International Journal of

Environmental Research
and Public Health

Article
Spatial Distribution, Contamination Assessment and Origin of
Soil Heavy Metals in the Danjiangkou Reservoir, China
Qiuyao Dong 1,2 , Chao Song 1,2, *, Dongxue Yang 3 , Yuqing Zhao 3 and Mingjiang Yan 1,2

1 Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences,

Shijiazhuang 050061, China
2 Key Laboratory of Quaternary Chronology and Hydro-Environmental Evolution, Chinese Geological Survey,
Shijiazhuang 050061, China
3 Institute of Earth Sciences, China University of Geosciences (Beijing), Beijing 100083, China
* Correspondence: [email protected]

Abstract: Soil heavy metal contamination is crucial due to menacing food safety and mortal health.
At present, with the fast advancement of urbanization and industrialization, heavy metals are
increasingly released into the soil by anthropogenic activities, and the soil ecosystem contamination
around the Danjiangkou Reservoir is directly associated with water quality security of the reservoir. In
this paper, using 639 soil samples from the Danjiangkou Reservoir, Henan Province, China, we studied
a variety of space distribution characteristics of heavy metals in soil. Geographic information system
analysis (GIS), geo-accumulation index (Igeo ), contamination factor (CF), principal component analysis
(PCA) model, and positive matrix factorization (PMF) model were used together to recognize and
quantify the distribution, contamination, and origin of heavy metals. We uncovered an exceptional
variety of heavy metal concentrations among the tested soils: the mean arsenic (As), cadmium (Cd),
cobalt (Co), chromium (Cr), manganese (Mn), nickel (Ni), zinc (Zn), lead (Pb) and mercury (Hg)
concentrations (14.54, 0.21, 18.69, 81.69, 898.42, 39.37, 79.50, 28.11, 0.04 mg/kg, respectively, in the
topsoil (0–20 cm depth)), all exceed their background values. The mean Igeo value and CF values of
these trace elements are both in descending order: Cd > Co > Mn > Ni > Pb > Zn > Cr > As > Hg. Cd
was the highest contributor to the assessment of heavy metal pollution, with an average Igeo value
Citation: Dong, Q.; Song, C.; Yang,
over three, indicating that the study area is modestly contaminated by Cd. The PCA analysis and
D.; Zhao, Y.; Yan, M. Spatial
PMF model revealed three potential sources, including natural sources (PC1) for Cr, Co, Mn and Ni;
Distribution, Contamination
agricultural sources (PC2) for Cd, Zn and Hg; and industrial emissions and transportation sources
Assessment and Origin of Soil Heavy
Metals in the Danjiangkou Reservoir,
(PC3) for Pb. This study displays a map of heavy metal contamination in the eastern area topsoil
China. Int. J. Environ. Res. Public of the Danjiangkou Reservoir, showing the most severe pollutant is Cd, which poses a threat to the
Health 2023, 20, 3443. https:// water quality security of Danjiangkou Reservoir and provides a significant source identification for
doi.org/10.3390/ijerph20043443 future contamination control.

Academic Editor: Paul B.

Keywords: topsoil; heavy metal; contamination assessment; spatial distribution; origin
Tchounwou

Received: 30 December 2022

Revised: 7 February 2023
Accepted: 11 February 2023 1. Introduction
Published: 15 February 2023
Soil is key to agricultural activity, human survival and ecosystem balance [1,2]. Cur-
rently, with the headway of urbanization, farming and industrialization, anthropogenic
impacts on the soil are intensifying, releasing more and more heavy metals into the soil,
Copyright: © 2023 by the authors.
and heavy metal contamination is having an increasing impact on soil ecosystems [3–5].
Licensee MDPI, Basel, Switzerland. Soil heavy metals are exceedingly poisonous, long-lasting, collect effectively in crops and
This article is an open access article are troublesome to biodegrade [6]. Once heavy metals contaminate the soil, they accumu-
distributed under the terms and late through trophic levels rather than easily decompose in the biological material cycle,
conditions of the Creative Commons causing irreversible and long-term harm to ecosystems and human health due to their
Attribution (CC BY) license (https:// ubiquity, bioavailability, toxicity and durability. In recent years, the contamination of soil
creativecommons.org/licenses/by/ by heavy metals has drawn incredible consideration from both analysts and environmental
4.0/). supervisors [7–9].

Int. J. Environ. Res. Public Health 2023, 20, 3443. https://doi.org/10.3390/ijerph20043443 https://www.mdpi.com/journal/ijerph
Int. J. Environ. Res. Public Health 2023, 20, 3443 2 of 15

