EURASIAN JOURNAL OF SOIL SCIENCE
(Published by Federation of Eurasian Soil Science Societies)
EDITORS-IN-CHIEF
Dr.Rıdvan KIZILKAYA
Ondokuz Mayıs University, Turkey
Dr.Ayten NAMLI
Ankara University, Turkey
Dr.Coşkun GÜLSER
Ondokuz Mayıs University, Turkey
EDITORIAL BOARD
DIVISION EDITORS
Dr.Fariz MIKAILSOY, Turkey
Dr.Hasan S.ÖZTÜRK, Soil Physics, Turkey
Dr.Sergei SHOBA, Russia
Dr.Rıfat DERİCİ, Soil Chemistry, Turkey
Dr.Evgeny SHEIN, Russia
Dr.Nur OKUR, Soil Biology & Biochemistry, Turkey
Dr.Abdulla SAPAROV, Kazakhstan
Dr.Günay ERPUL, Soil Erosion & Conservation, Turkey
Dr.Olga EROKHINA, Kazakhstan
Dr.Selim KAPUR, Soil Mineralogy & Micromorphology, Turkey
Dr.Konstantin PACHIKIN, Kazakhstan
Dr.Abdullah BARAN, Soil Mechanic & Technology, Turkey
Dr.Pavel KRASILNIKOV, Russia
Dr.Suat ŞENOL, Soil Genesis, Classification & Mapping, Turkey
Dr.Mikhail MAZIROV, Russia
Dr.Tayfun AŞKIN, Soil Pollution, Turkey
Dr.Garib MAMMADOV, Azerbaijan
Dr.Hikmet GÜNAL, Soil Health & Quality, Turkey
Dr.Galina STULINA, Uzbekistan
Dr.Hayriye İBRİKCİ, Soil Fertility, Turkey
Dr.Iraida SAMOFALOVA, Russia
Dr.Sait GEZGİN, Plant Nutrition & Fertilization, Turkey
Dr.Sara MAMMADOVA, Azerbaijan
Dr.Kadir SALTALI, Soil Salinity & Alkalinity, Turkey
Dr.Maharram BABAYEV, Azerbaijan
Dr.Yusuf KURUCU, Remote Sensing, Turkey
Dr.Velibor SPALEVIC, Montenegro
Dr.İlhami BAYRAMİN, Geography Information System, Turkey
Dr.Ilgiz KHABIROV, Russia
Dr.Taşkın ÖZTAŞ, Geostatistics, Turkey
Dr.Tatiana MINKINA, Russia
Dr.Gönül AYDIN, Soil Management & Reclamation, Turkey
Dr.Svetlana SUSHKOVA, Russia
Dr.Alhan SARIYEV, Modelling, Turkey
ADVISORY EDITORIAL BOARD
SCIENTIFIC EDITORS
Dr.Nicola SENESI, Italy
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Dr.Donald GABRIELS, Belgium
Dr.Mustafa BOLCA, Turkey
Dr.Mehmet AYDIN, Turkey
Dr.Metin TURAN, Turkey
Dr.İsmail ÇAKMAK, South Korea
Dr.Mehmet ÖGÜT, Turkey
Dr.Ajit VARMA, India
Dr.Refik UYANÖZ, Turkey
Dr.Yakov PACHEPSKY, USA
Dr.Salih AYDEMİR, Turkey
Dr.Jae YANG, South Korea
Dr.Yasemin KAVDIR, Turkey
Dr.David MULLA, USA
Dr.Tubukhanım GASIMZADE, Azerbaijan
Dr.Léon-Etienne PARENT, Canada
Dr.Amin BABAYEV, Azerbaijan
Dr.Amin ISMAYILOV, Azerbaijan
Dr.Svatopluk MATULA, Czech Republic
LINGUISTIC EDITOR
Oksana FOTINA, Russia
AIMS AND SCOPE
Eurasian Journal of Soil Science is a forum for presenting articles on basic and applied research of soil
science, thus making new findings, methods and techniques easily accessible and applicable in practice. It
publishes original papers on research in soil science. Invited reviews on popular topics are published. Articles
are published in English.
