Environ Geochem Health

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ORIGINAL PAPER

Potentially toxic elements in surface soils of the Lower Don

floodplain and the Taganrog Bay coast: sources, spatial
distribution and pollution assessment
Elizaveta Konstantinova . Tatiana Minkina . Dina Nevidomskaya .
Saglara Mandzhieva . Tatiana Bauer . Inna Zamulina . Marina Voloshina .
Ilia Lobzenko . Aleksey Maksimov . Svetlana Sushkova

Received: 28 February 2021 / Accepted: 21 June 2021

Ó The Author(s), under exclusive licence to Springer Nature B.V. 2021

Abstract The pollution of floodplain, deltaic and
adjacent coastal soils in large fluvial systems, consid-
ered an urgent environmental problem, as well as
potentially toxic elements in such environments, can
negatively affect aquatic ecosystems, as well as pose
significant risks to human health. This paper is devoted
to the geochemistry of potentially toxic elements in
soils of the Lower Don basin, which is one of the
largest and most anthropogenically transformed water
bodies in Southern Russia, as well as the adjacent
areas of the Taganrog Bay coast. The median element
concentrations in the soils of the study area were
consistent with the world soil average and the contents
of elements in background soils. Comparative assess-
ment of the spatial distributions as well as the results of
Pearson’s correlations, cluster analysis and principal
component analysis showed that Cr, Ni, Cu and Zn are
predominantly of natural origin; Mn and As are of
mixed sources; and Cd and Pb are predominantly of
E. Konstantinova (&)  T. Minkina 
D. Nevidomskaya  S. Mandzhieva 
T. Bauer  I. Zamulina  M. Voloshina 
I. Lobzenko  S. Sushkova
Southern Federal University, 194/1 Stachki ave,
Rostov-on-Don, Russian Federation 344090
e-mail: konstantliza@gmail.com
A. Maksimov
National Medical Oncology Research Center of Ministry
of Health of the Russian Federation, Rostov-on-Don,
Russian Federation
anthropogenic origin. The geochemical anomalies of
elements were associated with the impact of local
anthropogenic sources. Geochemical background val-
ues for Cr, Mn, Ni, Cu, Zn, As, Cd and Pb in the soils
of the Lower Don and the Taganrog Bay coast
determined using the ‘median ? 2 median absolute
deviations’ approach are presented. The highest values
of the integrated pollution indices were observed in
floodplain soils of small rivers.
Keywords Trace elements  Heavy metals 
Fluvisols  Geochemical threshold  Pollution index 
Southern Russia
Introduction
Floodplains and deltas of large rivers are territories
with a historically high population density, intensive
agriculture, developed industry and transport infras-
tructure, all of which results in a significant level of
anthropogenic pressure on such systems (Skala et al.,
2017). Long-term human impacts on the floodplain
and deltaic landscapes, as well as on the adjacent
coastal areas, lead to the degradation of natural
landscapes and aquatic ecosystems and pose a risk to
biodiversity and human health (Schindler et al., 2014).
Environmental pollution of floodplains and deltas is
considered one of the most negative results of