Extensive research shows that heavy metals in soils are broadly influenced by natural
background levels and anthropogenic activities. Natural sources include mainly parent
material and weathering of rocks [10,11]. Anthropogenic activities include industrial emis-
sions [12], mining and smelting activities [13], fertilizers and agrochemical application [12],
sewage irrigation [14], sludge application [15] and vehicle exhaust [16]. Subsequently,
determining and quantifying the distribution, pollution and origins of heavy metals in
soils are fundamental for territorial contamination control and administration [17,18]. As
of late, the assessment records of soil heavy metals, involving single factor pollution index
(PI), pollution factor (CF), potential ecological risk index (RI), geo-accumulation index (Igeo )
and so on, are normally utilized to assess the extent of the contamination of soil heavy
metals [19–21]. Geostatistical strategies are utilized to analyze the spatial variability of
heavy metals [22]. For example, geostatistical methods such as kriging interpolation and
inverse distance weight interpolation (IDW) are usually utilized to analyze the spatial dis-
semination of heavy metals on diverse spatial scales [23,24]. Different methods containing
multivariate statistical analysis, PCA and PMF are utilized for subjective or quantitative
source recognizable proof. The PMF divides a sample into diverse variables and analyzes
them [25]. The PMF has been prescribed by the US EPA for evaluating source apportion-
ment and calculating the commitment of natural poisons. It is the foremost prevalent
and successful strategy prescribed by the US EPA, and it is broadly utilized [26,27]. The
combination of PCA and PMF could improve the accuracy of quantitative identification of
soil heavy metal sources.
Several studies have reported that soil ecosystems around numerous reservoirs
are highly affected by human activities, with complex pollution sources and multiple
routes [28]. Danjiangkou Reservoir, as the largest man-made freshwater lake in Asia, is
one of the important pure-water sources for China’s Middle Route of South–North water
diversion project. The water diversion project from South to North, moreover, could be a
major vital infrastructure project in China [29]. It is concerned with the issue of water qual-
ity safety and the threat of soil quality degradation and soil pollution within the reservoir
ecosystem. The contamination of soil heavy metal is herein deemed to be one of the greatest
threats. However, there are few studies on the characteristics and contamination evaluation
of soil trace elements around the reservoir region. Therefore, to investigate the impacts of
different components on the content of trace elements in topsoil along the Danjiangkou
Reservoir, to determine the ecosystem dangers of soil heavy metals contamination to the
reservoir, and to provide scientific ways for ecological reconstruction of the reservoir area,
the purpose of this paper is to: (1) analyze the spatial pattern and the trend of change of
heavy metals in soil in the eastern area of the Danjiangkou Reservoir, Henan Province,
China; (2) assess heavy metal contamination from As, Cd, Co, Cr, Mn, Ni, Zn, Pb, and Hg
occurring in soil; and (3) identify potential origins of trace elements and evaluate their
relative contribution of pollutants.

2. Materials and Methods

2.1. Description of the Study Area
The study area (longitude: 111◦ 240 ~112◦ 000 , latitude: 32◦ 340 ~33◦ 210 ) is mainly situated
in the southwest of Nanyang City, Henan Province, with Nanyang Basin in the west
and the Qinling branch of Funiu Mountain foothills in the north, and the Danjiangkou
Reservoir, which is a significant water resource for more than 20 large and medium-sized
cities along the route, including Beijing, Tianjin and Shijiazhuang of China, in the south.
This area mainly consists of Xixi County, Neixiang County and Xixia County, and totals
approximately 2490 km2 (Figure 1). The topographic trend of higher elevation within the
northwest and lower elevation within the southeast is because the study area is situated on
the eastern extension of the Qinling Mountains. Hills and mountains constitute the main
types of landforms in this area [30]. It is a subtropical monsoon climate that is relatively
arid and has an annual mean temperature of around 15.3 ◦ C. The agrotypes in the study
area are primarily yellow-brown soil, brown soil and fluvo-aquic soil with some paddy soil.
 main types of landforms in this area [30]. It is a subtropical monsoon climate that is re
tively arid and has an annual mean temperature of around 15.3 °C. The agrotypes in t
study area are primarily yellow-brown soil, brown soil and fluvo-aquic soil
Int. J. Environ. Res. Public Health 2023, 20, 3443
with som
3 of 15
paddy soil. The land use pattern is mainly arable land, grassland and other land, and c
tivated land accounts for more than 80% of the full area. At the same time, several typ
of metallic
The land and
usenon-metallic deposits
pattern is mainly have
arable land, been discovered
grassland in the
and other land, andstudy area,
cultivated landand the d
posits are characterized by large reserves, wide distribution, stable levels and easy m
accounts for more than 80% of the full area. At the same time, several types of metallic
and non-metallic deposits have been discovered in the study area, and the deposits are
ing. According to the National Mineral Resources Database 2022, there are about 123 m
characterized by large reserves, wide distribution, stable levels and easy mining. According
eral occurrences
to the Nationalin the study
Mineral area.
Resources Rapid2022,
Database andthere
intensive
are aboutagricultural production in t
123 mineral occurrences
studyinarea, sucharea.
the study as fertilizer, animal excrement
Rapid and intensive and pesticide
agricultural production in thisapplication, and
study area, such as industr
production
fertilizer,related to steel,and
animal excrement metal and application,
pesticide press, may andmake theproduction
industrial number related
of trace to eleme
within the soil worse. In summary, the special surroundings (background, topograph
steel, metal and press, may make the number of trace elements within the soil worse. In
summary, the special surroundings (background, topography, agrotype, land use pattern,
agrotype, land use pattern, ore resources and other factors) affect the content and the sp
ore resources and other factors) affect the content and the spatial distribution patterns of
tial distribution
heavy metals.patterns of heavy metals.

Figure 1. Distribution
Figure ofofsampling
1. Distribution sitesininthethe
sampling sites study
study area.area.

