Environ Geochem Health (2024) 46:287

https://doi.org/10.1007/s10653-024-02086-0

ORIGINAL PAPER

Application of soil magnetometry and geochemical methods

to investigate soil contamination with antimony
Magdalena Jabłońska‑Czapla ·
Marzena Rachwał · Katarzyna Grygoyć ·
Małgorzata Wawer‑Liszka

Received: 16 November 2023 / Accepted: 18 June 2024 / Published online: 6 July 2024
© The Author(s) 2024

Abstract The aim of the study was an assessment impact of road traffic and wearing off brake blocks,
of the pollution level and identification of the anti- i.e. traffic anthropopression in general, has little effect
mony sources in soils in areas subjected to indus- on the surrounding soil in terms of antimony content.
trial anthropopressure from: transport, metallurgy Large amounts of Pb, Zn, As and Cd were found in
and electrical waste recycling. The combination of the soil collected in the vicinity of the heap after the
soil magnetometry, chemical analyzes using atomic processing of zinc–lead ores, the average antimony
spectrometry (ICP-OES and ICP-MS), Sb fractiona- (11.31 mg ­kg−1) content was lower in the vicinity of
tion analysis, statistical analysis (Pearson’s correla- the heap than in the area around the electrical and
tion matrix, factor analysis) as well as Geoaccumu- electronic waste processing plant, but still very high.
lation Index, Pollution Load Index, and Sb/As factor Antimony in the studied soils was demobilized and
allowed not only the assessment of soil contamination associated mainly with the residual fraction.
degree, but also comprehensive identification of dif-
ferent Sb sources. The results indicate that the soil Keywords Soil magnetometry · Soil
in the vicinity of the studied objects was character- contamination · PCA · PLI · WEEE · Traffic
ized by high values of magnetic susceptibility and
thus, high contents of potentially toxic elements. The
most polluted area was in the vicinity of electrical Introduction
waste processing plants. Research has shown that the
Naturally, antimony (Sb) occurs as a trace element
in soil and its main source is weathering of soil par-
Supplementary Information The online version ent material. The enrichment of the soil/rock with
contains supplementary material available at https://​doi.​
org/​10.​1007/​s10653-​024-​02086-0.
antimony typically took place in the early stages of
magmatic differentiation, and often occurs in hydro-
M. Jabłońska‑Czapla · K. Grygoyć · thermal metal sulfide deposits, either coprecipitated
M. Wawer‑Liszka (*) and associated with metal ores, or as separate mineral
Institute of Environmental Engineering of the Polish
ores (Ashley et al., 2007).
Academy of Sciences, 34 M. Skłodowska‑Curie Street,
41‑819 Zabrze, Poland Stibnite ­(Sb2S3) is the primary Sb ore, with valen-
e-mail: [email protected] tinite ­(Sb2O3) widely occurring (Filella et al., 2002a,
2002b). Typical crustal abundances of Sb is reported
M. Rachwał
as 0.2 mg ­kg−1 (Plant & Rainswell, 1983). Antimony
Institute of Safety Engineering, Fire University, 52/54
Slowackiego St., 01‑629 Warsaw, Poland concentrations are generally much lower than the

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corresponding values for As. According to Jones et al. can also be used to estimate the location of a potential
(1990), the antimony content in soils of various coun- metalloid accumulation, including Sb.
tries ranged from 0.3 to 9.5 mg ­kg−1, while Wede- Antimony is a toxic element, highly respirable, and
pohl (1964–1979) indicates that the average for soils its toxicity depends on many factors, including the
is 1 mg ­kg−1. In turn, the range of arsenic content in degree of oxidation (Basel Convention, 2005; Bolan
soils around the world ranges from 1 to 95 mg ­kg−1, et al., 2022; Filella et al., 2009; Tschan et al., 2009).
and it is assumed that the average arsenic content in Trivalent antimony compounds are toxic to humans,
soils is calculated to be 4.4 mg ­kg−1 for podzols and mainly to the central nervous system and blood
9.3 mg ­kg−1for histosols (Kabata-Pendias & Pendias, (Seńczuk, 1990; Yang & He, 2015).
1999). Antimony soil concentrations considered to The Upper Silesia is the highly urbanized and
be anthropogenic enrichment vary significantly due polluted region of Poland. An inactive metal-rich
to differences in background concentrations and con- waste dumps are one of the most significant sources
tamination limits between countries. Antimony soil of heavy metal contamination, which emit pollut-
concentrations have been comprehensively reviewed ants (including PTEs) even over long distances
up to 2000 (Filella et al., 2009). The development of (Jabłońska-Czapla et al., 2015; Rożek et al., 2015).
the mining and metallurgical, automotive and electri- The earlier studies indicated that soils in the sur-
cal industries, as well as the growing demand, rapid roundings of the metallurgical slag dump in Piekary
wear and “aging” of most products, including electri- Śląskie are characterized by high content of many
cal/electronic equipment, necessitating their regular elements (Cabała et al., 2008; Rachwał et al., 2017b;
replacement, increases the amount of antimony in the Rożek et al., 2015; Warchulski et al., 2015). Unfortu-
environment. Anthropogenic sources of antimony are, nately, these studies did not focus on an element such
for example: road traffic (Qi et al., 2011), recycling of as antimony (Sb).
electro-waste (Yurddaskal et al., 2018), as well met- The development of industry and communica-
allurgy and mining (Azevedo et al., 2017; Bi et al., tion infrastructure resulted in the emergence of many
2011; EU Council 1976; Guo et al., 2018; Perkins highways and expressways in Upper Silesia. Thou-
et al., 2014; Telford et al., 2008; Zeng et al., 2017). sands of cars travel daily through these roads, which
Sb contamination has most frequently been reported are also the source of metal and metalloid emissions
on and around mining and smelting sites often co- to the environment. In road traffic, the main and the
occurring with As (Ashley et al., 2007) and that rela- largest source of Sb contamination is car wearing
tive concentrations of both metalloids depend on con- parts such as car brake linings (0.07–201 mg ­kg−1 Sb)
tamination source. Sb can be strongly retained in soils and car brake dust (4–16, 900 mg ­kg−1 Sb) (Kennedy,
(Flynn et al., 2003; Wilson et al., 2010). Obviously, 2003a, 2003b; Qi et al., 2011 Thorpe & Harrison,
the extent of retention influences the bioavailable 2008).
and mobile Sb fractions. Many factors impact reten- Electro-waste treatment plants (e-waste) are
tion, including soil characteristics and metalloid spe- another source of antimony. Environmental contami-
cies present. Study of metalloid retention processes nation by e-waste recycling is an emerging global
is fundamental for understanding biogeochemical issue (Azevedo et al., 2017; Perkins et al., 2014).
cycling and for accurate risk assessment in different Compared to other types of waste produced in the
systems. Adsorption is one of the most important Sb world, the amount of e-waste is growing the fastest,
retention mechanisms in soil (Bhattacharya et al., both in terms of volume and environmental impact.
2002; King, 1988). Oxides and hydroxides are known Therefore it has gained significant popularity and
to be important for Sb adsorption in soil (Chen et al., scientific interest since 2010 (Kumar et al., 2017;
2003; Manaka, 2006; Mitsunobu et al., 2008). Anti- Perkins et al., 2014. E-waste has attracted global
mony has been positively correlated with the soil iron concern owing to huge generation amount, rich valu-
oxide component (Denys et al., 2008). Therefore, the able metal content, and potential environmental risk.
integrated geophysical-geochemical methods widely When e-waste is recycled, Sb (an element being
applied for assessment of soil quality with respect similar in chemical and physical properties to As) is
to trace element pollution (Magiera et al., 2006; released and contaminates the surrounding environ-
Rachwał et al., 2017a, 2017b; Wawer et al., 2017) ment. Therefore, the ratio of Sb/As can be used for

