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Journal of Environmental Management 180 (2016) 450e458

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Journal of Environmental Management


journal homepage: www.elsevier.com/locate/jenvman

Research article

Assessment of the risk of pollution by sulfur compounds and heavy


metals in soils located in the proximity of a disused for 20 years sulfur
mine (SE Poland)
Katarzyna Soek-Podwika a, *, Krystyna Ciarkowska a, **, Dorota Kaleta b
a
b

Soil Science and Soil Protection Department, University of Agriculture in Krakow, Aleja Mickiewicza 21, 31-120 Krakow, Poland
Department of Air Protection, Silesian University of Technology in Gliwice, ul. Konarskiego 22B, 44-100 Gliwice, Poland

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 15 July 2015
Received in revised form
22 May 2016
Accepted 28 May 2016
Available online 4 June 2016

The study assessed the long-term effects of anthropogenic pressure of the sulfur industry on turf-covered
w. The study assumes that 20 years which elapsed
soils located in the vicinity of the sulfur mine Grzybo
since the end of the exploitation of sulfur is a period sufciently long for the content of sulfur compounds
in soils not to exceed the permissible level and that soil of the region can be classied as not contaminated. A part of the study involved identication of changes in the contents Stot. and SeSO2
4 in soils
collected in the 1970s and early twenty-rst century. It was also traced the relationship between the
content of sulfur compounds and selected soil properties and estimated risk of soil environment
pollution by heavy metals. Mean contents of trace elements studied amounted to 10.2e10.8 mg kg1 for
Pb, 14.3e39.4 mg kg1 for Zn, 0.2e0.4 mg kg1 for Cd, 3.8e32.2 mg kg1 for Cr, 2.7e15.1 mg kg1 for Cu
and 2.9e18.7 mg kg1 for Ni. Based on the results of SeSO2
4 content in soils collected at a distance of
1 km from the mine, it was found out that despite the passage of years, the amount of this type of sulfur
still is increased and exceeds 0.14 g kg1. As the distance from the mine grew lower (from 0.017 to
0.03 g kg1) average content of the sulfur form was observed. In the studied soil material we found
generally positive, strong correlation between the Stot. and SeSO2
4 content and analyzed trace elements.
The degree of contamination of examined soils with heavy metals was estimated on the basis of the
integrated pollution index, which pointed to a moderate and low level of antropogenization of this area.
In addition, the relationship between the determined characteristics of soils (Corg. contents, the fraction
<0.002 mm and pH) and heavy metals conrms that the trace elements present in soils do not occur in
mobile forms in the soil solution.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Sulfur mine
Contamination
Heavy metals
Soil
Poland

1. Introduction
Until recently, the sulfur content in the soil was outside the area
of environmental research since its substantial inow came from
the atmosphere. Especially in industrial areas with an increasing
number of anthropogenic sources, the issues connected with sulfur
were examined for several years in terms of the excess of this
element (Lefohn et al., 1999; Stern, 2005). However, over the last
quarter of the century the situation has changed dramatically.
There has been an evidently smaller supply of S to the atmospheric

* Corresponding author.
** Corresponding author.
E-mail addresses: rrpodwik@cyf-kr.edu.pl (K. Soek-Podwika), rrciarko@cyf-kr.
edu.pl (K. Ciarkowska).
http://dx.doi.org/10.1016/j.jenvman.2016.05.074
0301-4797/ 2016 Elsevier Ltd. All rights reserved.

air and hence also its lower deposition in the soil. The main reason
was the reduction of emissions of sulfur compounds due to broadly
dened environmental measures aimed at reducing industrial
emissions. In Europe both sulfur dioxide emissions and sulfur
deposition gradually decreased from over 100 kg of S ha1$year1
in the 1970s to less than 20 kg of S ha1 year1 in 1995 and less
than 10 kg of S ha1 year1 at the beginning of the 21st century
(Riley et al., 2000; McGrath et al., 2003; Hu et al., 2005; CSO, 2014).
A similar situation occurred in Poland, where over the years
decreasing sulfur dioxide emissions of approx. 4 million Mg in the
70s of the twentieth century to approx. 1.5 million Mg in the early
twenty-rst century were observed. At the same time deposition of
sulfur decreased, from 70 kg S ha1 year1 in the 80s to
50 kg S ha1 year1 in the 90s. At the beginning of the twenty-rst
century, the largest sulfur deposition occurred in areas heavily