ISSN: 2147-4249
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
293
Anthropoghenic soil contamination connected with active
mines, smelting and plants in the Republic of Macedonia
Todor Serafimovski *, Goran Tasev, Violeta Stefanova
Goce Delcev University, Faculty of Natural and Technical Sciences, Stip, Macedonia
Abstract
Article Info
Received : 18.07.2014
Accepted : 17.10.2014
A few anthropogenic pollutants at the territory of the Republic of Macedonia, were studied, three
Pb-Zn mines with three mills, one copper mine with mill and copper leaching facility, one Pb-Zn
smelting and several mines and factories for raw minerals such is the Usje in our capital Skopje.
At the Usje factory were measured values in ranges of 1.46÷2.23% Fe, 440÷940 mg kg
-1
Mn,
93.4÷104.71mg kg
-1
Ni, 58.57÷83.1 mg kg
-1
Zn, 23.1÷34.9 mgkg
-1
Pb, 42.30÷60.3 mg kg
-1
Cu and
0.59÷1.61 mgkg
-1
Cd. The concentrations of heavy metals at Veles former smelting Pb-Zn plant
were in the range: 20÷1823 mg kg
-1
Pb, 29÷2395 mg kg
-1
Zn, 28÷65 mgkg
-1
Cd, 27÷81 mg kg
-1
Cu,
39÷164 mg kg
-1
Ni, 508÷938 mgkg
-1
Mn and 1.6÷3.8% Fe, all of them above reference values.
Around the Feni smelting plant concentrations of particular pollution elements were in the
range: 16÷31 mg kg
-1
Pb, 117÷286 mgkg
-1
Zn, 13÷30 mg kg
-1
Co, 43÷119 mg kg
-1
Cu, 158÷292 mg
kg
-1
Ni, 519÷903 mgkg
-1
Mn, 119÷236 mg kg
-1
Cr and 2.24÷3.79% Fe. At the ToranicaPb-Zn mine
all the measured values multiplexed above the standard values. Enrichment factors ranged from,
low 3.75 for nickel up to 362.5 for zinc and extreme 1587.5 for lead. The Zletovo Pb-Zn mine has
been characterized by all the measured values multiplexed above the standard values with an
exception of nickel. Enrichment factors ranged from mediate ones such were those for copper of
20.8, cadmium of 28.7, arsenic of 32.5 up to high ones for zinc with 341.7 and lead 925. In
regards to SasaPb-Zn mine all the measured values multiplexed above the standard values with
an exception of nickel. Enrichment factors ranged from low for manganese of 12.14 and arsenic
of 15.72, median for copper of 59.15, high for cadmium of 126 and extremely high for zinc with
892.7 and lead 1201.9. In regards to the Bucim copper mine the median values for Cu in samples
were 396 mg kg
-1
and the ranges from 94.8 to 1171 mg kg
-1
, for the Topolnica village the median
values in samples were 150 mg kg
-1
with ranges from 52.5 to 1183 mg kg
-1
and for the Bučim
village the median values were 145 mg kg
-1
and the ranges from 85.3 to 317 mg kg
-1
.
Keywords: heavy metals, contamination, mines, anthropogenic, R. Macedonia
© 2014 Federation of Eurasian Soil Science Societies. All rights reserved
Introduction
The aim of this study was to quantify the chemistry of soil in the important mining and mine products
processing areas in order to assess the environmental impacts of current and past mining activities (Figure
1). As major polluted localities, confirmed even with our latest results, are the areas around the open pit and
cement plant Usje located in the urban part of the capital Skopje, former Pb-Zn smelting plant located at the
Veles city limits, active ferro-nickel plant located in the well known wine region of Kavadarci, active lead and
zinc mines with their respective tailing dams in Eastern Macedonia (Toranica, Sasa and Zletovo) and active
open pit of the Buchim copper mine with large waste dump and tailing dam.
Preventative measures are a must where mine and mine related plant are processing and produce significant
environmental influx, so understanding the environmental impact of these processes is crucial. Metal mining
*
Corresponding author.
Goce Delcev University, Faculty of Natural and Technical Sciences, 2000 Stip, Macedonia
Tel.: +389325505752 E-mail address:
todor.serafimovski@ugd.edu.mk
ISSN: 2147-4249
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
294
has traditionally been an important part of the economy of the Republic of Macedonia and recently increased
in importance due to governmental efforts to stimulate mining through renewed exploration and
development, though the country relies on its agriculture and must safeguard its soil and water resources.
