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 Sołek-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 sufficiently long for the content of sulfur compounds
in soils not to exceed the permissible level and that soil of the region can be classified as not contaminated. A part of the study involved identification of changes in the contents Stot. and SeSO2
4 in soils
collected in the 1970s and early twenty-first 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 confirms 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 inflow 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. Sołek-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
defined 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 1970’s 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
70’s of the twentieth century to approx. 1.5 million Mg in the early
twenty-first century were observed. At the same time deposition of
sulfur decreased, from 70 kg S ha1 year1 in the 80’s to
50 kg S ha1 year1 in the 90’s. At the beginning of the twenty-first
century, the largest sulfur deposition occurred in areas heavily

The negative impact of the sulfur mine in Grzybo was associated not only with mining works and production processes. 1992. The years 1966e1976 were characterized by dynamic development of borehole sulfur mining. 1). The sand-like quality of top horizons may be the result of surface washout of sedimentary clays or it can be a layer of fluvioglacial sand _ z-Hara. A region of certain particularity in Poland is the area of exploitation of sulfur deposits in Tarnobrzeg (Bryk and Kołodziej. along the northern Carpathians of the southern Poland and all the way to Ukraine. any change of soil properties is a “chemical time bomb” posing the threat to the environment which may appear suddenly. As the time passed and the miners gained experience. From each horizon designated within a soil profile a representative soil sample for further laboratory analyses was taken. 2014). 2006). The mine in Grzybo which sulfur extraction was carried out by means of a new technology. The mining operations frequently led to contamination of soil and water with elemental sulfur as a result of spontaneous eruptions. soil organic matter abundance and pH. According to Facchinelli et al. Today. namely the method invented by Herman Frasch (patented w in USA in 1894). The evaluation of sulfur abundance in soils.g carbon and nitrogen). _ tionship also occur (Drozd 1978. In order to accept or reject the research hypothesis and thus determine whether 20 years is a sufficiently long period of time needed to eliminate harmful effects of sulfur mining activities which affect the soil environment. 2004). There is also a change in the quantitative and qualitative composition of soil microorganisms. 2001. used in agricultural production. B and C): 2 profiles were assigned to each of the four designated directions. Eight soil profiles were assigned to each area (A. which was then extracted in its liquid form to the surface through the same holes. while in areas remote from industrial plants it was low. _ deposited on sedimentary clay (Drozd 1978). Sampling Sampling was performed in the spring of 2014. 24 soil profiles were made. Negative effects of anthropogenic soil sulfating include the increment of sulfates content (SO2 4 . less than 10 kg S ha1 year1 (CSO. Scherer. 1992. The increase in soil acidification is a potential factor leading to the growth in the mobility of heavy metals which may constitute a threat to plants and groundwater. 1991e2008). 3 km (area B) and 10 km (area C) from the emission source of sulfur compounds. heavy metals contaminated soils account for less than 2. As arable land they were fertilized with both mineral and natural fertilizers.ions are anhydride of H2SO4) and soil acidification. and consequently e can cause incorporation of _ z-Hara. The rich deposit of native sulfur extends from the Pre-Carpathian depression. 2009). The geological structure of the investigated area is composed mainly of Quaternary deposits (sands or clays). 2. but also with transport. 2009).1. which remain on the Tertiary Cracovian clays. The study area w was located in the south-eastern The sulfur mine in Grzybo Poland (2105.. The authors of the study assumed that after 20 years which have 451 passed since the completion of mining. 2. During this period there was a strong focus on growth in sulfur exploitation.7% of the country (CSO. 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 classified as not contaminated. The negative impact of the mine was not only limited to the mining fields but also occurred _ z-Hara. 50 31. subsurface horizons e 24e40 cm (II) and bottom horizons e more than 120 cm (III). while less attention was paid to the requirements of environmental protecw was the first mine in Polish conditions in tion. The sites where samples were taken are presented in Fig. Eriksen et al. Fig. _ these elements into the food chain (Drozd 1978. The increase in soil pollution by . As the exploitation of sulfur intensified. smaller amounts of natural fertilizers. there are more and more areas which are deficient in this element because of the increased use of fertilizers with lower S content. The study area has an average annual temperature of 70  C and the average annual rainfall of 800 mm. The availability of heavy metals for plants depends on many environmental factors such as soil texture..20 N. Jaggi et al.01. A strong acidification of soils goes along with lowering availability of nutrients. _ outside their borders (Drozd 1978).2. 