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distinguishing the source of soil contamination, i.e. related to the mining and metallurgical industries are
high Sb/As ratio may help identify the contamina- located. The company itself is located in the southern,
tion due to the e-waste recycling activities (Bi et al., heavily forested district of Katowice (Fig. 1). WEEE
2011). plant has been operating since 1995, and started pro-
The aim of the study was an assessment of the cessing waste electrical and electronic equipment in
pollution level and identification of the antimony in 2006. The company collects used devices and com-
soils in areas subjected to industrial anthropopres- ponents from electrical and electronic devices. Addi-
sure from: transport, metallurgy and electrical waste tionally, the subject of interest of the company is any
recycling. An additional aim was to identify sites of waste containing precious metals such as gold, silver,
potential accumulation of technogenic magnetic par- palladium, platinum, rhodium, and iridium. Waste
ticles and accompanying PTEs, as well as antimony. is segregated and collected according to the type,
The research attempted to use the soil magnetometry stored in containers and big bags on a hard surface.
method in the quick estimation of soil contamination The storage site is covered, which protects the waste
with PTEs. Magnetic susceptibility as the proxy tool, from contact with rainfall and prevents the leakage of
traditional geochemical analyses, sequential chemical metal compounds and hazardous substances directly
fractionation analysis, as well as correlation and PCA into the soil. In one of the closed halls, manual dis-
analyses were applied in this research. While environ- assembly of electronic elements and components is
mental indices (Pollution Load Index—PLI, Geoac- carried out, and in another closed hall, the process
cumulation Index—Igeo) as well as the Sb/As ratio of "skinning" of copper cables is carried out with the
(Bi et al., 2011; Fu et al., 2011; Sharifi et al., 2016 use of a cable recycling machine. So far, no metal/
were computed in order to quantify the degree and metalloid content studies have been conducted in the
origin of soil contamination by investigated elements. area around this plant.
Compared to previous studies, this research provides
more complex information about source-diversified
soil contamination with antimony and other PTEs. Dump of slag remaining after Zn and Pb ore
processing

Materials and methods Soils in the vicinity of the mining and smelting slag
dump after Zn and Pb ores processing were selected
Characteristics of study areas for the research. This area consists of arable fields
where vegetables are grown. The heap contains waste
Three study areas were selected for the study: the area with a volume of approximately 3.3 × 106 m3 (mainly
around the mining and smelting slag dump, the area furnace slag with dolomite from rolling) from the
around WEEE plant, and the area near highway. Fig- former “Orzeł Biały" Mining and Smelting Com-
ure 1 shows the location of the areas. pany, which operated continuously for 150 years. The
closed dump is located in the town of Piekary Śląskie
Electro‑waste storage and processing plant (Upper Silesia, southern Poland; further in the text
named just Piekary). In this region one of the larg-
Soil samples were collected in the surrounding areas est resources of zinc and lead ores in Poland occur
of WEEE (Waste Electric and Electronic Equipment) which are bounded to the Middle Triassic ore-bearing
plant which was located in the Metropolis of Upper dolomites (Górecka, 1993). The soils in this area are
Silesia in Poland This region is dominated by luvi- rendzinas, formed on Triassic ore-bearing dolomites.
sols made of boulder clays and clay and loam sands The prevailing winds are west and north-west, the
(Kondracki, 2002). Western winds dominate (approx- average annual rainfall is 817 mm.
imately 60% of the share), and to a lesser extent The Piekary area has been monitored during recent
eastern and southern winds and the average annual years for several parameters, mainly heavy met-
rainfall is 855 mm (Tokarska-Guzik et al., 2002). als such as Pb, Zn, Cd, As (Kulka and Gzyl, 2008;
This area is heavily urbanized and is the most indus- Rachwał et al., 2017b; Ullrich et al., 1999; War-
trialized area of Poland, where numerous enterprises chulski et al., 2015), and only one work contained

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Fig. 1  The location of the study areas 1. The area around the mining and smelting slag dump, 2. The area near highway, 3. The area
around WEEE storage and processing plant

information, that antimony is present in the deposits containing hard coal deposits, and the prevailing soils
in this area (Gałkiewicz & Śliwiński, 1983). in this area are luvisols (Kondracki, 2002). Due to high
anthropogenic pressure, there are mainly anthropogenic
The area near a large communication junction soils composed of boulder clays. Characteristic here are
weak winds, with a speed not exceeding 2 m/s, blow-
The third research area was the area located in Kato- ing from the west (Tokarska-Guzik et al., 2002). The
wice in the vicinity of the A4 Motorway – the longest research area includes a park near the A4 motorway in
motorway in Poland, 672.75 km long, running from Katowice (Upper Silesia, Poland).
west to east through southern Poland. It belongs to the
3rd Pan-European Transport Corridor. Over one hun-
dred thousand cars pass the A4 motorway in Katowice
every day. Third research area is located in the Upper
Silesian coal basin. The geological substrate here con-
sists mainly of shales, sandstones and conglomerates

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Methodology the International ISO Standard (ISO 21226:2019,

