, D. Martino, Z. Ciais, et al., Agric. Ecosyst. Environ; 118 (2007) 6–28.
[4] EEA 2010. The European environment – state and outlook 2010: synthesis, European
Environment Agency, Copenhagen.
[5] LR Ministry of Environment 2012, National policy of climate change management (in
Lithuanian), Available on the following link: http://www.am.lt
[6] F.S. Chapin, P.A. Matson, H.A. Mooney, Terrestrial nutrient cycling, In: Principles of
Terrestrial Ecosystem Ecology, Springer-Verlag, New York, Inc. (2002), ISBN: 978-1-
4419-9504-9.
[7] S. Abiven, S. Menassero, C. Chenu, Soil Biol. Bioch; 41 (2009) 1–12.
[8] J.T. Randerson, F.S. Chapin, J. Harden, et al., Ecol. Appl; 12 (2002) 937–947.
[9] G.M. Woodwell, R.H. Whittaker, Am. Zool; 8 (1968) 19–30.
[10] J.D. Jastrow, T.W. Boulton, R. M. Miller, Soil Sc. Soc; 60 (2007) 801–807.
[11] S. Lehuger, B. Gabrielle, P. Cellier, et al., Agric. Ecosyst. Environ; 139 (3) (2011) 363–
383.
[12] U.M. Ruiz-Vera, M. Siebers, S.B. Gray, et al., Plant Physiol; 162 (2013) 410–423.
[13] P. Ciais, S. Gervois, N. Vuichard, et al., Global Change Biol; 17 (2011) 320–338.
[14] A.A. Gitelson, A. Vina, S.B. Verma, et al., J. Geoph. Res; 111 (2006)
DOI:10.1029/2005JD006017.
[15] Ž. Liatukas, A. Ronis, V. Ruzgas, Zemdirbyste-Agriculture; 96 (3) (2009) 3–15 (in
Lithuanian).
[16] F. Domingo, P. Serrano-Ortiz, A. Were, et al., J. Arid Environ; 75 (12) (2011) 1271–
1281.
[17] J. Aertsens, L. De Nocker, A. Gobin, Land Use Policy; 31 (2013) 584–594.
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[18] L. Baležentienė, A. Kusta, Method. The Sci. World J; 1–11 (2012).

[19] I. A. Janssens, A. Freibauer, P. Ciais, et al., Sc; 300 (2003) 1538–1542.
[20] FAO 1998, World reference base for soil resources, World Soil Resources Report 84,
Food and Agriculture Organization of the United Nations, Rome.
[21] U. Meier, Growth stages of mono-and dicotyledonous plants: BBCH Monograph.
Federal Biological Research Centre for Agriculture and Forestry, Berlin, Braunschweig
(2001), ISBN: 978-3-95547-071-5.
[22] A. Heinemeyer, N. McNamara, Plant and Soil; 346 (1–2) (2011) 145–151.
[23] H. Leith, R.H. Whittaker, Primary productivity of the biosphere, Springer-Verlag,
NewYork (2008), ISBN: 978-3-642-80913-2.
[24] J.S. Amthor, D.D. Baldocchi, Terrestrial higher plant respiration and net primary
production. In: J. Roy, B. Saugier, H.A. Mooney, eds., Terrestrial Global Productivity,
Academic Press, San Diego (2001), ISBN: 9780080518725.
[25] W. H. Schlesinger, E. S. Bernhardt Biogeochemistry: an analysis of global change. 3rd
ed., Academic Press Elsevier, New York (2013), ISBN: 9780123858740.
[26] D. Haboudane, J.R. Miller, E. Pattey, et al., Rem. Sens. Environ; 90 (2004) 337–352.
[27] J. Li, B. Zhao, X. Li, Agric. Sci. China; 7 (2008) 336–343.
[28] J.A. Berry, O. Bjorkman, An. Rev. of Plant Physiol; 31 (1980) 491–543.
[29] E.A. Davidson, K. Savage, L.V. Verchot, et al., Agric. Forest Meteor; 113 (2002) 21–37.
[30] M.C. Peel, B.L. Finlayson, T.A. McMahon, Hydrol. Earth Syst. Sc; 11 (2007) 1633–
1644.
297
Student Section
HONEY BEES AS BIOINDICATOR OF ENVIRONMENTAL POLLUTION
MEDONOSNA PČELA KAO BIOINDIKATOR ZAGAĐENJA ŽIVOTNE SREDINE
Student: Damnjan Trifunović1*