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458

industrialized and was over 30 kg S ha1 year1, while in areas


remote from industrial plants it was low, less than 10 kg S
ha1 year1 (CSO, 1991e2008).
Today, there are more and more areas which are decient in this
element because of the increased use of fertilizers with lower S
content, smaller amounts of natural fertilizers, especially manure,
used in agricultural production, as well as reduced use of fungicides
and pesticides (Scherer, 2001; Eriksen et al., 2004). The evaluation
of sulfur abundance in soils, sulfur supply in plants and the threat of
its excess in agro-ecosystems involves mainly its sulfate form
(Kabata-Pendias and Pendias, 1992; Kowalenko et al., 2014). In
Poland there are areas with distinct deciency or excess of sulfur in
the environment of crop plants. The spatial differences result
mainly from the impact of local sources of emissions of sulfur
compounds. A region of certain particularity in Poland is the area of
exploitation of sulfur deposits in Tarnobrzeg (Bryk and Koodziej,
2009). The years 1966e1976 were characterized by dynamic
development of borehole sulfur mining. During this period there
was a strong focus on growth in sulfur exploitation, while less
attention was paid to the requirements of environmental protecw was the rst mine in Polish conditions in
tion. The mine in Grzybo
which sulfur extraction was carried out by means of a new technology, namely the method invented by Herman Frasch (patented
w
in USA in 1894). The negative impact of the sulfur mine in Grzybo
was associated not only with mining works and production processes, but also with transport. The impact was multidirectional
and very difcult to predict at the time. The mining operations
frequently led to contamination of soil and water with elemental
sulfur as a result of spontaneous eruptions. Also the air was
contaminated as a result of emissions of hydrogen sulde and
sulfur dust from open sulfur deposits. The negative impact of the
mine was not only limited to the mining elds but also occurred
_ z-Hara,
_
outside their borders (Drozd
1978).
Negative effects of anthropogenic soil sulfating include the
increment of sulfates content (SO2
4 - ions are anhydride of H2SO4)
and soil acidication. A strong acidication of soils goes along with
lowering availability of nutrients, increasing solubility of
aluminium and manganese compounds and leaching of basic
components. There is also a change in the quantitative and qualitative composition of soil microorganisms, which causes disruption
of the natural cycle of elements (e.g carbon and nitrogen). These
changes lead to the destruction of aggregate structure and soil
crusting with salts or iron hydroxides eforescence formed on the
surface. In degraded soils the deterioration of water and air rela_ z-Hara,
_
tionship also occur (Drozd
1978; Scherer, 2009).
In Poland soils contaminated with heavy metals occur only
locally, mainly in the highly industrialized areas. In the light of the
studies carried out on a large scale by the Institute of Soil Science
and Plant Cultivation, heavy metals contaminated soils account for
less than 2.7% of the country (CSO, 2014). The availability of heavy
metals for plants depends on many environmental factors such as
soil texture, soil organic matter abundance and pH. The increase in
soil acidication is a potential factor leading to the growth in the
mobility of heavy metals which may constitute a threat to plants
and groundwater, and consequently e can cause incorporation of
_ z-Hara,
_
these elements into the food chain (Drozd
1978; KabataPendias and Pendias, 1992; Jaggi et al., 1999; Skwierawska et al.,
2008; Scherer, 2009).
According to Facchinelli et al., 2001, any change of soil properties is a chemical time bomb posing the threat to the environment
which may appear suddenly. Knowledge of the content of heavy
metals in soil and their possible interactions with soil properties
are often the main objectives in the assessment of anthropogenic
environmental risk (Qishlaqi and Moore, 2007).
The authors of the study assumed that after 20 years which have