123

anthropogenic activities within large river basins
(Kasimov et al., 2020a, 2020b).
Soil cover is an important component of floodplain
and deltaic systems; it accumulates matter, including
potentially toxic elements (PTEs), from the entire
basin (Chalov et al., 2017; Förstner et al., 2004; Lair
et al., 2009). Therefore, soil pollution with PTEs and
other contaminants is considered one of the most
dangerous consequences of long-term human activi-
ties that affect fluvial systems (Du Laing et al., 2009;
Rinklebe et al., 2019). In addition to floodplains and
deltas acting as geochemical barriers, sources of
pollutants can be rather diverse, varying from the
local scale to the basin-scale (Arafa et al., 2015), a
factor that significantly complicates their
identification.
Another important issue related to the pollution of
floodplain and deltaic soils is the dynamic nature of
these systems: fluctuations between floods and
droughts strongly influence physical–chemical prop-
erties of floodplain soils and, consequently, the
mobility of metals (Frohne et al., 2014; Rennert
et al., 2017; Schulz-Zunkel et al., 2015). Therefore,
soils in fluvial systems are both sinks and secondary
sources of matter, including PTEs (Schulz-Zunkel
et al., 2015). In deltaic and adjacent coastal environ-
ments, the geochemistry of soils is also affected by the
dynamic gradients that occur on the river–sea interface
(Dada et al., 2016). It is also important to note that
floodplains and deltas are rather heterogeneous sys-
tems where even small-scale changes in topography,
vegetation and land use can significantly affect the
geochemical conditions and temporal dynamics of the
current geomorphic surface (Pahlavan-Rad & Alireza,
2018).
In the past decades, researchers have assessed soil
pollution in a number of large fluvial systems in
different parts of the world (Elbehiry et al., 2019; Enya
et al., 2019; Ge et al., 2019; Shaheen & Rinklebe,
2014; Shaheen et al., 2017; Singh & Kumar, 2017;
Yan et al., 2018). In Russia, the most complex soil
geochemical studies have been performed for the
floodplain and deltaic environments of the Volga
(Lychagin et al., 2015) and Selenga (Chalov et al.,
2017; Kasimov et al., 2017). Other large fluvial
systems in the European and Asian parts of the
country, though they are also subjected to long-term
intensive anthropogenic pressure, have been studied
much less in terms of soil geochemistry and pollution.
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Environ Geochem Health
The situation is similar for the Don River basin and
adjacent areas of the Sea of Azov, even though it is one
of the largest water bodies of Southern Russia. Most of
the Don River basin is characterized by a high
population density, with the presence of both highly
developed industrial and agricultural centres (Bartsev
et al., 2016).
Assessment of the impact of local sources within
the study area and associated soil pollution involves
the determination of the geochemical background and
the threshold values of PTEs in soils. The threshold
separates the background values from the abnormal
ones; otherwise, it is in the outer limit of the natural
range (Reimann & Garret, 2005; Reimann et al.,
2005). There are two main groups of methods to
determine the background values of elements in soils,
namely ‘geochemical’ and ‘statistical’ (Labaz et al.,
2019). The first approach involves the use of a natural
background corresponding to the average content of
elements in natural, undisturbed soil at a distance from
the source (Reimann & Garret, 2005; Reimann et al.,
2005). However, the ‘geochemical’ approach assumes
that the compared soils are similar to the background
ones in terms of their physicochemical properties and
are formed in similar landscape conditions. The
‘statistical’ approaches approximate the ambient geo-
chemical baseline based on soil samples collected in
each area (Labaz et al., 2019). The most widely used
methods for the threshold determination are the
calculation of measures of central tendency (e.g.
mean, median and mode); the mean plus twice the
standard deviation; the median plus twice the median
absolute deviation (Med ? 2MAD); the estimation of
the 90th, 95th or 98th percentile after visual inspection
of cumulative probability plots; and using the upper
whisker of Tukey’s box-plot (Hawkes & Webb, 1962;
Kürzl, 1988; Reimann & Garret, 2005; Reimann et al.,
2005, 2018). The choice of a particular approach
depends on the statistical distribution of the geochem-
ical data as well as the presence of outliers and
extreme values.
Recent geochemical and hydrological studies have
shown that PTEs (Fedorov et al., 2001; Klyonkin et al.,
2007; Nikanorov, 2014; Tkachenko et al., 2017;
Minkina et al., 2017a, 2017b; Konstantinova et al.,
2020, 2021; Nevidomskaya et al. 2021) along with
pesticides (Nikanorov & Khoruzhaya, 2012), oil
products and polycyclic aromatic hydrocarbons (Kuz-
netsov & Fedorov, 2014; Sushkova et al., 2020) are the
Environ Geochem Health
most dangerous pollutants for the aquatic landscapes
of the Lower Don and adjacent areas of the Sea of
Azov. The aims of this study were: (i) to evaluate the
levels and spatial patterns of PTEs in soils of the
Lower Don and the Taganrog Bay coast; (ii) to identify
possible sources of PTEs using multivariate statistics;
(iii) to define the geochemical background and
threshold values for Cr, Mn, Ni, Cu, Zn, As, Cd and
Pb in the soils of the study area; and (iv) to assess soil
pollution within the study area.
Materials and methods
Study area and soil sampling
The study area is located within the Lower Don Delta
and the Taganrog Bay coast (Fig. 1). The bay is
shallow, with an average depth of 5–7 m. The
Taganrog Bay has an erosional genesis and likely is
a valley of an ancient river, broadened by abrasion and
slumping (Maev et al., 2009). The adjacent territory
can be subdivided into several parts based on the
geomorphological and geological features: the North-
ern Pryazovia region of Pliocene–Pleistocene plains
with intensive gully erosion, the Eastern Pryazovia
region of accumulative Pliocene–Pleistocene plains
with lower intensity of erosional processes, and the
Don Delta region of fluvial terraces and floodplains.
The predominance of abrasion is typical for the
modern dynamics of the coastal zone (Kosyan &
Krylenko, 2019). Anthropogenic activities have also
Fig. 1 Location of sampling sites of surface soils of the Lower Don and the Taganrog Bay coast (the base map is from www.
openstreetmap.org)
significantly affected the current state of the shores
(Krylenko et al., 2017).
The Don Delta, which includes the river segment
from the village of Razdorskaya to the Taganrog Bay,
is represented by several dozens islands, all of which
are composed of medium and fine-grained sands and
have saucer-shaped form. The area occupied by the
modern Don Delta is estimated to be 540 km2 (Ivanov
et al., 2013).
The Lower Don and the Don River mouth are
strongly affected by the up and down surges with
frequent flows of marine waters into the delta branches
(Chikin et al., 2019). Therefore, the Taganrog Bay and
the Don Delta are characterized by the interactions of
fresh, slightly brackish and brackish waters (Chikin
et al., 2019; Matishov & Grigorenko, 2017). The
mineralization changes from 300–500 mg L-1 in the
middle part of the river mouth to 1–2 g L-1 at the
estuarine seaside, and the chemical composition of the
water varies from sulphate-calcium to chloride-sul-
phate-sodium (Tkachenko et al., 2016).
The climate of the territory is continental, with an
annual temperature of 9.9 °C and annual precipitation
of 615 mm (Kazakov 2020). The most common
landscapes of the study area are coppice willows,
floodplain meadows, sand dunes, beaches and spits,
parks, gardens and other tree plantations, urbanized
areas and industrial areas. The macrophytes that are
the predominant type of vegetation of the floodplain,
deltaic and coastal areas belong to the families
Asteraceae, Poaceae, Fabaceae, Brassicaceae, Api-
aceae, Lamiaceae and Scrophulariaceae (Matishov
123

