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Journal of Environmental Management 180 (2016) 450e458

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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

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.

Sulfur mine
Heavy metals

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: (K. Sołek-Podwika), rrciarko@cyf-kr. (K. Ciarkowska).
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 injected hot water caused the melting of sulfur. During this period there was a strong focus on growth in sulfur exploitation. It formed as a result of biochemical processes which affected gypsum and anhydrite of the Lower Badenian (miocene) (Frankiewicz and Pucek. These changes lead to the destruction of aggregate structure and soil crusting with salts or iron hydroxides efflorescence formed on the surface. Scherer. From each horizon designated within a soil profile a representative soil sample for further laboratory analyses was taken. The geological structure of the investigated area is composed mainly of Quaternary deposits (sands or clays). prior to the start of mining activities conducted within the area of the mine (until the end of 1970’s). The years 1966e1976 were characterized by dynamic development of borehole sulfur mining. 1992. The spatial differences result mainly from the impact of local sources of emissions of sulfur compounds. 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.. 1). Also the air was contaminated as a result of emissions of hydrogen sulfide and sulfur dust from open sulfur deposits. The increase in soil pollution by .g carbon and nitrogen). used as agricultural soils. B and C): 2 profiles were assigned to each of the four designated directions. while in areas remote from industrial plants it was low.01. iii) to estimate the risk of heavy metal pollution of soils in the region. Eight soil profiles were assigned to each area (A. which causes disruption of the natural cycle of elements (e. A strong acidification of soils goes along with lowering availability of nutrients. The availability of heavy metals for plants depends on many environmental factors such as soil texture. The negative impact of the mine was not only limited to the mining fields but also occurred _ z-Hara. In total. 2004). heavy metals contaminated soils account for less than 2. In the light of the studies carried out on a large scale by the Institute of Soil Science and Plant Cultivation.. any change of soil properties is a “chemical time bomb” posing the threat to the environment which may appear suddenly. subsurface horizons e 24e40 cm (II) and bottom horizons e more than 120 cm (III). Today. along the northern Carpathians of the southern Poland and all the way to Ukraine. sulfur supply in plants and the threat of its excess in agro-ecosystems involves mainly its sulfate form (Kabata-Pendias and Pendias. As arable land they were fertilized with both mineral and natural fertilizers. 2001. Materials and research methods 2. As the exploitation of sulfur intensified. north. mainly in the highly industrialized areas. 1999.41. increasing solubility of aluminium and manganese compounds and leaching of basic components. _ tionship also occur (Drozd 1978. soil organic matter abundance and pH. 2. As the time passed and the miners gained experience. Initially. Kowalenko et al. 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. 2014). Jaggi et al. 2006). The authors of the study assumed that after 20 years which have 451 passed since the completion of mining. Sampling Sampling was performed in the spring of 2014. 2. Sołek-Podwika et al. but also with transport. The mine in Grzybo which sulfur extraction was carried out by means of a new technology.. 1. Scherer. the authors set the specific aims: i) To identify changes in Stot. while less attention was paid to the requirements of environmental protecw was the first mine in Polish conditions in tion. Precipitation lasts from 60 to 70 days a year and the snow cover persists from 65 to 90 days. 3 km (area B) and 10 km (area C) from the emission source of sulfur compounds. 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. namely the method invented by Herman Frasch (patented w in USA in 1894). 2009). 1992. KabataPendias and Pendias. According to Facchinelli et al. Fig. 