International Journal of

Environmental Research
and Public Health

Article
Accumulation Characteristics and Pollution Evaluation of Soil
Heavy Metals in Different Land Use Types: Study on the Whole
Region of Tianjin
Tiantian Ma 1,† , Youwen Zhang 1,† , Qingbai Hu 2 , Minghai Han 3 , Xiaohua Li 4 , Youjun Zhang 5,6 , Zhiguang Li 7
and Rongguang Shi 1, *

1 Agro-Environmental Protection Institute, Ministry of Agriculture and Rural Affairs, Tianjin 300170, China
2 School of Environmental Science & Safety Engineering, Tianjin University of Technology,
Tianjin 300384, China
3 Qamdo Institute of Agricultural Science, Qamdo 854000, China
4 Rual Energy and Environment Agency, Ministry of Agriculture and Rural Affairs, Beijing 100125, China
5 Tianjin North China Geological Exploration Bureau, 67, Guang-rui-xi-lu Rd., Tianjin 300170, China
6 School of Environmental Science and Engineering, Tianjin University, 92, Weijin Rd., Nankai District,
Tianjin 300350, China
7 Agricultural Technology Extension Service Centre of Jingyuan County, Baiyin 730900, China
* Correspondence: winsomesky@163.com
† These authors contributed equally to this work and share first authorship.

Abstract: Heavy metal pollution in soil has received much attention in recent decades. Many
studies have analyzed the interaction between specific soil quality and soil heavy metal pollution.
However, there is little information about the pollution status, spatial distribution and pollution
sources of heavy metals in the province of Tianjin. In this paper, the distribution characteristics
Citation: Ma, T.; Zhang, Y.; Hu, Q.;
and pollution sources of heavy metals in soil were studied by means of the surface soil of Tianjin,
Han, M.; Li, X.; Zhang, Y.; Li, Z.; Shi,
as the study area and object, conducted in combination with land use types, using multiple data
R. Accumulation Characteristics and
Pollution Evaluation of Soil Heavy analysis and multivariate statistics, while the pollution levels were evaluated by various indices.
Metals in Different Land Use Types: The results showed the mean contents of the seven heavy metals of the studied elements followed
Study on the Whole Region of Tianjin. an increasing order of Cd (0.15 mg/kg) < As (11.9 mg/kg) < Cu (24.3 mg/kg) = Pb (24.3 mg/kg) <
Int. J. Environ. Res. Public Health 2022, Ni (27.9 mg/kg) < Cr (70.7 mg/kg) < Zn (79.1 mg/kg). The median values of Cr and Ni were
19, 10013. https://doi.org/10.3390/ lower than the background values and did not exceed the screening values at the points, and the
ijerph191610013 median values of Cu, Zn and Pb were close to the background values, while the median contents
Academic Editors: Lei Zhong, Xiaoqi of As and Cd were higher than the background values. The highest accumulation of heavy metals
Zhou and Qianqian Yu was found in grassland, and the coefficient of variation of heavy metal contents were higher in
garden land, industrial and mining storage land, residential land and transportation land, indicating
Received: 29 May 2022
that the soil heavy metal contents under these land use types were more significantly disturbed by
Accepted: 10 August 2022
human factors. The evaluation results of the ground accumulation index method showed that the
Published: 14 August 2022
soil in Tianjin was free of pollution, except for Cd, which was at the non-polluted to moderately
Publisher’s Note: MDPI stays neutral polluted level. The Nemero integrated pollution index evaluation method and the pollution load
with regard to jurisdictional claims in index evaluation method together showed that the integrated pollution levels of heavy metals in
published maps and institutional affil-
Tianjin soils were both at no pollution level/safety level. Apart from Cd and As, which were not
iations.
correlated, the other heavy metals were correlated with each other two by two. Cd, Pb and Zn were
the main pollution contributors from traffic, industry and other anthropogenic factors, while Cr and
Ni were the main pollution contributors from soil parent material, and Cu was the main pollution
Copyright: © 2022 by the authors. contributor from mining and metal smelting. In addition, As was presumed to be the main source of
Licensee MDPI, Basel, Switzerland. pollution contribution from agriculture and surface runoff.
This article is an open access article
distributed under the terms and Keywords: soil; heavy metals; spatial distribution; source analysis; pollution assessment
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).

Int. J. Environ. Res. Public Health 2022, 19, 10013. https://doi.org/10.3390/ijerph191610013 https://www.mdpi.com/journal/ijerph
Int. J. Environ. Res. Public Health 2022, 19, 10013 2 of 15