2.2. Collecting Soil Samples and Physico-Chemical Property Analysis

2.2. Collecting Soil Samples and Physico-Chemical Property Analysis
This study is based on the results of the “1:250,000 Land Quality Geochemical Survey
This
Projectstudy is based
in Nanyang Basinon(Nanzhao-Xichuan
the results of the “1:250,000
Area)”, which wasLand Quality
carried Geochemical
out in the Nanzhao- Surv
Project in Nanyang
Xichuan area fromBasin
2019 to(Nanzhao-Xichuan
2022. There were 639 Area)”, which
topsoil (0–20 cm) was carried
samples outThe
in total. in the Na
zhao-Xichuan area from 2019 to 2022.2 There were 639 topsoil (0–20 cm) samples in tot
geolocation of sampling sites was tracked via GPS. Every analytical sample is composed
of four samples from an adjacent 1 km area. Within the same period, the altitude, land
The geolocation of sampling sites was tracked via GPS. Every analytical sample is co
use, crop species, longitude and latitude of sampling points were noted, and rocks, insects
posedandof other
four debris
samples from
in the soilan adjacent
were removed 1 km 2 area. Within the same period, the altitu
and put into cloth bags. All the tests were
land air-dried
use, crop species,
at room longitude
temperature, andthrough
passed latitude
2 mmof nylon
sampling
sifters,points were
and after noted,
that put awayand roc
insects and other debris in the soil were removed and put into cloth bags. All the te
in hermetically fixed polyethylene packs for chemical examination [31].
were air-dried at room temperature, passed through 2 mm nylon sifters, and after that p
away in hermetically fixed polyethylene packs for chemical examination [31].
The sample analysis and testing work for this project was tested by Henan Provin
Rock and Mineral Testing Center and North China Nonferrous Metals Yanjiao Center L
Int. J. Environ. Res. Public Health 2023, 20, 3443 4 of 15

The sample analysis and testing work for this project was tested by Henan Province
Rock and Mineral Testing Center and North China Nonferrous Metals Yanjiao Center Labo-
ratory Company Limited. Laboratory and tests have been analyzed. The testing of samples
was processed with concentrated acid (HNO3 -HF-HClO4 ) [32] and the concentrations of
Cd, Co, Ni and Pd were decided utilizing Inductively Coupled Plasma Mass Spectrometry
(ICP-MS, NexION 300Q, Perkin Elmer, MA, USA). The samples were digested with a con-
centrated acid (HNO3 -HC-HF-HClO4) and the contents of Cr, Mn and Zn were determined
utilizing an Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES, Optima
7300DV, Perkin Elmer, MA, USA) [33]. As and Hg were digested with a concentrated
acid (HNO3 and HCl) and their contents were determined using Atomic Fluorescence
Spectrometer (AFS, SK-2003A, Beijing, China) [34]. For quality control (QC) and quality
assurance (QA), clear control, copy tests and standard reference soils (GBW07419; Center
for Certified Reference Materials, Beijing, China) were utilized [7]. The detection limits
of each analytical method are shown in Table 1. The amounts measured for the standard
reference soils were inside stability ranges of the certified values.

Table 1. Detection limit requirement of each index analysis method (measurement unit: mg/kg).

As Cd Co Cr Hg Mn Ni Pb Zn
Detection Limits (DL) 0.3 0.03 1 3 0.0005 10 1 2 2

2.3. Assessment of Heavy Metal Pollution

2.3.1. Contamination Factor (CF)
The values of the CF index were obtained by isolating the concentration of each heavy
metal by the foundation concentrations [35]. The C f is calculated as follows:

Cm sample
Cf = , (1)
Cm backgroud

where ‘Cm sample ’ refers to the concentration value of an index and ‘Cm backgroud ’ is the metal
content from a natural reference, such as those reported in Hans Wedepohl [36]. When
C f < 1, it is described as low pollution level; 1 ≤ C f < 3 may be a moderate pollution level;
3 ≤ C f < 6 is a considerable pollution level, and C f ≥ 6 could be an exceptionally high
pollution level.

2.3.2. Geo-Accumulation Index (Igeo )

The Igeo was used to decide the extent of trace element contamination in the soil tests.
This assurance equation was presented by Müller [37] as a normal quantitative estimation
of the concentration of contamination in soils or aquatic sediments. The condition utilized
for the calculation of Igeo was:
Cn
Igeo = log2 , (2)
K ∗ Bn
where Cn is the content of metals in the soil; Bn is the background value and K = 1.5 is the
background matrix correction factor. Based on the Igeo values, the contamination could be
classified into seven categories: practically uncontaminated, uncontaminated to moderately
contaminated, moderately contaminated, moderately to strongly contaminated, strongly
contaminated, strongly to extremely contaminated, and extremely contaminated when the
Igeo is <0, 0–1, 1–2, 2–3, 3–4, 4–5 and >5. A translation of the values obtained from this
record is shown in Table 2.
Int. J. Environ. Res. Public Health 2023, 20, 3443 5 of 15

Table 2. Geo-accumulation index.