451

passed since the completion of mining, the content of sulfur compounds in turf-covered soils of the former mine area does not
exceed the prescribed limit and the soils of this region can be
classied as not contaminated. In order to accept or reject the
research hypothesis and thus determine whether 20 years is a
sufciently long period of time needed to eliminate harmful effects
of sulfur mining activities which affect the soil environment, the
authors set the specic aims: i) To identify changes in Stot. and
SeSO2
4 content in soils located outside the mine collected in the
1970s and at the beginning of the 21st century, ii) to investigate the
relationship between the content of sulfur compounds and selected
soil properties, iii) to estimate the risk of heavy metal pollution of
soils in the region.
2. Materials and research methods
2.1. The study area
w was located in the south-eastern
The sulfur mine in Grzybo
Poland (2105.01,70 E, 50 31.41,20 N, Fig. 1). The rich deposit of
native sulfur extends from the Pre-Carpathian depression, along
the northern Carpathians of the southern Poland and all the way to
Ukraine. It formed as a result of biochemical processes which
affected gypsum and anhydrite of the Lower Badenian (miocene)
(Frankiewicz and Pucek, 2006). The geological structure of the
investigated area is composed mainly of Quaternary deposits
(sands or clays), which remain on the Tertiary Cracovian clays. The
sand-like quality of top horizons may be the result of surface washout of sedimentary clays or it can be a layer of uvioglacial sand
_ z-Hara,
_
deposited on sedimentary clay (Drozd
1978). The Herman
w involved
Frasch method used in the sulfur mine in Grzybo
injecting overheated water (160  C) into the sulfur ore deposit by
means of a special system of extraction holes. The injected hot
water caused the melting of sulfur, which was then extracted in its
liquid form to the surface through the same holes. Initially, the
extracted sulfur was collected on open landlls, from where it was
blown out and transferred by wind over various distances. As the
time passed and the miners gained experience, they started to
transfer liquid sulfur into closed tanks in which it was then transported. Exploitation of sulfur and its processing in this area went on
continuously for 30 years (1966e1996). The study area has an
average annual temperature of 70  C and the average annual
rainfall of 800 mm. Precipitation lasts from 60 to 70 days a year and
the snow cover persists from 65 to 90 days.
2.2. Sampling
Sampling was performed in the spring of 2014. Soil samples
were collected from sites located towards the south, north, east and
west at a distance of 1 km (area A), 3 km (area B) and 10 km (area C)
from the emission source of sulfur compounds, which was the
sulfur mine. The sites where samples were taken are presented in
Fig. 1. Eight soil proles were assigned to each area (A, B and C): 2
proles were assigned to each of the four designated directions. In
total, 24 soil proles were made. From each horizon designated
within a soil prole a representative soil sample for further laboratory analyses was taken. Results of the determinations are shown
for three studied horizons: surface horizons at a depth of 0e25 cm
(I), subsurface horizons e 24e40 cm (II) and bottom horizons e
more than 120 cm (III). Studied soils were, prior to the start of
mining activities conducted within the area of the mine (until the
end of 1970s), used as agricultural soils. As arable land they were
fertilized with both mineral and natural fertilizers. As the exploitation of sulfur intensied, soils of the study area came within the
reach of elemental sulfur pollution. The increase in soil pollution by

452

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458

Fig. 1. Location of the research area. Circles A, B and C were used to designate the area where soil was sampled at a distance of respectively 1 km, 3 km and 10 km from the borders
of the mine. Dots mark the places where soil proles were made.

_ z_
Stot. and SeSO2
4 caused the agricultural activity to stop (Drozd
Hara, 1978). At the time of sampling soils of the study area were
turf-covered post-arable wasteland on which no reclamation
treatments were applied.

2.3. Methods
Representative soil samples were air dried and sieved with a
sieve of 2 mm. Chemical and physical soil properties were determined with the use of the following methods:
- Soil texture was determined according to Polish Norms PN-R04032 and PN-R-04033 (1998).
- pH value (in 1 M potassium chloride) was obtained using a soil/
solution ratio 1:2.5 potentiometrically (Tan, 2005).
- Total and inorganic carbon concentrations and total nitrogen
(Ntot) concentrations were determined with an automatic carbon and nitrogen analyzer (TOC-TN 1200 Thermo Euroglas).
Samples containing CaCO3 were washed in 10% HCl to remove
carbonates prior to the determination of Corg.. Organic carbon
concentrations (Corg.) were calculated as the difference between
the total and the inorganic carbon concentrations (Tan, 2005).

- Total Zn, Pb, Cr, Cu, Ni and Cd concentrations (Carter and


Gregorich, 2006) were assessed with an atomic emission spectrometer ICP-AES JY 238 ULTRACE and the use of a multielement ICP-IV Merck standard solution. The accuracy of the
analytical methods was veried using the GSS-8 certicated
reference material (GBW 07408e State Bureau of Metrology,
Beijing, China).
- To measure exchangeable acidity (Hh) the samples were treated
with 1 M Ca(CH3COO)2 using 1:2.5 soil/solution ratio. Suspensions were shaken for 1 h, ltered and titrated with 0.1 M NaOH
to pH 8.2. The exchangeable acidity was calculated from the
amount of base used and expressed in mmol()$kg1
(Ostrowska et al., 1991).
- The content of total sulfur and sulfate sulfur was determined by
the nephelometric method of Butters and Chenery (1959) and
Bardsley and Lancaster (1960).

2.4. Integrated pollution index IPI


In order to assess the degree of contamination with heavy
metals, it was considered advisable to calculate the Integrated
Pollution Index (IPI) for each area, dened as an average PI value for

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458

6 metals. Then IPI was classied into three categories: low (IPI  1),
average (1  IPI < 2] and high (IPI > 2) (Chen et al., 2005; Guo et al.,
2012). The PI for each metal was calculated as the ratio of the
content of the metal in the surface horizon to its content in the
bottom horizon by using the equation (Wei and Yang, 2010):

PIi

Ci
Bi

Where
Ci e the content of the heavy metal in the surface horizon,
Bi e the content of the heavy metal in the bottom horizon
(bedrock).