2019). Samples taken from the depth at which the
Magnetic investigations and sampling highest magnetic susceptibility value occurred in the
core were further analyzed.
Soil samples were collected around three above men-
tioned different sources of antimony emissions on the Chemical analyses
basis of the results of the preliminary in situ soil mag-
netic screening performed in accordance with the ISO Basic physicochemical parameters
Standard (ISO: 21226:2019, 2019). The magnetic
susceptibility meter MS2 Bartington was equipped Afterwards, the pH and Eh of the soils were meas-
with MS2D loop sensor (Bartington Instruments Ltd., ured using the multifunction meter CX-401 (Elmet-
Witney, UK). At each individual point, the κ value ron, Poland) in accordance with the standards (PN-
was calculated as mean value of 11 readings within ISO 10390:1997). An ERH-111 electrode (Elmetron,
a ­2m2 square. The κ value was expressed in ­10–5 SI Poland) was used for pH measurements, while Eh
units. On the areas around the dump 26 points, around were measured using ERPt-111 electrode (Elmetron,
WEEE plant 19 points, near the highway 12 points, of Poland).
surface magnetic susceptibility measurements were
performed. Localization of individual points was con- Digestion and determination of metals and metalloids
firmed using Garmin GPS navigation device. Based in soil samples
on the κ measurements, a maps of magnetic suscep-
tibility distribution using Surfer 8 software (Golden In order to determine the total element content, soil
Software Inc.) was prepared to select the most repre- samples were digested in a microwave oven (Micro-
sentative locations for soil sampling. Sampling was wave 3000, Anton Paar). 0.2 g of soil was prepared
performed using soil sampler enabling collection of and digested with 5 ml of H ­ NO3 (spectral purity,
undisturbed 30-cm long soil cores (two from each Merck, Germany), 2 ml of H ­ 2O2 and 3 ml of HF
place). Core samples were taken into plastic tubes at (spectral purity, Merck, Germany). Digestion pro-
different distances from the pollution source. Due to gram: 1400 W, 35 min. After microwave digestion
the fact that it was not possible to collect soil cores in samples were diluted to 50 ml in PP flask. After-
the vicinity of the motorway, soil samples were col- wards, they were stored in a fridge at 2–5 °C. Each
lected in bags using a plastic spatula. The soil was sample was measured three times using ICP-MS or
heavily transformed there, usually it contained road ICP-OES.
construction elements, and it was impossible to drive Elements such as As, Mo, Cd, Co, Tl and Sb were
a soil probe there. determined with an ICP-MS Elan DRC-e 6100 spec-
After transporting soil cores to the laboratory, in trometer (Perkin Elmer). Apparatus was equipped
order to determine the vertical distribution of mag- with a standard ICP torch, cross-flow nebulizer and
netic susceptibility and indirectly the depth of migra- nickel cones. Samples and standards were delivered
tion of pollutants along the soil cores, the magnetic with a peristaltic pump. The spectrometer was opti-
susceptibility was measured using the Bartington mized daily with a 10 μg.L−1 solution (Mg, Cu, Rh,
MS2C meter, with a resolution of 1 cm. From the Cd, In, Ba, Ce, Pb, U) in 1% ­HNO3 Elan 6100 Setup/
depths characterized by the highest values of mag- Stab./Masscal. Solution (Perkin-Elmer). Concentra-
netic susceptibility (mostly at the depth of 3–6 cm), tions of 59Co,75As, 98Mo, 114Cd, 205Tl and 123Sb were
soil samples were separated and subjected to chemi- measured with the internal 103Rh standard.
cal analysis after air drying (at 21 °C), averaging and Elements such as Ba, Cr, Cu, Pb, Sr, Zn, Al and
sieving through a sieve with a diameter of 2 mm. Fe were analyzed using Avio 200 ICP-OES spec-
Before chemical treatment, the volume magnetic sus- trometer. Apparatus was equipped with a standard
ceptibility (κ) of the samples was measured using a ICP torch, corundum nozzle, cross-flow nebulizer
Bartington MS2B sensor (Bartington Instruments and Scott fog chamber. The spectrometer was
Ltd., Witney, UK) and the corresponding mass-spe- optimized daily using the Optima Family Multi-
cific susceptibility (χ) was calculated according to Element Standard optimization solution (Perkin

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Elmer). The operating parameters of the ICP-MS Quality control

and ICP-OES spectrometer are presented in Sup-
plementary Information (Table S1). The analysis of real samples was preceded by the
preparation of a calibration curve (blank sample solu-
tion and certified standard solutions of known concen-
Reagents tration). As part of quality control, a calibration curve
was checked. After calibration and once every 5 real
The following substances were used for ICP-MS samples, a blank sample and control solutions with
analysis: Mix 1 (Sigma-Aldrich, Switzerland), Met- known concentrations of each analyte were analyzed
alloid and non-metal mix (Sigma-Aldrich, Switzer- to monitor cross-contamination. While the measured
land), Rhodium standard (Merck, Germany), ICP concentration of elements has changed by more than
multi-element standard XVI (Merck, Germany). 10%, recalibration and repeated sample analysis were
Multi Element ICP Standard solution (Chem-Lab, performed. Independently of the calibration solutions
Belgium) and ICP multi-element standard solution and to check the calibration, control samples with con-
IV (Merck, Germany) were used for ICP-OES anal- centrations from the lower and upper parts of the curve
ysis. Working standard solutions were obtained by were prepared. The results obtained were plotted on a
appropriate dilution of the stock standard solutions control chart to monitor warning values. During each
using Milli-Q-Gradient ultra-pure deionized water measurement series, a repeated sample was analyzed to
(Millipore, Milli-Q-Gradient ZMQ5V001). The verify the precision of preparation and analysis. Addi-
Merck suprapure (Germany) 65% nitric acid was tionally, the standard deviation was monitored by three
used for preparing samples, blanks and for appa- times measurement of each sample. To verify the meth-
ratus rinsing. Hydrogen peroxide 30% for analysis odology for determining the total metal/metalloid con-
(Merck, Germany), hydrofluoric acid 40% spec- tent, digestion, and analysis of the certified soil refer-
tral purity (Merck, Germany) and nitric acid 65% ence material NCS DC 73324 (China National Analysis
suprapure (Merck, Germany) were used for diges- Center for Iron and Steel) was carried out under the
tion soil samples. same conditions as other soil samples. Table 1 shows
the recovery of the tested metals and metalloids in
CRMs (Certified Reference Material) and the basic

Table 1  Basic validation parameters and soil Certified Reference Material NCS DC 73324 recovery
Analyte Isotope/spec- LOD [mg ­kg−] LOQ [mg ­kg−] Soil CRM values from the Measured soil CRM Recovery [%]
tral line [nm] certificate [mg ­kg−1] values [mg k­ g−1]

As 75 0.03 0.13 220 ± 14 222 101

Tl 205 0.05 0.15 2.4 ± 0.5 2.7 111
Mo 98 0.05 0.15 18 ± 2 19.1 106
Cd 114 0.02 0.07 0.13 ± 0.03 0.12 94
Co 98 0.002 0.014 7.6 ± 1.1 7.4 98
Sb 121 0.05 0.15 60 ± 7 62.7 104
Cr 205.560 2.0 6.0 75 ± 6 75.5 101
Pb 217.000 2.0 6.0 314 ± 13 341 108
Zn 213.857 2.0 6.0 97 ± 6 98.9 102
Cu 327.393 2.0 6.0 390 ± 14 455 116
Fe 239.562 1.8 5.3 56,582 ± 909 52,267 92
Al 394.401 10 2.5 212,300 ± 846 2,000,750 94
Sr 421.552 2.0 6.0 39 ± 4 38.2 98
Ba 233.527 2.0 6.0 118 ± 14 125 106
LOD limit of detection, LOQ limit of quantification, CRM certified reference material, LOQ = 3*LOD

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validation parameters for the determination of elements compensating for natural (lithological) variations in
using the ICP-OES and ICP-MS techniques. During geochemical data. ­Igeo describes the pollution of soil
each digestion, a blank (reagents without soil) sample by an element with respect to seven classes from 0 to
was prepared to monitor accidental sample contamina- 6. To the class 0 (­Igeo ≤ 0), belong non-polluted soils.
tion during sample preparation. First class (0 < ­Igeo ≤ 1) describes uncontaminated
to the moderately contaminated soils. Second class
Sequential chemical extraction (1 < ­Igeo ≤ 2) is moderately contaminated soils. The
third class (2 < ­Igeo < 3) concerns soils moderately or
The modified BCR (the Institute for Reference Materi- heavily polluted. The heavily contaminated soils are
als and Measurements) sequential chemical extraction included in the fourth class (3 < ­Igeo < 4). Then to the
helped to determine the antimony forms in soil and the fifth class (4 < ­Igeo < 5) belong heavily to very heavily
way in which they were bound. Sequential chemical polluted soils. And the last one is sixth class ­(Igeo > 5)
extraction included stages: F0 mobile dissolved anti- with very contaminated soils.
mony in water, F1 mobile exchangeable fraction associ- Pollution Load Index (PLI) is often used to deter-
ated with adsorbed cations and anions, carbonates, and mine the level of soils contamination compared to
very reactive oxy-hydroxides; F2 mobile reducible frac- background concentrations levels (Tomlinson, 1980).
tion associated with iron/manganese oxides; F3 immo- To calculate the PLI, the following equations were
bile oxidisable fraction associated with organic sub- used:
stance and sulfides; F4 (R) immobile residual fraction
CFEL = CEL ∕Cbackground
associated with non-silicate bound metals. The extrac-
tion methodology has been described previously in the
paper (Larner et al., 2006). (
PLI = CFEL1 × CFEL2 × CFEL3 × … … × cFELn
)1∕n

