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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 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

In total. 2009). The study area has an average annual temperature of 70  C and the average annual rainfall of 800 mm.7% of the country (CSO. As the time passed and the miners gained experience. It formed as a result of biochemical processes which affected gypsum and anhydrite of the Lower Badenian (miocene) (Frankiewicz and Pucek. used in agricultural production. The mining operations frequently led to contamination of soil and water with elemental sulfur as a result of spontaneous eruptions.2.01. north. 1991e2008). Skwierawska et al. Sampling Sampling was performed in the spring of 2014.K. 2009). In Poland soils contaminated with heavy metals occur only locally. The mine in Grzybo which sulfur extraction was carried out by means of a new technology. As arable land they were fertilized with both mineral and natural fertilizers. Precipitation lasts from 60 to 70 days a year and the snow cover persists from 65 to 90 days. while less attention was paid to the requirements of environmental protecw was the first mine in Polish conditions in tion. 50 31. Scherer. while in areas remote from industrial plants it was low. According to Facchinelli et al. 2001. sulfur supply in plants and the threat of its excess in agro-ecosystems involves mainly its sulfate form (Kabata-Pendias and Pendias.70 E. Negative effects of anthropogenic soil sulfating include the increment of sulfates content (SO2 4 .. 2014). which causes disruption of the natural cycle of elements (e. 2006). Sołek-Podwika et al. used as agricultural soils. _ these elements into the food chain (Drozd 1978. The negative impact of the mine was not only limited to the mining fields but also occurred _ z-Hara. The increase in soil pollution by . 24 soil profiles were made. The years 1966e1976 were characterized by dynamic development of borehole sulfur mining. A region of certain particularity in Poland is the area of exploitation of sulfur deposits in Tarnobrzeg (Bryk and Kołodziej. any change of soil properties is a “chemical time bomb” posing the threat to the environment which may appear suddenly. 2004). The rich deposit of native sulfur extends from the Pre-Carpathian depression. Exploitation of sulfur and its processing in this area went on continuously for 30 years (1966e1996). they started to transfer liquid sulfur into closed tanks in which it was then transported. and SeSO2 4 content in soils located outside the mine collected in the 1970’s and at the beginning of the 21st century. 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. 2014). 2001. The injected hot water caused the melting of sulfur. 2009).. _ tionship also occur (Drozd 1978. as well as reduced use of fungicides and pesticides (Scherer. The sites where samples were taken are presented in Fig. / Journal of Environmental Management 180 (2016) 450e458 industrialized and was over 30 kg S ha1 year1. Eriksen et al. 1). from where it was blown out and transferred by wind over various distances. Materials and research methods 2. the extracted sulfur was collected on open landfills. Also the air was contaminated as a result of emissions of hydrogen sulfide and sulfur dust from open sulfur deposits. 1992. Fig. ii) to investigate the relationship between the content of sulfur compounds and selected soil properties. In the light of the studies carried out on a large scale by the Institute of Soil Science and Plant Cultivation. prior to the start of mining activities conducted within the area of the mine (until the end of 1970’s). soils of the study area came within the reach of elemental sulfur pollution. 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. less than 10 kg S ha1 year1 (CSO. 3 km (area B) and 10 km (area C) from the emission source of sulfur compounds. The study area w was located in the south-eastern The sulfur mine in Grzybo Poland (2105. but also with transport. From each horizon designated within a soil profile a representative soil sample for further laboratory analyses was taken. 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. 2007). The spatial differences result mainly from the impact of local sources of emissions of sulfur compounds. During this period there was a strong focus on growth in sulfur exploitation.20 N. which was the sulfur mine.. Kowalenko et al. especially manure. 1. _ outside their borders (Drozd 1978). 1999. Scherer. there are more and more areas which are deficient in this element because of the increased use of fertilizers with lower S content. 