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. In Poland there are areas with distinct deficiency or excess of sulfur in the environment of crop plants. _ these elements into the food chain (Drozd 1978. Eriksen et al.2. which remain on the Tertiary Cracovian clays. In degraded soils the deterioration of water and air rela_ z-Hara. 2007). as well as reduced use of fungicides and pesticides (Scherer. / Journal of Environmental Management 180 (2016) 450e458 industrialized and was over 30 kg S ha1 year1. The study area has an average annual temperature of 70  C and the average annual rainfall of 800 mm.7% of the country (CSO. The evaluation of sulfur abundance in soils. ii) to investigate the relationship between the content of sulfur compounds and selected soil properties. A region of certain particularity in Poland is the area of exploitation of sulfur deposits in Tarnobrzeg (Bryk and Kołodziej. _ outside their borders (Drozd 1978). soils of the study area came within the reach of elemental sulfur pollution. there are more and more areas which are deficient in this element because of the increased use of fertilizers with lower S content. In Poland soils contaminated with heavy metals occur only locally. The impact was multidirectional and very difficult to predict at the time. smaller amounts of natural fertilizers. Negative effects of anthropogenic soil sulfating include the increment of sulfates content (SO2 4 .. Soil samples were collected from sites located towards the south. especially manure. The negative impact of the sulfur mine in Grzybo was associated not only with mining works and production processes.20 N. the extracted sulfur was collected on open landfills. which was then extracted in its liquid form to the surface through the same holes.1. The study area w was located in the south-eastern The sulfur mine in Grzybo Poland (2105.K. 2009).ions are anhydride of H2SO4) and soil acidification. 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. 2014). Exploitation of sulfur and its processing in this area went on continuously for 30 years (1966e1996). 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. and consequently e can cause incorporation of _ z-Hara. Results of the determinations are shown for three studied horizons: surface horizons at a depth of 0e25 cm (I). which was the sulfur mine.. less than 10 kg S ha1 year1 (CSO. 1991e2008). 50 31. The mining operations frequently led to contamination of soil and water with elemental sulfur as a result of spontaneous eruptions. they started to transfer liquid sulfur into closed tanks in which it was then transported.70 E. Skwierawska et al. from where it was blown out and transferred by wind over various distances. Studied soils were. 24 soil profiles were made. 2001. 2009). and SeSO2 4 content in soils located outside the mine collected in the 1970’s and at the beginning of the 21st century. There is also a change in the quantitative and qualitative composition of soil microorganisms. The sites where samples were taken are presented in Fig. _ deposited on sedimentary clay (Drozd 1978). 2008. The rich deposit of native sulfur extends from the Pre-Carpathian depression. used in agricultural production. east and west at a distance of 1 km (area A).

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

The same relationships were found at each of the analyzed soil horizons (Table 3). SeSO2 4 ) and the contents of individual heavy metals for the entire data set.9e27. taking into account of the designed horizons. Statistical analysis In order to present the general characteristics of the selected properties of the studied soils. Cu. 3. Correlation analysis: In order to investigate the relationship between physical and chemical properties of the soil (pH. 5).. Factor F2 contains Pb which belongs to the first group with .3 mmol(þ) kg1 (soil area B and C).. it was checked if the tested variables are normally distributed (Shapiro-Wilk test) and whether there is homogeneity of variance (Leven test).86e1. The first group included Pb. The average percentage of SeSO2 in S at the 4 tot. Prior to the variance analysis. in the case of sulfate sulfur.K. Non-parametric analysis ANOVA: In order to determine the significance of differences between the mean values obtained for the examined areas.67 to 2. for which the average content in soils of all the studied areas are similar and there are no significant changes between them.0 in bottom horizons (soil area B and A). i. average (1  IPI < 2] and high (IPI > 2) (Chen et al. Ntot.42 g kg1 (soil area B and A). Then IPI was classified into three categories: low (IPI  1).5 mmol(þ) kg1 (soil area A and C). in order to distinguish homogeneous groups. whereas the largest percentage was observed at the bottom horizon e 71% (Fig. 22. MannWhitney test was conducted. / Journal of Environmental Management 180 (2016) 450e458 6 metals. 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 g kg1 for Corg.440 g kg1 and 0. 3 and 10 km) has a statistically significant impact on the levels of sulfur compounds in soils (Table 2). 2 and 3). At the bottom horizon the Stot.9 in the surface horizons 453 (soil area C and A). at the subsurface horizon e 49%. the soils of all studied areas are characterized by a certain changeability. 