1. Introduction
With the rapid development of industry and urban construction and the improvement
of peoples’ living standards, a large number of pollutants have been poured into the soil.
A large quantity of heavy metals accumulates in the soil, causing serious impacts on the
soil environment, and endangering the ecological environment and human health [1].
Previous studies have revealed that human exposure to metals, such As, Pb and Hg,
lead to their accumulation in fatty tissues and affect the central nervous system [2,3]. A
large amount of untreated sewage is discharged indiscriminately, industrial solid waste
is piled up at will, and sewage irrigation, irrational application of agrochemicals, such as
fertilizers, pesticides, plant growth regulators, and agricultural films, are associated with
urban environmental quality, and, as a consequence, soil becomes heavily polluted and
its ecosystem function extremely degraded [4]. It has been reported that, as of 2014, more
than 70% of the soil (hundreds of thousands of sampling points) in the United States had
been damaged by pollutants, while tens of thousands of hectares of arable land in China
were also polluted by heavy metals [5]. Urban soils have some specific characteristics, such
as unpredictable layering, poor structure, and high concentrations of trace elements [6].
Due to the high population density and intensive anthropogenic activities, urban soils have
been severely disturbed. Consequently, a great number of environmental problems have
emerged, among which heavy metal pollution remains a major issue. Therefore, research
on the accumulation characteristics of heavy metals in urban soils and their pollution levels
is of great significance for the treatment and prevention of heavy metal pollution and the
improvement of peoples’ living quality [7].
Excessive heavy metal content in the soil causes soil dysfunction, deterioration of
environmental quality, and reduces crop yields. Enrichment of heavy metals through
the food chain eventually affects human health [8]. For example, Cadmium (Cd) can
cause prostatic hyperplasia, lung cancer and other chronic diseases. In addition, even
elements necessary for health may be harmful in high levels [9], such as zinc, which plays a
critical role in the development of the nervous system and Intelligence Quotient (IQ) [10].
Generally, exposure to heavy metals can lead to inflammation, skin irritation, immune
system damage and cancer risk [11].
The impact of human activities causes re-distribution of heavy metals in a specific
space. The types of pollution sources can be preliminarily judged and screened via ana-
lyzing the distribution pattern of heavy metal pollution [12]. In the analysis of pollution
sources, multivariate statistical analysis is mainly conducted through analyzing the data
to find out its internal laws, and, then, finding the main pollution factors. In addition,
combined with GIS technology, the spatial interpolation of soil heavy metal content can be
used to describe the two-dimensional and three-dimensional distribution of heavy metals,
so that the research results can be more accurately visualized [13]. Currently, soil ecological
risk assessment methods mainly include the index method, quotient method, fuzzy compre-
hensive evaluation, geoaccumulation index, potential ecological risk index and pollution
load index [14]. These evaluation methods can directly reflect the spatial changing trend
and pollution level of soil pollutants, and, thus, are used to qualitatively and quantitatively
assess soil ecological and environmental risks, thereby effectively solving practical prob-
lems in soil ecological risk assessment. There are various types of urban environmental
pollution sources and complex risk exposure pathways [15]. Multiple methods can be used
in a comprehensive manner.
Compared with other cities or rural areas, in addition to pollution from industry and
agriculture, Tianjin is also affected by factors such as seawater erosion and port construction.
Since the middle of the 20th century, Tianjin’s suburban farmland has been irrigated with
sewage for a long time, making Tianjin one of the five largest sewage irrigation areas in
China. Additionally, with the development of industry and the expansion of the city, heavy
metal pollution in Tianjin’s soil has become increasingly serious. Therefore, it is of great
importance to reveal the characteristics of heavy metal pollution in different types of land
in Tianjin.
 sewage for a long time, making Tianjin one of the five largest sewage irrigation areas in China.
Additionally, with the development of industry and the expansion of the city, heavy metal
pollution in Tianjin’s soil has become increasingly serious. Therefore, it is of great importance
to reveal the characteristics of heavy metal pollution in different types of land in Tianjin.
Int. J. Environ. Res. Public Health 2022, 19, 10013 3 of 15
Based on the above considerations, this study took Tianjin as the research area, soil
samples from different land use types were collected, and the content of heavy metals Cd,
Pb, Cu, Zn, Cr, As, Ni in soils were characterized. By using GIS spatial analysis technology
Based on the above considerations, this study took Tianjin as the research area, soil
with geostatistical technology to perform Kriging interpolation, combined with
samples from different land use types were collected, and the content of heavy metals
multivariate statistical
Cd, Pb, methods,
Cu, Zn, Cr,the
As,main
Ni insources of soil
soils were heavy metal
characterized. Byaccumulation andanalysis
using GIS spatial
distribution in Tianjin were analyzed. Using the combination of geoaccumulation index,
technology with geostatistical technology to perform Kriging interpolation, combined with
Nemerow comprehensive multivariatepollution
statistical index,
methods,and
thepollution loadofindex,
main sources soil pollution
soil heavy levels
metal accumulation and
of heavy metals were comprehensively evaluated.
distribution in Tianjin were analyzed. Using the combination of geoaccumulation index,
Nemerow comprehensive pollution index, and pollution load index, soil pollution levels of
2. Materials andheavy metals were comprehensively evaluated.
Methods
2.1. Sample Collection and Analysis
2. Materials and Methods
2.1. in
The land area Sample Collection
the outer and Analysis
suburbs is relatively large, about 3–4 km per grid, and the
land area in the suburbs is small,
The land about
area in 1–2 km
the outer per grid.
suburbs There large,
is relatively is oneabout
monitoring point
3–4 km per in and the
grid,
each grid. During landsoil
areasampling,
in the suburbs
areasis small, aboutmicro-domain
with poor 1–2 km per grid.geomorphology
There is one monitoring
were point
in each grid.
avoided, and samples Duringplots
in typical soil sampling, areas were
in each grid with poor micro-domain
collected. A total geomorphology
of 1031 soil were
samples were obtained (Figure 1a). According to the national land classificationAstandards
avoided, and samples in typical plots in each grid were collected. total of 1031 soil
samples were obtained (Figure 1a). According to the national land classification standards
(GB/T 21010-2017 and GB 50137-2016), the collected soil samples came from 12 different
(GB/T 21010-2017 and GB 50137-2016), the collected soil samples came from 12 different
types of soil (Table
typesS1). Land
of soil useS1).
(Table types were
Land usefilled
types with
were different
filled withcolors according
different to the to the
colors according
soil classifications,
soil and the detailsand
classifications, arethe
shown
detailsinare
Figure
shown1b.in Figure 1b.

Figure 1. Cont.
on. Res. Public Health 2022, 19, x FOR PEER REVIEW 4 of 15
Int. J. Environ. Res. Public Health 2022, 19, 10013 4 of 15

Figure 1. Sampling map of soil samples in Tianjin in this study. (a) Map of soil sampling location;
Figure 1. Sampling map of soil samples in Tianjin in this study. (a) Map of soil sampling location;
(b) Distribution map of land use types at sampling points.
(b) Distribution map of land use types at sampling points.
After removing the top soil, soils with a depth of 0–20 cm were collected. Soil was
After removing
mixed fromthe top soil, soils
5 sampling with
points, a depth
based on theof“Plum
0–20 Blossom
cm wereSampling
collected. Soil was
Method”. Each soil
sample was
mixed from 5 sampling obtained
points, based about 1.5 kg
on the by the
“Plum quarter Sampling
Blossom method and placed inEach
Method”. a double-layer
soil
plastic bag,
sample was obtained and1.5
about thekg field
bysampling
the quarterinformation
methodwas andrecorded.
placed inAfter the soil collection,
a double-layer
all samples were air-dried in a greenhouse, and plant residues,
plastic bag, and the field sampling information was recorded. After the soil collection, stones and other
all debris
were removed. All samples were crushed with a wooden hammer and passed through a
samples were air-dried in a greenhouse, and plant residues, stones and other debris were
100-mesh nylon sieve, and then stored in plastic bags for later use. Taking the sieved soil
removed. All samples
sample, were crushed
after HNO with a wooden hammer and passed through a 100-mesh
3 -HF combined digestion, we used an inductively coupled plasma mass
nylon sieve, and then stored(Agilent
spectrometer in plastic bags for later
Technologies 7900 use. Takingtothe
ICP-MS) sieved soil
determine sample, after of Cu,
the concentration
HNO3-HF combinedZn, As,digestion,
Pb, Cr, Ni, we
Cd. used an inductively
The experimental coupled
water plasma water
was ultrapure mass spectrometer
(18.2 MΩ). National
(Agilent Technologies 7900 samples
soil standard ICP-MS)(GSS-8,
to determine the concentration
GSS-23 and of Cu,during
GSS-27) were added Zn, As, Pb,
the Cr, Ni,process
analysis
for quality control. The recovery rate of standard samples
Cd. The experimental water was ultrapure water (18.2 MΩ). National soil standard sampleswas between 87% and 112%,
(GSS-8, GSS-23 and GSS-27) were added during the analysis process for quality control. The was
and the precision (RSD) was between 0.22% and 1.22%. The pH value of soil samples
recovery rate ofmeasured
standardbysamples
the potentiometric
was between method,
87% and from the extraction
112%, of deionized
and the precision water
(RSD) and soil
was
(water-soil ratio 1:1) [16].
between 0.22% and 1.22%. The pH value of soil samples was measured by the potentiometric
method, from the
2.2.extraction
Evaluation of deionized
Method of Soil water
Heavy and soil (water-soil ratio 1:1) [16].
Metals
2.2.1. Geoaccumulation Index Method
2.2. Evaluation Method
The of Soil Heavy Metals
geoaccumulation index method was used to evaluate the level of heavy metal
pollution inIndex
2.2.1. Geoaccumulation sediments,
Methodand is now widely used to evaluate soil heavy metal pollution [17].
This method uses the geochemical background value in the soil as the standard, and the
The geoaccumulation index method was used to evaluate the level of heavy metal
calculation formula is:
pollution in sediments, and is now widely used to evaluate Ci soil heavy metal pollution
 