2.5. Statistical analysis


In order to present the general characteristics of the selected
properties of the studied soils, basic statistical parameters were
calculated, i.e. the arithmetic mean, standard deviation, the median
and quartile gap, i.e. the difference between the rst (Q1) and the
third (Q3) quartile, where 50% of the value of the tested variable is
contained.
Non-parametric analysis ANOVA: In order to determine the
signicance of differences between the mean values obtained for
the examined areas, taking into account of the designed horizons,
the ANOVA variance analysis was used. Prior to the variance analysis, it was checked if the tested variables are normally distributed
(Shapiro-Wilk test) and whether there is homogeneity of variance
(Leven test). Due to the absence of normal distribution, the nonparametric variance analysis of Kruskal-Wallis was applied. Additionally, in order to distinguish homogeneous groups, MannWhitney test was conducted. Identical letters were used to
denote values for which there are no signicant differences at the
level of signicance p 0.05.
Correlation analysis: In order to investigate the relationship
between physical and chemical properties of the soil (pH, contents
Corg., Ntot, fraction <0.002 mm, Stot., SeSO2
4 ) and the contents of
individual heavy metals for the entire data set, Spearmans rank
correlation analysis was used.
Principal component analysis: PCA enables the reduction of data
and shows the relationship between the examined variables. This
allows us to specify metal groups correlated with each other, and
therefore likely to have similar properties and common origins
(Tahri et al., 2005). All statistical analyzes were conducted using
Statistica PL v 10 packet for n 24 for each of the studied horizons
of the soil.
3. Results
3.1. Description of the basic properties of the studied soils
In terms of grain size composition, the soils of all studied areas
are characterized by a certain changeability. Each of the designated
area is dominated (75%) by light and medium soils (loamy sands,
sandy clays and light clays). Also occasionally (25%) one can nd
heavy soils (common clays and loamy clays). In the surface horizons
the average content of Corg. ranges from 13.9 to 20.5 g kg1, and Ntot
from 1.67 to 2.42 g kg1 (soil area B and A), in the subsurface horizons e 7.7e9.9 (soil area B and A) and 0.86e1.46 (soil area C and
A) respectively, whereas in the bottom horizons the average content of marked elements is 0.4e4.3 g kg1 for Corg. and
0.23e0.60 g kg1 (soil area C and A) for Ntot. The mean values of pH
of the studied soils range from 4.3 to 5.9 in the surface horizons

453

(soil area C and A), from 4.4 to 5.5 in subsurface horizons and from
4.9 to 6.0 in bottom horizons (soil area B and A). The mean value of
hydrolytic acidity in the horizons of the soils of the studied areas is
as follows: 26.2e39.5 mmol() kg1 (soil area A and C);
22.9e27.3 mmol() kg1 (soil area B and C); 6.8e16.2 mmol() kg1
(soil area C and B, Table 1).
3.2. Stot. and SeSO2
4 content in the soils of studied areas
Assuming the level of signicance of p 0.05, rst we veried
the null hypothesis, which assumed that there was no signicant
difference between the mean sulfur content of determined sulfur
forms in the soils of studied areas. For this purpose we calculated
the critical value of H statistics for Kruskal-Wallis test, which is
c20,05;2 5.991. By taking this value into account and on the basis of
results of Kruskal-Wallis test (for each horizon the value of H statistics is greater than the critical value) at the signicance level of
0.05 one can reject the null hypothesis and conclude that the distance from the mine (1, 3 and 10 km) has a statistically signicant
impact on the levels of sulfur compounds in soils (Table 2). In
addition, the results of Mann-Whitney test indicated homogeneous
groups (Table 3). In studied soils the content of determined forms of
sulfur was as follows: in the humus horizon Stot. ranged from 0.031
1
to 0.680 g kg1, whereas SeSO2
and
4 from 0.005 to 0.210 g kg
analogically at the subsurface horizon e 0.001e0.440 g kg1 and
0.005e0.090 g kg1. At the bottom horizon the Stot. content ranged
1
from 0.003 to 0.220 g kg1 and SeSO2
4 e 0.010e0.340 g kg
(Figs. 2 and 3). The average percentage of SeSO2
in
S
at
the
4
tot.
surface horizon did not exceed 36%, at the subsurface horizon e
49%, whereas the largest percentage was observed at the bottom
horizon e 71% (Fig. 4).
The results of Mann-Whitney test showed that the biggest
changes in Stot. and SeSO2
4 content occur in soils at a distance of
3 km from the mine borders. In the case of the total sulfur, no
statistically signicant changes are noted between B and C regions.
The same relationships were found at each of the analyzed soil
horizons (Table 3). However, in the case of sulfate sulfur, only at the
subsurface horizon there were no statistically signicant differences between B and C regions. The studies showed that the content of individual forms of sulfur decreases when the distance from
the mine increases (Figs. 2 and 3). In the case of participation of the
sulfate sulfur in the total sulfur, similar relationships were noted as
in the case of total sulfur.
3.3. The content of heavy metals in the studied soils
The analyzed elements were divided into three groups (I, II and
III) depending on their content in the soils of the studied areas
(Table 4). The rst group included Pb, for which the average content
in soils of all the studied areas are similar and there are no significant changes between them. The second group consists of Zn and
Cd, which have a higher average content in soils of the A area and
gradually decreasing content in the soils of B and C areas. These
differences have proven to be signicant for the soils of A area in
relation to the soils of B and C areas in the case of Cd, as well as for
the soils of A and B areas in relation to the soils of C area in the case
of Zn. The third group consists of Cr, Cu and Ni with a higher
average content in the soils of A area, the lowest content in the soils
of C area and intermediate content in the soils of B area. Additionally, a factor analysis was conducted (Table 5). On the basis of
the scree plot (Fig. 5), it was stated that there are three factors
which should be taken into consideration and which explain 96% of
the variability of the analyzed results. Factor F1 contains elements
of the second and third group (Zn, Cr, Cu, Ni) with loads greater
than 0.7. Factor F2 contains Pb which belongs to the rst group with