2. The evaluation of sulfur abundance in soils. B and C): 2 profiles were assigned to each of the four designated directions.. smaller amounts of natural fertilizers. _ deposited on sedimentary clay (Drozd 1978). 2008. 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. which remain on the Tertiary Cracovian clays. 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.ions are anhydride of H2SO4) and soil acidification. the authors set the specific aims: i) To identify changes in Stot. which was then extracted in its liquid form to the surface through the same holes.g carbon and nitrogen). Soil samples were collected from sites located towards the south. As the exploitation of sulfur intensified. A strong acidification of soils goes along with lowering availability of nutrients. 2.41. The availability of heavy metals for plants depends on many environmental factors such as soil texture.1. east and west at a distance of 1 km (area A). heavy metals contaminated soils account for less than 2. and consequently e can cause incorporation of _ z-Hara. In degraded soils the deterioration of water and air rela_ z-Hara. In Poland there are areas with distinct deficiency or excess of sulfur in the environment of crop plants. The impact was multidirectional and very difficult to predict at the time. Today. soil organic matter abundance and pH. iii) to estimate the risk of heavy metal pollution of soils in the region. 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. mainly in the highly industrialized areas. subsurface horizons e 24e40 cm (II) and bottom horizons e more than 120 cm (III). 1992. The authors of the study assumed that after 20 years which have 451 passed since the completion of mining. 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. Results of the determinations are shown for three studied horizons: surface horizons at a depth of 0e25 cm (I). along the northern Carpathians of the southern Poland and all the way to Ukraine. The geological structure of the investigated area is composed mainly of Quaternary deposits (sands or clays).. Eight soil profiles were assigned to each area (A. Studied soils were. Jaggi et al. KabataPendias and Pendias. 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. These changes lead to the destruction of aggregate structure and soil crusting with salts or iron hydroxides efflorescence formed on the surface. Initially.

Methods Representative soil samples were air dried and sieved with a sieve of 2 mm. Ni and Cd concentrations (Carter and Gregorich. Suspensions were shaken for 1 h. China). Cr.Soil texture was determined according to Polish Norms PN-R04032 and PN-R-04033 (1998).Total Zn. Samples containing CaCO3 were washed in 10% HCl to remove carbonates prior to the determination of Corg. Beijing. / Journal of Environmental Management 180 (2016) 450e458 Fig. 1991).3. . Circles A. 2.2. At the time of sampling soils of the study area were turf-covered post-arable wasteland on which no reclamation treatments were applied. The accuracy of the analytical methods was verified using the GSS-8 certificated reference material (GBW 07408e State Bureau of Metrology. 1.452 K.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. .) were calculated as the difference between the total and the inorganic carbon concentrations (Tan. 1978). B and C were used to designate the area where soil was sampled at a distance of respectively 1 km. Integrated pollution index IPI In order to assess the degree of contamination with heavy metals.. Dots mark the places where soil profiles were made. Chemical and physical soil properties were determined with the use of the following methods: . Cu. Organic carbon concentrations (Corg. _ z_ Stot. . Sołek-Podwika et al. 2005).. 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. Location of the research area. filtered and titrated with 0.The content of total sulfur and sulfate sulfur was determined by the nephelometric method of Butters and Chenery (1959) and Bardsley and Lancaster (1960). it was considered advisable to calculate the Integrated Pollution Index (IPI) for each area.4.5 potentiometrically (Tan.1 M NaOH to pH ¼ 8. 2005).5 soil/solution ratio.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. defined as an average PI value for . The exchangeable acidity was calculated from the amount of base used and expressed in mmol(þ)$kg1 (Ostrowska et al. . 3 km and 10 km from the borders of the mine. . and SeSO2 4 caused the agricultural activity to stop (Drozd Hara.