et al., 2016). The most common soils of the Don Delta
are Fluvisols (IUSS Working Group WRB, 2015).
The main industrial and transport facilities within the
Don Delta and the Taganrog Bay coast correspond to
the agglomeration of the Rostov-on-Don as well as the
cities of Azov and Taganrog, which is a large port.
A total of 86 soil samples (Fig. 1) were collected in
the summer of 2020 using an envelope method (GOST
17.4.4.02–2017, 2018) from the surface soil horizon
(0–20 cm deep). The soil samples were air-dried,
mixed, ground and passed through a 1-mm sieve
(Vorobyova, 2006).
Analytical methods
The particle size analysis was conducted using the
pipette method with the pyrophosphate procedure of
soil preparation (Soil Survey Staff, 2011) to obtain the
total clay fraction (particles \ 0.002 mm). The total
organic carbon (TOC) content in the soils was
determined using the dichromate oxidation method
according to Tyurin. The pH was measured by
potentiometry in the supernatant suspension of soil
and water in a ratio of 1:2.5. The CaCO3 content was
determined by the complexometric method proposed
by Kudrin (Vorobyova, 2006). The exchangeable
cations Ca2? and Mg2? were determined using the
method described by Shaimukhametov (1993).
The total concentrations of Cr, Mn, Ni, Cu, Zn, As,
Cd and Pb were determined by X-ray fluorescence
analysis using a Spectroscan MAX-GV spectrometer
(Spectron, Russia) (OST 10–259–2000, 2001). All
laboratory tests were performed in triplicate. The
accuracy of element determination was verified using
duplicates, reagent blanks, and state standard refer-
ence samples (no. GSS 10412–2014, State Service for
Standard Specimens Relating to Composition and
Properties of Substances and Materials) and complied
with standards of certified methods (OST 10–259–
2000, 2001). The recovery rates and quantification
ranges for the PTEs were based on the standard
certificates.
Data analysis and visualization
The software package STATISTICA 12 (StatSoft, the
USA) was used to analyze the data. Basic descriptive
statistics included mean, median, minimum, maxi-
mum, standard deviation (SD) and coefficient of
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Environ Geochem Health
variation (CV) for all physical–chemical parameters
and PTE concentrations. The median value was
preferred as a robust measure of the central tendency
of the dataset instead of the mean value, because the
median was not adversely affected by extreme outliers
(Glennon et al., 2014). The Kolmogorov–Smirnov test
was used to check the normality of the data. Before
multivariate statistical analysis, the data were stan-
dardized to obtain a symmetrical distribution for all
parameters and achieve normal distribution.
The one-way analysis of variance (ANOVA) was
followed by the Scheffe post hoc test for the soils of
various subsystems of the Lower Don–Taganrog Bay
system to evaluate the differences in the total PTE
content. If the analyzed data failed Levene’s test for
the homogeneity of variances, the Kruskal–Wallis
ANOVA followed by multiple comparisons of mean
ranks for all groups was applied.
Pearson’s correlation coefficients (r) were calcu-
lated to determine the relationship between PTEs and
the physical–chemical properties of soils. Hierarchical
cluster analysis (HCA) was applied to classify the
studied PTEs in the soil samples and performed
according to Ward’s method. The measure of similar-
ity used 1- r, and the results are reported in the form of
a dendrogram. The critical level of amalgamation for a
set of 86 samples was 0.788 at p \ 0.05. Principal
component analysis (PCA) was carried out to identify
the relationship between the measured parameters by
determining the individual component loadings. Only
components with eigenvalues [ 1.0 were considered,
following the Kaiser criterion.
Maps illustrating the spatial distribution of eight
PTEs were created in Surfer 15 (Golden Software, the
USA). Data interpolation was conducted using the
inverse weighted distance method with a power of 2.
Determination of geochemical threshold values
Calculation of soil pollution indices requires an
assessment of the geochemical background (Cb) to
differentiate between normal ‘natural’ concentrations
of PTEs in the soils from abnormal concentrations
(Reimann & Garret, 2005). Local geochemical back-
ground concentrations of PTEs in topsoils of the
studied region were defined using a statistical
approach. In the present study, the calculation of
Med ? 2MAD on log-transformed data and subse-
quent back-transformation was used to derive the
Environ Geochem Health

Table 1 Criteria for soil classification according to geochemical indices

Index Equation Range Class Reference
 
Geoaccumulation index (Igeo) Igeo ¼ log2 Ci
; B0 Unpolluted Müller (1986)
1:5C b
0–1 Unpolluted to moderately polluted
1–2 Moderately polluted
2–3 Moderately to highly polluted
3–4 Highly polluted
4–5 Highly to extremely high polluted
[5 Extremely high polluted
 
Enrichment factor (EF) Ci B1 Absent Sutherland (2000)
C Al
EF ¼   sample 1–2 Minimal pollution
Cb
C b Al
background 2–5 Moderate pollution
5–20 Significant pollution
20–40 Very strong pollution
[ 40 Extreme pollution
Single pollution index (PI) Ci B1 Absent Kowalska et al. (2018)
PI ¼ Cb
1–2 Low pollution
2–3 Moderate pollution
3–5 Strong pollution
[5 Very strong pollution
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Pn ffi
Nemerow pollution index (NPI) 1
ðn
2 2
PIÞ þPI max
B 0.7 Clean Nemerow (1991)
NPI ¼ i1
2 0.7–1 Warning limit
1–2 Slight pollution
2–3 Moderate pollution
C3 Heavy pollution
Pollution load index (PLI)  Qn 1n \1 Denote perfection Kowalska et al. (2018)
PLI ¼ i¼1 PI i
=1 Only baseline levels of pollution
[1 Deterioration of soil quality
Ci content of element i in a soil sample, Cb calculated geochemical threshold value, CAl content of aluminium taken as a reference
element

threshold values of the studied PTEs. Reimann et al.
(2005) proposed this approach for geochemical studies
as a much more robust method against the effect of
data outliers, especially for data with skewed distri-
butions (Reimann & de Caritat, 2017).
Pollution assessment
The assessment of soil pollution was carried out using
some geochemical indices that allow taking into
account both the effect of individual PTEs and the
combined effect. In this study, the most common
indices were used, including the geoaccumulation
index (Igeo), the enrichment factor (EF), the single
pollution index (PI), the Nemerov pollution index
(NPI), and the pollution load index (PLI). The
geochemical indices, their equations and interpreta-
tion are presented in Table 1. The Igeo, introduced by
Müller (1986), is widely used to assess soil pollution
by individual elements, including soils of river basins
(Elbehiry et al., 2019; Jiménez-Ballesta et al., 2017;
Wang et al., 2019; Zhou et al., 2020; Zhuang & Lu,
2020). Its main advantage is to reduce the influence of
lithogenic variability in element contents and precise
scale (Kowalska et al., 2018). The EF is used not so
much to assess soil and sediment pollution as to
determine the degree of anthropogenic influence on
the level of elements (Sutherland, 2000). The main
feature of the EF is the use of geochemical normal-
ization of elements relative to conservative elements,