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. In the light of the studies carried out on a large scale by the Institute of Soil Science and Plant Cultivation. sulfur supply in plants and the threat of its excess in agro-ecosystems involves mainly its sulfate form (Kabata-Pendias and Pendias. Also the air was contaminated as a result of emissions of hydrogen sulfide and sulfur dust from open sulfur deposits. The spatial differences result mainly from the impact of local sources of emissions of sulfur compounds. 2009). east and west at a distance of 1 km (area A). which causes disruption of the natural cycle of elements (e. In total. 1. used as agricultural soils. 1999. 2007). they started to transfer liquid sulfur into closed tanks in which it was then transported. as well as reduced use of fungicides and pesticides (Scherer. north. mainly in the highly industrialized areas. In Poland soils contaminated with heavy metals occur only locally. 2014). The impact was multidirectional and very difficult to predict at the time. These changes lead to the destruction of aggregate structure and soil crusting with salts or iron hydroxides efflorescence formed on the surface..70 E. Kowalenko et al. Results of the determinations are shown for three studied horizons: surface horizons at a depth of 0e25 cm (I). 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. It formed as a result of biochemical processes which affected gypsum and anhydrite of the Lower Badenian (miocene) (Frankiewicz and Pucek. / Journal of Environmental Management 180 (2016) 450e458 industrialized and was over 30 kg S ha1 year1. Soil samples were collected from sites located towards the south. Exploitation of sulfur and its processing in this area went on continuously for 30 years (1966e1996). 2008. Initially. soils of the study area came within the reach of elemental sulfur pollution. the extracted sulfur was collected on open landfills. Studied soils were. Materials and research methods 2. increasing solubility of aluminium and manganese compounds and leaching of basic components. the authors set the specific aims: i) To identify changes in Stot. ii) to investigate the relationship between the content of sulfur compounds and selected soil properties. Sołek-Podwika et al. prior to the start of mining activities conducted within the area of the mine (until the end of 1970’s). In degraded soils the deterioration of water and air rela_ z-Hara. from where it was blown out and transferred by wind over various distances. Skwierawska et al. especially manure. Scherer. iii) to estimate the risk of heavy metal pollution of soils in the region.41. 2001... which was the sulfur mine. The injected hot water caused the melting of sulfur. KabataPendias and Pendias. Precipitation lasts from 60 to 70 days a year and the snow cover persists from 65 to 90 days. and SeSO2 4 content in soils located outside the mine collected in the 1970’s and at the beginning of the 21st century. In Poland there are areas with distinct deficiency or excess of sulfur in the environment of crop plants.K.

1991). and SeSO2 4 caused the agricultural activity to stop (Drozd Hara. Integrated pollution index IPI In order to assess the degree of contamination with heavy metals.pH value (in 1 M potassium chloride) was obtained using a soil/ solution ratio 1:2.To measure exchangeable acidity (Hh) the samples were treated with 1 M Ca(CH3COO)2 using 1:2. 1.Total and inorganic carbon concentrations and total nitrogen (Ntot) concentrations were determined with an automatic carbon and nitrogen analyzer (TOC-TN 1200 Thermo Euroglas). 2. The accuracy of the analytical methods was verified using the GSS-8 certificated reference material (GBW 07408e State Bureau of Metrology.2. 2005). Dots mark the places where soil profiles were made. 1978). 2. . _ z_ Stot. Sołek-Podwika et al.Total Zn.The content of total sulfur and sulfate sulfur was determined by the nephelometric method of Butters and Chenery (1959) and Bardsley and Lancaster (1960). 2005).5 soil/solution ratio. Beijing.4. Location of the research area. Chemical and physical soil properties were determined with the use of the following methods: . . Circles A. . 2006) were assessed with an atomic emission spectrometer ICP-AES JY 238 ULTRACE and the use of a multielement ICP-IV Merck standard solution. Pb. Organic carbon concentrations (Corg.5 potentiometrically (Tan. 3 km and 10 km from the borders of the mine.Soil texture was determined according to Polish Norms PN-R04032 and PN-R-04033 (1998).) were calculated as the difference between the total and the inorganic carbon concentrations (Tan. Cr... Samples containing CaCO3 were washed in 10% HCl to remove carbonates prior to the determination of Corg. Cu. / Journal of Environmental Management 180 (2016) 450e458 Fig.452 K. Suspensions were shaken for 1 h. China). . B and C were used to designate the area where soil was sampled at a distance of respectively 1 km. it was considered advisable to calculate the Integrated Pollution Index (IPI) for each area. . filtered and titrated with 0. Ni and Cd concentrations (Carter and Gregorich. Methods Representative soil samples were air dried and sieved with a sieve of 2 mm. The exchangeable acidity was calculated from the amount of base used and expressed in mmol(þ)$kg1 (Ostrowska et al. defined as an average PI value for . At the time of sampling soils of the study area were turf-covered post-arable wasteland on which no reclamation treatments were applied.1 M NaOH to pH ¼ 8.3.