2012). Factor F1 contains elements of the second and third group (Zn. from 4. and therefore likely to have similar properties and common origins (Tahri et al. the arithmetic mean. The content of heavy metals in the studied soils The analyzed elements were divided into three groups (I. and Ntot from 1. Cr.9 (soil area B and A) and 0. Spearman’s rank correlation analysis was used. In studied soils the content of determined forms of sulfur was as follows: in the humus horizon Stot. On the basis of the scree plot (Fig. Also occasionally (25%) one can find heavy soils (common clays and loamy clays).5. surface horizon did not exceed 36%.003 to 0. Each of the designated area is dominated (75%) by light and medium soils (loamy sands. whereas SeSO2 and 4 from 0. a factor analysis was conducted (Table 5).9 to 6.e. the difference between the first (Q1) and the third (Q3) quartile.. first we verified the null hypothesis. In addition.2. i. fraction <0. Results 3. The second group consists of Zn and Cd. the median and quartile gap. Description of the basic properties of the studied soils In terms of grain size composition. content ranged 1 from 0.9 to 20. Identical letters were used to denote values for which there are no significant differences at the level of significance p ¼ 0.5 in subsurface horizons and from 4. 2. contents Corg. which is c20. which assumed that there was no significant difference between the mean sulfur content of determined sulfur forms in the soils of studied areas.220 g kg1 and SeSO2 4 e 0.05.60 g kg1 (soil area C and A) for Ntot. In the surface horizons the average content of Corg.e. 2005. However. as well as for the soils of A and B areas in relation to the soils of C area in the case of Zn.4 to 5. Principal component analysis: PCA enables the reduction of data and shows the relationship between the examined variables. All statistical analyzes were conducted using Statistica PL v 10 packet for n ¼ 24 for each of the studied horizons of the soil.340 g kg (Figs. no statistically significant changes are noted between B and C regions. the results of Mann-Whitney test indicated homogeneous groups (Table 3).3 to 5. This allows us to specify metal groups correlated with each other. In the case of participation of the sulfate sulfur in the total sulfur. The mean values of pH of the studied soils range from 4. Bi e the content of the heavy metal in the bottom horizon (bedrock). ranged from 0. Additionally.680 g kg1.2 mmol(þ) kg1 (soil area C and B. The mean value of hydrolytic acidity in the horizons of the soils of the studied areas is as follows: 26. 2 and 3). The studies showed that the content of individual forms of sulfur decreases when the distance from the mine increases (Figs. ranges from 13.05. where 50% of the value of the tested variable is contained. standard deviation.031 1 to 0.23e0.4e4. Guo et al.5 g kg1. the nonparametric variance analysis of Kruskal-Wallis was applied. II and III) depending on their content in the soils of the studied areas (Table 4).2e39. and 0..002 mm.010e0.46 (soil area C and A) respectively.7.210 g kg analogically at the subsurface horizon e 0. 2005). whereas in the bottom horizons the average content of marked elements is 0. 3.1.8e16. 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. the ANOVA variance analysis was used. The third group consists of Cr. 3. For this purpose we calculated the critical value of H statistics for Kruskal-Wallis test. the lowest content in the soils of C area and intermediate content in the soils of B area. sandy clays and light clays). Sołek-Podwika et al. Cu and Ni with a higher average content in the soils of A area. 4). only at the subsurface horizon there were no statistically significant differences between B and C regions.05 one can reject the null hypothesis and conclude that the distance from the mine (1. Additionally.001e0. 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 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.090 g kg1.7e9. similar relationships were noted as in the case of total sulfur.05. Table 1).991. Stot. The results of Mann-Whitney test showed that the biggest changes in Stot. In the case of the total sulfur.005 to 0. which have a higher average content in soils of the A area and gradually decreasing content in the soils of B and C areas. Ni) with loads greater than 0.2 ¼ 5. 2010): PIi ¼ Ci Bi Where Ci e the content of the heavy metal in the surface horizon..3. basic statistical parameters were calculated.005e0. Due to the absence of normal distribution. in the subsurface horizons e 7. and SeSO2 4 content in the soils of studied areas Assuming the level of significance of p ¼ 0. 6. Stot. and SeSO2 4 content occur in soils at a distance of 3 km from the mine borders.