454

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458

Table 1
Physical and chemical properties of soils in the studied areas of A, B and C.
Area

Horizon

Parameters
% clay (<0.002 mm)
% silt (0.05e0.002 mm)
% sand (2e0.05 mm)
Corg. g kg1
Ntot g kg1
pHKCl
Hh mmol() kg1
% clay (<0.002 mm)
% silt (0.05e0.002 mm)
% sand (2e0.05 mm)
Corg. g kg1
Ntot g kg1
pHKCl
Hh mmol() kg1
% clay (<0.002 mm)
% silt (0.05e0.002 mm)
% sand (2e0.05 mm)
Corg. g kg1
Ntot g kg1
pHKCl
Hh mmol() kg1

I (surface)

II (subsurface)

III (bottom)

Mean SD

Mean SD

Mean SD

10 9
32 18
58 28
20.5 14.1
2.42 1.42
5.9 1.0
26.2 20.8
14 10
31 13
55 22
9.9 5.7
1.46 0.70
5.5 0.6
24.0 4.8
23 11
35 11
42 22
4.3 3.1
0.60 0.23
6.0 0.7
9.5 1.6

10 8
29 12
61 18
13.9 3.7
1.67 0.91
4.7 1.5
33.8 21.9
97
31 14
60 20
7.7 6.3
0.89 0.51
4.8 1.4
22.9 20.1
20 11
30 12
50 22
2.1 1.6
0.57 0.17
4.9 1.4
16.2 7.5

74
33 12
60 15
19.5 21.4
2.01 1.67
4.3 0.7
39.5 30.2
95
29 11
62 16
8.2 11.1
0.86 0.75
4.4 0.5
27.3 27.5
19 11
32 10
49 19
0.4 0.1
0.23 0.13
5.1 0.6
6.8 2.6

Corg. e soil organic carbon, Ntot e total nitrogen, Hh e exchangeable acidity.

Table 2
The results of the test of Kruskal-Wallis for Stot. and SeSO2
4 horizons in the tested
soils of areas A, B and C.
Horizon

p*

I (surface)
II (subsurface)
III (bottom)

Stot.

SeSO2
4

Stot.

SeSO2
4

8.426
6.180
15.748

13.007
14.381
17.160

0.0148
0.0455
0.0004

0.0015
0.0008
0.0002

H e statistical values for Kruskal-Wallis test.


p* e calculated level of signicance.

Table 3
The mean and standard deviation (SD) for SeSO2
4 and Stot.. Identical letters were
used for means for which there is no signicant difference when the Mann-Whitney
test is applied for p 0.05.
Area