No. Class Igeo Value Contamination Level

0 Igeo ≤ 0 Practically uncontaminated
1 0 < Igeo < 1 Uncontaminated to moderately contaminated
2 1 < Igeo < 2 Moderately contaminated
3 2 < Igeo < 3 Moderately to strongly contaminated
4 3 < Igeo < 4 Strongly contaminated
5 4 < Igeo < 5 Strongly to extremely contaminated
6 5 > Igeo Extremely contaminated

2.3.3. Positive Matrix Factorization (PMF) Model

The PMF, a method suggested by the U.S. Environmental Protection Agency (EPA),
could demonstrate, based on PCA, the number of origins and the contribution of each
origin based on the origins’ profile [38]. It offers a remarkable advantage for data prepro-
cessing, determining the values of missing data in datasets, unpredictability estimation,
and data plausibility analysis [39,40]. In this study, EPA PMF 5.0 was utilized to recog-
nize and measure the soil samples from the diverse origins. The PMF breaks down the
sample information matrix xij into the origins profile matrix hmj and a source contribution
matrix gim :
t
xij = ∑m=1 gim hmj + eij ,


(3)
where i is the number of samples, j is the heavy metal types, t is the number of sources, and
eij is the error for each sample.
In PMF analysis, the content and uncertainty of the sample need to be determined.
The uncertainty (uij ) is calculated as follows:

5
xij ≤ MDL, uij = × MDL, (4)
6
q
2
xij > MDL, uij = error f raction × xij + MDL2 , (5)
where MDL is the species-particular methodology detection limit, and the errorfraction is
a percentage of the measurement uncertainty.
The point of the PMF is obtained through minimizing the object function Q:
#2
xij − ∑tm=1 gij hij
"
p q
Q= ∑ i=1 ∑ j=1 uij
, (6)

where xij is the heavy metal content, uij is the uncertainty of samples, p is the number of
samples, q is the heavy metal type, and t is the number of sources.

2.4. Data Analysis

Geochemical maps and multivariate statistical analysis are effective tools for identify-
ing pollution sources. The chart of the spatial interpolation of the nine topsoil heavy metals
and properties were drawn utilizing ArcGIS 10.6 (ESRI, Redlands, CA, USA) computer
program utilizing the inverse distance weighting (IDW) method. A cartogram of the PCA
of the soil’s heavy metal contents and the chemical and physical properties of soil were
obtained using SPSS 20.1 (SPSS Inc., Chicago, IL, USA). At that point, information prepro-
cessing, containing numerical and graphic information and box or line graphs of the heavy
metals, was made using Microsoft Excel 2019 and Origin 10.0. Based on the understanding
of the sources of heavy metals in soil, the contribution of different contamination sources
of soil heavy metals was quantitatively analyzed using EPA PMF 5.0.
Int. J. Environ. Res. Public Health 2023, 20, 3443 6 of 15

3. Results and Discussion

3.1. The Descriptive Statistical Parameters of Heavy Metal Concentrations in Topsoil
Analysis of heavy metal concentration in the soil can reveal the degree of pollution.
The descriptive characteristics of heavy metals in the topsoil are listed in Table 3. The
descriptive data for nine soil heavy metals from 639 soil samples of the study area are
displayed. The mean values of Cd (0.21 mg/kg), Co (18.69 mg/kg), Mn (898.41 mg/kg), Ni
(39.37 mg/kg), Pd (28.11 mg/kg), Hg (0.04 mg/kg), and Zn (79.50 mg/kg) were beyond the
median values. Only the average of As (14.45 mg/kg) and Cr (81.69 mg/kg) were below
the median values. The mean of all nine heavy metals is larger than the background values
(BV) of Henan Province of heavy metals in soil, which were obtained from [41], and the
mean of Cd content was 3.04 times higher than the BV of Henan Province, reflecting a
greater influence by anthropogenic activities. The standard deviations of Cr, Zn, and Mn
were larger than that of other heavy metals, proposing a better degree of scattering [42]. A
higher coefficient of variety (CV) shows more prominent irregularity and wide potential
for anthropogenic impacts [43]. Concurring to Wilding [44], tall variety, moderate variety,
and low variety are characterized by values of CV > 36%, 16% < CV < 36%, and CV < 16%,
in sequence. Hg (113%) had the greatest variation. Cd (48%) was high variation. Both
exhibit high variability, higher coefficients of variation, greater potential for discontinuity
and widespread anthropogenic influence.

Table 3. The descriptive statistical parameters of heavy metals concentrations in soils (mg/kg).

As Cd Co Cr Mn Ni Zn Pb Hg
N(a) 639 639 639 639 639 639 639 639 639
Mean 14.45 0.21 18.69 81.69 898.41 39.37 79.50 28.11 0.04
Median 14.6 0.186 17.9 81.9 873 39.3 77.1 27.8 0.033
Maximum 38.9 1.153 52.9 202 1783 83.2 237 107 0.662
Minimum 5.2 0.099 5.9 20.5 367 9.6 40.1 14.2 0.015
Standard deviation 4.5 0.099 5.6 17.3 205 9.1 17.2 6 0.047
CV (%) 31 48 30 21 23 23 22 21 113
Background values of Henan Province 11.4 0.074 10 63.8 579 26.7 60.1 19.6 0.034

In the absence of obvious human activities, the value of trace element content in
regional soil usually follows normal distribution [45]. As shown in Figure 2, the soil heavy
metals As, Co, Cr, Mn, Ni, and Zn are normally distributed. Heavy metals are not obviously
affected by anthropogenic activities. However, there are many extremely high values of
Cd, Pb, and Hg, a right deviation trend. Therefore, it is suggested that the abnormally high
values of these three heavy metals are influenced by human activities, representing man-
made imports of heavy metals to the soils. Therefore, it is believed that these three elements
are affected by anthropogenic activities to some extent, and the abnormally high values
may represent their accumulation and enrichment in the soil due to human emissions.