Igeo = log2 (1)
[17]. This method uses the geochemical background value1.5B
in the
i soil as the standard, and
the calculation formula
In the is:
formula, Igeo is the geoaccumulation index of heavy metals; Ci is the measured
value of heavy metal i (mg/kg); Bi is the geochemical background value of heavy metal
 Ci  value of Tianjin as the evaluation standard
i (mg/kg). This study used the soil background
I geo = log 2  coefficient,
(Table S2); 1.5 was the compensation  which represented natural fluctuations
(1)
 1.5
and slight human input caused by diagenetic
B i  effects. The geoaccumulative index can be

divided into 7 levels (Table S3).

In the formula, Igeo is the geoaccumulation index of heavy metals; Ci is the measured
value of heavy metal i (mg/kg); Bi is the geochemical background value of heavy metal i
(mg/kg). This study used the soil background value of Tianjin as the evaluation standard
(Table S2); 1.5 was the compensation coefficient, which represented natural fluctuations
and slight human input caused by diagenetic effects. The geoaccumulative index can be
divided into 7 levels (Table S3).
Int. J. Environ. Res. Public Health 2022, 19, 10013 5 of 15

2.2.2. Nemeiro Composite Index Method

On the basis of the single factor index, the Nemeiro comprehensive index method takes
into account the average value and the highest value of the single factor pollution index,
and highlights the impact of the most polluted pollutants on environmental quality [18].
The calculation formula of Nemeiro composite index method is:
v
u 1 n
u 2
u ( n ∑ Pi ) + [max( Pi )]2
t n =1
Psum = (2)
2

In the formula, Pi is the single factor pollution index of heavy metal i in the soil; Ci is
the measured value of heavy metal i (mg/kg); Si is the evaluation standard value of heavy
metal i (mg/kg). Soil pollution risk control standard (for trial implementation)” (GB15618-
2018) and “Soil pollution risk control standard for construction land for soil environmental
quality (for trial implementation)” (GB36600-2018) were used as the evaluation criteria
(Table S2); Psum is the Nemerow comprehensive pollution index; max (Pi ) is the maximum
value of the single-factor pollution index of each heavy metal element in the soil; n is the
number of heavy metal species measured in the soil, and n = 7 in this study. The index P
was divided into the same level in the single factor index method and Nemeiro composite
index method (Table S4).

2.2.3. Pollution Load Index

The pollution load index method is also an evaluation method that combines single
factor index and comprehensive evaluation [19]. It can be used to evaluate the overall
pollution status of soil heavy metals. It is widely used in the evaluation of air, water and
soil pollution. Its formula is:
C
CFi = i (3)
Bi
p
PLI = n CF1 × CF2 × L × CFn (4)
In the formula, Ci and Bi are the same as Equation (1); PLI is the heavy metal pollution
load index; n is the number of heavy metals to be evaluated, and n = 7 in this study. The
value of PLI was divided into 4 levels (Table S5).

3. Results and Discussion

3.1. Spatial Distribution Characteristics of Soil Heavy Metals in Different Land Use Types
in Tianjin
As shown in Table 1, the median contents of the seven heavy metal elements in the
soil of Tianjin were Cr (70.7 mg/kg), Ni (27.9 mg/kg), Cu (24.3 mg/kg), Zn (79.1 mg/kg),
As (11.9 mg/kg), Pb (24.3 mg/kg), and Cd (0.15 mg/kg). The element content of Cr, Ni, Cu
was lower than the background value. The element content of Zn and Pb was close to the
background value, and the element content of As and Cd was higher than the background
value. Compared with the study of [20], the geometric means of Cr, Ni and Zn in urban
soils of our research were higher than that of Beijing. In addition, in comparison with the
heavy metal contents of agricultural soils in Shanghai area by [21], the contents of Cd, Cr
and Pb in this study were relatively low, while the contents of As were relatively high.
High-quality cultivated land distributed in suburban regions is strongly affected by human
activities, which has resulted in high heavy metal contents. The As concentration was
significantly higher in soils of a moderate quality level. Moreover, although nonsignificant,
the Cd content was higher in moderate-quality cultivated land. In recent years, due to the
requirement of cultivated land quality improvement, moderate-quality farmland must be
upgraded to a high quality level, which could lead to the intensive application of fertilizers
and pesticides to raise the quality of arable land and agricultural production, and Cd and
As are usually present in fertilizers, especially phosphate fertilizers and pesticides [22].
Int. J. Environ. Res. Public Health 2022, 19, 10013 6 of 15

Table 1. Statistic of heavy metal concentrations in the soil of Tianjin (mg/kg).

Project Cr Ni Cu Zn As Pb Cd
Minimum value 8.33 7.1 0.02 16.4 0.24 5.3 0.015
Maximum value 259.3 278.8 326.3 1223.0 52.4 783.8 7.97
Arithmetic mean 70.7 29.4 27.5 94.7 13.3 27.1 0.20
Geometric mean 68.1 27.6 23.2 82.3 11.2 24.5 0.15
25th percentile 59.3 23.1 17.8 63.1 8.0 20.1 0.11
50th percentile 70.7 27.9 24.3 79.1 11.9 24.3 0.15
75th percentile 79.9 33.4 30.9 101.4 17.2 29.3 0.20
90th percentile 89.3 38.8 42.8 136.0 22.4 36.6 0.28
Standard deviation 19.5 16.3 20.3 80.9 7.4 29.0 0.34
Coefficient of variation 0.28 0.55 0.74 0.85 0.56 1.07 1.70