123

for example, Al, Fe, Li or Ti, the distribution of which
in soils is relatively homogeneous. In this study, Al
was used as a reference element. The calculation of the
PI is the basic approach for assessing soil contamina-
tion by individual elements; in addition, it is used to
calculate complex indicators, such as the NPI and the
PLI (Kowalska et al., 2018). The calculation of the
NPI and the PLI accounts for all elements, regardless
of their quantity (Nemerow, 1991; Tomlinson et al.,
1980). The NPI makes it possible to identify anomalies
where pollution is caused by a high content of one or
several elements with relatively low values of the
remaining ones. The PLI is the geometric mean for all
studied elements, that is, it allows identifying a typical
value that characterizes pollution.
Results and discussion
Physical–chemical properties of soils
The soil cover of the study area is formed mainly by
hydromorphic and semi-hydromorphic undisturbed
soils. The floodplains and coastal landscapes of the
study area are dominated by Eutric and Calcaric
Gleyic Fluvisols, Gleyic Fluvisols (Humic) and Gleyic
Phaeozems. On the southern coast of the Taganrog
Bay, in depressions on marine and alluvial deposits,
Fluvic Solonchaks (Hypersalic) are widespread.
Haplic Chernozems are formed on loess-like sedi-
ments under automorphic conditions. The descriptive
statistics for the physical–chemical properties of the
studied soils of the Lower Don floodplain and the
Taganrog Bay coast are presented in Table 2. The
acidity of the soils varied greatly, from neutral to
strongly alkaline (pHH2O = 7.2–8.9). The high pH
values are due to the high content of CaCO3 (up to
8.3%) and the saturation of soils with Ca2?and Mg2?
(up to 42.3 cmol kg-1). The average TOC content was
1.3%, ranging from 0.1% to 3.9%. According to the
particle size distribution, soils are mainly character-
ized by a light texture from sandy to loamy, while a
small percentage of the samples were clayey in
texture. The differences in the contents of SiO2,
Fe2O3 and Al2O3 correspond to the variations in soil
texture: maximum SiO2 values are characteristic for
soils of sandy beaches and a higher proportion of
Fe2O3 and Al2O3 is characteristic for well-developed
Fluvisols with higher contents of the clay fraction.
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Environ Geochem Health
Levels of PTEs in soils
Table 3 summarizes the descriptive statistics for eight
PTEs identified in the soil samples. The mean
concentrations of Mn, Zn, Cd and Pb were signifi-
cantly higher than their median, indicating a right-
skewed distribution bias. The mean and median values
were not greatly different for the remaining elements.
The Kolmogorov–Smirnov test showed that none of
the distributions of the PTEs were normal (p \ 0.05).
Consequently, the median values of the elements
better characterize the central tendency of the distri-
bution. The elements, in descending order of median
concentration, were Mn, Cr, Zn, Ni, Cu, Pb, As and
Cd. The median contents of Cd and Cr were 1.8 and
1.6 times higher, respectively, than the world soil
average (Kabata-Pendias, 2011), and the contents of
Mn, Zn, Ni, Cu, Pb and As were comparable to the
global geochemical background. The median contents
of PTEs in the soils of the study area were consistent
with those identified in the Fluvisols of the Chumbur-
Kosa protected area (Minkina et al., 2017a, 2017b),
except for Cd (3.7 times higher in soils of the study
area).
Concentrations of PTEs in soils of the Lower Don
and the Taganrog Bay coast varied considerably,
reflecting both the heterogeneity of ecological factors
and the diversity of their anthropogenic sources.
Cadmium had the highest SD and CV values, findings
that indicate its anthropogenic origin. There were high
SD and CV values for Zn, As and Pb, while Cr, Mn, Ni
and Cu had moderate values. Therefore, the input into
the soils of the first group of elements is probably
associated with the presence of significant anthro-
pogenic sources, while the elements of the second
group are mainly controlled by natural factors.
Spatial distribution of PTEs in soils
The spatial distribution of the concentration of eight
PTEs in the surface soils of the Lower Don and the
Taganrog Bay coast is illustrated in Fig. 2. The spatial
variability patterns of Cr, Ni, Cu and Zn were
generally similar. There were elevated levels of these
PTEs in soils near large settlements such as the cities
of Novocherkassk, Taganrog and Azov. The areas
with maximum concentrations were confined to the
mouth of the Kagalnik River in the central part of the
study area. Cadmium and lead exhibited a completely
Environ Geochem Health

Table 2 Descriptive statistics for the physical–chemical properties of soils from the Lower Don and the Taganrog Bay coast
Soils pH CaCO3 TOC Ca2? ? Mg2? (cmol SiO2 Fe2O3 Al2O3 Clay
H2O (%) (%) kg-1) (%) (%) (%) (%)