Stot. g kg1

1
SeSO2
4 g kg

SeSO2
4 in Stot. %

Mean SD

Mean SD

Mean SD

0.14 0.02a
0.017 0.006b
0.03 0.053c

35.79 11.54a
11.60 5.26b
10.33 7.42b

0.08 0.01a
0.012 0.005b
0.012 0.004b

48.74 32.53a
22.83 21.02b
26.75 18.76b

0.14 0.03a
0.011 0.09b
0.003 0.002c

70.91 21.33a
40.99 25.18b
28.55 22.99b

Horizon I e surface
A
0.44 0.20a
B
0.18 0.10b
C
0.19 0.16b
Horizon II e subsurface
A
0.26 0.18a
B
0.11 0.09b
C
0.09 0.08b
Horizon III e bottom
A
0.20 0.02a
B
0.03 0.03b
C
0.02 0.02b

a high load (>0.9), whereas factor F3 contains Cd which belong to


the second group (load > 0.9).
4. Discussion
4.1. Changes in the content of Stot. and SeSO2
4 in the soils adjacent
to the sulfur mine.
The most important source of sulfur for plants is its sulfate form,

the content of which in the soil usually accounts for less than 5% of
the total sulfur content (Hu et al., 2005; Scherer, 2009). In the soils
of the studied area, participation of SeSO2
4 in Stot. content is much
higher than 5% (Table 3), which proves its anthropogenic origin
(Kabata-Pendias et al., 1993). The obtained results of sulfur forms in
the soils of A and C areas were compared with the results of
_ z-Haras
_
Drozd
research (1978), conducted in the soils of the same
areas in 1970s, in the period of intensive mining works. In the soils
_ z-Hara
_
collected by Drozd
(1978), the average content of determined sulfur forms e Stot. and SeSO2
4 e were higher and for surface horizons they amounted respectively to 0.74 g kg1 and
0.57 g kg1, while for the bottom horizons they were estimated at
0.44 g kg1 and 0.30 g kg1 (A area). In the soils of C area the
average content for Stot. was 0.31 g kg1 and for SeSO2
was
4
0.18 g kg1 at the surface horizons, whereas at the bottom horizons
it was 0.28 g kg1 and 0.08 g kg1 respectively. On the basis of
Mann-Whitney test (Table 6), it can be inferred at 0.05 signicance
level that in the currently collected soils, both in A and C area,
contents of both sulfur forms are statistically signicantly lower
than in the soils collected in the 1970s (the calculated level of
signicance p* is in each case lower than that p 0.05, which was
assumed, which allows for rejection of the hypothesis of the
equality of means. Based on the limit values of Stot. content proposed by IUNG (Kabata-Pendias et al., 1993) for horizons 0e20 cm
thick, the studied soils which are currently collected at a distance of
1 km (A area) and 10 km (C area) from mine borders were classied
as I, that is soils with the natural content of this form of the
element. However, at surface horizons of the soils of A area, we can
still observe an increased (due to anthropogenic pressure) content
of sulfate sulfur, despite the passage of nearly 20 years since the end
of the exploitation of the sulfur deposits. In terms of content of this
type of sulfur, the studied soils are classied as IV. With increasing
distance from the source of contamination (soils of C region), at
present lower contents of the examined sulfur form are observed.
Consequently, according to IUNG classication (Kabata-Pendias
et al., 1993) and by comparing the contents of SeSO2
4 at various
time periods, there has been a change from IVo to Io. Decrease in Stot.
content in the studied soils over a few decades (1970s and the
beginning of the 21s century) may result from the slow oxidization
of Stot. into SeSO2
4 . Oxidation occurs under the inuence of

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458


0,8

0,5

0,7

0,3

-1

0,3

0,15

0,4

S t ot. g kg

0,5

S t ot. g .kg -1

-1

0,20

0,4

0,6

S t ot. g kg

455

0,2

0,2

0,10

0,05

0,1
0,1
0,0

1 km

3 km

0,0

10 k m

0,00

1 km

dsitance

3 km

10 k m

1 km

a) surface horizon

3 km

10 k m

distance

distance

b) subsurface horizon

c) bottom horizon

Fig. 2. Box-and-whisker diagram of the Stot. in g kg1 depending on the area (distance from the source), where: the focal point e the median, the box (Q1, Q3), whisker e the range
(min-max).

1
Fig. 3. Box-and-whisker diagram of the SeSO2
depending on the area (distance from the source), where: the focal point e the median, the box (Q1, Q3), whisker e the
4 in g kg
range (min-max).

S-SO4 2- in St ot. %

S-SO4 2- in St ot. %

50
40
30
20

100

80

80

60

40

20

10
0

100

S-SO4 2- in St ot. %

60

1 km

3 km

10 k m

40

20

1 km

3 km

10 k m

distance

distance

a) surface horizon

60

b) subsurface horizon

1 km

3 km

10 k m

distance

c) bottom horizon

Fig. 4. Box-and-whisker diagram of the participation of SeSO2


4 in Stot. indicated in %, depending on the area (distance from the source), where: the focal point e the median, the
box (Q1, Q3), whisker e the range (min-max).