Pollution from current and past mine and mine related processing represents a significant problem in
several parts of the Republic of Macedonia. This problem continuously is solved at active mines and mine
related processing plants while the solution of this particular problem is harder to solve at mines or plants
with ceased production such is the Veles former Pb-Zn smelting plant. This paper presents the latest findings
related to soil pollution at all above mentioned localities followed by respective interpretation.
Material and Methods
Sampling was carried out over a prolonged period of time (2005-2014). Soil surface samples (0 cm to 5 cm
depth) were collected from several localities pointed earlier as potential so-called “hot spots” in regards to
heavy metal pollution (Figure 1). Samples were located using the Global Positioning System (GPS),
topographic maps at scale of 1:25 000 and Google Earth maps (http://earth.google.com/). Each sample
represented the composite material collected at the central sampling point itself together with at least four
points collected around a central one with а radius of 1 m towards N, E, S and W directions.
The composite material of each sample
(about 0.5 kg) was placed into plastic self-
closing bags and brought to the Faculty of
Natural and Technical Sciences, University
“Goce Delcev” Stip, Republic of Macedonia,
where they were prepared for atomic
spectroscopy. All of the collected soil samples
(at Toranica we were forced to sample
sediments due to morphology of nature)
were then shipped to the Institute of
Chemistry at the Faculty of Natural Sciences,
University “Sts.Cyril and Methodius” Skopje,
R. Macedonia. Analyses were conducted using
emission spectrometry with inductively
coupled plasma (ICP-AES) after Aqua Regia
Digestion. All samples as well as geological
standards were submitted to the laboratory
in a random order. This procedure assured an
unbiased treatment of samples and a random
distribution of the possible drift of analytical
conditions for all samples and the precision
was less than 5%.
Figure 1. Studied locations of anthopoghene pollution
1. Usje cement plant, Skopje; 2. Former Pb-Zn smelting plant,
Veles; 3. FENI smelting plant, Kavadarci; 4. Toranica Pb-Zn mine,
Kriva Palanka; 5. Zletovo Pb-Zn mine, Probistip; 6. Sasa Pb-Zn
mine, M. Kamenica; 7. Buchim Cu mine, Radovis
Results and Discussion
The Usje cement plant: The major inhabited area within the Skopje basin is the capital of the Republic of
Macedonia, Skopje. The limits of soil pollution in Macedonian capital are still to be determined. As in every
large populated conglomerate in the World the pollution sources to soil are numerous and diverse. However,
we have limited our research to an area adjacent to the cement producing plant Usje located on the
southeastern limit of the city. The environmental awareness arise recently since in the close vicinity of the
plant witnessed progressive residential area building (
Serafimovski et al., 2011a
). In the direction of giving
an initial clue about the contamination of soils around the aforementioned plant we have performed
sampling along two parallel profiles and one profile perpendicular to the parallel ones. The total of 15
specimens were sampled and analyzed. Measured values were in ranges of 1.46÷2.23% Fe, 440÷940 mg kg
-
1
Mn, 93.4÷104.71mg kg
-1
Ni, 58.57÷83.1mg•kg
-1
Zn, 23.1÷34.9 mg•kg
-1
Pb, 42.30÷60.3 mg•kg
-1
Cu and
0.59÷1.61 mg kg
-1
Cd. Also, the calculated enrichment ratio (measured values over the reference value) spe-
aks itself regarding the level of contamination. Calculated enrichment ratios ranged from relatively low 0.98
for Fe, 1.4865 for Zn, 1.89 for Mn and 1.8975 for Pb, through 3.016 for Cu up to higher 5.92 for Cd and
7.5098 for Ni. Obtained results served as a basis for plots construction of particular heavy metals vs. their
maximally allowed concentrations in soils (Figure 2). All the elements in all analyzed samples have shown
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
295
increased values compared to the respective standard values. It was noticeable that the concentration of
most of the heavy metals was the highest in samples taken from the closest vicinity of the Usje plant.
a)
b)
c)
d)
Figure 2. Measured concentrations of some heavy metals vs. standard values around the Usje cement production plant
on the city limits of Skopje, Macedonia
a) Nickel; b) Cadmium; c) Copper and d) Lead
Bearing in mind sound geochemical and geological logic, the increased values should be attributed to the
geological composition of the background as well as to the plant’s production process and organic fertilizers
used in arable areas around the plant.