3.2. Space Distribution Pattern of Heavy Metals

The spatial distribution pattern of soil trace elements is shown in Figure 3. In general,
the spatial distribution pattern was clearly diverse from the north to the south of the study
area. The concentrations of heavy metals were more prominent within the south than in
the north. Laoguan River, a river of Han River system in Yangtze River Basin of China,
drains into Danjiangkou Reservoir and passes through the northwest of the whole study
area. Thus, the geomorphological features of the northwest portion of the study area are
predominantly flooded river valley plains and erosion and denuded low hills. Soil with
high porosity, large particles, poor organic matter concentrations and poor water and
fertilizer conservation capacity, and the topsoil of the northeastern region of the study
area have a low concentration of heavy metals. The high heavy metal hotspot areas are
mainly distributed in the center of the south and southwest of the study area, whereas
the low heavy metal hotspot areas are distributed in the northeast of the study area, with
Int. J. Environ. Res. Public Health 2023, 20, 3443 7 of 15

obvious scattered distribution. It appears that Mn, Cr, Co and Ni had a similar spatial
distribution pattern. A few recent studies have detailed that Mn, Cr, Co and Ni in topsoil
primarily started from the soil parent fabric [46]. Pb and As have similar spatial distribution
characteristics and both are probably influenced by the same pollution sources. The high
values are mainly distributed in the south-central region of the study area. Past studies
found the most noteworthy concentrations of Pb and As within the soils encompassing
industrial facilities and streets [47,48]. In comparison, the scattered dissemination within
the high Cd region was more concentrated. The spatial distribution map of Cd, its high
value area is roughly the same distribution as the agricultural production area, and its
pollution source may come from agricultural pollution. Within the farmland soils, sources
of contamination for the most part come from industrial production or other human
activities. Subsequently, the areas with the greatest concentrations of soil heavy metals are
Int. J. Environ. Res. Public Health 2023, 20, x FOR PEER REVIEW 7 of 17
those where anthropogenic activities are most intensive, especially industrial production
and transportation.

Figure 2. Histograms
Figure Histogramsof ofheavy
heavymetal
metalconcentrations in topsoil
concentrations for for
in topsoil (a) As, (b) Cr,
(a) As, (b)(c)
Cr,Co,
(c)(d)
Co,Ni,
(d)(e)Ni,
Mn,(e)
Mn, (f)(g)
(f) Zn, Zn,Cd,
(g)(h)
Cd,Pb
(h)and
Pb(i)
and (i) Hg.
Hg.

3.3. Space
3.2. Assessment of Heavy
Distribution Metal of
Pattern Pollution
Heavy Metals
For further research, to evaluate the degree of trace element contamination in the
The spatial distribution pattern of soil trace elements is shown in Figure 3. In general,
topsoil in the study area, indicators such as CF and Igeo were calculated (Figure 4). CF
the spatial distribution pattern was clearly diverse from the north to the south of the study
and Igeo are relatively well-established statistical methods and are commonly used for
area. The concentrations of heavy metals were more prominent within the south than in
evaluating heavy metals pollution in soil. The mean CF values of soil heavy metals in order
the north. Laoguan River, a river of Han River system in Yangtze River Basin of China,
were Cd > Co > Mn > Ni > Pb > Zn > Cr > As > Hg. The mean CF values of the heavy
drains into Danjiangkou Reservoir and passes through the northwest of the whole study
metals in the study area ranged from 1 to 3, which is moderately heavy metal contamination
area.
(Figure 4a).the
Thus, Thisgeomorphological
demonstrates that features of the northwest
the pollution portion
of soil heavy of the
metals study
within thearea are
study
predominantly flooded river valley plains and erosion and denuded low
zone comes from anthropogenic activities. The values of Igeo are shown in Figure 4 and hills. Soil with
high porosity,
demonstrate large
that theparticles, poor
mean values oforganic
the Igeo matter concentrations
of six heavy metals, As,and
Cr, poor water
Hg, Ni, andZn,
Pb and fer-
tilizer
were allconservation capacity,
less than 0, while the Iand the topsoil of the northeastern region of the study area
geo of Cd, Co and Mn were greater than 0. It can be seen that
have a low concentration of heavy
the topsoil in the study area was, overall,metals.free
Theofhigh
As,heavy
Cr, Hg,metal
and hotspot areas are mainly
Zn contamination; was
distributed in the center of the south and southwest of the study area,
slightly contaminated with Cd, Co, Mn, Ni, and Pb; and had localized medium-intensity whereas the low
heavy metal hotspot areas are distributed in the northeast of the study area, with obvious
scattered distribution. It appears that Mn, Cr, Co and Ni had a similar spatial distribution
pattern. A few recent studies have detailed that Mn, Cr, Co and Ni in topsoil primarily
started from the soil parent fabric [46]. Pb and As have similar spatial distribution charac-
teristics and both are probably influenced by the same pollution sources. The high values
Int. J. Environ. Res. Public Health 2023, 20, 3443 8 of 15

contamination of Cd and Hg. The average Igeo values of heavy metals in topsoil were Cd
(0.81) > Co (0.26) > Mn (0.01) > Ni (−0.06) > Pb (−0.09) > Zn (−0.22) > Cr (−0.26) > As
(−0.31) > Hg (−0.54) in that order. Like the values of CF, Cd was the highest contributor
Int. J. Environ. Res. Public Health 2023, 20, x FOR PEER REVIEW
to
8 of 17
the appraisal of heavy metal pollution, with the mean value of Igeo above 3. Therefore, Cd
was the foremost predominant contaminant in the topsoil of the study area.