atmospheric oxygen, moisture and with the contribution of soil


microorganisms - mainly bacteria Thiobacillus thiooxidans (Scherer,
2001; Kertesz and Mirleau, 2004; Burgos et al., 2013). Forming
sulfates are washed down from the soil prole together with
migrating water. This process has been conrmed in eld studies by
many authors (Jaggi et al., 1999; Skwierawska et al., 2008).
Reduction in sulfate sulfur content at surface horizons of soils is the
result of its being absorbed by plants, low level of fertilization and
migration of sulfates to lower levels of soils and groundwater (Zhao
et al., 1999; Fismes et al., 2000; Scherer, 2001; Matula, 2004). The

movement of sulfates in the soil proles is currently proven by the


fact that SeSO2
4 percentage in Stot. content increases as the depth
grows (Table 3).
4.2. The relationship between determined forms of sulfur, selected
soil properties and content of heavy metals in the soils of the studied
areas
The calculated Spearman rank correlation coefcients and their
level of signicance are presented in Table 7. There is a strong

456

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458

Table 4
The mean and standard deviation of the elements in all horizons of the soils in
studied areas. The same letters were used to indicate the means for which there are
no statistically signicant differences based on the Mann-Withneya test (p 0.05).

Pb mg kg1
Zn mg kg1
Cd mg kg1
Cr mg kg1
Cu mg kg1
Ni mg kg1

Group

Mean

SD

Mean

SD

Mean

SD

I
II
II
III
III
III

10.799a
39.364a
0.450a
32.192a
15.083a
18.688a

8.766
25.245
0.0441
16.178
5.981
10.053

10.967a
27.207a
0.239b
13.011b
7.762b
8.783b

4.390
14.086
0.175
11.419
7.230
8.637

10.185a
14.280b
0.253b
3.813c
2.726c
2.941c

4.304
7.578
0.192
2.372
1.554
1.581

SD e standard deviation.

Table 5
Matrix of rotation of standardized factor charges approached by the Varimax
method of studies metals. The table only includes charges >0.5
Metal

Factor
F1

Cr mg kg1
Zn mg kg1
Pb mg kg1
Cu mg kg1
Cd mg kg1
Ni mg kg1
Cumulative variance %

F2

F3

0.929
0.823
0.968
0.933
0.953
0.959
57.12

77.79

96.19

5,0
4,5
4,0
3,5

value

3,0
2,5
2,0
1,5

positive correlation between Stot. content and organic carbon content (r 0.88***) and averagely correlation with fraction content of
< 0.002 mm (r 0.50***). Te sulfate sulfur content is averagely
positively correlated with soil pH, Corg. and clay content. A positive
correlation between the content of SeSO2
and pH values
4
(r 0.36***), which is rarely seen in literature, can be explained by
the precipitation of poorly soluble calcium sulfate in the form of
gypsum or anhydrite, due to the existence in some soils of calcium
carbonate. This assumption is conrmed by high content of calcium
cations in sorption complex, more than 300 mmol() kg1 (data not
published). According to Scherer (2009), an important factor
affecting the content of sulfates in the soil prole is their particle
size. The soils showed a signicant above-average correlation co***
efcient between the content of SeSO2
). The
4 and clay (r 0.53
determined Stot. content is highly signicantly correlated with all
the analyzed trace elements. Similar relationships exist in the case
of SeSO2
4 , with the exception of Pb, which reported weak positive
correlation (r 0.29***). The calculated correlation coefcients also
showed a highly signicant (p 0.001) correlation between fractions of clay and the contents of Cr, Cu and Ni, as well as Pb content
and Corg.. The present study found an average positive correlation
between pH and the content of heavy metals, with the exception of
Pb, for which we observed no signicant statistically relationship.
In case of most metals: Ni, Cr, Cu and Zn in the soils we observed
signicant and strong positive correlations between pairs of these
metals. It is widely recognized that soil pH, the smallest fraction
content (<0.002 mm) and organic matter signicantly affect the
content of heavy metals and their mobility in the soil environment
(Antoniadis et al., 2008; Zeng et al., 2011; Candeias et al., 2014).
Higher pH values lead to the reduction in the mobility of heavy
metals, which results in their accumulation in soil (Ciarkowska
et al., 2014; Paja k et al., 2015). The results reveal that only in the
case of Pb there is indeed very high correlation with the organic
matter content. For other heavy metals we recorded an average
correlation. The relationship between the content of the smallest
fraction (<0.002 mm) and trace elements conrmed a highly signicant positive correlation in the case of most metals (Cr, Zn, Cu,
Cd, Ni) (Table 7).
4.3. Assessment of the risk of heavy metal contamination

1,0
0,5
0,0

eigenvalue number
Fig. 5. Chart of eigenvalues (screes) which visually assess components or factors
explaining most of the variability in the data.