Due to the absence of normal distribution.5 mmol(þ) kg1 (soil area A and C). / Journal of Environmental Management 180 (2016) 450e458 6 metals. where 50% of the value of the tested variable is contained.2 ¼ 5.9 (soil area B and A) and 0.991. The same relationships were found at each of the analyzed soil horizons (Table 3). In the surface horizons the average content of Corg.2 mmol(þ) kg1 (soil area C and B.220 g kg1 and SeSO2 4 e 0. In addition. The results of Mann-Whitney test showed that the biggest changes in Stot. Stot.005 to 0.005e0.. 2012). for which the average content in soils of all the studied areas are similar and there are no significant changes between them.210 g kg analogically at the subsurface horizon e 0. Spearman’s rank correlation analysis was used.9 to 6.46 (soil area C and A) respectively. Also occasionally (25%) one can find heavy soils (common clays and loamy clays). the ANOVA variance analysis was used. Ntot. Factor F2 contains Pb which belongs to the first group with . standard deviation.7.e.680 g kg1. similar relationships were noted as in the case of total sulfur. The mean values of pH of the studied soils range from 4. which is c20.003 to 0.05. At the bottom horizon the Stot.002 mm.60 g kg1 (soil area C and A) for Ntot. basic statistical parameters were calculated. The content of heavy metals in the studied soils The analyzed elements were divided into three groups (I. contents Corg. The mean value of hydrolytic acidity in the horizons of the soils of the studied areas is as follows: 26. which assumed that there was no significant difference between the mean sulfur content of determined sulfur forms in the soils of studied areas.3 to 5.05.440 g kg1 and 0. Correlation analysis: In order to investigate the relationship between physical and chemical properties of the soil (pH. first we verified the null hypothesis. whereas in the bottom horizons the average content of marked elements is 0. 3 and 10 km) has a statistically significant impact on the levels of sulfur compounds in soils (Table 2). it was checked if the tested variables are normally distributed (Shapiro-Wilk test) and whether there is homogeneity of variance (Leven test).e. All statistical analyzes were conducted using Statistica PL v 10 packet for n ¼ 24 for each of the studied horizons of the soil.1. whereas SeSO2 and 4 from 0.. 2 and 3). Bi e the content of the heavy metal in the bottom horizon (bedrock). 2010): PIi ¼ Ci Bi Where Ci e the content of the heavy metal in the surface horizon.4e4.2e39. Cr. MannWhitney test was conducted.2. Additionally. taking into account of the designed horizons. in the subsurface horizons e 7.9e27. ranges from 13. i. In the case of the total sulfur. from 4. The first group included Pb. However. 22.23e0. Principal component analysis: PCA enables the reduction of data and shows the relationship between the examined variables.7e9.090 g kg1. Then IPI was classified into three categories: low (IPI  1). a factor analysis was conducted (Table 5). and SeSO2 4 content occur in soils at a distance of 3 km from the mine borders. sandy clays and light clays).5 g kg1. Each of the designated area is dominated (75%) by light and medium soils (loamy sands.3. Identical letters were used to denote values for which there are no significant differences at the level of significance p ¼ 0.05 one can reject the null hypothesis and conclude that the distance from the mine (1. Guo et al. Additionally. the median and quartile gap.K. 3. and Ntot from 1. and 0. content ranged 1 from 0. The third group consists of Cr. fraction <0. the lowest content in the soils of C area and intermediate content in the soils of B area.3 g kg1 for Corg. only at the subsurface horizon there were no statistically significant differences between B and C regions.67 to 2.0 in bottom horizons (soil area B and A). In studied soils the content of determined forms of sulfur was as follows: in the humus horizon Stot. Statistical analysis In order to present the general characteristics of the selected properties of the studied soils. 