Calculation and data analysis where ­CFEL—the pollution factor defined as the ratio
of the element concentration in the analyzed soil
The obtained results were statistically analyzed in sample to the concentration of this element in the
Excel and Statistica 12. In order to better interpret the background.
obtained results, the correlation coefficients in the form In order to compute the above-mentioned indices,
of a correlation matrix were calculated and the princi- the following geochemical background values (in
pal components analysis (PCA) was performed. Calcu- mg ­kg−1) were adopted after Geochemical Atlas of
lation of complex linear correlations between content Europe (de Vos et al., 2006): As—11.6; Tl—0.821;
of all elements was carried out by PCA. Afterwards, Mo—0.943; Cd—0.284; Co—10.4; Sb—1.04;
as a result of orthogonal varimax rotation, factor load- Ba—400; Cr—94.8; Cu—17.3; Mn—524; Pb—32.6;
ings of principal components were extracted (using Sr—130; and Zn—68.1.
their content in the soil of the studied objects). For each
research area, two principal components, responsible
for the cumulative variance from PCA were extracted. Results and discussion
The evaluation of soil pollution was performed using
Sb/As factor, which is one of the indicators of pollution Magnetic properties of soils from studied area
sources (Bi et al., 2011; Fu et al., 2011), Geoaccumu-
lation Index ­(Igeo) proposed by Müller (Müller, 1969, A large diversification of the degree of soil contami-
1979) and Pollution Load Index (Tomlinson, 1980). nation in the area impacted by various sources was
Geoaccumulation Index (Igeo) is defined as: stated. The magnetic susceptibility values measured
( ) in the field (κ) show that the most contaminated soils
Igeo = log2 CEL ∕1.5 Cbackground , where are found in the area of the mining and metallurgical
slag dump and motorway (up to 330 and 270 × ­10–5
CEL is total element concentration in soil samples,
SI, respectively), and the lowest in the area of the
­Cbackground is the geochemical background of ele-
electrical and electronic waste treatment plant (up
ment concentration, factor 1.5 is a correction factor
to 170 × ­10–5 SI) (Figs. 2, 3, and 4). Compared to

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magnetic background of the soils (26–50 × ­10–5 SI; Magiera et al., 2011). The points with the lowest ĸ
Rachwał et al., 2017b), the tested soils with much values are located in wooded areas (surroundings
higher values of κ can be considered heavily con- of WEEE plant), where soil profile is undisturbed.
taminated with the technogenic magnetic particles Much higher κ values were observed in places heavily
resulting from the various technological processes transformed by human activity, i.e. area around dump
and combustion of solid fuels (Catinon, et al., 2014; with fields fertilized with sewage sludge and surfaces

Fig. 2  Spatial distribution

of soil magnetic susceptibil-
ity in the area of the impact
of the mining and smelting
slag dump. Geographic
coordinates are located at
the edges of maps (source
of the base map: Google
Earth)

Fig. 3  Spatial distribution

of soil magnetic suscepti-
bility in the highway area.
Geographic coordinates are
located at the edges of maps
(source of the base map:
Google Earth)

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Fig. 4  Spatial distribution

of soil magnetic susceptibil-
ity in the area affected by
the electrical and electronic
waste processing plant.
Geographic coordinates are
located at the edges of maps
(source of the base map:
Google Earth)

polluted by resuspended metallurgical dusts or area Mass-specific magnetic susceptibility values of

near highway regularly contaminated by traffic. The individual samples cut from soils cores collected in
soil in these places is a typical technosol with numer- the dump area varied from 62 to 308 × ­10−8 ­m3 ­kg−1
ous artifacts in the form of pieces of asphalt, bricks or (average 212 × ­10−8 ­m3 ­kg−1) (Table 2). The region
debris. of Piekary has been a place of mining and processing
However, in all tested objects, the magnetic sus- of zinc–lead ores for centuries, therefore it is strongly
ceptibility values decrease with the distance from the transformed by human activity. The contamination
source of emission of technogenic magnetic particles
(dump, WEEE plant, highway), but the spatial distri-
bution of κ indicates the presence of numerous “hot A B
spots”, i.e. points with higher κ values. In the case of 0 200 400 600 800
metallurgical dump, higher values of κ were observed 0
not only in the vicinity of the dump, but also in the
3
fields fertilized with sewage sludge (Fig. 2). Around
the electrical and electronic waste processing plant 6
(Fig. 4), high κ values in the north-west part of the 9
study area are due to the impact of low emissions
from domestic furnaces (low-rise single- and multi- 12

family buildings). 15

18

Dump area 21

24
The cores collected in the cultivated area in the vicin-
ity of the dump were characterized by a disturbed 27
profile associated with plowing. Particular soil lev- 30
els are disturbed and the magnetic signal has been
33
diluted due to the mixing of the arable soil layer with
the lower soil horizons as a result of agrotechnical
Fig. 5  Vertical distribution of magnetic susceptibility (ĸ) in
treatments (Magiera et al., 2006). Despite these treat-
soil profiles from: A the area of the impact of the mining and
ments, the susceptibility values in these cores were smelting slag dump and B WEEE plant (ordinate axis: depth in
high (from 50 to over 300 × ­10–5 SI) (Fig. 5). cm; abscissa: ĸ values (× ­10–5 SI)

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Table 2  The results of total elements concentration as well as magnetic susceptibility (χ) in selected soil samples from the dump
area
χ As Tl Mo Cd Co Sb Ba Cr Cu Mn Pb Sr Zn Al Fe
unit 10–8 ­m3 ­kg−1 mg ­kg−1 g ­kg−1