Figure 2 shows the spatial distribution of seven heavy metals in the soil of the study
area. The Cr content at most points was lower than the background value of Tianjin soil. In
the east, especially the southeast, Cr had a high accumulation index. In the east of Wuqing
District, the north of Tanggu District and the northeast corner of Ninghe District, the value
of Cr was relatively higher. The green filled area of Ni and Cu was relatively large, and the
content in most areas of Tianjin was lower than the background value. The content of Ni
over background value was more scattered, while the yellow area of Cu was connected
together, showing obvious non-point source pollution. Furthermore, especially in Jizhou
District, almost all the points of Cu content exceeded the background value, and there
was also a cluster of over-standard points at the junction of southern Jinghai District and
Hebei Province. The accumulation of Zn and As in the study area was slightly higher,
and there was almost no light green area. The accumulation of Zn in Baodi District was
below the background value, and there were accumulations of over-standard points in
other jurisdictions of Tianjin. The coefficient of variation of the As element data was small.
The yellow patches in the figure were connected in a large area, and the content showed
obvious characteristics of being high in the south and low in the north. The accumulation
value was the highest in the Binhai New Area. The Pb and Cd content data showed strong
variations. It can be seen from Figure 2 that they were characterized by obvious point
source pollution. The accumulation of the two in the soil of the study area was likely to be
related to man-made production and living activities.
All soil samples collected in the study area were classified according to land use types,
and the statistical results of the accumulation of heavy metal content are shown in Table 2.
It can be seen from Table 2 that the element content of Ni element in the soil was lower
than the background value under all land use types, and the value was higher under the
four types of farm land, garden, woodland and grassland and special land types, exceeding
70 mg/kg. The lowest content was in the type of commercial drug (only 61.3 mg/kg). The
content of Ni in grassland was significantly higher than other land use types (34.5 mg/kg),
and the coefficient of variation was higher in industrial and mining storage land.
The Cu content was the highest in grassland (28.6 mg/kg), which was close to the
background value, and the coefficient of variation was extremely high (over 2) in commer-
cial and transportation land. The content of Zn in arable land, garden land, woodland,
residential land, and public management and public service land all exceeded the standard
value, especially the highest, which was in grassland (107.6 mg/kg). Although the content
of Zn in industrial and mining storage land and transportation did not exceed the standard,
it showed extremely high coefficient of variation, indicating that Zn in these two land use
types was significantly affected by the specific location.
Int. J. Environ. Res. Public Health 2022, 19, x FOR PEER REVIEW 7 of 15
Int. J. Environ. Res. Public Health 2022, 19, 10013 7 of 15

Figure
Figure2. Spatial distributions
2. Spatial of of
distributions seven heavy
seven metals
heavy (a: ((a):
metals Cr; b: Ni;
Cr; c: Cu;
(b): d: As;
Ni; (c): Cu;e:(d):
Pb; As;
f: Cd and
(e): Pb;g:(f):
Zn)Cd
in and
soils(g):
of Tianjin.
Zn) in soils of Tianjin.

All soil samples collected in the study area were classified according to land use
2. Statistic
Tableand
types, of heavyresults
the statistical metals centent in soils of different
of the accumulation land use
of heavy types
metal in Tianjin
content are(mg/kg).
shown in
Table 2. It can be seen from Table 2 that the element content of Ni element in the soil was
Land Use
Type Project lower
Cr
than theNi background Cu value under allZn land use types,Asand the valuePb
was higher Cdunder
the four types of farm land, garden, woodland and grassland and special land types,
Number
exceeding 70 mg/kg. The lowest content was in the type of commercial drug (only 61.3
1 content ± 17.2 The
73.8mg/kg). 28.6 ± 7.8 of Ni
content 25.6in±grassland
19.7 was±significantly
80.8 49.9 ± 6.6 than
11.2higher 24.5 ± 10.1
other use ±
land 0.15 0.24
types
n = 294 CV 0.2 0.3 0.8 0.6 0.6 0.4 1.6
(34.5 mg/kg), and the coefficient of variation was higher in industrial and mining storage
2 content ± 18.9
73.2land. 27.6 ± 7.5 26.2 ± 17.2 86.9 ± 116.1 10.1 ± 5.8 24.1 ± 96.9 0.18 ± 1.00
n = 62 CV 0.3 The Cu content
0.3 was the0.7 highest in grassland
1.3 (28.6 0.6
mg/kg), which 4.0 was close 5.6
to the
3 content background
70.7 ± 19.4 value,
29.3 ± 9.3 and the coefficient
25.2 ± 13.7 of variation
76.2 ± 54.2 was extremely
11.0 ± 6.0 high
24.6 ± 10.4 (over
0.15 ±2)0.22
in
commercial and transportation land. The content of Zn in arable land, garden land,
n = 94 CV 0.3 0.3 0.5 0.7 0.5 0.4 1.4
woodland, residential land, and public management and public service land all exceeded
the standard value, especially the highest, which was in grassland (107.6 mg/kg).
Although the content of Zn in industrial and mining storage land and transportation did
Int. J. Environ. Res. Public Health 2022, 19, 10013 8 of 15

Table 2. Cont.

Land Use
Type Project Cr Ni Cu Zn As Pb Cd
Number
4 content 78.4 ± 17.1 34.5 ± 7.7 28.6 ± 8.4 107.6 ± 96.4 20.5 ± 9.6 27.1 ± 5.5 0.17 ± 0.10
n = 10 CV 0.2 0.2 0.3 0.9 0.5 0.2 0.6
5 content 61.3 ± 18.0 27.0 ± 7.4 25.2 ± 53.5 75.0 ± 24.7 10.7 ± 1.8 23.3 ± 12.3 0.16 ± 0.05
n=7 CV 0.3 0.3 2.1 0.3 0.2 0.5 0.3
6 content 65.7 ± 30.9 26.0 ± 36.2 20.1 ± 22.7 68.7 ± 147.8 14.9 ± 8.5 22.8 ± 26.5 0.13 ± 0.37
n = 51 CV 0.5 1.4 1.1 2.2 0.6 1.2 2.9
7 content 66.3 ± 18.7 26.0 ± 13.8 25.2 ± 27.1 90.1 ± 93.9 8.6 ± 6.1 26.1 ± 52.1 0.16 ± 0.34
n = 59 CV 0.3 0.5 1.1 1.0 0.7 2.0 2.1
8 content 69.6 ± 20.9 29.4 ± 23.2 26.0 ± 12.4 82.6 ± 41.9 10.9 ± 5.7 25.4 ± 11.1 0.15 ± 0.23
n = 209 CV 0.3 0.8 0.5 0.5 0.5 0.4 1.5
9 content 73.6 ± 5.4 28.5 ± 3.5 27.3 ± 16.8 71.8 ± 18.9 14.3 ± 6.4 21.3 ± 8.4 0.10 ± 0.04
n=5 CV 0.1 0.1 0.6 0.3 0.5 0.4 0.4
10 content 69.3 ± 17.8 28.2 ± 7.8 22.9 ± 46.2 76.5 ± 193.9 10.2 ± 8.4 22.9 ± 8.9 0.15 ± 0.25
n = 48 CV 0.3 0.3 2.0 2.5 0.8 0.4 1.7
11 content 67.7 ± 18.8 26.8 ± 9.7 20.3 ± 18.2 75.3 ± 59.3 17.4 ± 7.9 23.6 ± 7.9 0.11 ± 0.28
n = 116 CV 0.3 0.4 0.9 0.8 0.5 0.3 2.5
12 content 69.7 ± 17.9 26.0 ± 22.7 20.0 ± 11.5 69.4 ± 85.1 16.0 ± 9.7 22.9 ± 9.0 0.13 ± 0.06
n = 76 CV 0.3 0.9 0.6 1.2 0.6 0.4 0.5

Except for residential land, the content of As in the soil of other land use types was
higher than the background value, and the highest was in grassland (20.5 mg/kg). The
content of Pb and Cd in all land use types exceeded the background value. The content of
Pb in special land types was slightly lower (21.3 mg/kg), and the coefficient of variation of
the content in garden soil was extremely high (4.0). The coefficient of variation of the Cd
element in gardens was as high as 5.6, and it was also extremely high in the soil of industrial
and mining storage land, residential land and land and water conservancy facilities around
the water area.
In general, among the 12 land use types, the seven heavy metals in the grassland soil
all exceeded the background value, and the content values of Zn and As were much higher
than the content levels of other land use types. The coefficient values of each element were
low, indicating that the cumulative distribution of heavy metals in grassland was relatively
even. The coefficients of variation of metals in garden land, industrial and mining storage
land, residential land and land for transportation were also higher than that of other land
use types. It has been reported that heavy metals with relatively wide concentration ranges
and high coefficients of variation mean that anthropogenic sources are present [23].