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.9 to 20.5 in subsurface horizons and from 4. Description of the basic properties of the studied soils In terms of grain size composition. whereas the largest percentage was observed at the bottom horizon e 71% (Fig.4 to 5. 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 significance level of 0. the difference between the first (Q1) and the third (Q3) quartile. 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. Stot. 3. at the subsurface horizon e 49%. ranged from 0. Cu and Ni with a higher average content in the soils of A area. These differences have proven to be significant for the soils of A area in relation to the soils of B and C areas in the case of Cd.8e16. 3.05. the results of Mann-Whitney test indicated homogeneous groups (Table 3).5. The second group consists of Zn and Cd. Sołek-Podwika et al.3 mmol(þ) kg1 (soil area B and C). as well as for the soils of A and B areas in relation to the soils of C area in the case of Zn. Ni) with loads greater than 0. Results 3. Factor F1 contains elements of the second and third group (Zn. and SeSO2 4 content in the soils of studied areas Assuming the level of significance of p ¼ 0. Cu. in order to distinguish homogeneous groups. 2 and 3).340 g kg (Figs. surface horizon did not exceed 36%.010e0.. 2005). the arithmetic mean. no statistically significant changes are noted between B and C regions. The average percentage of SeSO2 in S at the 4 tot. For this purpose we calculated the critical value of H statistics for Kruskal-Wallis test. 5). Non-parametric analysis ANOVA: In order to determine the significance of differences between the mean values obtained for the examined areas. II and III) depending on their content in the soils of the studied areas (Table 4). 4). and therefore likely to have similar properties and common origins (Tahri et al. 6. i. the soils of all studied areas are characterized by a certain changeability.031 1 to 0. 2005. the nonparametric variance analysis of Kruskal-Wallis was applied..9 in the surface horizons 453 (soil area C and A). The studies showed that the content of individual forms of sulfur decreases when the distance from the mine increases (Figs. Table 1). In the case of participation of the sulfate sulfur in the total sulfur. On the basis of the scree plot (Fig. SeSO2 4 ) and the contents of individual heavy metals for the entire data set.86e1.42 g kg1 (soil area B and A). in the case of sulfate sulfur. Prior to the variance analysis. which have a higher average content in soils of the A area and gradually decreasing content in the soils of B and C areas.001e0.. average (1  IPI < 2] and high (IPI > 2) (Chen et al. 2. This allows us to specify metal groups correlated with each other.

which proves its anthropogenic origin (Kabata-Pendias et al. B and C. content in the studied soils over a few decades (1970’s and the beginning of the 21s century) may result from the slow oxidization of Stot.1. at present lower contents of the examined sulfur form are observed.91 ± 21.454 K.5 ± 21.9 ± 3.18b 28.. which was assumed.02 ± 0.5 ± 14.67 4.003 ± 0.55 ± 22.7 9.03a 0. both in A and C area.6 0. Sołek-Podwika et al.0455 0.76b 0.03 ± 0.9).6 Corg.6 6. there has been a change from IVo to Io.67 ± 0. whereas at the bottom horizons it was 0.381 17. g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 % clay (<0.51 4. at surface horizons of the soils of A area. In the soils of C area the average content for Stot.02a B 0.91 4.74 ± 32.1 ± 1.18a B 0.002 mm) % sand (2e0. p* e calculated level of significance.11 ± 0.9 ± 1. 