g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 % clay (<0.004b 48.002 mm) % silt (0.002 mm) % sand (2e0. 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.012 ± 0.18 g kg1 at the surface horizons.002 mm) % sand (2e0.08b Horizon III e bottom A 0.5 ± 21.05 mm) Corg.6 24.42 5.7 ± 6.02a 0.20 ± 0.017 ± 0. according to IUNG classification (Kabata-Pendias et al.2 ± 7.18 ± 0.5 ± 14.5 ± 30.1 ± 0.005b 0.74 g kg1 and 0.0002 H e statistical values for Kruskal-Wallis test..03 ± 0.01a 0.83 ± 21.002 mm) % silt (0.002c 70.0 26.9 ± 3.3 ± 27.23 ± 0.8 ± 2.4 ± 0. it can be inferred at 0. 1993) and by comparing the contents of SeSO2 4 at various time periods.79 ± 11.9 ± 1. at present lower contents of the examined sulfur form are observed. both in A and C area. B and C.1 ± 1.60 ± 0.1 0.002 mm) % sand (2e0.6 10 ± 8 29 ± 12 61 ± 18 13.44 g kg1 and 0. was 0. SeSO2 4 8.03a 0.012 ± 0. there has been a change from IVo to Io.053c 35.2 ± 20.9 ± 20.42b 0. 1993) for horizons 0e20 cm thick.1 0.28 g kg1 and 0.7 9.10b C 0.0148 0.02 ± 0.55 ± 22. In the soils _ z-Hara _ collected by Drozd (1978). the average content of determined sulfur forms e Stot.007 14. content proposed by IUNG (Kabata-Pendias et al. into SeSO2 4 . participation of SeSO2 4 in Stot.14 ± 0. e soil organic carbon.57 ± 0. Identical letters were used for means for which there is no significant difference when the Mann-Whitney test is applied for p ¼ 0.002 mm) % silt (0. 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. Consequently. In terms of content of this type of sulfur.09 ± 0.4 22.67 4.6 0. Table 3 The mean and standard deviation (SD) for SeSO2 4 and Stot.02b 26.99 ± 25.89 ± 0. With increasing distance from the source of contamination (soils of C region).180 15. % Mean ± SD Mean ± SD Mean ± SD 0.9 ± 5.3 ± 3.9 ± 1.011 ± 0.7 1.31 g kg1 and for SeSO2 was 4 0. at surface horizons of the soils of A area.11 ± 0.05e0.44 ± 0.4 16.2 ± 11. g kg1 1 SeSO2 4 g kg SeSO2 4 in Stot.05e0.75 ± 18. despite the passage of nearly 20 years since the end of the exploitation of the sulfur deposits.006b 0.454 K.7 39.4 ± 0.33a 40.05 mm) Corg.9 9±7 31 ± 14 60 ± 20 7.74 ± 32.5 33.8 14 ± 10 31 ± 13 55 ± 22 9.426 6..1 0.7 1. 2009).57 g kg1.16b Horizon II e subsurface A 0. Area Stot.0455 0. while for the bottom horizons they were estimated at 0.60 ± 5.748 13.30 g kg1 (A area).91 4.09b C 0. and SeSO2 4 in the soils adjacent to the sulfur mine. that is soils with the natural content of this form of the element. the studied soils are classified as IVº. and SeSO2 4 e were higher and for surface horizons they amounted respectively to 0.6 6..05e0. 4.1 2. which proves its anthropogenic origin (Kabata-Pendias et al.76b 0. Scherer.23 6. Sołek-Podwika et al.5 ± 1.51 4. which allows for rejection of the hypothesis of the equality of means. The most important source of sulfur for plants is its sulfate form. Hh e exchangeable acidity.0015 0. Ntot e total nitrogen. Discussion 4.003 ± 0.3 0.46 ± 0.03 ± 0.01 ± 1. Area Horizon Parameters % clay (<0. Table 2 The results of the test of Kruskal-Wallis for Stot. However.02b a high load (>0.0 ± 4. whereas at the bottom horizons it was 0.5 27.7 ± 1.08 g kg1 respectively. p* e calculated level of significance. SeSO2 4 Stot.14 ± 0. we can still observe an increased (due to anthropogenic pressure) content of sulfate sulfur.91 ± 21. Oxidation occurs under the influence of .42 ± 1.9).0008 0. conducted in the soils of the same areas in 1970’s. which was assumed. 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 0.08 ± 0.0004 0.0 ± 0.18a B 0. Decrease in Stot.8 ± 1.160 0. and SeSO2 4 horizons in the tested soils of areas A.75 4. content is much higher than 5% (Table 3).17 4.54a 11.1 20 ± 11 30 ± 12 50 ± 22 2.9).02a B 0.05 mm) Corg.13 5.19 ± 0.1.03b C 0.5 19 ± 11 32 ± 10 49 ± 19 0.18b 28.05.8 23 ± 11 35 ± 11 42 ± 22 4.5 ± 0.99b Horizon I e surface A 0.2 9±5 29 ± 11 62 ± 16 8.26b 10.70 5. 2005.53a 22. 1993). 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. in the period of intensive mining works.4 2.67 ± 0.8 ± 21. B and C.20a B 0.05.09b 0. On the basis of Mann-Whitney test (Table 6).381 17.3 ± 0.5 7±4 33 ± 12 60 ± 15 19. whereas factor F3 contains Cd which belong to the second group (load > 0. Based on the limit values of Stot. g kg1 Ntot g kg1 pHKCl Hh mmol(þ) kg1 % clay (<0.05 significance level that in the currently collected soils. 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)..86 ± 0. In the soils of the studied area. / Journal of Environmental Management 180 (2016) 450e458 Table 1 Physical and chemical properties of soils in the studied areas of A. In the soils of C area the average content for Stot.6 Corg. the content of which in the soil usually accounts for less than 5% of the total sulfur content (Hu et al. Changes in the content of Stot. Horizon p* H I (surface) II (subsurface) III (bottom) Stot.33 ± 7.26 ± 0..