P02 198 30.48 2.14 0.89 23.32 5.76 7.02 285 54.41 38.47 625 805 47.50 2157 14.76 19.47
P06 308 39.93 1.82 1.29 12.59 7.92 21.32 195 55.79 84.82 723 1054 40.17 1736 12.53 24.67
P07 268 28.08 0.72 0.81 8.38 5.90 2.67 299 40.21 21.85 571 294 51.49 1022 6.29 16.68
P08 249 51.36 1.46 1.15 16.59 7.91 4.82 221 58.73 90.05 400 699 39.23 1835 13.36 20.28
P11 252 73.69 2.11 1.27 24.74 9.39 6.15 131 49.23 75.64 852 698 35.52 2298 9.46 26.45
P12 62 11.37 0.97 0.65 8.07 5.14 12.14 210 41.73 24.49 342 435 37.96 681 15.28 12.89
P14 117 14.94 1.45 1.67 10.94 7.82 3.01 270 52.32 22.98 757 400 54.88 1156 16.48 17.67
P17 242 57.22 1.29 1.07 4.85 9.35 33.35 492 26.71 54.58 534 1220 194 1323 3.12 11.65
Mean 212 38.38 1.50 1.10 13.69 7.40 11.31 263 47.39 51.61 601 701 62.55 1526 11.41 18.72

of the soil in this place is caused not only by the vertical distribution of the κ value indicates a high
blowing and washing of material from the heap, but concentration of dust pollutants in the topsoil (Blaha
also by the use of sewage sludge to fertilize the field et al., 2008; Fialová et al., 2006).
(Rachwał et al., 2017b). Sewage sludge is rich in met- The samples from the WEEE region had signifi-
als and metalloids and therefore their use increases cantly higher values of mass-specific magnetic sus-
accumulations of Cd, Cr and Pb in soil (Singh & ceptibility—it ranged from 292 to 862 × ­10−8 ­m3 ­kg−1
Agrawal, 2008; Urionabarrenetxea et al., 2022). (average 681 × ­10−8 ­m3 ­kg−1) (Table 3). Previous
studies conducted in this area by Łukasik et al. (2015)
WEEE area revealed lower values of the magnetic susceptibil-
ity of soils (340 × ­10−8 ­m3 ­kg−1 on average), which
In the case of the area affected by the electrical and indicates the direct impact of the WEEE company on
electronic waste processing plant, the cores were col- pollution.
lected mostly in wooded areas, which is reflected in
the vertical distribution of magnetic susceptibility, Highway area
the highest values of which are in the top organic soil
horizons (3–5 cm), and then they drop even to val- Unfortunately, it was not possible to collect soil cores
ues close to zero down to a depth of 30 cm. Such a in the vicinity of the motorway. The land there has

Table 3  The results of total elements concentration as well as magnetic susceptibility (χ) in selected soil samples from the area of
the electrical and electronic waste processing plant
χ As Tl Mo Cd Co Sb Ba Cr Cu Mn Pb Sr Zn Al Fe
Unit 10–8 ­m3 ­kg−1 mg ­kg−1 g ­kg−1

E02 862 70.17 3.27 6.41 7.43 21.61 27.39 455 128 91.51 630 1476 46.70 631 14.38 37.26
E04 804 62.03 3.72 4.99 4.66 14.23 14.47 299 88.38 92.66 301 1435 42.81 732 16.61 34.53
E05 685 57.34 2.54 4.64 5.58 15.68 16.57 428 117 92.47 594 1369 44.61 593 14.60 32.07
E07 292 13.43 1.95 2.24 2.69 6.24 6.58 187 52.19 21.40 140 434 32.53 239 15.23 14.07
E09 514 50.32 2.66 3.69 3.90 12.76 12.84 358 77.76 60.70 291 809 34.03 349 12.82 27.16
E13 716 55.40 2.96 5.85 6.10 16.72 20.78 555 104 110 299 1424 53.15 522 16.21 38.35
E15 751 57.67 2.19 7.66 35.93 17.23 17.15 234 132 111 252 1319 32.01 413 15.22 35.81
E17 824 50.67 2.70 5.43 3.47 21.26 14.64 343 124 78.05 251 665 43.23 413 14.41 33.35
Mean 681 52.13 2.75 5.11 8.72 15.72 16.30 358 102 82.18 345 1116 41.13 487 14.94 31.58

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been heavily transformed, the soil is poorly devel- the dump. In the case of elements such as Cr, Mn, Fe,
oped, being rather a mixture of soil and road con- Mo, Tl in all soil samples in this area, the content of
struction materials, therefore soil samples were col- these metals differed slightly. With regard to the limit
lected in bags using a plastic spatula. values regulated by Polish legislation, the soils in
Surprisingly, the lowest average value of χ the area surrounding the dump in Piekary are heav-
was observed for soil in the vicinity of the motor- ily contaminated with Cd, Zn, Pb (Regulation of the
way: 195.7 × ­10−8 ­m3 ­kg−1 (min. 12 and max. Minister of the Environment, 2016). The sampling
419 × ­10−8 ­m3 ­kg−1) (Table 4). Still, these values were area was located east from the dump in the prevailing
higher than the background values for this region wind direction. The Polish legislation does not spec-
(approx. 50 × ­10−8 ­m3 ­kg−1, Jordanova, 2016). Simi- ify the maximum content of antimony in soil. The
lar values in the vicinity of the roads of Upper Silesia antimony content in most of Polish soils reaches a
were obtained by Wawer et al., (2015, 2017). These maximum of 0.52 mg ­kg−1, and on average it amounts
data prove a significant contamination of soils from to 0.17 mg ­kg−1 in the areas of permanent grassland
the studied areas with technogenic magnetic particles, (Pasieczna, 2012. Even in the areas enriched with
which are good carriers of potentially toxic elements antimony such as the Pszczyna region, the content of
(Magiera et al., 2013; Rachwał et al., 2015). this element did not exceed 3 mg ­kg−1 (Loska et al.,
2004). The antimony content in the research areas
Total antimony and other elements in soils from significantly differs from those naturally occurring of
studied area geogenic origin.
Literature data indicated that anthropogenic activ-
Dump area ity may cause a significant increase in antimony con-
tamination of soil. For example, in the area affected
In all tested soil samples in the vicinity of the dump, by the lead and zinc smelter, the antimony concentra-
the antimony content was high and amounted to an tion in the urban topsoil was recorded at the level of
average of 11.31 mg ­kg−1. The highest concentration 2.5–175 mg ­kg−1 (Douay et al., 2008), while in the
of antimony amounted to 33.35 mg ­kg−1 was found area polluted by mining, the concentration of anti-
closest to the heap in the soil sample P17 (Table 2). mony ranged from 26 to 1150 mg ­kg−1 (Denys et al.,
In samples taken in the nearby dump, a high content 2008). Qi et al. (2011), examining soil samples col-
of this element was found in sample P06, amounting lected from a coal mine area in Anhui Province,
to 21.32 mg ­kg−1. As expected, very high amounts China, found that more than 75% of soil samples
of lead (up to 1220 mg ­kg−1 in the P17 sample) and showed a significant degree of Sb contamination,
zinc (up to 2298 mg ­kg−1 in the P11 sample) were with an average Sb concentration of mg ­kg−1. It is
found in all soil samples collected in the vicinity of disturbing that the object of the presented research in

Table 4  The results of total elements concentration as well as magnetic susceptibility (χ) in selected soil samples from the highway
area
χ As Tl Mo Cd Co Sb Ba Cr Cu Mn Pb Sr Zn Al Fe
unit 10–8 ­m3 ­kg−1 mg ­kg−1 g ­kg−1