2e39. taking into account of the designed horizons.05.46 (soil area C and A) respectively. Guo et al.. whereas SeSO2 and 4 from 0.9e27. In studied soils the content of determined forms of sulfur was as follows: in the humus horizon Stot. 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. Statistical analysis In order to present the general characteristics of the selected properties of the studied soils. At the bottom horizon the Stot. This allows us to specify metal groups correlated with each other. 6. Prior to the variance analysis. the arithmetic mean.K. The second group consists of Zn and Cd.2. 3. The same relationships were found at each of the analyzed soil horizons (Table 3). Description of the basic properties of the studied soils In terms of grain size composition. 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. ranges from 13. Then IPI was classified into three categories: low (IPI  1). Cu and Ni with a higher average content in the soils of A area. content ranged 1 from 0.005 to 0. only at the subsurface horizon there were no statistically significant differences between B and C regions. from 4. Results 3.05 one can reject the null hypothesis and conclude that the distance from the mine (1. 3..42 g kg1 (soil area B and A). which is c20.86e1. where 50% of the value of the tested variable is contained.9 to 20. Spearman’s rank correlation analysis was used. in the case of sulfate sulfur. For this purpose we calculated the critical value of H statistics for Kruskal-Wallis test. Factor F2 contains Pb which belongs to the first group with . first we verified the null hypothesis.67 to 2. All statistical analyzes were conducted using Statistica PL v 10 packet for n ¼ 24 for each of the studied horizons of the soil. the soils of all studied areas are characterized by a certain changeability. The average percentage of SeSO2 in S at the 4 tot. i. Ntot. Also occasionally (25%) one can find heavy soils (common clays and loamy clays). at the subsurface horizon e 49%.440 g kg1 and 0. The third group consists of Cr. On the basis of the scree plot (Fig. in order to distinguish homogeneous groups. Due to the absence of normal distribution.2 ¼ 5. In the case of the total sulfur.2 mmol(þ) kg1 (soil area C and B. the difference between the first (Q1) and the third (Q3) quartile.991. The first group included Pb. The studies showed that the content of individual forms of sulfur decreases when the distance from the mine increases (Figs. 2012). and SeSO2 4 content occur in soils at a distance of 3 km from the mine borders. However. the median and quartile gap.9 in the surface horizons 453 (soil area C and A). sandy clays and light clays). 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. fraction <0.5. 2. and 0.5 g kg1. 4). / Journal of Environmental Management 180 (2016) 450e458 6 metals. 3 and 10 km) has a statistically significant impact on the levels of sulfur compounds in soils (Table 2). the nonparametric variance analysis of Kruskal-Wallis was applied.010e0.5 mmol(þ) kg1 (soil area A and C).220 g kg1 and SeSO2 4 e 0. the results of Mann-Whitney test indicated homogeneous groups (Table 3). The results of Mann-Whitney test showed that the biggest changes in Stot. whereas in the bottom horizons the average content of marked elements is 0.001e0.031 1 to 0.e. Stot.05. standard deviation. The mean values of pH of the studied soils range from 4. Principal component analysis: PCA enables the reduction of data and shows the relationship between the examined variables.1.9 (soil area B and A) and 0. it was checked if the tested variables are normally distributed (Shapiro-Wilk test) and whether there is homogeneity of variance (Leven test). and SeSO2 4 content in the soils of studied areas Assuming the level of significance of p ¼ 0. Additionally. whereas the largest percentage was observed at the bottom horizon e 71% (Fig. SeSO2 4 ) and the contents of individual heavy metals for the entire data set. the lowest content in the soils of C area and intermediate content in the soils of B area. Cr. Each of the designated area is dominated (75%) by light and medium soils (loamy sands... Additionally.3 mmol(þ) kg1 (soil area B and C).002 mm.7.8e16. no statistically significant changes are noted between B and C regions. In addition. The content of heavy metals in the studied soils The analyzed elements were divided into three groups (I. 2 and 3). Non-parametric analysis ANOVA: In order to determine the significance of differences between the mean values obtained for the examined areas. and therefore likely to have similar properties and common origins (Tahri et al. similar relationships were noted as in the case of total sulfur.4 to 5. The mean value of hydrolytic acidity in the horizons of the soils of the studied areas is as follows: 26. 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.3 to 5. 3. Correlation analysis: In order to investigate the relationship between physical and chemical properties of the soil (pH. 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.7e9. for which the average content in soils of all the studied areas are similar and there are no significant changes between them. Bi e the content of the heavy metal in the bottom horizon (bedrock). i. 22. which assumed that there was no significant difference between the mean sulfur content of determined sulfur forms in the soils of studied areas. 5). 2005.003 to 0. MannWhitney test was conducted. a factor analysis was conducted (Table 5). In the surface horizons the average content of Corg.090 g kg1. Stot. Cu.340 g kg (Figs. 2 and 3).e.210 g kg analogically at the subsurface horizon e 0. contents Corg.4e4. which have a higher average content in soils of the A area and gradually decreasing content in the soils of B and C areas.23e0. Identical letters were used to denote values for which there are no significant differences at the level of significance p ¼ 0. average (1  IPI < 2] and high (IPI > 2) (Chen et al. the ANOVA variance analysis was used. Table 1).05.680 g kg1.0 in bottom horizons (soil area B and A). in the subsurface horizons e 7. ranged from 0. II and III) depending on their content in the soils of the studied areas (Table 4).5 in subsurface horizons and from 4. 2005).3.60 g kg1 (soil area C and A) for Ntot. surface horizon did not exceed 36%. 2010): PIi ¼ Ci Bi Where Ci e the content of the heavy metal in the surface horizon. In the case of participation of the sulfate sulfur in the total sulfur.005e0.9 to 6. basic statistical parameters were calculated. Sołek-Podwika et al. Factor F1 contains elements of the second and third group (Zn. and Ntot from 1..3 g kg1 for Corg.