Forming sulfates are washed down from the soil profile together with migrating water. 1999.15 . Q3).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. 2000. indicated in %. % S-SO4 2. / Journal of Environmental Management 180 (2016) 450e458 0. Fismes et al. 2004.8 0. 1999. whisker e the range (min-max). Scherer. -1 -1 0.3 -1 0.2 St ot. Box-and-whisker diagram of the Stot. Kertesz and Mirleau.. 1 Fig.. 4.6 S t ot.7 0.5 0. 0. 3.mainly bacteria Thiobacillus thiooxidans (Scherer. S-SO4 2. whisker e the 4 in g kg range (min-max).4 S t ot. g kg 0. atmospheric oxygen. where: the focal point e the median. 2001. the box (Q1. Box-and-whisker diagram of the participation of SeSO2 4 in Stot. g kg 455 0.20 0. moisture and with the contribution of soil microorganisms .in St ot. Q3).in St ot. There is a strong . Sołek-Podwika et al. 4. The relationship between determined forms of sulfur. Burgos et al. content increases as the depth grows (Table 3). % 50 40 30 20 100 80 80 60 40 20 10 0 100 S-SO4 2. where: the focal point e the median. % 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. 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. This process has been confirmed in field studies by many authors (Jaggi et al..10 0. Q3).5 S t ot. depending on the area (distance from the source). 2004). the box (Q1. where: the focal point e the median.1 0. g . the box (Q1. Skwierawska et al. Matula. . 2008).. in g kg1 depending on the area (distance from the source). The movement of sulfates in the soil profiles is currently proven by the fact that SeSO2 4 percentage in Stot.05 0.4 0. Box-and-whisker diagram of the SeSO2 depending on the area (distance from the source). low level of fertilization and migration of sulfates to lower levels of soils and groundwater (Zhao et al.. 2013). whisker e the range (min-max). 2001.K.3 0.0 1 km 3 km 0.1 0.2 0.2. Reduction in sulfate sulfur content at surface horizons of soils is the result of its being absorbed by plants.

207a 0.968 0.175 11. Assessment of the risk of heavy metal contamination 1. The table only includes charges >0. Horizon p* Surface Bottom Surface Spa˛ gowy 0. The present study found an average positive correlation between pH and the content of heavy metals.29***). Table 6 Results of Mann-Whitney test for soil properties at the surface and bottom horizon for areas A and C. i. such as Cr. Ni) (Table 7). Cu and Ni.0368 0.. Those hypotheses confirm significant correlations between specific pairs of heavy metals (Table 7).002 mm) and organic matter significantly affect the content of heavy metals and their mobility in the soil environment (Antoniadis et al. the smallest fraction content (<0.929 0.05). The results reveal that only in the case of Pb there is indeed very high correlation with the organic matter content. explaining 18.280b 0.5 value 3.0362 0. for which we observed no significant statistically relationship. due to the existence in some soils of calcium carbonate. which is rarely seen in literature. and clay content. lead.5 2. 2014.. Paja˛ k et al. an important factor affecting the content of sulfates in the soil profile is their particle size.5 4.5 positive correlation between Stot.. content and organic carbon content (r ¼ 0. 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 0.36***). / 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. which reported weak positive correlation (r ¼ 0. Cu and Ni. which results in their accumulation in soil (Ciarkowska et al.0472 Surface Bottom Surface Bottom 0. as well as Pb content and Corg. which explains about 57% of the total tivity of Grzybo variability and is the most important factor. more than 300 mmol(þ) kg1 (data not published).0 3.0 4.0274 The analysis of principal components indicates that the analyzed metals create 3 distinct groups (Table 5).12 77.. Sołek-Podwika et al.981 10.799a 39.192 2.e. 2015).0 1.0 1 2 3 4 5 6 eigenvalue number Fig. The soils showed a significant above-average correlation co*** efficient between the content of SeSO2 ). Cr. 5. is relatively low.002 mm (r ¼ 0. Its presence in soils may be associated with a local emission. According to Scherer (2009). The calculated correlation coefficients also showed a highly significant (p ¼ 0. as the distance from the mine increases. with the exception of Pb. Zn.0405 0.53 determined Stot.002 mm) and trace elements confirmed a highly significant positive correlation in the case of most metals (Cr. 2014). with the exception of Pb.0 2. content is highly significantly correlated with all the analyzed trace elements.19 5.5 0. Cu and Zn in the soils we observed significant and strong positive correlations between pairs of these metals. Zeng et al. Candeias et al. 2008.5 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. 2003). 