Mentor: Maja Nujkić1
1
University of Belgrade, Technical Faculty in Bor, Vojske Jugoslavije 12, Bor, SERBIA
*
daki97trifunovic@gmail.com
Abstract
Honey bee and bee products are very good indicators of pollution. The bee is active
throughout the area surrounding the hive. The bee can range over long distances, even up to
ten kilometers under exceptional circumstances: a hive can keep an area of seven square
kilometers under its control. The bee as a biological indicator possesses several important
morphological and ecological factors. Keeping the bees can have a good effect on humans.
The bee acts as a detector of environmental pollution in two ways. First as a high mortality
rate from the presence of toxic molecules and over residues in honey, pollen and larvae of the
presence of heavy metals, fungicides and herbicides. Bees are exposed to many contaminants
during feeding, pollutants from the air can be easily applied to their hairs during the collection
of pollen and nectar from flowers or through water. Bees can carry to the hive many
contaminants deposited on plants. Pesticides used in agriculture may not only be a cause of
high bee mortality, but may also enter the bee product. One of the methods used in pollen
analysis is the GC-MS/MS analytical method. This method was used for the determination of
multiple residues of 26 pesticides in pollen has been developed and validated in accordance
with the recommendations of the European Union SANCO guide. The presence of xenobiotic
in these products can compromise their quality and properties and endanger human health.
Bee samples are collected in three periods: March, June and September. Sampling choices
should be closely related with seasons and different insect activities. Beekeeping, in addition
to environmental studies, is used to produce ecological and health maps for specific areas. A
large problem in honey is heavy metals. Heavy metals are coming from the industries. Not
just industries area are affected, a lot of pollution are travelling by air or water and that
affected to an area with very clean nature. In Table 1 are analyzed levels of different metals in
honey.
Table 1 Data are expressed as mg/g of honey for the first group of metals (Al to Zn) analyzed
and as μg/g of honey for the second group (As to Ti)
Metals May August November
Al 114.69±16.7 79.61±11.11 128.83±32.5
B 174.64±35.21 191.64±24.91 181.72±17.9
Ca 9889.96±976.4 10114.31±910.15 10103.37±959.13
Cu 226.59±18.9 239.96±16.8 225.56±20.15
Fe 1201.67±157.8 1170.39±71.3 1151.76±92.56
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Table 1 continued
K 17779.13±1134.4 17.192.42±656.15 16.875.86±1500.63
Mg 9288.43±641.25 9126.76±239.97 9052.62±705.56
Mn 1239.51±293.53 1501.84±157.39 1285.41±88.54
Na 4833.71±299.31 4588.18±101.57 4362.16±528.49
Si 556.4±74.25 586.31±102.62 608.79±53.69
Zn 1302.34±57.82 1333.13±125.35 1195.84±31.38
As 357.02±57.42 312.44±37.37 335.47±39.31
Cd 3654.57±441.54 4336.48±126.76 4347.66±291
Co 1117.42±147.38 1273.06±170.98 1112.75±37.37
Cr 6835.71±1506.8 8369.91±1761.01 7849.12±1329.58
Ni 2484.15±234.6 2614.26±274.44 2993.54±295.18
Pb 816.06±330.27 534.39±58.74 585.41±161.7
Sb 41.45±19.2 53.52±59.27 25.83±2.67
Se 968.42±187.7 877.3±229.69 798.42±177.76
Ti 180279.31±10342.0 187846.41±19091.61 174537.76±7871.31
Figure 1 Pollen analysis
Keywords: Honey bee, Pollutions, Biomonitoring, Environmental marker
ACKNOWLEDGEMENT
REFERENCES
[1] E. Skorbiłowicz, M. Skorbiłowicz, I. Cieśluk, Journal of Ecological Engineering; 19 (3)
(2018) 229–234.
[2] G. Celli, B. Maccagnani, B. Insectol; 56 (1) (2003) 137–140.
[3] Ż. Bargańska, M. Ślebioda, J. Namieśnik, Crit. Rev. Env. Sci. Tec; 46 (3) (2016) 235–248.
[4] R.C. Oliveira, S.C. do Nascimento Queiroz, C.F. Pinto da Luz, et al., Chemosphere; 163
(2016) 525–534.
[5] A. Badiou-Bénéteau, A. Benneveau, F. Géret, et al., Environ. Int; 60 (2013) 31–41.
300
THERMOSTABLE PLASTIC POLYMERS
TERMOSTABILNI POLIMERI PLASTIKE
Student: Nemanja Milošević1*