The Veles smelting plant: This plant was the largest capacity for lead and zinc in former Yugoslavia with
the capacity for producing 65 000 tons of zinc and 45 000 tons of lead per year whereas the entire
production was exported. The anthoprogenic impact in that particular part of the Veles basin has been
studied at two regions around the former Pb-Zn smelting plant near Veles, performed during the 2008. In
fact the study was concentrated on two separate areas, one of them around the Bashino Selo, a village to the
north of the smelting plant and area to south of the smelting plant located close to the city limits. Within the
first area were sampled two parallel profile lines and one profile line normal to them while at the second
area were sampled only two parallel lines. The samples were taken at distances of 30 meters between each
other (Figure 3).
The concentrations of these particular elements were in the range as follows: 20÷1823 mg·kg
-1
Pb, 29÷2395
mg·kg
-1
Zn, 28÷65 mg·kg
-1
Cd, 27÷81 mg·kg
-1
Cu, 39÷164 mg·kg
-1
Ni, 508÷938 mg·kg
-1
Mn and 1.6÷3.8% Fe.
All of them were significantly above the reference values. Also, the calculated enrichment ratio (measured
values over the reference value) speaks itself regarding the level of contamination. Namely, the enrichment
ratios ranged from relatively low 1.67 for Fe, 2.41 for Mn and 3.27 for Cu, through the medium 8.33 for Ni
and 29.95 for Zn up to high 64.05 for Pb and the highest 237.67 for Cd.
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
296
These results and findings perfectly matched those
by other researchers that very same year (
Stafilov
et al., 2008a
). The group that comprises of Cd, Pb
and Zn, as chemical elements that have been
introduced into the environment through the
anthropogenic activities (
Stafilov et al., 2010
), have
shown the highest values in sampled and analyzed
soils around the Veles smelting plant.
That was expected even at the beginning of the
study, but tremendously high values exceeded
expectations. These findings are given very
illustratively on the plots at Figure 4. Also, after
detailed study it was determined that values from
respective sampling points were spatially
dependent. Namely, as can be seen from the plots
and sampling location map, the lowest values were
determined at topographically higher places than
those for lower ones. Ones again this makes clear
the correlation between the pollution and smoke
dust produced by the activity of former smelting
plant in Veles.
Figure 3. Spatial distribution of profile lines and sampling
points along them
a)
b)
c)
d)
Figure 4. Measured concentrations of some heavy metals vs. standard values around the former MHKZletovo’s
smelting plant near the city of Veles, Macedonia
a) Lead; b) Zinc; c) Cadmium and d) Nickel (Note: Plots a, band chave logarithmic vertical scale)
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
297
Also, after detailed study it was determined that values from respective sampling points were spatially
dependent. Namely, as can be seen from the plots and sampling location map, the lowest values were
determined at topographically higher places than those for lower ones. Ones again this makes clear the
correlation between the pollution and smoke dust produced by the activity of former smelting plant in Veles.
The FENI smelting plant: The supposed major source of anthropogenic environmental impact within this
basin is the FENI Industries’s smelting plant. The environmental concern has been intensified by the fact that
the smelting facility is accommodated in the hearth of the well-known wine producing Tikveš region where
remains of old civilizations point out to a wine producing even at 4
th
century BC. The FENI Industries’s nickel
ore, the one that goes into the smelting process, is a mixture of the lower grade ore from the Rzanovo Mine
and ores imported from Indonesia, Philipines, Greece, Turkey and Albania. In general the FENI Industries’s
plant is a two-line, rotary kiln electric furnace facility with the biggest rectangular electric furnaces of their
kind in the world. The plant has been in operation since 1982 and produced approximately 5 000 t of nickel
metal annually. Since it has been acquired by Cunico Resources in 2005 it steadily increased the production
to 16 000 tonnes per year, while with planned refurbishments and improvements it will reach an annual
production of up to 22 000 tons eventually. Bearing in mind these facts we have proceeded with a soil
sampling programme around the FENI Industries facility at two separate localities, one on the northwest of
the smelting plant and the other one on the south-southeast in regards to the position of the smelting plant.