2011..4% of the total variability. Corg. 4.941c 4.245 0.50***).253b 3.766 25. Soil parameter Area A Stot SeSO2 4 Area C Stot SeSO2 4 p* e calculated level of significance.390 14.178 5.0472 0.823 0. Similar relationships exist in the case of SeSO2 4 .967a 27. and then. which are characterized by high contents in the soil area A.0 0.688a 8.578 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 .0441 16.953 0. Cu. The third factor (F3) describes only part of Cd.88***) and averagely correlation with fraction content of Ø < 0. The first F1 factor is represented by elements.. The second factor (F2) contains only one element.086 0. Correlation between Pb and other elements. In case of most metals: Ni.192a 15.456 K. can be explained by the precipitation of poorly soluble calcium sulfate in the form of gypsum or anhydrite.053 10. 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. Higher pH values lead to the reduction in the mobility of heavy metals. which is widely distributed in the environment and whose contents in all designated areas are similar. The relationship between the content of the smallest fraction (<0. except for zinc.001) correlation between fractions of clay and the contents of Cr.0318 0.230 8.0205 0.185a 14. It is widely recognized that soil pH.304 7. This allows us to define this factor as the impact of long-term acw sulfur mine. This assumption is confirmed by high content of calcium cations in sorption complex.762b 8. Zn.3.364a 0. A positive correlation between the content of SeSO2 and pH values 4 (r ¼ 0. The 4 and clay (r ¼ 0.581 SD e standard deviation.419 7.554 1.637 10.959 57. 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. both from the so-called “low emission” which takes place in urban areas and the movement of transport.083a 18. Cd.372 1. Te sulfate sulfur content is averagely positively correlated with soil pH.813c 2.011b 7. Table 5 Matrix of rotation of standardized factor charges approached by the Varimax method of studies metals.783b 4.79 96.933 0.239b 13.726c 2. Chart of eigenvalues (screes) which visually assess components or factors explaining most of the variability in the data.. Its content is significantly higher in the soils of the area A (Table 4). their content is clearly reduced.450a 32. For other heavy metals we recorded an average correlation.

Frossard... it is still elevated. State Research Institute in Pulawy. 3435e3444..001. C... 609e615.. Bot. M. J. Madejo n.69*** 0. http://dx. Studies on the effect of pollution by sulphur on the transformation of arable soils in the neighbourhood of a sulphur mine.00 0.70*** 0. B.61*** 1.*** 0.36*** 0.. Blake-Kalff. Bardsley. P. Plant availability of catch crop sulfur following spring incorporation.1002/ldr.. Zhao.47*** 0.56*** 0.. IPI index calculated for all analyzed metals in the soils of studied areas is formed according to the following pattern: Area A e 1.42*** 1. Butters. Soil Sci. Robinson. J. Xie.doi. CRC Press. 265e268. in Polish. M. 2005. H. M.M. A. Sulphur fractionation in calcareous soils and bioavailability to plants. 2003.H.022.33*** 0. http://dx.. Manag. T. Influence of sulphur on apparent N-use efficiency.. http://dx.chemosphere. R. 1999. and SeSO2 4 are generally highly significantly correlated with the analyzed trace elements.doi.44*** 0. and SeSO2 4 in soils situated at a distance of 1 km and 10 km from the borders of w. Kołodziej.1016/j.1002/jpln.34. T. Plant Soil Environ. Teixeira. K. 36e45. Soil Sampling and Methods of Analysis.71*** 1. J. Chemosphere 71. 1992. (Central Statistical Office) (1991-2003).  Candeias. D. Madejo remediation of an unremediated soil twelve years after a mine accident: trace element mobility and plant composition. 103e109.. 10e20.G.2007.. Warsaw.00 0. J. Zhang.10. 542e551.. 2004. 50. 1999.53*** 0. http://dx.65*** 0.. I. Based on the demonstrated relationships between designated properties of soils (especially the content of Corg.. Atmos.25* 0.31** 0. S. G. Barley response to the soil reserve of sulphur and ammonium sulphate in short-term experiments under controlled conditions of cultivation. nickel. 2014. http://dx. Chemosphere 60 (4). 2. S... V. Estimating historical anthropogenic global sulphur emission patterns for the period 1850-1990. J. Environ. second ed. and zinc availability to ryegrass in a sewage sludge-amended field.00 0..928.. Fertil. Gucker. Environ.. Multivariate statistical and GIS-based approach to identify heavy metal sources in soils. Sołek-Podwika.. Lefohn. Taylor and Francis Group. B.49*** 0.E. pHKCl Corg..J. 135e150..200420415.. (2012). F. C.. http:// dx.002 mm and pH) and heavy metals. Assessment of Agricultural Quality and Possibilities of Use of Soils Contaminated with Heavy Metals.29*** 0. ** (Kabata-Pendias et al. C..00 0. A.44*** 0.2004. 759e764. which confirmed moderate and low level of anthropogenization of this area. 2000. 2013. 2004.F. P. Giro n.jenvman.2014.doi. J. Land Degrad. Correlation is significant at 0. Conclusions Based on the comparison of the contents of Stot.. .43*** 0..1016/ j. G.30** 1. J. F.. Vong.. Boca raton.. Z. R. and soil area C was qualified as scantily polluted. New York. Temperature effects on soil organic sulphur mineralization and elemental sulphur oxidation in subtropical soils of varying pH.doi. J.. Warsaw. Sacchi. Contents of Stot. McGrath. Environ.. McGrath. 