Table 6
Results of Mann-Whitney test for soil properties at the surface and bottom horizon
for areas A and C.
Soil parameter
Area A
Stot
SeSO2
4
Area C
Stot
SeSO2
4
p* e calculated level of signicance.

Horizon

p*

Surface
Bottom
Surface
Spa gowy

0.0405
0.0368
0.0472
0.0472

Surface
Bottom
Surface
Bottom

0.0205
0.0318
0.0362
0.0274

The analysis of principal components indicates that the


analyzed metals create 3 distinct groups (Table 5). The rst F1 factor
is represented by elements, such as Cr, Zn, Cu and Ni, which are
characterized by high contents in the soil area A, and then, as the
distance from the mine increases, their content is clearly reduced.
This allows us to dene this factor as the impact of long-term acw sulfur mine, which explains about 57% of the total
tivity of Grzybo
variability and is the most important factor. The second factor (F2)
contains only one element, i.e. lead, which is widely distributed in
the environment and whose contents in all designated areas are
similar. Correlation between Pb and other elements, except for zinc,
is relatively low. Its presence in soils may be associated with a local
emission, both from the so-called low emission which takes place
in urban areas and the movement of transport. The third factor (F3)
describes only part of Cd, explaining 18.4% of the total variability. Its
content is signicantly higher in the soils of the area A (Table 4).
This may be associated with increased trafc during mining activities in mines and intensive use of phosphate fertilizers in this area
in order to improve soil properties (Satarug et al., 2003). Those
hypotheses conrm signicant correlations between specic pairs
of heavy metals (Table 7). The assessment of the intensity of
anthropogenization may be done by comparing the amount of
determined metals in the soils with maximum permissible values
given by the Institute of Soil Science and Plant (IUNG) in Pulawy

K. Soek-Podwika et al. / Journal of Environmental Management 180 (2016) 450e458

457

Table 7
Spearmans rank correlation coefcient between selected physicochemical properties and heavy metals in the soils of studies areas.
Parameter

Cr

Zn

Pb

Cu

Cd

Ni

SeSO2
4

Stot.

pHKCl

Corg.

Clay <0.002

Cr
Zn
Pb
Cu
Cd
Ni
SeSO2
4
Stot.
pHKCl
Corg.
Clay <0.002

1.00

0.63***
1.00

0.36***
0.61***
1.00

0.87***
0.70***
0.30**
1.00

0.49***
0.25*
0.36***
0.37***
1.00

0.87***
0.63***
0.29***
0.90***
0.42***
1.00

0.69***
0.47***
0.29***
0.62***
0.43***
0.59***
1.00

0.65***
0.56***
0.65***
0.51***
0.57***
0.48***
0.71***
1.00

0.44***
0.31**
0.07
0.52***
0.33***
0.59***
0.36***
0.25*
1.00

0.47***
0.44***
0.74***
0.33***
0.46***
0.23*
0.54***
0.88***
0.07
1.00

0.88***
0.59***
0.25*
0.81***
0.39***
0.84***
0.53***
0.50***
0.39***
0.31**
1.00

Correlation is signicant at 0.05.


Correlation is signicant at 0.01.
***
Correlation is signicant at 0.001.
**

(Kabata-Pendias et al., 1993) for uncontaminated soils and by


estimating the value of IPI. In the analyzed soil material the content
of heavy metals represents the lowest level (0 ) of trace element
content in a 6 scale. IPI index calculated for all analyzed metals in
the soils of studied areas is formed according to the following
pattern: Area A e 1.34; Area B e 1.02 and Area C e 0.90. As specied
by Guo et al. (2012), soil areas A and B were classied as moderately
polluted with heavy metals, and soil area C was qualied as scantily
polluted.
5. Conclusions
Based on the comparison of the contents of Stot. and SeSO2
4 in
soils situated at a distance of 1 km and 10 km from the borders of
w, it was observed that there was signicantly
sulfur mine Grzybo
lower content of both determined forms of this element in soils
collected at the beginning of the twenty-rst century than in the
1970s. However, the hypothesis which assumed that the period of
20 years elapsed since the end of sulfur compounds emissions was
enough to reduce the concentration of these compounds in soils to
a level of content limit, must be rejected, since the SeSO2
4 content
in soils located in close proximity to the mine (1 km), despite the
passage of years, it is still elevated. Contents of Stot. and SeSO2
4 are
generally highly signicantly correlated with the analyzed trace
elements. Pollution of the studied soils with heavy metals was
rated with the use of the integrated pollution index, which
conrmed moderate and low level of anthropogenization of this
area. Based on the demonstrated relationships between designated
properties of soils (especially the content of Corg., the fraction
<0.002 mm and pH) and heavy metals, we can conclude that in the
soils of studied areas trace elements are not present in mobile
forms in the soil solution.
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