03a 0. there has been a change from IVo to Io.1 0. 4.1 20 ± 11 30 ± 12 50 ± 22 2.74 ± 32.02b 26. Scherer.5 ± 1.5 19 ± 11 32 ± 10 49 ± 19 0. and SeSO2 4 in the soils adjacent to the sulfur mine.75 4. Sołek-Podwika et al.454 K.03 ± 0.9 ± 1.002 mm) % sand (2e0. With increasing distance from the source of contamination (soils of C region). which proves its anthropogenic origin (Kabata-Pendias et al. Decrease in Stot.8 ± 2.20 ± 0.60 ± 5.6 0. e soil organic carbon. Table 2 The results of the test of Kruskal-Wallis for Stot.053c 35.748 13. content proposed by IUNG (Kabata-Pendias et al.86 ± 0.08 g kg1 respectively.99 ± 25. 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.75 ± 18. In the soils _ z-Hara _ collected by Drozd (1978). in the period of intensive mining works. and SeSO2 4 horizons in the tested soils of areas A. Consequently. Hh e exchangeable acidity.6 10 ± 8 29 ± 12 61 ± 18 13.03 ± 0.9).03b C 0. However.9 ± 3.60 ± 0. conducted in the soils of the same areas in 1970’s.012 ± 0. the studied soils are classified as IVº.05e0. Oxidation occurs under the influence of .5 33.08b Horizon III e bottom A 0. In the soils of the studied area.9 ± 20. 2005.57 g kg1. / Journal of Environmental Management 180 (2016) 450e458 Table 1 Physical and chemical properties of soils in the studied areas of A. Discussion 4. % Mean ± SD Mean ± SD Mean ± SD 0.14 ± 0.02a B 0.426 6.9). Area Stot.012 ± 0. In the soils of C area the average content for Stot. the content of which in the soil usually accounts for less than 5% of the total sulfur content (Hu et al.2 ± 7.002 mm) % sand (2e0.. Changes in the content of Stot. g kg1 1 SeSO2 4 g kg SeSO2 4 in Stot.7 1. Ntot e total nitrogen.4 16. whereas at the bottom horizons it was 0.2 ± 11.004b 48.14 ± 0. Table 3 The mean and standard deviation (SD) for SeSO2 4 and Stot.002 mm) % silt (0. p* e calculated level of significance.99b Horizon I e surface A 0.44 ± 0.1 0.02a 0.1 ± 1.1 2.011 ± 0.33a 40.0 26. despite the passage of nearly 20 years since the end of the exploitation of the sulfur deposits. while for the bottom horizons they were estimated at 0.7 39. The most important source of sulfur for plants is its sulfate form.7 9.0 ± 4. whereas factor F3 contains Cd which belong to the second group (load > 0.05 mm) Corg.10b C 0.0002 H e statistical values for Kruskal-Wallis test.19 ± 0.42 5. the average content of determined sulfur forms e Stot.26b 10.0015 0.8 ± 21. On the basis of Mann-Whitney test (Table 6). Based on the limit values of Stot.01a 0.74 g kg1 and 0.26 ± 0.11 ± 0.003 ± 0.8 ± 1.91 4.7 ± 1. into SeSO2 4 .76b 0.17 4.007 14. 2009).5 ± 0. that is soils with the natural content of this form of the element. 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. 1993).6 Corg.5 27.9 9±7 31 ± 14 60 ± 20 7.23 ± 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. participation of SeSO2 4 in Stot..381 17.05.31 g kg1 and for SeSO2 was 4 0.7 1.02b a high load (>0.05e0.0148 0.0004 0.57 ± 0.002 mm) % silt (0.4 ± 0.42b 0. 1993) for horizons 0e20 cm thick.8 23 ± 11 35 ± 11 42 ± 22 4. both in A and C area.3 0. In terms of content of this type of sulfur.16b Horizon II e subsurface A 0.5 ± 14.23 6.0 ± 0. Horizon p* H I (surface) II (subsurface) III (bottom) Stot.55 ± 22. was 0. 