In both cases the samples were sampled
along two parallel profiles and one
perpendicular to them (Figure 5). The
samples were analyzed to a standard array of
elements: Pb, Zn, Cu, Ni, Fe, Cr, Co and Mn, in
general characterized as heavy metals. The
concentrations of these particular elements
were in the range as follows: 16÷31 mg·kg
-
1
Pb, 117÷286 mg·kg
-1
Zn, 13÷30 mg·kg
-1
Co,
43÷119 mg·kg
-1
Cu, 158÷292 mg·kg
-1
Ni,
519÷903 mg·kg
-1
Mn, 119÷236 mg·kg
-1
Cr and
2.24÷3.79% Fe. All of them were significantly
above the reference values (Figure 6). Also,
the calculated enrichment ratio (measured
values over the reference value) speaks itself
regarding the level of contamination. Namely,
the enrichment ratios ranged from relatively
low 1.873 for Fe, 2.188 for Mn and 3.801 for
Cu, through the medium 16.987 for Ni and
3.225 for Zn up to high 1.471 for Pb and the
highest 2.823 for Co and 5.0124 for Cr.
Figure 5. Sampling locations around the FENI Industries smelting
plant, small inset at the right upper corner gives the satellite
position of the area.
a)
b)
Figure 6. Measured concentrations of some heavy metals vs. standard values around the Feni-industries’s smelting
plant near the city of Kavadarci, Macedonia
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
298
These concentrations are increased without any doubts, but bearing in mind the findings of
Stafilov et al.,
(2008b, 2010)
, they probably cannot be attributed solely to the anthropogenic input. Namely, even
background values of the heavy metals, especially of those for Ni, Cu, Co, Sb, Zn etc. It is probable that the
FENI Industry plant, oposite to the obvious environmental impact has not contributed enormously to the
measured heavy metals, since their background values were already at naturally higher levels (
Stafilov et al.,
2008b, 2010; Serafimovski et al., 2011a
). Our believes are that the situation will not change much since the
current operator and owner the Cunico Resources is committed to upholding environmental laws, which
dedication have resulted in a recent IPCC (Integrated Pollution Prevention and Control) permit that was
granted on among the first in Macedonia.
The Toranica mine area: Concerning the environmental impact of this mine, we have started our studies
with analysis of airborne dust produced during the processes of crushing and grinding of ore (
Walton et al.,
2003a; Serafimovski et al., 2011b
). During this operation was released significant amount of dust, which may
pose serious threats to the environment. Analyzes have shown that heavy metal concentrations in the dust
are as those given in Table 1, where can be seen that all the measured values multiplexed above the standard
values. Enrichment factors ranged from relatively low 3.75 for nickel up to 362.5 for zinc and extreme
1587.5 for lead. Such high levels of concentration of heavy metals introduced by deposition from airborne
dust and potential dispersion by wind activity pose very serious threat to the adjacent environment.
Table 1. Analytical data of major heavy metal pollutants in the airborne dust around the crushing and grinding facility
at Toranica mine, Macedonia (in mg kg
-1
)
Metal
Measured
concetrations
Standard
(NOAA)
Arsenic
69.5
5.2
Cadmium
118
3
Copper
681
17
Nickel
48.7
13
Lead
25400
16
Zinc
17400
48
In the vicinity of the Toranica mine was not possible to take soil samples due to fact that the mine has been
located in mountanious area (1400-1800 m) with steep canyon of the Toranicka Reka, so we have decided to
sample stream sediments instead of soils (Table 2). Their analysis reflects the situation with environmental
pollution as a direct consequence of the mine processing although on part of the metals have been deposited
by water courses. The contamination from the Toranica mine and its operations is visible not only at the
downstream end of the tailings disposal area, but also several kilometers downstream. All the metals are
showing increased concentrations in the sediment samples taken from the vicinity of the Toranica Mine
area. After inensive result analysis there were constucted a lot of plots, comparing actual metal values
certain standard values.