3.2. Evaluation of Soil Heavy Metal Pollution in Tianjin

3.2.1. Evaluation of Geoaccumulation Index
The average geoaccumulation index of seven heavy metals in Tianjin soil was Cu
(−0.90) < Cr (−0.89) < Ni (−0.86) < Zn (−0.53) < Pb (−0.36) = As (−0.36) < 0 < Cd (0.15)
(Table 3). Except for Cd, the other heavy metal elements were at the pollution-free level, and
Cd was pollution-free to moderate pollution level. From the view of different jurisdictions,
the geoaccumulation index of As in Binhai New Area (Tanggu, Hangu, Dagang) was
pollution-free to moderate pollution level (0.22), and in the urban and suburban districts
Int. J. Environ. Res. Public Health 2022, 19, 10013 9 of 15

(Dongli, Xiqing, Beichen and Jinnan) the accumulation index of Cd element was higher
than that of other jurisdictions. From the view of different types of land use, As was at a
pollution-free to moderate pollution level in waters and water conservancy facilities, Cd
was at a pollution-free accumulation level in industrial and mining storage land, water
areas and water conservancy, and the accumulation level in commercial areas was also low
(0.00), The accumulation index of garden land, residential land and land for transportation
was higher than that of other land use types, which can be considered due to the addition
of new man-made pollution sources.

Table 3. Geoaccumulation index of heavy metals in soils of Tianjin.

Classification Num Cr Ni Cu Zn As Pb Cd
Tianjin 1031 −0.89 ± 0.41 −0.86 ± 0.48 −0.90 ± 0.90 −0.53 ± 0.67 −0.36 ± 0.92 −0.36 ± 0.54 0.15 ± 0.86
Four suburban districts 339 −0.92 ± 0.37 −0.88 ± 0.47 −0.97 ± 1.10 −0.47 ± 0.77 −0.31 ± 0.71 −0.43 ± 0.53 0.30 ± 0.87
Outer suburb five
397 −0.86 ± 0.41 −0.92 ± 0.49 −0.92 ± 0.88 −0.68 ± 0.64 −0.64 ± 0.97 −0.48 ± 0.51 0.02 ± 0.93
districts
Binhai New Area 214 −0.86 ± 0.49 −0.72 ± 0.48 −0.85 ± 0.58 −0.41 ± 0.51 0.22 ± 0.87 −0.12 ± 0.46 0.07 ± 0.71
Urban district 81 −0.98 ± 0.35 −0.83 ± 0.36 −0.60 ± 0.66 −0.35 ± 0.65 −0.77 ± 0.79 −0.16 ± 0.70 0.39 ± 0.67
Cultivated land 294 −0.83 ± 0.36 −0.85 ± 0.42 −0.81 ± 0.82 −0.55 ± 0.58 −0.48 ± 0.91 −0.38 ± 0.43 0.20 ± 0.82
Garden plot 62 −0.86 ± 0.42 −0.89 ± 0.43 −0.68 ± 0.77 −0.47 ± 0.76 −0.68 ± 1.03 −0.31 ± 0.82 0.34 ± 1.05
Woodland 94 −0.85 ± 0.39 −0.80 ± 0.46 −0.85 ± 0.77 −0.60 ± 0.57 −0.43 ± 0.78 −0.39 ± 0.44 0.17 ± 0.86
Place of commercial use 7 −1.12 ± 0.46 −0.96 ± 0.41 −0.62 ± 1.37 −0.67 ± 0.49 −0.40 ± 0.25 −0.41 ± 0.61 0.00 ± 0.55
Industrial and mining
51 −1.09 ± 0.69 −0.95 ± 0.65 −1.18 ± 1.11 −0.53 ± 0.90 −0.15 ± 0.92 −0.41 ± 0.75 −0.02 ± 1.05
storage
Residential land 59 −0.97 ± 0.42 −0.90 ± 0.52 −0.68 ± 0.88 −0.27 ± 0.82 −0.70 ± 0.84 −0.21 ± 0.76 0.34 ± 0.90
Public service land 209 −0.88 ± 0.37 −0.79 ± 0.52 −0.85 ± 0.68 −0.51 ± 0.60 −0.43 ± 0.81 −0.29 ± 0.53 0.23 ± 0.77
Traffic land 48 −1.00 ± 0.48 −0.91 ± 0.42 −0.93 ± 0.98 −0.38 ± 0.92 −0.73 ± 1.28 −0.40 ± 0.47 0.35 ± 0.90
Water area land 116 −0.93 ± 0.39 −0.93 ± 0.48 −1.12 ± 0.76 −0.65 ± 0.67 0.14 ± 0.79 −0.45 ± 0.50 −0.15 ± 0.94

3.2.2. Evaluation of Nemeiro Comprehensive Pollution Index

The single-factor pollution index of the seven heavy metal elements was calculated by
the single-factor pollution index method, and then the Nemeiro comprehensive pollution
index of the sample was calculated. According to the results of the Nemeiro comprehensive
index in Table 4, the level of heavy metal pollution in the soil in Tianjin was relatively low,
and the pollution levels in the soil in different jurisdictions and different land use types
in Tianjin were all low. The Nemeiro composite index of Binhai New Area was close to
the warning limit (0.7), and the Nemeiro composite index of land use types for industrial,
mining, storage and transportation land was close to the warning limit.

Table 4. Single factor pollution index and comprehensive pollution index of soil heavy metals.