1993) and by comparing the contents of SeSO2 4 at various time periods. at surface horizons of the soils of A area.53a 22.3 ± 0.44 g kg1 and 0. we can still observe an increased (due to anthropogenic pressure) content of sulfate sulfur.91 ± 21.79 ± 11.002 mm) % sand (2e0.05. and SeSO2 4 e were higher and for surface horizons they amounted respectively to 0.1 0.6 6.4 ± 0. at present lower contents of the examined sulfur form are observed.2 9±5 29 ± 11 62 ± 16 8.180 15.18 ± 0.01 ± 1.4 22.09b 0.3 ± 3. SeSO2 4 Stot.0008 0. according to IUNG classification (Kabata-Pendias et al. Identical letters were used for means for which there is no significant difference when the Mann-Whitney test is applied for p ¼ 0.006b 0.5 7±4 33 ± 12 60 ± 15 19.09 ± 0.017 ± 0.30 g kg1 (A area)..89 ± 0.05 mm) Corg.002c 70.67 4.002 mm) % silt (0.9 ± 1.83 ± 21.18a B 0.33 ± 7.005b 0. g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 % clay (<0. it can be inferred at 0. B and C.05e0.28 g kg1 and 0.46 ± 0.9 ± 5. which allows for rejection of the hypothesis of the equality of means. 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). which was assumed.5 ± 30.1.05 mm) Corg.7 ± 6.1 ± 0.2 ± 20.5 ± 21. B and C.70 5.18b 28.09b C 0.6 24.3 ± 27. g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 % clay (<0.54a 11.05 significance level that in the currently collected soils.18 g kg1 at the surface horizons.02 ± 0. Area Horizon Parameters % clay (<0.08 ± 0.13 5. content is much higher than 5% (Table 3). SeSO2 4 8.0455 0.42 ± 1.51 4.160 0..4 2..20a B 0.8 14 ± 10 31 ± 13 55 ± 22 9. 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 0.67 ± 0.

1999.1 0. This process has been confirmed in field studies by many authors (Jaggi et al. low level of fertilization and migration of sulfates to lower levels of soils and groundwater (Zhao et al. 4. 0. Kertesz and Mirleau.in St ot.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. 2004).2 0. 2004.15 . 1 Fig. Sołek-Podwika et al. where: the focal point e the median.3 -1 0. 3. Box-and-whisker diagram of the Stot.5 0. Burgos et al. Scherer. depending on the area (distance from the source). moisture and with the contribution of soil microorganisms . . g . g kg 0. % 50 40 30 20 100 80 80 60 40 20 10 0 100 S-SO4 2. Skwierawska et al. the box (Q1. 2013).kg -1 -1 0. Matula.K. 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 7.0 10 k m 0. whisker e the range (min-max).. 2000. There is a strong . Fismes et al.20 0.2 0. % 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. The relationship between determined forms of sulfur. Box-and-whisker diagram of the SeSO2 depending on the area (distance from the source).in St ot..3 0. 4. Box-and-whisker diagram of the participation of SeSO2 4 in Stot.6 S t ot. Reduction in sulfate sulfur content at surface horizons of soils is the result of its being absorbed by plants. S-SO4 2.4 0. in g kg1 depending on the area (distance from the source).1 0. Q3).in St ot. g kg 455 0. where: the focal point e the median. content increases as the depth grows (Table 3).05 0. the box (Q1.2. / Journal of Environmental Management 180 (2016) 450e458 0. 1999.5 S t ot. 2.8 0. 2001. whisker e the range (min-max). whisker e the 4 in g kg range (min-max). 2008).0 1 km 3 km 0. indicated in %. 2001.4 S t ot. Q3)... % S-SO4 2. Forming sulfates are washed down from the soil profile together with migrating water.10 0.mainly bacteria Thiobacillus thiooxidans (Scherer. The movement of sulfates in the soil profiles is currently proven by the fact that SeSO2 4 percentage in Stot.7 0. atmospheric oxygen. Q3). the box (Q1. where: the focal point e the median..