Eutric Gleyic Fluvisols Mean 7.8 2.1 1.2 17.5 65.8 3.3 7.9 12.2
(n = 61) Med 7.9 1.6 1.0 16.0 66.1 3.4 8.3 11.0
Min 7.2 0.1 0.1 4.2 40.4 0.4 1.2 0.1
Max 8.9 8.3 3.1 42.3 85.2 5.2 11.8 31.7
SD 0.3 1.7 0.7 8.9 9.1 1.2 2.7 9.2
CV 4.3 79.9 64.3 50.9 13.8 37.3 33.9 75.9
(%)
Calcaric Gleyic Fluvisols Mean 7.7 2.3 1.0 11.2 59.1 3.8 8.6 8.1
(n = 12) Med 7.8 2.0 1.0 10.6 56.3 4.3 8.9 7.8
Min 7.3 0.7 0.7 7.0 52.8 2.3 5.9 5.9
Max 8.1 4.8 1.5 19.7 77.7 4.8 10.9 11.7
SD 0.2 1.5 0.3 4.0 7.3 0.8 1.6 1.7
CV 3.2 62.5 25.6 35.5 12.4 22.1 18.2 20.8
(%)
Gleyic Phaeozems (n = 5) Mean 8.0 1.3 1.6 19.8 62.3 4.2 8.0 15.3
Med 8.0 0.9 1.8 27.8 62.9 4.2 7.4 21.2
Min 7.7 0.7 0.5 5.4 39.5 3.8 5.9 2.8
Max 8.2 2.6 2.8 31.9 75.8 4.8 11.2 24.8
SD 0.2 0.8 1.0 13.0 15.0 0.5 2.2 10.6
CV 2.4 62.1 61.4 65.4 24.1 10.8 27.3 69.0
(%)
Fluvic Solonchaks Mean 7.9 2.0 1.8 31.6 51.1 4.8 10.6 25.7
(Hypersalic) (n = 3) Med 7.9 1.4 1.8 35.4 52.0 4.8 10.7 25.5
Min 7.8 1.1 1.7 23.2 45.3 4.6 10.1 20.2
Max 7.9 3.6 2.0 36.1 56.0 4.9 11.0 31.5
SD 0.1 1.4 0.2 7.3 5.4 0.2 0.5 5.7
CV 0.7 67.1 8.3 23.0 10.6 3.2 4.3 22.0
(%)
Haplic Chernozems (n = 3) Mean 7.7 2.1 2.4 33.3 66.7 5.0 9.6 26.3
Med 7.8 1.9 2.2 32.7 68.2 5.3 11.0 25.1
Min 7.5 0.7 2.0 31.0 63.3 4.5 6.1 24.0
Max 7.8 3.7 3.1 36.3 68.5 5.3 11.7 29.8
SD 0.2 1.5 0.6 2.7 2.9 0.5 3.1 3.1
CV 2.2 71.9 24.1 8.1 4.4 9.2 31.8 11.7
(%)
Gleyic Fluvisols (Humic) (n = 1) 7.8 1.5 3.9 29.1 54.8 4.6 8.7 17.6
Tidalic Arenosols (n = 1) 7.7 2.3 0.1 7.9 81.8 0.7 1.4 2.9
Total (n = 86) Mean 7.8 2.1 1.3 17.8 64.2 3.5 8.1 12.7
Med 7.8 1.6 1.1 15.9 64.4 3.8 8.5 10.9
Min 7.2 0.1 0.1 4.2 39.5 0.4 1.2 0.1
Max 8.9 8.3 3.9 42.3 85.2 5.3 11.8 31.7
SD 0.3 1.6 0.8 9.6 9.6 1.2 2.6 9.2
CV 4.0 75.3 63.8 53.7 15.0 34.9 32.1 72.4
(%)
TOC total organic carbon, Med median, Min minimum, Max maximum, SD standard deviation, CV coefficient of variation

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Table 3 Statistical Element Mean Median Minimum Maximum SD CV

summary of total potentially
toxic element (PTE) Cr 97.8 93.9 34.1 297.0 44.3 45.3
concentrations (mg kg-1) in
Mn 843.8 723.9 202.3 2466.2 390.7 46.3
topsoils from the Lower
Don and the Taganrog Bay Ni 45.8 43.9 19.0 98.0 17.9 39.1
coast (n = 86) Cu 42.5 40.4 4.1 106.9 17.3 40.8
Zn 120.7 92.0 30.2 631.5 94.7 78.5
As 7.7 7.6 1.1 18.2 3.9 50.2
Cd 1.42 0.74 0.10 6.21 1.44 101.3
SD standard deviation, CV Pb 38.8 32.3 5.3 129.6 24.9 64.1
coefficient of variation

different pattern of spatial distribution: they tended to Sources of PTEs in soils

accumulate in soils far from potential sources of
pollution. The spatial distribution of Mn and As was
characterized as a transitional variant, with the pecu-
liarity that increased values of these PTEs were also
found in the soils of the southwest part of the study
area, which is a zone predominantly used for recre-
ational purposes.
It is probable that the hydrological regime of the
soils and the lithological and geomorphological con-
ditions were of the greatest importance for the
distribution of PTEs within the study area. According
to Wilks’ criterion, the confinement of soils to a
specific zone of the Lower Don and the Taganrog Bay
coast was highly significant for all studied PTEs
(p \ 0.0005). There were statistically significant dif-
ferences in the Cr, Cu and Zn contents in soils of
various river–marine subsystems according to the one-
way ANOVA (Table 4). Furthermore, there were
differences in the Ni and Pb contents identified by the
Kruskal–Wallis ANOVA (p = 0.0004 and 0.0001,
respectively; \ 0.0005). The average contents of Cr,
Ni, Cu, Zn and Pb in the soils of the floodplains of
small rivers were 1.5–2 times greater than in the soils
of other zones of the study area (Fig. 3). It should be
noted that the levels of Cr, Cu and Zn in the soils of
small rivers are comparable to the threshold values of
these metals in the soils of the entire study area; this
finding indicates a geochemical anomaly. This
anomaly is assumed to be natural and is due to the
composition of the parent rocks, which are alluvium
formed by the redeposition of eroded loamy sediments
of the ancient plains. There were no significant
differences in the contents of Mn, As and Cd in the
soils of different zones (Fig. 3, Table 4), data that
indicate the presence of local anthropogenic sources of
these elements within the study area.
Correlation analysis was performed to assess the
relationship between individual elements as well as
the physical–chemical properties of surface soils
(Table 5). There were significant (p \ 0.05) moderate
positive correlations for the group of elements Cr, Ni,
Cu and Zn (r = 0.517–0.669) and between Cr and As
(r = 0.517). Correlation within the Mn–Ni, Ni–As and
Zn–Cd pairs, as well as between Pb and Cr, Ni, Cu, Zn
and Cd, was low and positive. Correlation analysis
showed that soil properties were not the major factor
controlling PTE concentrations in the floodplain and
coastal soils (Table 5). There were significant low
positive correlations (r = 0.308–0.406) between the
TOC and clay with Cd and Pb, between exchangeable
Ca2? ? Mg2? with Cu and Pb, and between Fe2O3
and Al2O3 with Ni and Pb, while there were low
negative correlations between SiO2 with Zn (- 0.321)
and Pb (- 0.346). Based on Pearson’s correlation
coefficients, the following groups of intercorrelated
elements likely have similar sources: the first group
included Cr, Ni, Cu and Zn; the second group included
Cd and Pb; and the third group included Mn and As.
Cluster analysis was performed according to
Ward’s method and was applied to define sources of
PTEs. Figure 4 presents a hierarchical dendrogram
showing the clustering of PTEs. The results of HCA
revealed three separate clusters: Pd–Cd (Cluster 1),
As–Mn (Cluster 2) and Zn–Ni–Cu–Cr (Cluster 3).
These results are consistent with the correlation
analysis data (Table 5). It was previously shown that
Cluster 1 (Pb and Cd) has a strong anthropogenic
origin, while elements of Cluster 3 likely have a
geogenic origin with significant contribution from
anthropogenic sources. The elements representing
Cluster 2 are likely related to mixed sources.