Pi Class of
Classification Psum
Cr Ni Cu Zn As Pb Cd Pollution

Tianjin 0.52 0.11 0.16 0.32 0.42 0.11 0.19 0.56 Security
Four suburban districts 0.56 0.10 0.14 0.35 0.38 0.09 0.17 0.57 Security
Outer suburb five districts 0.42 0.13 0.21 0.28 0.40 0.12 0.26 0.51 Security
Binhai New Area 0.55 0.11 0.14 0.32 0.59 0.11 0.16 0.63 Security
Urban district 0.78 0.06 0.004 0.35 0.20 0.05 0.004 0.58 Security
Cultivated land 0.29 0.15 0.29 0.30 0.49 0.15 0.32 0.47 Security
Garden plot 0.29 0.15 0.31 0.35 0.44 0.22 0.52 0.57 Security
Woodland 0.29 0.16 0.27 0.29 0.49 0.15 0.32 0.46 Security
Place of commercial use 0.72 0.03 0.002 0.26 0.18 0.03 0.002 0.53 Security
Industrial and mining storage 0.78 0.03 0.001 0.37 0.26 0.04 0.003 0.62 Security
Residential land 0.80 0.19 0.02 0.40 0.52 0.09 0.01 0.64 Security
Public service land 0.84 0.04 0.001 0.30 0.20 0.03 0.003 0.61 Security
Traffic land 0.78 0.03 0.002 0.43 0.20 0.03 0.003 0.66 Security
Water area land 0.27 0.15 0.23 0.29 0.72 0.14 0.28 0.60 Security
 Residential land 0.80 0.19 0.02 0.40 0.52 0.09 0.01 0.64 Security
Public service land 0.84 0.04 0.001 0.30 0.20 0.03 0.003 0.61 Security
Int. J. Environ. Res. Public Health 2022, 19, 10013
Traffic land 0.78 0.03 0.002 0.43 0.20 0.03 0.003 0.66 Security10 of 15
Water area land 0.27 0.15 0.23 0.29 0.72 0.14 0.28 0.60 Security

In order to visually
In order to visuallyfindfind
outout
thethe
points where
points thethe
where Nemeiro
Nemeiro Comprehensive
Comprehensive Pollution
Pollution
Index exceeds the warning limit from the overall data and
Index exceeds the warning limit from the overall data and reach light, or evenreach light, or even severe,
severe,
pollution,
pollution, ESRI
ESRIArcMap
ArcMap 13.0 wasused
13.0 was used to interpolate
to interpolate the Nemeiro
the Nemeiro Comprehensive
Comprehensive Pollution
Pollution Index of
Index value value
the of the sampling
sampling points, points,
and theandresults
the results are shown
are shown in Figure
in Figure 3a. 3a.
TheThehigh
high pollution
pollution index
index points
points were were scattered
scattered in thein study
the study
area, area,
but thebut the points
points where where the
the pollution
pollution level exceeded
level exceeded the warning
the warning limit
limit were
were gatheredininthe
gathered the central part
partofofJizhou
JizhouDistrict
District
andand
the the
southeastern part of Dagang District, showing the characteristics of
southeastern part of Dagang District, showing the characteristics of non-point non-point source
pollution. CombinedCombined
source pollution. with the with sampling point table,
the sampling point the
table,high valuevalue
the high points of the
points of the
comprehensive
comprehensive pollution
pollutionindex were:
index the the
were: urban areaarea
urban of Jizhou District,
of Jizhou easteast
District, of Yuqiao
of Yuqiao
Reservoir;
Reservoir; the the
cultivated
cultivated landlandof Lingtou
of Lingtou Village in in
Village Ninghe
Ninghe District; Shangmatai
District; Shangmatai Town
Town
Industrial
IndustrialZone in Wuqing
Zone in Wuqing District; Danjiang
District; DanjiangRoad in Beichen
Road in BeichenDistrict With
District WithHuaidong
Huaidong RoadRoad
Industrial
IndustrialZone; Dongli
Zone; District
Dongli JunyiJunyi
District Industrial Park;Park;
Industrial Duliujian RiverRiver
Duliujian on theonnorth bank bank
the north of
Tuanbowa
of TuanbowaReservoir in Jinghai
Reservoir District;District;
in Jinghai and cultivated land in Yangkezhuang
and cultivated Village, Xiqing
land in Yangkezhuang Village,
Xiqing District.
District.

Figure 3. Nemerow comprehensive evaluation index (a) and Pollution load index (b) of heavy metals
Figure 3. Nemerow comprehensive evaluation index (a) and Pollution load index (b) of heavy
in soil.
metals in soil.
3.2.3. Pollution Load Index Evaluation
3.2.3. Pollution Load Index Evaluation
The heavy metal pollution load index of Tianjin was 0.73, which was a pollution-free
The(Table
level heavy5).metal
The pollution
pollution load
load index
index of Tianjin
was was 0.73,
calculated whichto
according was a pollution-free
different jurisdictions
level
and(Table 5). The
different pollution
land load The
use types. index was
PLI calculated
value of eachaccording to different
jurisdiction and land jurisdictions
use type had
andlittle
different land use
difference, and types. The all
they were PLIatvalue of each jurisdiction
the pollution-free and land
level, which wasuse type had
consistent with
little difference,
Nemeiro’s and they were
comprehensive all at theindex.
evaluation pollution-free level,ofwhich
The PLI value Binhaiwas
Newconsistent
Area was with
slightly
Nemeiro’s comprehensive
higher (0.80), and the PLIevaluation
value of theindex. The suburbs
five outer PLI value of Binhai
(Jizhou, Wuqing,New Area Jinghai,
Ninghe, was
slightly higher (0.80), and the PLI value
and Baodi) was slightly lower (0.68). of the five outer suburbs (Jizhou, Wuqing, Ninghe,
Jinghai, and Baodi) was slightly lower (0.68).
Table 5. Results and comparison of pollution load index and Nemerow comprehensive
evaluation index.

Nemero Comprehensive
Pollution Load Index
Evaluation Index
Classification Num
Class of Class of
PLI Psum
Pollution Pollution
Tianjin 1031 0.73 ± 0.25 Pollution-free 0.56 Security
Four suburban districts 339 0.74 ± 0.26 Pollution-free 0.57 Security
Outer suburb five districts 397 0.68 ± 0.25 Pollution-free 0.51 Security
Binhai New Area 214 0.80 ± 0.22 Pollution-free 0.63 Security
Urban district 81 0.76 ± 0.26 Pollution-free 0.58 Security
Int. J. Environ. Res. Public Health 2022, 19, 10013 11 of 15

Table 5. Cont.

Nemero Comprehensive
Pollution Load Index
Evaluation Index
Classification Num
Class of Class of
PLI Psum
Pollution Pollution
Cultivated land 294 0.73 ± 0.22 Pollution-free 0.47 Security
Garden plot 62 0.77 ± 0.40 Pollution-free 0.57 Security
Woodland 94 0.72 ± 0.23 Pollution-free 0.46 Security
Place of commercial use 7 0.70 ± 0.28 Pollution-free 0.53 Security
Industrial and mining storage 51 0.72 ± 0.36 Pollution-free 0.62 Security
Residential land 59 0.76 ± 0.28 Pollution-free 0.64 Security
Public service land 209 0.74 ± 0.24 Pollution-free 0.61 Security
Traffic land 48 0.71 ± 0.27 Pollution-free 0.66 Security
Water area land 116 0.70 ± 0.23 Pollution-free 0.60 Security

The areas with higher soil heavy metal pollution load index in Tianjin were mainly
in the central part of Jizhou, the southern part of Jinghai District, the northern part of
Tanggu District, the central part of Jinnan District and the northern part of the urban area
(Figure 3b). The pollution load index of most areas in the northern area of Wuqing and
Baodi was very low. In general, the interpolation results of the pollution load index value
and the Nemeiro comprehensive evaluation index value were consistent. Combining the
sampling points and satellite image, the high pollution load index points, or areas, were: the
south bank of Yuqiao Reservoir in Jizhou District; Yunjingdao Industrial Park, Shangmatai
Town, Wuqing District; two industrial zones in Dongli District; Jinghai District Ziya River
and Daqiuzhuang town residential area; Tuanbo Express Road in Xiqing District (Along
the Chentaizi Drainage River); Tanggu District Yangbei Logistics Park and Babao Village
urban residential area; Jinnan District G319 Jinjin Expressway (Dagu sewage discharge on
the north bank of Hebei); urban area (near Tianjin North Station).