Table 2. Concentrations of metals in sediment samples from adits and streams in the Toranica mine area
n
Median
Range
Dutch list
standard optimal
Dutch list
standard action
above
standard
below
standard
min
max
Fe (%)
11 3,86
1,41
7,9
1,8
-
10
1
Zn(mg kg
-1
)
11 8100
600
134700
140
720
11
0
Pb (mg kg
-1
)
11 14100
310
44500
85
530
11
0
Cu (mg kg
-1
)
11 802,3
68,22 7434,6
36
190
11
0
Cd (mg kg
-1
)
11 69,81
5,98
1026,8
0,8
12
11
0
Co (mg kg
-1
)
11 19,81
4,99
47,76
9
240
8
3
Ni (mg kg
-1
)
11 43,51
23,06 81,28
35
210
8
3
Ag (mg kg
-1
)
11 11,73
0,15
58,14
0,5
15
4
7
As (mg kg
-1
)
11 66,1
4,13
214,9
29
55
9
2
Cr (mg kg
-1
)
11 43,98
22,92 56,47
100
380
0
11
Sample of those increased values of Pb and Zn against standard values is given at Figure 7 and 8. Increase of
measured values is especially intense in the area of taillings dam (TS10, TS11, TS12). Deposition of metals in
tailling took place during the long period of time and that is why the metal concentrations in sediments are
very high there.
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
299
Figure 7. Diagram of lead distribution in the soil
compared with optimal and action values
Figure 8. Diagram of zinc distribution in the soil
compared with optimal and action values
The Zletovo Pb-Zn Deposit: Study of environmental impact of the Zletovo mine was in the same manner as
for the previous Toranica mine. We have started with study of airborne dust produced during the processes
of primary crushing of ore, since during this operation is released significant amount of dust, which pose se-
rious threats to the environment (
Walton et al., 2003b; Serafimovski et al., 2011b; Tasev and Serafimovski,
2011
). Analyzes displaying heavy metal concentrations in the dust are given in Table 3.
Table 3. Analytical data of major heavy metal pollutants in the airborne dust around the primary crushing facility at
Zletovo mine, Macedonia (in mg kg
-1
)
Metal
Measured concentrations
Standard (NOAA)
Arsenic
169
5,2
Cadmium
86
3
Copper
354
17
Nickel
10
13
Lead
14800
16
Zinc
16400
48
As can be seen from the table above all the measured values multiplexed above the standard values with an
exception of nickel. Enrichment factors ranged from mediate ones such were those for copper of 20.8,
cadmium of 28.7, arsenic of 32.5 up to high ones for zinc with 341.7 and lead 925. Such high levels of
concentration of heavy metals introduced by deposition from airborne dust and potential dispersion by
wind activity, pose very serious threat to the adjacent environment.
Soil sampling around the Zletovo mine have been performed by numerous researchers but without any
systematics and due to such fact it was very hard to prepare one complete analysis, which would reflect real
situation regarding soil pollution. In this occasion we have decided to use the results of soil analysis around
the Pisica village in the heart of Zletovo mine area (
Sijakova-Ivanova and Paneva-Zajkova, 2005
) that reflect
more realistic situation at that part of the area. The results are given statistically in Table 4, while its
interpretation is illustrated at plots on the Figure 9 and 10).
Table 4. Values of macroelements and micro elements in the soils of Pisica.
n
Median
Range
Dutch standard
optimal
Dutch standard
action
above
standard
below
standard
min
max
Fe (%)
12 4,21
3,87
5,11
1,8
-
12
0
Ni (mg kg
-1
)
12 19,5
16,18
22,64
35
210
0
12
Cr (mg kg
-1
)
12 26,01
22,63
29,08
100
380
0
12
Zn (mg kg
-1
)
12 538,55 134,7
1649,7
140
720
11
1
Cu (mg kg
-1
)
12 55,03
31,97
133,49
36
190
8
4
Pb (mg kg
-1
)
12 431,81 102,26
1164,8
85
530
12
0
Cd (mg kg
-1
)
12 7,88
6,44
14,51
0,8
12
12
0
Co (mg kg
-1
)
12 17,055 14,91
18,59
9
240
12
0
As (mg kg
-1
)
12 16,545 1,93
66,1
29
55
5
7
Ag mg kg
-1
)
12 0,947
0,04
3,33
0,5
15
8
4
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
300
Figure 9. Diagram of lead distribution in the soil
compared with optimal and action values
Figure 10. Diagram of zinc distribution in the soil
compared with optimal and action values
Data correlation analysis found especially high correlation coefficients between certain elemental pairs: Pb-
Zn 0.9869, Pb-Cd 0.9851, Pb-Cu 0.9621, Pb-Ag 0.9357, Pb-As 0.9224, Zn-Cd 0.9834, Zn-Ag 0.9220, Cu-As
0.9669, Cu-Cd 0.9466, Cu-Ag 0.9272, Ag-Cd 0.9480 etc.