A01 12 6.74 0.54 0.92 1.45 6.03 1.06 130 46.69 20.06 655 75 32.42 288 9.07 13.34
A03 255 25.11 0.92 1.74 6.52 13.64 3.00 260 96.58 60.33 896 825 57.01 3000 20.11 27.51
A04 58 2.98 0.30 0.69 0.72 2.17 0.69 177 26.94 7.26 202 23.91 24 95 8.63 4.86
A06 136 28.52 1.23 3.52 5.55 11.15 2.33 247 68.26 40.86 403 270 38.97 1205 11.08 18.41
A07 419 40.52 1.17 1.60 8.34 17.14 9.98 385 83.71 77.63 1016 567 88.05 2315 17.72 27.73
A08 72 37.77 0.90 1.74 2.86 11.83 6.61 146 51.80 69.24 341 525 32.97 1497 11.44 15.10
A09 330 40.06 0.85 3.92 5.58 12.43 5.7 218 127 72.99 1016 471 55.80 1992 15.61 24.78
A11 170 11.59 0.73 0.97 3.09 6.47 2.13 181 62.36 29.77 454 244 38.68 823 14.38 15.09
Mean 195.7 24.16 0.83 1.89 4.26 10.11 3.88 218 70.47 47.27 623 375 46.02 1402 13.51 18.35

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the vicinity of the heap was arable soil, and it turns Highway area
out that long-term fertilization may increase the con-
tent of potentially toxic elements in the soil, including Increased car traffic causes additional pollutants to
antimony (Leita et al., 1999). appear in the environment, which, when removed
from the road surface by wind or rainfall, accumulate
WEEE area in the soil. Automotive brake pads can be a serious
threat to the environment. During braking, the brake
Large amounts of antimony were also found in the pads are worn down, which, combined with the high
soils around the WEEE plant (Table 3). The highest temperature, can release the brake pads material.
content of 27.39 mg ­kg−1 was found in sample E02, ­Sb2S3, is a solid lubricant, plays an important role in
located in the immediate vicinity of this plant. Taking brake performance and can react, oxidize or decom-
into account all research objects, it was stated that the pose with exposure to high temperatures (Martinez &
WEEE plant has the utmost effect on the antimony Escheberria, 2016).
content in the soil. In its vicinity, the average Sb con- In the case of the research area near the A4 motor-
tent in the soil was as much as 16.30 mg ­kg−1 (for way, the highest concentration of antimony was
comparison: the average Sb content in the area of the found in the soil sample number A07 and it was
heap and the highway was 11.31 and 3.88 mg ­kg−1, 9.98 mg ­kg−1 Sb, but the mean concentration of anti-
respectively). mony in this area was below 10 mg ­kg−1, average
As in the soils of the area surrounding the dump, 3.88 mg ­kg−1 (Table 4). This is the lowest content
high amounts of antimony were found in the soils compared to other research areas. This means that
around the WEEE plant (Table 3). In sample no. road traffic and brake pad wear have little effect on
E02, located in the immediate vicinity of this plant, the antimony content in roadside soil. Unfortunately,
the Sb content was even 27.39 mg ­kg−1. Taking into research has shown that car traffic has a significant
account all the results of the quantitative analysis of impact on the increase in the content of manganese
antimony in the tested soil samples, it turns out that and zinc in the soil which was comparable to the
the WEEE processing and sorting plant has the great- concentration of these elements around the dump in
est impact on the content of antimony in the soil. In Piekary. Interestingly, the concentration of lead in
the vicinity of this plant, the average concentration soils surrounding the expressway is high, averaging
of Sb in the soil was as high as 16.3 mg ­kg−1. Our 375 mg ­kg−1, despite the fact that lead-containing
results confirm previous studies conducted by Quan fuels have not been used for almost 20 years. The
et al. (2015), which stated that Sb concentration in increased concentration of manganese in soils in the
soil around e-waste processing plant, was the highest area surrounding the A4 motorway is most likely
in surface and middle soil, with Sb concentration of related to the abrasion of the road surface during car
16.3 and 20.2 mg ­kg−1. Similar results were obtained traffic. In turn, high zinc content is associated with
by Bi et al., (2011). In addition to the high antimony corrosion of galvanized panels, safety barriers or
content in the soil, the e-waste processing and sorting other elements constituting the infrastructure of the
plant is a source of metals such as lead, manganese motorway. This phenomenon has been confirmed pre-
and cadmium. The concentration of lead in the soils viously by Hjortenkrans et al. (2007), Świetlik et al.
surrounding this source even exceeded the content of (2013 or Wawer et al. (2017).
this element in the soils in the area under the pres-
sure of the dump in Piekary. The content of lead in
the topsoil was even 1476 mg ­kg−1 Pb in sample E02 Mobility of antimony in soil in areas of varying
(closest to the plant). At this point, apart from lead, anthropopressure
there were high contents of Cd, Mn, Co. The high
lead content in the soils of this place results not only Table S2 (Supplementary Information) shows the
from emissions from the neighboring heap, but is also results of pH and Eh analyzes of soils collected from
related to the local geological structure and the occur- three study areas. In order to determine the mobility
rence of Triassic ore dolomites (Cabała et al., 2008; of antimony, six soil samples were selected from each
Rachwał et al., 2017b). area and tested for pH and Eh.

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As shown in Fig. S1 (Supplementary Information), moderately reduced), and from − 100 to − 300 mV
antimony in the soils in the study areas was associated (sulphate reduction processes and subsequent meth-
mainly with the residual fraction. In all soil samples, ane formation—reduced soils). On this basis, it can
the residual fraction had the largest share. In the sam- be concluded that in the soils from the areas around
ples of soils collected around the dump and around the dump and the motorway, the processes of reduc-
the motorway, there was a greater proportion of anti- ing oxygen connections of nitrogen, manganese and
mony in the F0 (dissolved in pore water) and F1 (ion iron prevail (soils with low and moderate reduction).
exchange and carbonate) fractions, compared to the On the other hand, the soils collected from the areas
soils collected in the areas affected by the e-waste surrounding the electrowaste treatment plant are char-
processing plant. The highest share of antimony in acterized by higher Eh (over 300 mV) and they are
the ion exchange and carbonate fractions was found oxygenated soils. Depending on origin, the relation-
in the A11 soil sample collected at the A4 motorway. ship of antimony with silicates can be very important.
In turn, the share of antimony in the oxide fraction In many natural environments, adsorption of Mn and
(F2) was significantly higher in the soils subjected to Fe oxides and hydroxides is responsible for retaining
the pressure of the WEEE plant. The soils around the antimony in the soil. The extent of antimony retention
WEEE plant, as shown in Table S2 (Supplementary in soil may be smaller or greater than the analogous
Information), are characterized by different physico- behavior of arsenic in this environment, depend-
chemical parameters. The soils in these areas have ing on the forms and sorption surface present. This
a lower pH (from 3.35 to 4.33) and a higher redox has an impact on the bioavailability and mobility of
potential (from 349.3 to 425.5 mV) compared to the antimony. The mechanisms by which Sb interacts
soils collected from the areas around the dump and with the various phases are still largely unknown
the motorway. The transformations of many soil com- as the effects of protonation and specific adsorption
ponents and the introduced pollutants are related to of antimony in acidic soils have not been studied so
redox transformations. By determining the redox far. Hence, it is important and necessary to study the
potential in soil, its oxygen state can be determined. mobility of antimony in soils of various origins and
The value of + 300 mV has been proposed as the the impact of human activity. There are general trends
boundary between oxidation and soil reduction con- in Sb fractionation in soil. These include low mobil-
ditions (Stępniewska et al., 2004). The redox poten- ity of Sb and a high proportion of Sb associated with
tial expresses the oxidation–reduction state of the the oxyhydroxide containing fraction of the soil or the
soil, which is a measure of the system’s reduction. residual fraction depending on the source of the met-
It presents the proportions between the oxidized and alloid. It is known that the metalloid associated with
reduced forms of elements present in the soil and the the crystalline and non-crystalline oxide and hydrox-
resilience of free electrons displaced in redox reac- ide minerals is immobile (Tighe & Lockwood, 2007).
tions taking place under various oxygenation condi- Nevertheless, desorption and/or reductive dissolution
tions. With its help, it is possible to determine the rate of the oxygen-hydroxide phase of soil may occur as a
of oxidation–reduction changes taking place and the result of redox changes under various environmental
time after which anaerobic conditions begin to appear conditions (Filella et al., 2002b). This has important
in excessively moist soils and the reduction process implications for the potential availability and mobility
begins. The value of + 200 mV was assumed as this of metalloids under certain environmental conditions.
limit. A higher potential occurs when the soil is domi-
nated by electron acceptors, creating a positive poten- Assessment of soil contamination
tial, e.g. O
­ 2, ­NO3, ­MnO2, ­Fe2O3. The limiting value is
the potential of + 300 mV, which corresponds to the The conducted research indicate a wide variation in
reduction of iron (III) to iron (II). Other boundaries the degree of soil contamination in areas affected
of the ranges divide the redox potential that character- by various facilities on the environment. All studied
izes soil conditions into three ranges: over + 300 mV areas are characterized by excessive metal/metal-
(oxygenated soils), from + 300 to –100 mV (pro- loid content in the soil. Aluminum and iron have the
cesses of reduction of oxygen connections of nitro- highest levels in the soils of the studied areas, but
gen, manganese and iron–soils that are slightly and they are major elements, so their amounts will not