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. Effects of short-term pH fluctuations on cadmium.00 * Correlation is significant at Sołek-Podwika et al. B.jenvman.. 1993) for uncontaminated soils and by estimating the value of IPI. Ferreira da Silva. Dev. Y. P. Agroecosyst.001. 24 (2). Murillo.T. Hu. Eriksen. Clay <0. in Polish. A.74****** 1. As specified by Guo et al. 33. Evaluation of Soil Contamination and Plants. Aulakh. Manag. 114. J. Husar. Hunt.P. 2009.M. Wu. H. E. Z. Area B e 1. 153e162.. Sci.65*** 0. Assessment of heavy metal pollution in surface soils of urban parks in Beijing. Trace Elements in Soil and Plants.1016/S1001-0742(11)60762-6. L.00 0. Potential for improving sulfur tests on agricultural soils in contrasting ecoregions of British Columbia.00 0. Nutr. *** Correlation is significant at 0. Statistical Publishing Establishment. we can conclude that in the soils of studied areas trace elements are not present in mobile forms in the soil solution..chemosphere.51*** 0. Pulawy: IUNiG Institute of Soil Science and Plant Cultivation. London. 5. References Antoniadis.88*** 0.39*** 0. A. 313e324.47*** 0. Cabrera.K.10. 25.C. Fismes. 2004. Eur. Agron.52*** 0. 5e10. 1993.015. In the analyzed soil material the content of heavy metals represents the lowest level (0 ) of trace element content in a 6 scale.25* 1. Determination of reserve sulfur and soluble sulfates in soils. Chenery. in Polish Rocz. 1959. Identifying sources and assessing potential risk of exposure to heavy metals and hazardous materials in mining areas: the Case Study of Panasqueira Mine (Central Portugal) as an example. _ Drozd M. 509e521. Szczubiałka. it was observed that there was significantly sulfur mine Grzybo lower content of both determined forms of this element in soils collected at the beginning of the twenty-first century than in the 1970s..D. Kertesz..63*** 0. M.. 2006...29*** 10.06. Wu.02 and Area C e 0. Pucek..S. Lancaster.25* 0. Matula..B. 2012. Frankiewicz. must be rejected. Pollution of the studied soils with heavy metals was rated with the use of the integrated pollution index. yield and quality of oilseed rape (Brassica napus L. Natural Burgos. Guo. Cycl.doi.. 2014. Kenney. in Polish. 235e242.  ski.10.07 1.00 0. E. Plant Soil 268.J..1007/ s11104-004-0229-0.002 Cr Zn Pb Cu Cd Ni SeSO2 4 Stot. A. 24. http://dx..36*** 0. Hydrogeological and hydrochemical characteristics of the partially flooded Piaseczno Opencast Sulphur Mine in Southeastern Poland. Gregorich. 2005. Jaggi. 12..1093/jxb/erh176.. History and outlook of sulphur fertilizers in Europe.59*** 0. J. Kabata-Pendias.A. 20. E. the fraction <0. Lei. Institute of Environmental Protection.48*** 0.1016/j.doi.. Enzyme activity as an indicator of soil-rehabilitation processes at a zinc and lead ore mining and processing area.2012.. A. 175e182. http://dx. The role of soil microbes in plant sulphur nutrition.. LLC. Clay <0.. E.. 167.. D. Kabata-Pendias. 54. Huang. Gawlin Analysis.geodrs.. E. (Eds.87*** 0. 2014. Askegard.. E. China.G. 132. 5e27. 55 (404). 2014.) grown on a calcareous soil. J.63*** 1.00 0.59*** 0.. R.59*** 1. 1991. 250e256.57*** 0.).12. Chen. Can. Bryk. http://dx. Pendias. Alloway. http://dx. F.00 0.81*** 0. Parameter Cr Zn Pb Cu Cd Ni SeSO2 4 Stot. pp. 1939e1945. A.90.88*** 0. Statistical Information and Elaborations. R. Procedures for Soil and Plants Ostrowska. 1.C. Neilsen. Piotrowska. Plant Nutr.62*** 0.50*** 0. Analist 84. Z. S. Soil Soc. CSO. Environ. Glebozn. Zheng. Zhao.002 1..23* 0. Facchinelli. pHKCl Corg. J.. F. Kowalenko.060.E.46*** 0.3390/ geosciences4040240. Geoderma Reg. Bittman. Thorup-Christensen.33*** 0.M. _ z-Hara. Mirleau.doi. despite the passage of years. 410e418. n.. Proc. K. Witek. Environment Protection. 24 (3). 1960.. 1978. J.doi..36*** 0.01... K.1016/j.. 2008. Spatial distribution and pollution assessment of heavy metals in urban soils from southwest China. Mine Water Environ.doi. However.07 0.. J..00 0. M. Environ. Avila...31** 1. Pollut 114. Ciarkowska. T.90*** 0.R. / Journal of Environmental Management 180 (2016) 450e458 457 Table 7 Spearman’s rank correlation coefficient between selected physicochemical properties and heavy metals in the soils of studies areas.J. since the SeSO2 4 content in soils located in close proximity to the mine (1 km).072. Reclamation problems for the area of a former borehole sulphur mine with particular reference to soil air properties. lead..S. E.C...05. 2006. J. F.P.doi.84*** 0.. 240e268.P. Mallen.. Wieczorek. http://dx. soil areas A and B were classified as moderately polluted with heavy metals.87*** 0.1016/ j.. P. Geosciences 4.doi. M.54*** 0. M. 127e141. M. A rapid method for determination of the total sulphur in soils and plants. 2001. S. 239e245.