2005.0008 0.33 ± 7. according to IUNG classification (Kabata-Pendias et al.08b Horizon III e bottom A 0.5 ± 30.4 22. However. and SeSO2 4 in the soils adjacent to the sulfur mine.57 ± 0.16b Horizon II e subsurface A 0. Oxidation occurs under the influence of . conducted in the soils of the same areas in 1970’s.0004 0.004b 48.8 23 ± 11 35 ± 11 42 ± 22 4.011 ± 0.05.1 ± 0.002c 70.1 0.17 4.42 5. Consequently. g kg1 1 SeSO2 4 g kg SeSO2 4 in Stot.8 ± 21.74 g kg1 and 0.03 ± 0.99 ± 25.002 mm) % sand (2e0.18 g kg1 at the surface horizons.28 g kg1 and 0.75 4.7 1. and SeSO2 4 horizons in the tested soils of areas A. Table 2 The results of the test of Kruskal-Wallis for Stot.0148 0. whereas factor F3 contains Cd which belong to the second group (load > 0.7 ± 6.9 ± 5.09b 0. Decrease in Stot.42b 0.0 ± 0. which allows for rejection of the hypothesis of the equality of means.6 10 ± 8 29 ± 12 61 ± 18 13.7 39.4 ± 0. In the soils of the studied area. B and C.18 ± 0.89 ± 0. g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 % clay (<0. g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 I (surface) II (subsurface) III (bottom) A B C Mean ± SD Mean ± SD Mean ± SD 10 ± 9 32 ± 18 58 ± 28 20.44 g kg1 and 0.9 ± 1. we can still observe an increased (due to anthropogenic pressure) content of sulfate sulfur.02b a high load (>0. despite the passage of nearly 20 years since the end of the exploitation of the sulfur deposits.05e0.44 ± 0.002 mm) % silt (0.02a 0.1 0.5 33.54a 11. was 0.5 ± 1. In terms of content of this type of sulfur.7 1.2 ± 11.14 ± 0.20 ± 0.053c 35. that is soils with the natural content of this form of the element.05.1 0.160 0.005b 0. With increasing distance from the source of contamination (soils of C region). Scherer.46 ± 0.. In the soils _ z-Hara _ collected by Drozd (1978). The most important source of sulfur for plants is its sulfate form. / Journal of Environmental Management 180 (2016) 450e458 Table 1 Physical and chemical properties of soils in the studied areas of A.09 ± 0.75 ± 18.01a 0.23 6.012 ± 0. Table 3 The mean and standard deviation (SD) for SeSO2 4 and Stot. the studied soils which are currently collected at a distance of 1 km (A area) and 10 km (C area) from mine borders were classified as Iº.0002 H e statistical values for Kruskal-Wallis test.017 ± 0.5 7±4 33 ± 12 60 ± 15 19.012 ± 0.03b C 0.4 2.0 ± 4. the average content of determined sulfur forms e Stot. Discussion 4.01 ± 1. % Mean ± SD Mean ± SD Mean ± SD 0.05e0.748 13.10b C 0.57 g kg1.0015 0. the content of which in the soil usually accounts for less than 5% of the total sulfur content (Hu et al..70 5.26b 10.4 ± 0. content is much higher than 5% (Table 3). in the period of intensive mining works. On the basis of Mann-Whitney test (Table 6).8 ± 1. content proposed by IUNG (Kabata-Pendias et al. The obtained results of sulfur forms in the soils of A and C areas were compared with the results of _ z-Hara’s _ Drozd research (1978).5 ± 0.002 mm) % silt (0.33a 40. it can be inferred at 0.05e0. 4.42 ± 1.7 ± 1.426 6. Area Stot.53a 22.83 ± 21. into SeSO2 4 . Changes in the content of Stot.1 20 ± 11 30 ± 12 50 ± 22 2. SeSO2 4 Stot.002 mm) % silt (0. participation of SeSO2 4 in Stot. 1993).05 mm) Corg. 1993) and by comparing the contents of SeSO2 4 at various time periods.60 ± 5.8 ± 2.006b 0. Area Horizon Parameters % clay (<0. Based on the limit values of Stot.05 mm) Corg. Hh e exchangeable acidity. Ntot e total nitrogen.08 g kg1 respectively. and SeSO2 4 e were higher and for surface horizons they amounted respectively to 0.0 26. while for the bottom horizons they were estimated at 0.79 ± 11. the studied soils are classified as IVº.6 24. Horizon p* H I (surface) II (subsurface) III (bottom) Stot.19 ± 0.3 ± 27.002 mm) % sand (2e0. 1993) for horizons 0e20 cm thick.3 ± 3.09b C 0.20a B 0.180 15.4 16.08 ± 0.60 ± 0.9 9±7 31 ± 14 60 ± 20 7.. Identical letters were used for means for which there is no significant difference when the Mann-Whitney test is applied for p ¼ 0.3 0. e soil organic carbon.9 ± 20.23 ± 0.05 mm) Corg.13 5. SeSO2 4 8.5 27.8 14 ± 10 31 ± 13 55 ± 22 9.14 ± 0..2 9±5 29 ± 11 62 ± 16 8. 2009).31 g kg1 and for SeSO2 was 4 0.26 ± 0.2 ± 20.9).3 ± 0.05 significance level that in the currently collected soils.02b 26.007 14. contents of both sulfur forms are statistically significantly lower than in the soils collected in the 1970’s (the calculated level of significance p* is in each case lower than that p ¼ 0.1 2.30 g kg1 (A area).2 ± 7.5 19 ± 11 32 ± 10 49 ± 19 0.99b Horizon I e surface A 0.86 ± 0.