Mentor: Snežana Milić1
1
University of Belgrade, Technical Faculty in Bor, Vojske Jugoslavije 12, Bor, SERBIA
*
necanecke13@gmail.com
Abstract
Thermostable polymers are a class of polymers obtained by curing or crosslinking thermo-
resins. These are polymers that use heat or radiation energy with the addition of some
hardener, in the presence or without the presence of a catalyst. Thermostable polymers are
obtained by various chemical processes, polymerization, condensation or addition. Once the
polymer mass has solidified, it can no longer change shape. The most significant
representatives are:
-epoxy resins;
-formaldehyde and phenolic resins;
-polyurethanes;
-polyesters;
-silicone organic polymers (silicones).
Epoxy resin is a thermostable polymer composed of epoxy groups in its molecular structures,
and is formed by the condensation reaction between bisphenol A (BPA) and epichlorohydrin
(ECH).
Phenol-formaldehyde polymers are the first synthetically produced polymers. Phenol-
formaldehyde resins are obtained by condensation in the presence of acidic or basic catalysts
during the polymerization of phenol and formaldehyde. When the conditions of preparation
are such that there is more formaldehyde than phenol, a resol is obtained, and when the case is
opposite, a novolac is obtained. Phenolic resins are prepared in both acidic and base
environments. They can be divided into several groups, of which the most significant are:
- phenol-formaldehyde polymers (PF);
- amino-formaldehyde polymers (AF):
- urea-formaldehyde polymers (UF);
- melamine-formaldehyde polymers (MF);
- melamine-urea-formaldehyde polymers (UMF).
Polyurethanes are obtained by exothermic alcohol reactions with two or more reactive
hydroxyl groups (-OH) per molecule (diols, triols, polyols) and isocyanates. One of the
significant representatives of this group is poly-thiourea, which contains S in its structure.
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EcoTERS'20, 16-19 June 2020, Kladovo, Serbia
Depending on the characteristics of the catalyst, there are two different tipes of activation,
nucleophilic and electrophilic activation.
Polyesters are obtained by the condensation of multibasic acids and polyhydroxyl alcohols.
Condensation produces quality products only when the water is completely removed.
Thermostable silicones are made of linear silicone polymers, most commonly polydimethyl-
siloxane. Silicones with organic polymers contain a C-Si bond, and many silicones instead of
carbon contain a Si-Si bond, which is more unstable than a C-Si bond. Silicones can be
divided into four groups: silicone gels, silicone fluids, silicone elastomers and silicone resins.
The poor properties of thermostable polymers, such as low flexibility and low recyclability
and biodegradability, are being studied and eliminated, so the use of biodegradable,
thermostable plastics polymers is expected in the near future.
Keywords: Plastic, epoxy resins, formaldehyde and phenolic resins, silicones
ACKNOWLEDGEMENT
REFERENCES
[1] K. Urdl, A. Kandelbauer, W. Kern, et al., Prog. Org. Coat; (2017) 232–249.
[2] M.J. Mullins, D. Liu, H.-J. Sue; Chapter 2 - Mechanical properties of thermosets;
Thermosets (Second Edition) Structure, Properties, and Applications; (2018) 35–68.
[3] M.R. Vengatesan, A.M. Varghese, V. Mittal; Chapter 3 - Thermal properties of thermoset
polymers; Thermosets (Second Edition); Structure, Properties, and Applications; (2018)
69–114.
[4] F. Gamardella, X. Ramis, S. D. Flor, et al., React. Funct. Polym; 134 (2019) 174–182.
[5] P.A. Sreekumar, S. P. Thomas. J. Saiter, et al., Composites: Part A; (2009) 1777–1784.
[6] M. Skolik, A. Domanowska, P. Karasinski, et al., Mater. Lett; 251 (2019) 210–213.
302
Author Index
A J
Adamović, D. 237 Jelić, I. 275
Adedayo, A.V. 184, 189 Jovanović, M. 269
Alagić, S. 106, 111 Jovović, M. 255
Anđelković, D. 77, 136, 143, 148
Anđelković, T. 24, 30, 148 K
Antonijević, M. 42, 116, 203 Kalinović, J. 54, 60, 66
Avdagić, M. 281 Kalinović, T. 54, 60, 66
Kaluđerović, B. 171, 198
B Kocić, G. 24, 30, 77, 136, 143, 148
Baleta, J. 100 Kodranov, I. 72
Baležentienė, L. 292 Komadinić, V. 275
Belanović-Simić, S. 231 Košanin, M. 88
Beloica, J. 231 Kostić, B. 30
Bežanović, V. 237, 243 Kostić, I 24, 30, 148
Bigović, M. 82, 178 Kostić, M. 154, 165
Bjedov, I. 225, 231 Kovačević, R. 261
Bogdanović, D. 24, 30, 148 Krgović, R. 255
Bogojević, V. 88 Kričak, L. 36
Bojić, A. 154, 160, 165 Krivokapić, S. 82, 178
Bojić, D. 154, 160 Krstić, J. 5
Bošnjaković, J. 275
Branković, M. 77, 136, 143 L
Laković, D. 193
C Lazarević, K. 249
Cerinski, D. 100 Lazić, L. 100
Crnogorac, L. 17 Lučić, A. 94
Cupara, N. 82, 178, 193 Lutovac, S. 17
Cvetković, T. 30
Cvetković, V. 88 M
Majstorović, J. 17
Č Malešević, Z. 255
Čergić, S. 286 Manojlović, D. 72
Čokeša, Đ. 171,198 Marilović, D. 48
Čučulović, A. 11 Marković, M. 171, 198
Čučulović, R. 11 Medić, D. 209, 215
Čule, N. 94 Mihajlović, S. 221
Mikić, M. 261, 269
Ć Milašević, I. 178
Ćemer, S. 281 Miletić, Z. 94
Milić, S. 106, 111, 116, 209, 215, 301
D Milosavljević, J. 54, 60, 66
Dimitrijević, D. 5 Milošević, N. 301
Milovanović, D. 237, 243
Mitrović, J. 154, 160, 165
Đ Mitrović, S. 94
Đorđević, I. 209
Đorđević, N. 221 N
Đurović, D. 82, 178, 193 Najdanović, S. 160, 165
Negovanović, M. 36
G Nešić, M. 225, 231
Gajić-Kvaščev, M. 171 Nestorović, S. 11
Gligorić, M. 17 Nikolić, G. 30
Grkajac G. 88 Nikolić, I. 82, 193
Novaković, M. 237, 243
H Nujkić, M. 54, 106, 209, 215, 299
Husić, H. 286
304
O
Obratov-Petković, D. 225, 231 Veličković, J. 5
Velinov, N. 154, 160, 165
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Publisher: University of Belgrade, Technical Faculty in Bor