3.3. Sources of Soil Heavy Metals in Tianjin

Spearman correlation analysis was performed on seven soil heavy metals in Tianjin,
and the results are shown in Table 6. Except for Cd and As, the heavy metal elements in the
soil of Tianjin had significant correlations in pairs. Among them, the significant correlation
level of Cu and As was p < 0.05, and the correlation levels of the other elements all reached
p < 0.01.

Table 6. Spearman correlation analysis of seven heavy metals in soils of Tianjin.

Cr Ni Cu Zn As Pb Cd
Cr 1.000
Ni 0.762 ** 1.000
Cu 0.562 ** 0.790 ** 1.000
Zn 0.533 ** 0.726 ** 0.797 ** 1.000
As 0.325 ** 0.299 ** 0.071 * 0.095 ** 1.000
Pb 0.549 ** 0.722 ** 0.761 ** 0.824 ** 0.181 ** 1.000
Cd 0.443 ** 0.615 ** 0.713 ** 0.786 ** −0.052 0.688 ** 1.000
Note: *, p < 0.05; **, p < 0.01.

Considering that there may be differences in the accumulation of heavy metal elements
in the soils of different regions, a correlation analysis of heavy metal elements in the soil of
each jurisdiction was further done, and the results are shown in Table 7. The significant
correlation between the seven heavy metals was roughly the same in different jurisdictions
of Tianjin, but the correlation strength was different. Cr-Ni had a significant correlation
in all jurisdictions, and a strong and significant correlation in Baodi, Ninghe, Jizhou
and the urban area; Cr-Pb had a significant correlation in all jurisdictions, and a strong
and significant correlation in Wuqing; Ni-Cu, Ni-Zn, Ni-Pb, and Ni-Cr had significant
Int. J. Environ. Res. Public Health 2022, 19, 10013 12 of 15

correlations in most jurisdictions, and Ni-Cu and Ni-Pb were mostly highly correlated;
Cu-Ni, Cu-Cr, Cu-Zn, Cu-Pb had a significant correlation in most jurisdictions and Cu-
Ni, Cu-Zn, Cu-Pb showed a strong and significant correlation; Cu-Cd showed a highly
significant correlation in Dongli, Beichen, Ninghe and urban areas; Zn-Ni, Zn-Cu, Zn-Pb,
and Zn-Cd had significant correlations in most jurisdictions, among which Zn-Cd had a
strong and significant correlation in all jurisdictions; As and other elements were weakly
correlated or uncorrelated in all jurisdictions. As-Zn and As-Pb showed weak negative
correlation in Binhai New Area, and As-Cd showed weak negative correlation in Beichen,
Baodi, Jizhou and Binhai New Area; Cd -Zn and Cd-Pb showed a strong and significant
correlation in most jurisdictions, and the degree of significant correlation in each jurisdiction
was relatively consistent.

Table 7. Spearman correlation analysis of seven heavy metals in soils of different districts of Tianjin.

DL XQ JN BC WQ BD JH NH JZ UD BH
Element
n = 93 n = 72 n = 78 n = 96 n = 82 n = 76 n = 78 n = 79 n = 82 n = 81 n = 214
Cr-Ni 0.680 ** 0.828 ** 0.580 ** 0.697 ** 0.638 ** 0.955 ** 0.756 ** 0.854 ** 0.895 ** 0.914 ** 0.805 **
Cr-Cu 0.555 ** 0.693 ** 0.153 0.566 ** 0.648 ** 0.890 ** 0.454 ** 0.710 ** 0.493 ** 0.792 ** 0.791 **
Cr-Zn 0.514 ** 0.569 ** 0.242 * 0.492 ** 0.826 ** 0.774 ** 0.639 ** 0.680 ** 0.385 ** 0.722 ** 0.624 **
Cr-As 0.443 ** 0.390 ** 0.333 ** 0.521 ** 0.086 0.427 ** 0.387 ** 0.377 ** 0.079 0.570 ** 0.158 *
Cr-Pb 0.577 ** 0.567 ** 0.308 ** 0.633 ** 0.862 ** 0.775 ** 0.641 ** 0.822 ** 0.274 * 0.814 ** 0.623 **
Cr-Cd 0.425 ** 0.428 ** 0.166 0.465 ** 0.659 ** 0.435 ** 0.601 ** 0.617 ** 0.092 0.732 ** 0.616 **
Ni-Cu 0.855 ** 0.777 ** 0.625 ** 0.863 ** 0.903 ** 0.891 ** 0.779 ** 0.902 ** 0.599 ** 0.884 ** 0.833 **
Ni-Zn 0.751 ** 0.622 ** 0.600 ** 0.720 ** 0.794 ** 0.764 ** 0.721 ** 0.830 ** 0.507 ** 0.797 ** 0.756 **
Ni-As 0.458 ** 0.353 ** 0.135 0.428 ** 0.379 ** 0.488 ** 0.293 ** 0.358 ** 0.257 * 0.485 ** −0.046
Ni-Pb 0.707 ** 0.641 ** 0.782 ** 0.761 ** 0.803 ** 0.742 ** 0.776 ** 0.877 ** 0.344 ** 0.787 ** 0.805 **
Ni-Cd 0.582 ** 0.446 ** 0.584 ** 0.676 ** 0.600 ** 0.401 ** 0.697 ** 0.651 ** 0.191 0.815 ** 0.680 **
Cu-Zn 0.913 ** 0.689 ** 0.724 ** 0.823 ** 0.861 ** 0.899 ** 0.611 ** 0.944 ** 0.813 ** 0.904 ** 0.731 **
Cu-As 0.285 ** 0.214 −0.027 0.200 0.260 * 0.190 0.142 0.270 * −0.103 0.252 * −0.092
Cu-Pb 0.878 ** 0.715 ** 0.656 ** 0.781 ** 0.818 ** 0.895 ** 0.838 ** 0.907 ** 0.567 ** 0.862 ** 0.711 **
Cu-Cd 0.742 ** 0.622 ** 0.621 ** 0.776 ** 0.655 ** 0.656 ** 0.684 ** 0.730 ** 0.611 ** 0.887 ** 0.743 **
Zn-As 0.274 ** 0.044 −0.063 0.076 0.190 0.024 0.110 0.282 * −0.131 0.158 −0.191 **
Zn-Pb 0.932 ** 0.680 ** 0.830 ** 0.901 ** 0.940 ** 0.885 ** 0.804 ** 0.913 ** 0.727 ** 0.878 ** 0.687 **
Zn-Cd 0.805 ** 0.789 ** 0.752 ** 0.855 ** 0.780 ** 0.706 ** 0.789 ** 0.786 ** 0.810 ** 0.885 ** 0.793 **
As-Pb 0.222 * 0.194 0.007 0.184 ** 0.225 * 0.041 0.203 0.285 * 0.063 0.358 ** −0.173 *
As-Cd 0.023 0.025 −0.072 −0.03 ** 0.051 −0.281 * 0.094 0.233 * −0.24 ** 0.190 −0.23 **
Pb-Cd 0.747 ** 0.566 ** 0.783 ** 0.856 ** 0.728 ** 0.777 ** 0.824 ** 0.786 ** 0.675 ** 0.815 ** 0.598 **
Note: *, p < 0.05; **, p < 0.01. DL: Dongli, XQ: Xiqing, JN: Jinnan, BC: Beichen, WQ: Wuqing, BD: Baodi, JH: Jinghai,
NH: Ninghe, JZ: Jizhou, UD: Urban district, BH: Binhai New Area.