123
Environ Geochem Health

123

b Fig. 2 Spatial distribution of Cr, Mn, Ni, Cu, Zn, As, Cd and Pb
in surface soils of the Lower Don and the Taganrog Bay coast
(n = 86)
The results of PCA are presented graphically in
Fig. 5. Two principal components (PCs) were
extracted with eigenvalues [ 1, accounting for
61.9% of the cumulative variance. The first compo-
nent (PC1) explained 43.5% of the total variance and
showed strong negative loadings for Cr (- 0.81), Ni
(- 0.85), Cu (- 0.79) and Zn (- 0.75). The same
component had moderate negative loading for As
(- 0.52) and Pb (- 0.61), as well as weak negative
loadings for Mn (- 0.40) and Cd (- 0.33). The
Fig. 2 continued
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Environ Geochem Health
second component (PC2) described 18.4% of the total
variance and exhibited a strong positive loading for Cd
(0.84) and a moderate negative loading for As
(- 0.54). In addition, PC2 showed a weak positive
correlation with Pb (0.44) and a weak negative
correlation with Mn (- 0.42). Physical–chemical
properties of soils were used as supplementary vari-
ables in the PCA, the results of which showed that PC1
had weak negative correlations with the TOC, Fe2O3
and Al2O3, and weak positive correlations with SiO2,
while PC2 was characterized by a weak positive
loading of the TOC. The first principal component is
probably a natural factor, and the second principal
component corresponds to the severity of
Environ Geochem Health
Fig. 3 Box-plots for Cr, Mn, Ni, Cu, Zn, As, Cd and Pb in the
surface soils of the Lower Don and the Taganrog Bay coast,
grouped by subsystems. Different letters indicate significant
anthropogenic impact. These results are consistent
with the cluster analysis data (Fig. 4). Biplot grouping
soil samples by river–marine subsystems (Fig. 5)
demonstrate that floodplain soils of small rivers are
enriched with Cr, Ni, Cu and Zn, while Cd and Pb tend
to accumulate in coastal soils. Manganese and As
accumulate in soils, regardless of their association
with subsystems.
differences (p \ 0.05) resulting from the post hoc tests. The
dashed line indicates the geochemical threshold value for each
element, calculated as median ? 2 median absolute deviations
Background values of PTEs in soils
The first step in assessing soil contamination of the
study area was to determine the geochemical threshold
values of Cr, Mn, Ni, Cu, Zn, As, Cd and Pb. The
threshold values of PTEs in the soils of the Lower Don
and the Taganrog Bay coast, calculated using the
Med ? 2MAD method, are presented in Table 6.
Table 6 also provides the global background levels of
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 Environ Geochem Health