INTERNATIONAL Conference Ecological Truth & Environmental Research (28 ; 2020 ;

а) Животна средина -- Зборници б) Екологија -- Зборници

UNIVERSITY OF BELGRADE, TECHNICAL FACULTY IN

Co–organizers of the Conference:

University of Banja Luka, Faculty of Technology

University of Montenegro, Faculty of Metallurgy and Technology

University of Zagreb, Faculty of Metallurgy

University of Pristina, Faculty of Technical Sciences

Association of Young Researchers – Bor (Serbia)

The Ministry of Education, Science and Technological

Development of the Republic of Serbia

On behalf of the 28th EcoTER Organizing Committee,

Jelena Kalinović, S. Šerbula, T. Kalinović, J. Milosavljević, A. Radojević,

Darko Anđelković, M. Branković, G. Kocić

Marija Nešić, D. Obratov-Petković, I. Bjedov, D. Skočajić

Student: Damnjan Trifunović

Slavica Stevanović1*, Jovana Krstić1, Branka Stojanović1, Dušan Paunović1,

MATERIALS AND METHODS

RESULTS AND DISCUSSION

Ana Čučulović1*, Jelena Stanojković1, Rodoljub Čučulović2, Saša Nestorović3,

MATERIALS AND METHODS

D (nGyh-1) = 0.462ARa+0.604ATh+0.042AK (2)

H (mSv) = D×0.7×0.2×8760 (3)

RESULTS AND DISCUSSION

Suzana Lutovac1, Miloš Gligorić1*, Jelena Majstorović1, Luka Crnogorac1

ROCK MASS OSCILLATION EQUATION

– velocity of rock mass oscillation cm/s,

MODELS OF DETERMINING THE PARAMETERS OF EQUATION OF ROCK

According to Simpson’s formula (2) we have:

from Equation (10) we find:

For Equation (1) is reduced to:

DEFINING STATISTICAL CRITERIA

Method of blasting in Majdanpek open pit

CALCULATION FOR PARAMETERS OF ROCK MASS OSCILLATION

Table 1 Review of blasting parameters and measurement results

Oscillation velocities, v(cm/s) 2.0

1.4 v1 = 146.7047 R-1.8326

Tatjana Anđelković1, Danica Bogdanović1*, Ivana Kostić1, Gordana Kocić2

MATERIALS AND METHODS

RESULTS AND DISCUSSION

Comparison of influence of temperature and ultrasound on the migration of DEHP

increasedtemperature, as well as by influence of temperature assisted with ultrasound

Tatjana Anđelković1, Danica Bogdanović1*, Ivana Kostić1, Goran Nikolić2,

MATERIALS AND METHODS

RESULTS AND DISCUSSION

Characterization of FTIR spectra of P-free PVC sample

Figure 3 The FTIR spectrum of dialysis bag without phthalates

Determination of dissolved phthalates in methanol-THF supernatant

Table 1 Mass % of phthalates of PVC sample

Qualitative comparison of obtained polymer films

Milanka Negovanović1*, Lazar Kričak1

REDUCTION OF DRILLING DUST

– wet suppression system or,

DRY DUST COLLECTION SYSTEMS

Table 1 Technical specification of ILMEG hydraulic dust collectors [7]

Dust collection system used for small– to medium–diameter drill rigs

Dust collection system on surface crawler drill rig FlexiROC T35