The Sasa Pb-Zn Deposit: The last but not least important in the series of study of lead-zinc mines was the
Sasa mine. Study of its environmental impact was in the same manner as for the previous Toranica and
Zletovo mines. First of all we started with the study of airborne dust produced during the processes of
primary and secondary crushing of ore, since during these operationsare released significant amounts of
dust, which can lead to serious threats to the environment (
Walton et al., 2003c; Serafimovski et al., 2011b
).
Analyzes of heavy metal concentrations in the dust are given in Table 5. As can be seen from the table all the
measured values multiplexed above the standard values with an exception of nickel. Enrichment factors
ranged from low ones such were those manganese of 12.14 and arsenic of 15.72, median for copper of 59.15,
high for cadmium of 126 and extremely high for zinc with 892.7 and lead 1201.9.
Table 5. Analytical data of major heavy metal pollutants in the airborne dust around the primary crushing facility at
Sasa mine, Macedonia (in mg kg
-1
)
Metal
Measur.conc.
Primary crushing
Measur.conc.
Secondary crushing
Standard
(NOAA)
Arsenic
68.3
95.2
5,2
Cadmium
160
596
3
Copper
811
1200
17
Manganese
3750
4260
330
Lead
30900
7560
16
Zinc
18400
67300
48
Increased concentration of heavy metals introduced by deposition from airborne dust and potential
dispersion by wind activity, without any doubts poses very serious threat to the adjacent environment, being
compatible with findings of
Alderton et al. (2005).
The Buchim Cu Deposit: The only one active copper mine within the Macedonia joined the lead-zinc mines
in our study of their environmental impact. We have followed the sampling and analysis programme as for
lead-zinc mines. Considering airborne dust pollution we would like to stress out that the study on this
subject already exists (
Balabanova et al., 2011a, 2011b
), so we used it as representative one. Also,
interesting copper and other elements anomalies in soils, in the Buchim mine vicinity, were given by
Stojanovska (2005)
and
Serafimovski et al. (2011b).
The results are displayed in Table 6, while the
distribution of major pollutants Cu and As are displayed at Figure 11 and 12.
From the copper plot can be seen that in all the samples it was above optimal reference values and majority
of them were above the action reference values, too. The arsenic have several samples with concentration
above optimal reference values and none above the action reference value.
T. Serafimovski et al. / Eurasian Journal of Soil Science 3 (2014) 293 - 302
301
Table 6. Values of macroelements and micro elements in the soils of the Buchim mine vicinity.
n
Median
Range
Dutch Standard
optimal
Dutch standard
action
Above
standard
Below standard
min
max
Al (%)
16 2,03
1,51
2,92
4,7
-
0
16
Fe (%)
16 3,67
2,43
5,26
1,8
-
16
0
Cu (mg kg
-1
)
16 165,19 35
4248
36
190
15
1
Ni (mg kg
-1
)
16 40,67
15,28
360,42
35
210
8
8
Cr (mg kg
-1
)
16 57,54
28,6
203,25
100
380
2
14
Zn (mg kg
-1
)
16 74,82
40,64
261,41
140
720
1
15
Pb (mg kg
-1
)
16 23,46
8,71
151,73
85
530
3
13
Co (mg kg
-1
)
16 17,08
10,24
41,82
9
240
16
0
Cd (mg kg
-1
)
16 5,01
3,15
7,08
0,8
12
16
0
V (mg kg
-1
)
16 56
38
88
42
250
15
1
As (mg kg
-1
)
16 10,66
0,7
51,92
29
55
4
12
Ag (mg kg
-1
)
16 0,405
0,16
1,01
0,5
15
4
12
Figure 11. Diagram of copper distribution in the soil
compared with optimal and action values
Figure 12. Diagram of arsenic distribution in the soil
compared with optimal and action values
Conclusion
The results of this study have shown that at all the localities are characterize by increased values of pollutant
heavy metals in soil, which can be attributed to the anthropoghenic influx around the aforementioned mines
and mine related processing facilities. Pollution halo diameter around them sometimes reaches over 20 km,
especially in stream sediments along active water flows (ex. Toranica and Sasa). Along common pollutants
(Pb, Zn, Cd) at lead-zinc and Veles smelting were determined increased concentrations of As, Ag, W, Ni, Co
etc., while around the FENI smelting along to Fe and Ni were determined increased values of Cr, V, Co, Mn
etc.
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