. 172. Gruffat.. 2010.J. J. Eurasian J. Bounakhla..J. 10. Zhang.. J. http:// Chemosphere 58. Moore. Tan. Soil Sampling..doi. A case study of two extremely different conditions of the forest environment in Poland.. D. Statistical analysis of accumulation and sources of heavy metals occurrence in agricultural soils of Khoshk River Banks. H. Plant Soil 222. Baker. E.1016/ Yang.022.. Scherer. Pb. 71e76.. A global perspective on cadmium pollution an toxicity in non-occupationally exposed population. Multivariate analysis of heavy metal contents in soils. L.08.. J.. Qishlaqi.J. J. urban road dusts and agriculture soils from China. H. PKN.doi. McGrath.E. Zhang. B.. 2 (5). A review of heavy metal contaminations in urban soils. 2007. Eur. M. Fresenius Environ. 2005. Sulphur assimilation and effects on yield and quality of wheat. 2001.2004.. Zhao. sediments and water in the region of Meknes (central Morocco). G. Ga˛ siorek.2010. 102.doi. D.09. P. 405e417... Global sulphur emissions from 1850 to 2000.. Preparation and Analysis. Sulphur in crop production e invited paper.doi. J.. B. 137.P. H. M.J. Satarug. Sci. 565e573. Zawartka. 326e335. PN-R-04033. http://dx. 99e107.doi. London.. B. 65e83. S. Hawkesford. 2005.. 2008.envpol. Availability of different forms of sulphur fertilisers to wheat and oilseed rape.R. Urbenjapol.G. 54 (4). Riley. PN-R-04032. Soil Sci. 2015. T. F. 163e175.1016/ j. Environ. 139e147. Moutte. Garcia. M. http://dx. Scherer. Wanic.W. 81e111. Concentration of Cd.. 1e17. L. 1999. / Journal of Environmental Management 180 (2016) 450e458 Paja˛ k. Assess. F.1016/j. J. 2011.1016/j.R.09. Boca Raton. Cygan.. 94. Pollut 159.chemosphere. Plant Soil Environ.2009. The influence of pH and organic matter content in paddy soil on heavy metal availability and their uptake by rice plants. Ouyang. S. Y. Am. Taylor & Francis Group. Lett. McGrath.05.. F... 171e177. N. Reilly.jhazmat. A. F. Sulfur in soils.081.014. Sampling and Soil Texture Evaluation (in Polish). Zawadzki... S. D. Zhao.. Qiu. 2000.2010.. http://dx. Williams. F.. Microchem. 84e91.W. 30. S. 14..doi. Skwierawska..).. 23 (1).200900037.P. Bull. 2003. Ali. F. Benyaich. .1002/jpln.B. A. Environ.019. Soils and Mineral Deposits. Zeng. M. Wu. 2009. M.. Moore. Bilal... http://dx. The effect of different rates and forms of sulphur applied on changes of soil agrochemical properties. S.. Tahri. Toxicol. Shiraz. Plant Nutr. Singapore. and Zn in the top layer of soil and needles of scots pine (Pinus sylvestris L. M.1007/s10661-005-6572-7. Monit.. http:// dx.. New York. J.. K... 1998.microc.. Agron.. M. Agric. Cereal Sci. Haswell-Elkins. Sołek-Podwika et al. Environ. K. Stern.