Figure3.3. Spatial
Figure Spatialdistributions
distributionsinintopsoil
topsoilfor
for(a)(a)Cr,Cr,
(b)(b)
Co,Co,
(c)(c)
Ni,Ni,
(d)(d)
Mn,Mn,
(e) (e)
Zn,Zn, (f) Cd,
(f) Cd, (g) Pb,
(g) Pb, (h)
(h) As
As and (i)
and (i) Hg. Hg.

3.3. Assessment of Heavy Metal Pollution

For further research, to evaluate the degree of trace element contamination in the
topsoil in the study area, indicators such as CF and Igeo were calculated (Figure 4). CF and
Igeo are relatively well-established statistical methods and are commonly used for evaluat-
ing heavy metals pollution in soil. The mean CF values of soil heavy metals in order were
Cd > Co > Mn > Ni > Pb > Zn > Cr > As > Hg. The mean CF values of the heavy metals in
 slightly contaminated with Cd, Co, Mn, Ni, and Pb; and had localized medium-intensity
contamination of Cd and Hg. The average Igeo values of heavy metals in topsoil were Cd
(0.81) > Co (0.26) > Mn (0.01) > Ni (−0.06) > Pb (−0.09) > Zn (−0.22) > Cr (−0.26) > As (−0.31)
> Hg (−0.54) in that order. Like the values of CF, Cd was the highest contributor to the
appraisal of heavy metal pollution, with the mean value of Igeo above 3. Therefore, Cd was
Int. J. Environ. Res. Public Health 2023,the foremost predominant contaminant in the topsoil of the study area.
20, 3443 9 of 15

Figure
Figure 4.4.Boxplot
Boxplotofof
(a)(a)
contamination factor
contamination (CF)
factor andand
(CF) (b) geo-accumulation indexindex
(b) geo-accumulation (Igeo) of each
(Igeo ) ofmetal
each
in the study
metal in the area.
study area.

3.4. Source Identification of Heavy Metals

3.4. Source Identification of Heavy Metals
3.4.1. Source Identification Using PCA
3.4.1. Source Identification Using PCA
PCA is a well-established and demonstrated statistical strategy routinely utilized to
PCA is potential
distinguish a well-established
sources ofand heavydemonstrated statistical
metals in topsoil strategy
[49,50]. In thisroutinely utilized
study, heavy to
metal
distinguish potential sources of heavy metals in topsoil [49,50].
concentration information was analyzed by PCA, yielding three components based on In this study, heavy metal
concentration
varimax that ininformation was analyzed
total contributed 69.6% of the by change
PCA, yielding
in topsoil three components
contamination based
(Table on
4 and
varimax
Figure 5).that in total contributed 69.6% of the change in topsoil contamination (Table 4
and Figure 5).
PC1 contributed 40.9% of the fluctuation and included a strong positive stacking of
PC1 contributed
Mn, Co, Ni and Cr (Figure 40.9% 5),of the fluctuation
illustrating thatand included
those heavy ametalsstrongappear
positive to stacking
come from of
Mn, Co, Ni and Cr (Figure 5), illustrating that those heavy metals
a comparable origin. The soil profile investigation for this seems clear. The CV values of appear to come from a
comparable
Cr, Co, Ni, Mn origin.
andThe soil profile
Zn contents investigation
were 21%, 30%,for this23%
23%, seemsandclear.
22%,The CV valuessetting
respectively, of Cr,
Co, Ni, Mn
it within theand
lowZn contents
spatial were 21%,
variability. Most30%, 23%, 23% and
Cr aggregation 22%,was
in soils respectively,
close to the setting
normal it
within
backgroundthe low spatial
levels thatvariability.
were controlledMost Cr by aggregation in soils[48].
the natural factors was Thus,
close to PC1thecould
normal be
background
attributed to levels
naturalthat were The
sources. controlled
study areaby the naturalinfactors
is located [48].section
the eastern Thus, PC1 of thecould
Qinlingbe
attributed to natural sources. The study area is located in the eastern
folded orogenic belt, with complex geology and wide stratigraphic distribution, mainly for section of the Qinling
folded orogenic
the Paleozoic belt, with
Qinling rock complex
group. The geology and wide
rock types includestratigraphic distribution,
gabbro, monazite, mainly
amphibolite,
for the Paleozoic
orthogabbro, Qinling
granite rock group.
porphyry The rock
and alkalic types
feldspar includeThe
granite. gabbro, monazite,
lithological amphibo-
effects are also
lite, orthogabbro,
attributed to naturalgranite porphyry
sources. and alkalic
The lithological feldspar
effects granite.
are also The lithological
attributed effects
to natural sources.
are
Sincealso attributed
the average to naturalofsources.
contents Co, Cr Theandlithological effects are
Ni in the surface soilalso attributed
are close to thetoregional
natural
sources.
background Since the average
values and theycontents of Co,
have similar Cr and
spatial Ni in the characteristics
distribution surface soil are close
with thetoDEM
the
regional background values and they have similar spatial distribution characteristics with
map (Figure 6), the geochemical characteristics of Co, Cr, Ni and Mn in the surface soil
the
mainlyDEM map (Figure
depend on the 6),
soilthe geochemical
parent material characteristics
and natural soil offormation
Co, Cr, Niprocess.
and Mn in the sur-
face soil
PC2, mainly
whichdepend
accounts on for
the soil
16.1% parent material
of this, add upandtonatural soil formation
fluctuation and contain process.
a solid
PC2,stacking
positive which accounts
of Cd (77%),for 16.1%
and aofdirect
this, add up tostacking
positive fluctuation and
of Pb, Zncontain
and Hg a solid
(Figurepos-5).
itive stacking
The high valueof Cd
area(77%), and a direct
of cadmium positivethe
is roughly stacking
same of Pb, Zn and as
distribution Hgthe(Figure 5). The
agricultural
production area, and its pollution source may come from agricultural production. Previous
studies found Cd is usually susceptible to soil entry by anthropogenic activities, mainly
agricultural fertilizers, sewage discharge and industrial production [51]. The results of
lasting (1989–2001) trials conducted at the Agricultural Experiment Station displayed that
the contents of Pb, Zn and Cd within the soil indicated an increasing trend under different
fertilization treatments [52]. The extensive use of phosphate and compound fertilizers
has led to a persistent increment within the concentration of Cd in the soil [53–55]. Cd is
additionally regularly utilized within the industrial production of various products, such
as pigments, plastics and electroplating [56]. Thus, PC2 could be mainly attributed to the
agricultural sources.
PC3 explained 12.61% of this total variance and includes a strong positive loading of
Pb (69%), and a moderate positive loading of As (Figure 5). Earlier research has confirmed
that the enrichment of Pb within the soil primarily related to vehicle exhaust [57]. This can
 Int. J. Environ. Res. Public Health 2023, 20, 3443 10 of 15