Table 4 Effects of the soil location within the Lower Don— lithogenic conditions. The high values of Cd and Pb
Taganrog Bay system on PTE content as indicated by one-way are most likely associated with the presence of
ANOVA
significant anthropogenic sources of these elements
Element SS MS F p in the study area.
Compared with the Russian TACs, the calculated
Cr* 26,539.7 8846.6 5.1700 0.002536
threshold values are 1.7–7.6 times higher than the
Mn* 1,140,303 380,101 2.6337 0.055323
standard values of PTEs for sandy soils and lower than
Ni 6787.9 2262.6 9.0500 0.000030
or equal to the values in neutral and alkaline loamy
Cu* 7102.5 2367.5 10.5244 0.000006
soils (Table 6). An exception is As, for which the
Zn* 104,428 34,809 4.3422 0.006847
Med ? 2MAD value exceeded the TAC for loamy
As* 31.517 10.506 0.6903 0.560522
soils by 2.5 times. Nevertheless, the assessment of the
Cd* 5.9047 1.9682 0.95335 0.418859
soils of the territory relative to the TAC showed that
Pb 10,268.6 3422.9 6.6348 0.000456
4.6–55.8% of the samples exceeded the standards, a
Bold values are significant at p \ 0.05. * the homogeneity of finding that is associated with a significant abundance
variances was proven by Levene’s test of soils characterized by a light texture. It should be
noted that Russian TACs are the most ‘conservative’
compared with national soil guideline values in
Europe, Canada and Australia (CCME, 1999; Reim-
PTEs, based on the world soil average (Kabata-
ann et al., 2018). Thus, the choice of one or another
Pendias, 2011) and the results of Geochemical Map-
approach to assess soil contamination and the associ-
ping of European Agricultural Soil (GEMAS) project
ated environmental and human health risk should be
(Reimann et al., 2018), the regional background level,
considered with protection goals.
considered equal to the concentration of PTEs in the A
horizon of Fluvisols of the Chumbur-Kosa protected
PTE pollution in soils
area (Minkina et al., 2017a, 2017b), as well as the
tentative allowable concentrations (TACs) of PTEs in
In the presented study, the obtained threshold values
soils of Russia (SanPiN 1.2.3685–21, 2021).
were used as a comparison standard to calculate
Obviously, the threshold values of PTEs obtained
geochemical indices of pollution (Table 1). Analysis
for the soils of the Lower Don and Taganrog Bay were
of individual indices, including the Igeo, the EF and the
higher than the world soil average and the content of
PI (Fig. 6), showed that the Igeo was the least sensitive.
elements in natural background soils. World soil
The elements, in descending order of the median Igeo
averages illustrate the central trend, that is, the most
value, were Cr (0.50), Cu (0.47), Mn (0.42), Zn (0.36),
‘typical’ values of the elements. The natural geo-
Ni (0.36), As (0.33), Pb (0.26) and Cd (0.18). All
chemical background of elements is an absolute value,
studied soils were classified as unpolluted in terms of
determined for a specific type of soil, and does not take
Ni and As. According to the calculated Igeo values,
into account the natural abundance of elements in
soils were unpolluted to moderately polluted with Cr,
various landscape conditions characteristic of the
Mn, Cu, Zn, Cd and Pb (5.8%, 2.3%, 4.7%, 7.0%,
territory. When using the global and regional geo-
7.0% and 2.3% of the samples, respectively). The
chemical background, an unjustifiably large number of
maximum Igeo value was observed for Zn (2.5),
the samples fell into the category of ‘anomalous’ in
corresponding to a moderate pollution level.
terms of the content of elements (Table 6). Compar-
The most detailed assessment was obtained by
ison between the Med ? 2MAD values derived from
calculating the EF. The median EF values for all
the dataset in this study and the GEMAS project
studied PTEs did not exceed 1.0 except for Cr (1.1),
showed that the threshold values of Mn, Ni, Cu, Zn and
data that revealed depletion in these PTEs. In general,
As in the soils of the Lower Don and the Taganrog Bay
the EF values in soils of the Lower Don and the
coast were comparable or slightly lower than these of
Taganrog Bay coast indicated minimal to moderate
European agricultural soils. The threshold values of Cr
pollution with Cr (46.5% and 11.6% of the samples,
were almost 1.5 times higher than the background
respectively), As (24.4% and 7.0%, respectively), Cd
level of European soils, a difference that is due to
(20.9% and 9.3%, respectively) and Pb (23.3% and

123
 Table 5 Pearson’s correlations between potentially toxic elements and properties of soils from the Lower Don and the Taganrog Bay coast
pH CaCO3 TOC Ca2? ? Mg2? SiO2 Fe2O3 Al2O3 Clay Cr Mn Ni Cu Zn As Cd Pb
Environ Geochem Health

pH 1.000
CaCO3 0.357* 1.000
TOC - 0.085 0.091 1.000
Ca2? ? Mg2? 0.032 0.051 0.826* 1.000
SiO2 - 0.122 - 0.075 - 0.214* - 0.175 1.000
Fe2O3 0.193 0.191 0.323* 0.370* - 0.472* 1.000
Al2O3 0.121 0.239* 0.323* 0.401* - 0.389* 0.854* 1.000
Clay 0.102 0.281* 0.807* 0.885* - 0.200 0.424* 0.444* 1.000
Cr 0.082 0.108 0.027 0.068 - 0.269* 0.343* 0.371* 0.040 1.000
Mn 0.009 - 0.005 0.240* 0.201 - 0.605* 0.276* 0.158 0.143 0.222* 1.000
Ni - 0.011 0.071 0.253* 0.269* - 0.277* 0.457* 0.389* 0.252* 0.560* 0.350* 1.000
Cu 0.035 0.095 0.283* 0.308* - 0.295* 0.290* 0.273* 0.272* 0.669* 0.259* 0.631* 1.000
Zn - 0.091 0.067 0.178 0.050 - 0.321* 0.204 0.149 0.028 0.571* 0.167 0.559* 0.554* 1.000
As 0.046 0.059 - 0.064 - 0.016 0.003 0.191 0.177 - 0.135 0.517* 0.251* 0.442* 0.234* 0.176 1.000
Cd 0.095 0.013 0.401* 0.281* - 0.149 0.263* 0.187 0.325* 0.058 - 0.101 0.274* 0.140 0.350* - 0.167 1.000
Pb 0.023 0.060 0.406* 0.345* - 0.346* 0.272* 0.307* 0.330* 0.325* 0.142 0.448* 0.313* 0.366* 0.226* 0.499* 1.000

*Significant at p \ 0.05

123

Fig. 4 Hierarchical dendrogram showing clustering of poten-
tially toxic elements according to Ward’s method, using the
1-Pearson r distance. The dashed line represents the critical level
of amalgamation
4.7%, respectively). The highest EF values were
characteristic of Mn (8.2), Ni (6.7), Cu (5.2) and Zn
(6.0), which correspond to significant pollution of
1.2%, 1.2%, 2.3% and 1.2% of the samples, respec-
tively. There was minimal pollution by Mn, Ni, Cu and
Zn in 41.9%, 23.3%, 31.4% and 24.4% of the samples,
while there was moderate pollution with these PTEs in
8.1%, 3.5%, 11.6% and 12.8% of the samples,
respectively.
Estimates of soil pollution based on the PI were
close to those based on the Igeo.; the distribution of
PTEs in decreasing order of the median PI values was
similar (Fig. 6). In general, the soils of the studied area
were not contaminated or were lightly contaminated
with Ni (95.3% and 4.7%, respectively), Cu (88.4%
and 11.6%, respectively), As (94.2% and 5.8%,
Fig. 5 Plots of factor loadings revealed from principal
component analysis, indicating the relationships between
potentially toxic element (PTE) contents and soil properties
123
Environ Geochem Health
respectively) and Pb (96.5% and 3.5%, respectively).
The maximum PI values for Cr, Mn and Cd were 2.4,
2.2 and 2.2, respectively, which indicated moderate
pollution. The PI value for Zn (3.8) revealed strong
pollution. The spatial distribution of the PI values is
presented in Fig. 2.
A comprehensive assessment of soil pollution
based on the calculated NPI values indicated four
classes of soil pollution (presented in decreasing order
of the number of soil samples): warning limit [ slight
pollution [ clean [ moderate pollution (Fig. 7).
Overall, the NPI values of the soils varied from 0.5
to 2.9, with a median of 0.9. Analysis of the PLI
provided a more optimistic assessment: only 2.3% of
the samples showed a decrease in soil quality. The
median PLI value in soils of the Lower Don and the
Taganrog Bay coast was 0.5. On average, the highest
NPI and PLI values were observed in floodplain soils
of small rivers (Table 7).
Conclusion
The results of our studies have shown that the Lower
Don basin as well as the adjacent areas of the Taganrog
Bay represent a complex system with a numerous
natural and anthropogenic factors that affect the
geochemical behaviour of PTEs. The spatial patterns
of PTE distribution showed elevated levels of Cr, Ni,
Cu and Zn for the soils close to urbanized areas,
industrial and transportation centres. There was a
(left), and reflecting the influence of factors on the PTE content
in the soils of sampling sites (right)
Environ Geochem Health