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be considered as contamination. On the other hand, Table 5  Mean values of the calculated indexes of pollutants
elements such as As, Cd, Pb and Zn, considered as
substances causing risk, accumulated in the soil to a Igeo
degree significantly exceeding statutory limit values Dump Motorway WEEE plant
amounted to 25, 2, 200 and 500 mg ­kg−1 for As, Cd, Ba -1.29 -1.51 -0.88
Pb and Zn, respectively (Regulation of the Minister Cr -1.62 -1.14 -0.58
of the Environment, 2016). The highest exceedances
Cu 0.77 0.59 1.48
over limit values of these elements in soils were
recorded in the area of the dump and the electrical Mn -0.45 -0.49 -1.49
and electronic waste processing plant, and the lowest Pb 3.69 2.34 4.32
(except Zn) near the A4 motorway. The results indi- Sr -1.90 -2.17 -2.30
cating high soil contamination in WEEE plants cor-
Zn 3.80 3.21 2.11
respond to previous observations regarding pollution
from various urban-industrial sources presented in the As 0.90 0.12 1.38
publication by Albanese and Breward (2011) based Tl 0.20 -0.67 1.09
on data from Reimann and de Caritat (1998). Alba- Mo -0.42 0.27 1.72
nese and Breward (2011) also found that the elec- Cd 4.82 2.99 3.75
tronics industry probably produces the widest range
Co -1.11 -0.78 -0.15
of pollutants and this is reflected in these results. The
contents of almost all analyzed elements were the Sb 2.33 0.90 3.17
highest in the vicinity of WEEE (except Cd, Mn, Sr PLI (all elements)
and Zn). The high values of these elements in soils min 1.71 0.49 1.52
sampled in the vicinity of the heap and the highway max 3.29 3.50 4.52
are the result of their high contents in the geological
mean 2.59 2.24 3.40
background (near the heap) as well as, in the case of
the highway, vehicle emissions and corrosion of gal- PLI (Pb, Zn, Cd, Sb)
vanized road infrastructure elements (Wawer et al., min 10.06 1.14 7.27
2017). max 29.42 20.20 26.76
Table 5 presents the results of calculations of mean
mean 20.21 10.34 17.18
geochemical index (Igeo) and pollution load index
(PLI). The mean values of Igeo confirm that Cd, Pb 0 uncontaminated
and Zn, but also Sb and to a lesser extent also Cu, As, 1 uncontaminated to moderately polluted
Tl and Mo (in the area of WEEE plant) are the con- 2 moderately polluted
taminating elements in the studied areas. In the case Igeo class 3 moderately polluted to highly polluted
of soils from the metallurgical dump, the Igeo mean 4 highly polluted
values of Pb, Zn, Cd and Sb are in the 3–5 class, i.e. 5 highly polluted to extremely polluted
the soils are moderately polluted or highly polluted to 6 extremely polluted
extremely polluted with these elements. In the case of PLI
the WEEE plant, the Igeo mean values change in a < 1—excellent soil quality; ~ 1—basic level of soil contamina-
tion; > 1—deterioration of soil quality
similar range: from class 3 (moderately polluted—for
Zn) to 5 (highly polluted to extremely polluted—for
Pb). In case of soil in the area of motorway, the high- in Table 5 and limiting their number to those ele-
est Igeo class is 4th class and it concerns Zn. For Pb ments for which mean Igeo was above one in more
and Cd class 3 is defined. than one area (i.e. Pb, Zn, Cd, Sb). Regardless of the
The PLI index, as a more universal parameter, calculation method, the PLI was always > 1, indicat-
allows comparison of the studied areas regarding the ing a deterioration in soil quality. PLI calculated on
degree of contamination with a selected group of ele- the basis of all elements oscillated around 2–3 for
ments. For the purposes of this study, PLI was calcu- all investigated areas, while for selected contaminat-
lated in two ways: taking into account all 13 elements ing elements the mean values were: 10.34; 17.18 and

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20.21 for the areas of motorway, WEEE plant and for example for Fe and Tl, Cd, Zn, for Sr and Sb, Ba,
metallurgical slag dump, respectively, suggesting while Fe–Ba or Sr–Cr correlation was below − 0.70
extreme contamination. (Table S3—Supplementary Information). The lack
The Sb/As ratio has been used to identify the of strong correlations between the greater number
source of antimony in soil (Bi et al., 2011; Fu et al., of analyzed variables in this region can be explained
2011; Sharifi et al., 2016. In the case of the presented by the use of sewage sludge as fertilizer in the field,
study conducted in areas with known dominant the composition of which can be very diverse. PTEs
sources of elements emission, including antimony, it present in sewage sludge can pose a real threat, espe-
is possible to accurately assign ranges of values of this cially due to the presence of mobile forms (Feng
ratio to specific sources. This ratio ranged from 0.08 et al., 2018; Shamuyarira & Gumbo, 2014; Tytła &
to 0.58 for the dump area, 0.23–0.49 for the impact of Widziewicz-Rzońca, 2021).
the electrical and electronic waste treatment plant and In the case of samples from the vicinity of WEEE
0.08–0.25 for the motorway area. Similar and higher (Fig. S3—Supplementary Information) factor analy-
ranges of this parameter for the areas of the e-waste sis also showed that two factors were mainly respon-
plant and metallurgical dump indicate that these both sible for the variables. The first one conditioned about
objects are the dominant source of antimony. This 60% of the variables. Only cadmium and aluminum
is consistent with the literature data stating that the corresponded to the second and third factors, which
dominant source of this element is mining and metal- may indicate their different origins. High Pearson’s
lurgy of metal ores (He et al., 2019), including anti- correlation coefficients (over 0.70) between most of
mony itself (Herath et al., 2017), as well as the burn- the analyzed variables may suggest their common
ing of fossil fuels and wear of brake blocks in cars source (Table S4—Supplementary Information).
(Varrica et al., 2013). The obtained results clearly Most likely, it is an electrical waste processing plant.
confirmed that the excessive levels of antimony in the One factor was responsible for over 70% of soil
soil, many times exceeding the level of the geochemi- contamination in the vicinity of the motorway (Fig.
cal background, are of anthropogenic origin in all the S4—Supplementary Information). All associated var-
studied areas. Taking into account that the research iables can be derived from road emissions, indicat-
was conducted in the highly industrialized Upper ing that this was the main source of potentially toxic
Silesia, it must be stated that in the case of the studied elements in the area. Mutual relations and a common
areas mixed sources of antimony and other elements source of PTEs confirm strong correlation coefficients
in the soil occur. Both, in the WEEE plant and dump between most variables (Table S5—Supplementary
areas, transport emissions from adjacent roads had a Information).
significant impact on the soil contamination.