be attributed to the fact that gasoline contains lead, which enters the air through vehicle
exhaust emissions and eventually leads to particulate matter containing lead entering the
soil through atmospheric deposition [58]. In spite of the fact that China prohibited the
generation and selling of leaded gasoline in 2000, the substance of lead in soil is still a hot
point in our society nowadays since lead incorporates a half-life of hundreds of years–a
long time [59,60]. Pb is usually the signature trace element of motor vehicle pollution, and
vehicle engines and tire wear and tear can emit large amounts of Pb into the environmental
medium, accumulating into the soil through atmospheric deposition [61]. Metal smelters
have a significant impact on the content of various trace elements in the atmosphere and
soil and cause the increasing input of some heavy metals in the soil [62]. Thus, PC3 might
be related to both industrial emissions and transportation sources.

Table 4. Results of PCA of nine heavy metals concentrations in topsoil.

F1 F2 F3
As 0.49 0.39 0.47
Cd 0.28 0.77 −0.16
Co 0.86 −0.31 −0.02
Cr 0.83 −0.1 −0.02
Mn 0.79 −0.27 0.21
Ni 0.94 −0.02 0.05
Pb −0.15 0.46 0.69
Int. J. Environ. Res. Public Health 2023, 20, x FORZn
PEER REVIEW 0.63 0.36 −0.43 11 of 1
Hg 0.04 0.42 −0.43

Figure5.5.Contributions
Figure Contributions of sources
of sources to nine
to nine heavyheavy
metalsmetals based
based on PCAon PCA model.
model.
Int. J. Environ. Res. Public Health 2023, 20, 3443 11 of 15

Figure 5. Contributions of sources to nine heavy metals based on PCA model.

Figure 6. Digital elevation model (DEM) map of the study area.

3.4.2. Quantitative Source Apportionment Using the PMF Model

In this query, we utilized PMF to measure the sources of poison in soil and contribu-
tions of trace elements and to superior partitioned trace elements from natural sources
and the sources of human activities (Figure 7a). The PMF was utilized to quantitatively
analyze the potential sources of heavy metals in the topsoil. After a few times of computer
program debugging, to attain the objective of minimizing Q value, the optimal analytical
outcomes about were obtained, and the factor number three was at long last decided as
the optimal [63]. The values of the scaled residuals were from −3 to 3, and the fitting
coefficients R2 between the measured and forecasted values of the trace elements were
more noteworthy than 0.8. The strongest dependencies (R2 > 0.8) between the predicted
and measured values were found for Pb and As, and the strong correlations (R2 > 7) were
found for Co, Cr, Mn and Zn, suggesting that PMF can be well applied to prediction in this
study. Thus, the PMF model could be effectively utilized for the assignment of soil heavy
metal sources in this area [56].
Compared with other trace elements, the first source factor for Co (46%), Zn (41.2%),
Cr (40.8%), Mn (39%) and Ni (40.3%) occupied a greater proportion, as shown in Figure 7a.
The natural sources are the primary reason that restricts the distribution of these soil trace
elements. Therefore, Factor 1 is considered as the natural source. The second source figure
is related with moderately rich contents of Cd (Figure 7b), and source contribution of
Cd reached 48.9%. Previous studies have shown that the study area has been affected
by broadly active agrarian activities, counting the application of chemical fertilizers and
 Int. J. Environ. Res. Public Health 2023, 20, 3443 12 of 15

sewage water system over the past few years [64]. These results demonstrated that the
human activities sources are the major sources of Cd contamination, which is close to
the results from PCA. Therefore, Cd originated mainly from the source of agricultural
production [65–67]. For the third contamination source (Figure 7c), the weight value
of Pb (62.9%) was more than that of other trace elements. High concentrations of lead
in topsoil close most industrial foundations and along streets are comparative to past
studies, proposing that lead in topsoil may too be related with industrial production and
transportation sources [47,68,69].
es. Public Health 2023, 20, x FOR PEER REVIEW The PMF analysis results are consistent with the PCA model results.
13 The three potential
of 17
sources in topsoil are the natural sources, the agricultural sources, and the mixture of
industrial production and transportation sources.