Table 6 Geochemical threshold values and permissible concentrations for eight potentially toxic elements in soils
Element Threshold values (mg kg-1) Number of samples above threshold n [
Med ? 2MAD WSA GEMAS CK TAC Med ? 2MAD WSA GEMAS CK TAC
SS LS

Cr 124.9 59.5 92 95 – – 9 75 45 40 –
Mn 1139.1 488 2141 720 1500 16 78 2 45 4
Ni 80.8 29 105 35 20 80 5 70 0 56 36
Cu 57.1 38.9 69 45 33 132 10 46 9 26 22
Zn 168.6 70 161 71 55 220 15 61 15 61 32
As 15.2 6.8 36 – 2 10 5 51 0 – 48
Cd 2.78 0.41 0.73 0.2 0.5 2.0 12 70 43 82 39
Pb 82.7 27 58 26 32 130 3 53 17 55 18
Med ? 2MAD median ? 2 median absolute deviations (This study), WSA world soil average (Kabata-Pendias, 2011), GEMAS
Geochemical Mapping of European Agricultural Soil (Reimann et al., 2018), CK Chumbur-Kosa protected area (Minkina et al.,
2017a, 2017b), TAC tentative allowable concentration (SanPiN 1.2.3685–21, 2021) for sandy soils (SS) and loamy soils (pH [ 5.5)
(LS). The maximum allowable concentration used for Mn (SanPiN 1.2.3685–21, 2021)

Fig. 6 Box-plots for values of the geoaccumulation index (Igeo), of the Lower Don and the Taganrog Bay coast and the
the enrichment factor (EF), and the single pollution index, percentage of distribution of soil pollution classes
calculated for Cr, Mn, Ni, Cu, Zn, As, Cd and Pb in surface soils

different pattern for Cd and Pb; the areas with soils
enriched with these PTEs were likely related to the
geochemical-barrier zones of the Lower Don fluvial
systems. The spatial distributions of Mn and As were
characterized as a transitional variant when the
elevated concentrations of these elements were also
characteristic for the zone of predominantly recre-
ational land use. The identification of PTE sources
using statistical methods revealed that the studied
elements can be subdivided into several groups—Pb–

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 Environ Geochem Health

Fig. 7 Percentage of soil pollution classes according to the Nemerow pollution index (NPI) and the pollution load index (PLI)

Table 7 Descriptive statistics for the values of the Nemerow pollution index (NPI) and the pollution load index (PLI) calculated for
Cr, Mn, Ni, Cu, Zn, As, Cd and Pb in soils from the Lower Don and the Taganrog Bay coast
Subsystem Index Mean Median Minimum Maximum SD CV (%) Average class

Lower Don floodplain (n = 10) NPI 0.8 0.9 0.6 1.2 0.2 20.9 Warning limit
PLI 0.5 0.5 0.2 0.8 0.1 28.0 Denote perfection
Don Delta (n = 28) NPI 1.0 0.8 0.5 2.9 0.5 53.5 Warning limit
PLI 0.5 0.4 0.2 0.9 0.2 33.4 Denote perfection
Coastline (n = 29) NPI 0.9 0.9 0.5 1.7 0.3 31.2 Warning limit
PLI 0.5 0.5 0.3 0.9 0.2 29.4 Denote perfection
Floodplains of small rivers (n = 19) NPI 1.3 1.2 0.7 2.2 0.5 35.2 Slight pollution
PLI 0.7 0.6 0.4 1.2 0.3 35.2 Denote perfection
Total area (n = 86) NPI 1.0 0.9 0.5 2.9 0.4 42.4 Slight pollution
PLI 0.6 0.5 0.2 1.2 0.2 36.5 Denote perfection
SD standard deviation, CV coefficient of variation

Cd, As–Mn, and Zn–Ni–Cu–Cr—based on their Declarations

sources and factors affecting their geochemical
Conflicts of interest The authors declare that there is no
behaviour. The assessment of the geochemical status conflict of interests.
of floodplain and coastal soils using pollution indices
revealed that the soils of floodplains of small rivers
presented the highest values of both the NPI and PLI. References

Arafa, W. M., Badawy, W. M., Fahmi, N. M., Ali, K., Gad, M.

Authors’ contributions TM: supervised the whole research,
EK: composed the main chapters of the manuscript, DN, MV,
IZ: performed the detailed field study and soil sampling, SM,
TB, SS: performed the analytical works, EK, DN, SM, AM, SS:
performed statistical evaluation, contributed with several
paragraphs in chapters Results and Discussion, prepared the
formal shape of the manuscript.
Funding The reported study was funded by Russian Science
Foundation, Project No. 20–14-00317.
Data availability The authors confirm that the summary of
data supporting the findings of this study are available within the
article. However, detailed data of this study are available from
corresponding author upon request.
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