Scherer. Box-and-whisker diagram of the SeSO2 depending on the area (distance from the source). Q3). Q3).in St ot. the box (Q1.K. the box (Q1.6 S t ot.15 . Q3). Fismes et al. 4. Kertesz and Mirleau. 2008).3 -1 0. Box-and-whisker diagram of the Stot.in St ot. % 60 1 km 3 km 10 k m 0 40 20 1 km 3 km 10 k m distance distance a) surface horizon 60 b) subsurface horizon 0 1 km 3 km 10 k m distance c) bottom horizon Fig. 2001.1 0. Forming sulfates are washed down from the soil profile together with migrating water.. 1999. whisker e the range (min-max). 1 Fig.mainly bacteria Thiobacillus thiooxidans (Scherer.4 S t ot. whisker e the 4 in g kg range (min-max). 2000. / Journal of Environmental Management 180 (2016) 450e458 0. where: the focal point e the median.2. depending on the area (distance from the source). 2004.in St ot.kg -1 -1 0. 4.2 0. This process has been confirmed in field studies by many authors (Jaggi et al.5 S t ot. .8 0. content increases as the depth grows (Table 3). S-SO4 2. 3. where: the focal point e the median. where: the focal point e the median.10 0. selected soil properties and content of heavy metals in the soils of the studied areas The calculated Spearman rank correlation coefficients and their level of significance are presented in Table 7. 2001.20 0.3 0. The relationship between determined forms of sulfur. Skwierawska et al.0 10 k m 0.05 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. Sołek-Podwika et al.. 2013). Box-and-whisker diagram of the participation of SeSO2 4 in Stot. Matula. in g kg1 depending on the area (distance from the source). 2. g .5 0. the box (Q1. Burgos et al. indicated in %.4 0.1 0. % 50 40 30 20 100 80 80 60 40 20 10 0 100 S-SO4 2. low level of fertilization and migration of sulfates to lower levels of soils and groundwater (Zhao et al. 0. moisture and with the contribution of soil microorganisms . g kg 455 0.2 0.. The movement of sulfates in the soil profiles is currently proven by the fact that SeSO2 4 percentage in Stot. 2004). whisker e the range (min-max). 1999. atmospheric oxygen. There is a strong . % S-SO4 2.. g kg 0.0 1 km 3 km 0..7 0. Reduction in sulfate sulfur content at surface horizons of soils is the result of its being absorbed by plants.