Figure 7. Source
Figure 7. Source contribution of ninecontribution
heavy metalsof nine heavy
for (a) F1, metals
(b) F2 for
and(a)(c)F1,F3(b) F2 and
based on(c)
PMFF3 based on PMF model.
model. 4. Conclusions
Based on the analysis of 639 topsoil samples and nine heavy metals in this study area,
4. Conclusions
the spatial distribution maps, multivariate statistics and receptor model were utilized to
Based on the analysis
elucidateofthe 639 topsoiland
content samples
spatialand nine heavy
distribution metals
features of in this metals
heavy study area,
to investigate the
the spatial distribution
sourcesmaps, multivariate
of heavy metals in statistics and receptor
soil and calculate model
the relative were utilized
contribution to
of various potential
elucidate the content and spatial
sources. distribution
In conclusion, the meanfeatures of As,
values for heavy
Cd, metals to investigate
Co, Cr, Mn, Ni, Zn, Pb and theHg surpassed
the corresponding
sources of heavy metals Henan background
in soil and calculate the relativevalues in the study
contribution area around
of various the Danjiangkou
potential
Reservoir
sources. In conclusion, in Henan
the mean Province,
values for As,China, which
Cd, Co, Cr,showed
Mn, Ni,thatZn,the
Pbsoil
andmight be influenced by
Hg sur-
passed the corresponding Henan background values in the study area around the Dan-which mainly
human activities. The concentrations of Co, Cr and Ni in topsoil were low,
came from natural weathering. The high value regions of Cd, Zn and As were primarily
jiangkou Reservoir in Henan Province, China, which showed that the soil might be influ-
influenced by agricultural production, and the contribution of agricultural productions
enced by human activities. The concentrations of Co, Cr and Ni in topsoil were low, which
to Cd, Zn and As was 48.9%, 33.6% and 30.8%, respectively. Pb and Hg are primarily
mainly came frominfluenced
natural weathering. The high
by transportation value regions
and industrial of Cd,
emissions, andZntheir
andcontribution
As were rates to Pb
primarily influencedand Hg are 62.9% and 21.2%, respectively. The average value of the Igeopro-
by agricultural production, and the contribution of agricultural and CF that the
ductions to Cd, Zntopsoil
and As is was 48.9%, 33.6%
pollution-free andbut
overall, 30.8%, respectively.ofPb
the accumulation Cdandand Hg
Hg are pri-areas is high,
in local
marily influenced byandtransportation
there is a locally and industrial
moderate levelemissions, and their
of contamination contribution
of Cd, Co and Hg.ratesCd displayed the
greatest
to Pb and Hg are 62.9% and potential
21.2%, for environmental
respectively. Thepollution, as it possessed
average value the
of the Igeo highest
and CF thatthe values of CF
and I
the topsoil is pollution-free
geo . Moreover,
overall, but the accumulation of Cd and Hg in local areastheir
these discoveries can advise administrative offices in is endeavors
to execute focused control methodologies for anticipating
high, and there is a locally moderate level of contamination of Cd, Co and Hg. Cd dis- the advance spread of heavy
played the greatest potential for environmental pollution, as it possessed the highest the
values of CF and Igeo. Moreover, these discoveries can advise administrative offices in their
endeavors to execute focused control methodologies for anticipating the advance spread
of heavy metals. Although the quantitative distribution of soil heavy metals can be per-
Int. J. Environ. Res. Public Health 2023, 20, 3443 13 of 15

metals. Although the quantitative distribution of soil heavy metals can be performed using
the PMF model and PCA model, we suggest combining isotope tracing techniques with
the PMF model in future studies to conduct regular temporal and spatial sampling of
potential contamination sources to enhance the accuracy of the distribution of soil heavy
metal sources.

Author Contributions: Conceptualization, Q.D. and C.S.; methodology, Q.D. and M.Y.; software,
Q.D.; validation, C.S.; formal analysis, Q.D.; investigation, C.S., D.Y. and Y.Z.; resources, C.S.; data
curation, C.S.; writing—original draft preparation, Q.D. and Y.Z.; writing—review and editing, Q.D.
and Y.Z.; supervision, C.S.; project administration, C.S.; funding acquisition, C.S. All authors have
read and agreed to the published version of the manuscript.
Funding: This work was supported by the National Natural Science Foundation of China (number
41877398) and China Geological Survey Project (DD20221773).
Data Availability Statement: No new data were created or analyzed in this study. Data sharing is
not applicable to this article.
Acknowledgments: The authors thank the editor and anonymous reviewers for the constructive
comments on this article.
Conflicts of Interest: The authors declare no conflict of interest.

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