with the exception of Pb. The results reveal that only in the case of Pb there is indeed very high correlation with the organic matter content. Cu and Ni.178 5.5 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 0.002 mm) and trace elements confirmed a highly significant positive correlation in the case of most metals (Cr. A positive correlation between the content of SeSO2 and pH values 4 (r ¼ 0.36***).5 2. The calculated correlation coefficients also showed a highly significant (p ¼ 0.766 25. Cd.0362 0... and then.0472 0. which reported weak positive correlation (r ¼ 0. which are characterized by high contents in the soil area A. 2008.450a 32.19 5. Te sulfate sulfur content is averagely positively correlated with soil pH.823 0. Assessment of the risk of heavy metal contamination 1.5 4. Table 5 Matrix of rotation of standardized factor charges approached by the Varimax method of studies metals.002 mm (r ¼ 0. explaining 18. an important factor affecting the content of sulfates in the soil profile is their particle size. The second factor (F2) contains only one element. except for zinc.001) correlation between fractions of clay and the contents of Cr.0 4. For other heavy metals we recorded an average correlation. Paja˛ k et al.192a 15.083a 18. Zn.813c 2. Horizon p* Surface Bottom Surface Spa˛ gowy 0. Those hypotheses confirm significant correlations between specific pairs of heavy metals (Table 7).419 7. 2003). which explains about 57% of the total tivity of Grzybo variability and is the most important factor. The present study found an average positive correlation between pH and the content of heavy metals.799a 39. Soil parameter Area A Stot SeSO2 4 Area C Stot SeSO2 4 p* e calculated level of significance. Its content is significantly higher in the soils of the area A (Table 4).88***) and averagely correlation with fraction content of Ø < 0. The first F1 factor is represented by elements. i.253b 3. The relationship between the content of the smallest fraction (<0.968 0. content is highly significantly correlated with all the analyzed trace elements.0368 0.50***).304 7. Sołek-Podwika et al. Chart of eigenvalues (screes) which visually assess components or factors explaining most of the variability in the data..29***)..783b 4.372 1.364a 0. which results in their accumulation in soil (Ciarkowska et al. The soils showed a significant above-average correlation co*** efficient between the content of SeSO2 ).e.578 0.581 SD e standard deviation. This allows us to define this factor as the impact of long-term acw sulfur mine.0 3.053 10.390 14. 2014). 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.185a 14. is relatively low.941c 4.0 0.175 11. Ni) (Table 7). for which we observed no significant statistically relationship.280b 0.011b 7.0318 0.959 57.5 positive correlation between Stot. Correlation between Pb and other elements. The 4 and clay (r ¼ 0.002 mm) and organic matter significantly affect the content of heavy metals and their mobility in the soil environment (Antoniadis et al.0205 0..5 value 3. 4. as well as Pb content and Corg. which is rarely seen in literature. Cu and Zn in the soils we observed significant and strong positive correlations between pairs of these metals.207a 0.0405 0. The table only includes charges >0. both from the so-called “low emission” which takes place in urban areas and the movement of transport.230 8. 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. their content is clearly reduced. content and organic carbon content (r ¼ 0. the smallest fraction content (<0. and clay content.0274 The analysis of principal components indicates that the analyzed metals create 3 distinct groups (Table 5). / 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. Table 6 Results of Mann-Whitney test for soil properties at the surface and bottom horizon for areas A and C. This assumption is confirmed by high content of calcium cations in sorption complex.953 0. Zeng et al.239b 13. Cr. Corg.726c 2. with the exception of Pb. According to Scherer (2009). Similar relationships exist in the case of SeSO2 4 .762b 8.929 0.637 10.. Its presence in soils may be associated with a local emission.933 0. 2011. can be explained by the precipitation of poorly soluble calcium sulfate in the form of gypsum or anhydrite. Zn. The third factor (F3) describes only part of Cd. Cu.12 77. Cu and Ni. It is widely recognized that soil pH.0 2. lead.3.554 1. In case of most metals: Ni. 2014.688a 8. Higher pH values lead to the reduction in the mobility of heavy metals.456 K.086 0.0441 16. due to the existence in some soils of calcium carbonate. Candeias et al.4% of the total variability.981 10. such as Cr.245 0.5 0.05).192 2. which is widely distributed in the environment and whose contents in all designated areas are similar. 2015). as the distance from the mine increases.0472 Surface Bottom Surface Bottom 0. 5.967a 27.0 1.53 determined Stot.. 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 . more than 300 mmol(þ) kg1 (data not published).79 96.0 1 2 3 4 5 6 eigenvalue number Fig. 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.

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