5 4.245 0. According to Scherer (2009). Those hypotheses confirm significant correlations between specific pairs of heavy metals (Table 7)..0441 16..799a 39. which explains about 57% of the total tivity of Grzybo variability and is the most important factor.0472 Surface Bottom Surface Bottom 0. 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 . 2003).0 4. content and organic carbon content (r ¼ 0. an important factor affecting the content of sulfates in the soil profile is their particle size.053 10.637 10. Ni) (Table 7).239b 13.364a 0. the smallest fraction content (<0. Assessment of the risk of heavy metal contamination 1. The same letters were used to indicate the means for which there are no statistically significant differences based on the Mann-Withneya test (p ¼ 0. 2015).941c 4. more than 300 mmol(þ) kg1 (data not published).5 value 3. The first F1 factor is represented by elements.3.5 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. Cu and Ni.05).372 1.823 0. i.450a 32. for which we observed no significant statistically relationship. Zn. Te sulfate sulfur content is averagely positively correlated with soil pH.5 2.5 0. Correlation between Pb and other elements.304 7. The soils showed a significant above-average correlation co*** efficient between the content of SeSO2 ).456 K. and then.933 0. Its content is significantly higher in the soils of the area A (Table 4). In case of most metals: Ni. Horizon p* Surface Bottom Surface Spa˛ gowy 0. which are characterized by high contents in the soil area A. which reported weak positive correlation (r ¼ 0. such as Cr.0318 0.959 57. explaining 18. Zn. with the exception of Pb. This assumption is confirmed by high content of calcium cations in sorption complex.0205 0. can be explained by the precipitation of poorly soluble calcium sulfate in the form of gypsum or anhydrite.207a 0. Candeias et al. as the distance from the mine increases. 5. due to the existence in some soils of calcium carbonate. 2011.419 7.5 positive correlation between Stot.968 0. / 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.88***) and averagely correlation with fraction content of Ø < 0.12 77. Corg.390 14.175 11.001) correlation between fractions of clay and the contents of Cr..762b 8. For other heavy metals we recorded an average correlation.0362 0. 2014).230 8. except for zinc. The third factor (F3) describes only part of Cd.002 mm (r ¼ 0.4% of the total variability. The calculated correlation coefficients also showed a highly significant (p ¼ 0.0 1.280b 0..688a 8. Cd.29***).192a 15. content is highly significantly correlated with all the analyzed trace elements. Zeng et al. which is widely distributed in the environment and whose contents in all designated areas are similar.0368 0. Chart of eigenvalues (screes) which visually assess components or factors explaining most of the variability in the data.086 0. The present study found an average positive correlation between pH and the content of heavy metals.0 1 2 3 4 5 6 eigenvalue number Fig.002 mm) and organic matter significantly affect the content of heavy metals and their mobility in the soil environment (Antoniadis et al. as well as Pb content and Corg. Higher pH values lead to the reduction in the mobility of heavy metals. Pb mg kg1 Zn mg kg1 Cd mg kg1 Cr mg kg1 Cu mg kg1 Ni mg kg1 Group A B C Mean SD Mean SD Mean SD I II II III III III 10.e.0 0. Similar relationships exist in the case of SeSO2 4 .953 0. Table 6 Results of Mann-Whitney test for soil properties at the surface and bottom horizon for areas A and C. which results in their accumulation in soil (Ciarkowska et al. This may be associated with increased traffic during mining activities in mines and intensive use of phosphate fertilizers in this area in order to improve soil properties (Satarug et al. The second factor (F2) contains only one element.766 25. their content is clearly reduced. A positive correlation between the content of SeSO2 and pH values 4 (r ¼ 0.083a 18. Paja˛ k et al. Cu. This allows us to define this factor as the impact of long-term acw sulfur mine.178 5.253b 3. The 4 and clay (r ¼ 0. is relatively low.36***).192 2. Cr.002 mm) and trace elements confirmed a highly significant positive correlation in the case of most metals (Cr. The relationship between the content of the smallest fraction (<0.0 2. Its presence in soils may be associated with a local emission. which is rarely seen in literature.578 0.50***).929 0.726c 2..0472 0. The results reveal that only in the case of Pb there is indeed very high correlation with the organic matter content. 2008. Soil parameter Area A Stot SeSO2 4 Area C Stot SeSO2 4 p* e calculated level of significance.185a 14. Cu and Zn in the soils we observed significant and strong positive correlations between pairs of these metals.53 determined Stot.0274 The analysis of principal components indicates that the analyzed metals create 3 distinct groups (Table 5). Sołek-Podwika et al.581 SD e standard deviation.554 1.79 96.0405 0. It is widely recognized that soil pH. Cu and Ni. 2014. Table 5 Matrix of rotation of standardized factor charges approached by the Varimax method of studies metals. 4.0 3. with the exception of Pb.783b 4..19 5.981 10. and clay content.011b 7.813c 2. lead..967a 27. The table only includes charges >0. both from the so-called “low emission” which takes place in urban areas and the movement of transport.

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