Soil pollution source apportionment Conclusions

The results of the factor analysis of samples col- The results of the research indicate that the soil in
lected in the region of dump of slag revealed two the vicinity of the studied objects was characterized
main sources responsible for around 30 and 40% of by high values of mass-specific magnetic susceptibil-
the variables (Fig. S2—Supplementary Information). ity (above 50 × ­10–8 ­m3 ­kg−1), and thus, high contents
Factor I was responsible mainly for Tl, Mo, Cd, Cu, of PTEs. In all analyzed areas the antimony content
Mn, Zn, Fe and the other one for Co, Sb, Pb, Sr, Al. was significantly higher than the reported average
Interestingly, both factors determined χ, As, Ba, Cr content of natural origin in soils in Poland, amount-
to a similar degree, which proves that these elements ing to 0.17 mg ­kg−1. Thus, obtained results clearly
could have had two common sources. These chemi- confirmed that the excessive levels of antimony in the
cal elements are connected with the composition of soil, many times exceeding the level of the geochemi-
slag deposited on dump but also very likely to the cal background, are of anthropogenic origin.
composition of the sewage sludge. In the research The most polluted area was in the vicinity of an
area adjacent to the dump, strong positive Pearson’s electrical waste processing plant. It is true that the
correlation coefficients (above 0.70) were obtained values of magnetic susceptibility were lower there

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than in the other studied areas, but it only proves a for a faster assessment of the condition of problem
lower content of technogenic magnetic particles, i.e. areas and the identification of areas that may pose a
mainly iron oxides and hydroxides. Soil contamina- potential threat to the local population.
tion in the vicinity of the WEEE plant was not the
result of high-temperature technological processes Author Contributions Conceptualization Magdalena
Jabłońska-Czapla; Data curation Magdalena Jabłońska-Czapla;
in which TMPs are formed, but it was the result of Formal analysis Magdalena Jabłońska-Czapla, Katarzyna
mechanical treatment of used electrical and electronic Grygoyć; Marzena Rachwał; Małgorzata Wawer-Liszka. Fund-
devices. Therefore, the recorded high PTEs content ing acquisition Magdalena Jabłońska-Czapla; Investigation
(Sb, As, Cr, Cu and Pb) was not accompanied by Magdalena Jabłońska-Czapla, Katarzyna Grygoyć; Marzena
Rachwał. Methodology Magdalena Jabłońska-Czapla; Marzena
high values of magnetic susceptibility. What is more, Rachwał. Project administration Magdalena Jabłońska-Czapla;
taking into account all the results of the quantitative Resources Magdalena Jabłońska-Czapla, Katarzyna Grygoyć;
analysis of antimony in the tested soil samples, it can Marzena Rachwał; Małgorzata Wawer-Liszka. Software;
be concluded that the WEEE processing and sorting Supervision Magdalena Jabłońska-Czapla, Katarzyna Grygoyć;
Marzena Rachwał; Małgorzata Wawer-Liszka. Validation
plant has the greatest effect on the antimony content Magdalena Jabłońska-Czapla, Katarzyna Grygoyć; Marzena
in the soil. Rachwał; Małgorzata Wawer-Liszka. Visualization Magda-
Large amounts of Zn and Cd were found in the soil lena Jabłońska-Czapla, Katarzyna Grygoyć; Marzena Rachwał;
collected in the vicinity of the heap after the process- Małgorzata Wawer-Liszka. Roles/Writing – original draft
Magdalena Jabłońska-Czapla, Katarzyna Grygoyć; Marzena
ing of zinc–lead ores. These elements were not only Rachwał; Małgorzata Wawer-Liszka. Writing – review &
from the emissions of dust and material from the editing Magdalena Jabłońska-Czapla, Katarzyna Grygoyć,
heap, but were also delivered to the soil along with Marzena Rachwał; Małgorzata Wawer-Liszka.
sewage sludge used in the farmlands as fertilizer. The
Funding The research was carried out in the frame of project
average antimony content was lower than in the vicin-
which received funding from statutory research of the Institute
ity of the area of the electrical and electronic waste of Environmental Engineering, Polish Academy of Sciences,
processing plant but still very high. for 2020, No. 1A-127/20.
Research has shown that the impact of road traf-
fic and wearing off brake blocks, i.e. traffic anthropo- Availability of data and materials Samples of the com-
pounds are available from the authors.
pression in general, has little effect on the antimony
content in the surrounding soil. Surprisingly, the soil Declarations
in the vicinity of the highway was the least polluted.
The area around WEEE plant was characterized by Conflict of interests The authors declare that they have no
known competing financial interests or personal relationships
the following 9 elements with Igeo > 1: Pb > Cd > S that could have appeared to influence the work reported in this
b > Zn > Mo > Cu > As > Tl, the area of metallurgic paper.
waste dump area by the following 5 elements with
Igeo > 1: Cd > Zn > Pb > Sb, while the area near the Ethical Approval The Authors confirm that the manuscript
entitled “The study of antimony in soils in areas subjected to
highway by the following 4 elements: Zn > Cd > Pb. various industrial sources using geophysical-geochemical meth-
The Igeo for Pb, Zn and Cd was high in all studied ods” has not been published previously and is not under consid-
areas, which may indicate that these elements can be eration for publication elsewhere.
emitted by all considered pollution sources.
Consent to Participate All authors agree to participate.
The research confirmed that thanks to the use of
soil magnetometry, it was possible to quickly identify Consent to Publish All authors declare their consent to pub-
places with a potentially increased content of PTE. lication.
Magnetic susceptibility measurements combined
with chemical analysis and calculations of pollution
indices provided sufficient data for a comprehensive
assessment of the condition and degree of soil con-
tamination in the study area. Similar research con-
ducted in the future in other industrial areas with an
equally complex impact of emitters will allow the Open Access This article is licensed under a Creative Com-
development of specific operating patterns, allowing mons Attribution 4.0 International License, which permits

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use, sharing, adaptation, distribution and reproduction in any Cabała, J., Żogała, B., & Dubiel, R. (2008). Geochemical and
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original author(s) and the source, provide a link to the Crea- waste dump areas (southern Poland). Polish Journal of
tive Commons licence, and indicate if changes were made. The Environmental Studies, 17(5), 693–700.
images or other third party material in this article are included Catinon, M., Ayrault, S., Boudouma, O., Bordier, L., Agnello,
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