Generally, the correlation between Cr and other metal elements was relatively general
in the four suburbs (Dongli, Xiqing, Jinnan, Beichen), and strong in the five outer suburbs
(Beichen, Wuqing, Baodi, Jinghai and Jizhou), the strongest was in the urban area. There
was a correlation between heavy metal elements in urban soils (except As), the correlation
between heavy metal elements in the soil of Ninghe was also strong (except As, Cr), and the
correlation between heavy metal elements in the soil of Jinnan was relatively not obvious.
Principal component analysis was performed on the contents of seven heavy metal
elements in 1031 soil samples. The results of the principal component analysis are shown
in Table S6. The component matrices and rotating component matrices of the 4 principal
components extracted by the principal component analysis are shown in Table S7. The
principal component analysis gravel diagram and the component diagram in the rotating
space are shown in Figure 4. In this study, the components with eigenvalues greater than
0.8 were selected as the principal components, and a total of 4 principal components were
extracted, which could explain 85.2% of the variance in total.
Int. J. Environ. Res. Public Health 2022, 19, x FOR PEER REVIEW 13 of 15

principal component analysis gravel diagram and the component diagram in the rotating
space are shown in Figure 4. In this study, the components with eigenvalues greater than
Int. J. Environ. Res. Public Health 2022, 19, 10013 13 of 15
0.8 were selected as the principal components, and a total of 4 principal components were
extracted, which could explain 85.2% of the variance in total.

Figure
Figure4.4.Gravel
Gravelmap
mapofofprincipal
principalcomponent
componentanalysis
analysis(a)
(a)and
andcomponent
componentmap
mapofofrotating
rotatingspace
space(b).
(b).

PC1
PC1 mainly reflectsthe
mainly reflects thecomposition
composition information
information of Pb,
of Zn, Zn,andPb,Cd, and Cd, explaining
explaining 37.799%
37.799% of the variance variable. These three heavy metals
of the variance variable. These three heavy metals showed strong correlations showed strong correlations in
in most
most
soilssoils in Tianjin
in Tianjin (Figure(Figure
4 and 4 and
Table Table
7). In7).nature,
In nature,
Cd isCdanisassociated
an associated element
element of lead-
of lead-zinc
zinc ore copper-lead-zinc
ore and and copper-lead-zinc ore The
ore [24]. [24].mainThe human
main humanfactorsfactors of Cd accumulation
of Cd accumulation include:
include:
lead-zinc lead-zinc
ore mining, ore mining,
three waste threeemissions
waste emissions in the smelting
in the smelting process, process,
coal and coal
crude andoil
combustion,
crude and cadmium-containing
oil combustion, and cadmium-containing fertilizers infertilizers
agricultural
in production
agriculturalactivities
production and
so on [25].
activities and Pbsoinonthe[25].
soil mainly
Pb in the comes from thecomes
soil mainly three from
wastesthedischarged
three wastes from lead mine
discharged
mining and atmospheric deposition from vehicle exhaust emissions
from lead mine mining and atmospheric deposition from vehicle exhaust emissions [26]. [26]. The accumulation
of Zn
The in the soil is
accumulation ofnot
Zn inonlytheaffected
soil is not byonlythe soil parent
affected material,
by the but also
soil parent mainly
material, butduealsoto
emissions
mainly duefrom industrialfrom
to emissions production
industrial[27].production
In addition,[27].
Tianjin has a long
In addition, historyhas
Tianjin of asewage
long
irrigation.
history The sewage
of sewage irrigation
irrigation. area of
The sewage Beijing Sewage
irrigation River in
area of Beijing Wuqing
Sewage District,
River Dagu
in Wuqing
Sewage Dagu
District, River Sewage
Sewage RiverIrrigation
Sewage District in Xiqing,
Irrigation andinBeitang
District Xiqing,Sewage RiverSewage
and Beitang Sewage
Irrigation
River Sewage District in Dongli,
Irrigation District allinexerted
Dongli,the all effect
exerted of the
accumulation of Cd, Pb, Zn,
effect of accumulation Cu Pb,
of Cd, and
As [28]. Cd, Pb and Zn in the study area, all exceeding the background
Zn, Cu and As [28]. Cd, Pb and Zn in the study area, all exceeding the background value, value, and the
variability of the data was strong to extremely strong. Therefore, it
and the variability of the data was strong to extremely strong. Therefore, it was speculated was speculated that the
sources
that of theseof
the sources three elements
these in the study
three elements in thewere
studymainly
werederived from man-made
mainly derived activities,
from man-made
such as industrial
activities, production
such as industrial and transportation.
production This wasThis
and transportation. consistent with a previous
was consistent with a
study [29]. PC2 mainly reflected the composition information
previous study [29]. PC2 mainly reflected the composition information of Cr and Ni, of Cr and Ni, explaining the
information with a variance of 22.03%. Both of these two elements
explaining the information with a variance of 22.03%. Both of these two elements are are diagenetic elements.
The average
diagenetic content The
elements. in theaverage
study was lowerinthan
content the the
studybackground
was lowervalue thanandthe the coefficient
background
value and the coefficient of variation was small, so PC2 was the source of soilreflected
of variation was small, so PC2 was the source of soil parent material. PC3 mainly parent
the composition information of Cu. The explained variance accounted
material. PC3 mainly reflected the composition information of Cu. The explained variance for 13.93%. It was
obvious from
accounted the distribution
for 13.93%. It was obvious of Cu from
in Tianjin that the points
the distribution of Cu with high Cu
in Tianjin content
that were
the points
clustered in the east and the east of Jizhou District. In the west of Jinghai District, Tianjin’s
with high Cu content were clustered in the east and the east of Jizhou District. In the west
main metal and non-metal mineral resources were concentrated in the Jizhou mountain
of Jinghai District, Tianjin’s main metal and non-metal mineral resources were
area, while in the west of Jinghai District, there were many non-ferrous metal smelting
concentrated in the Jizhou mountain area, while in the west of Jinghai District, there were
and processing plants, such as copper mills, copper demolition plants, copper rice plants,
many non-ferrous metal smelting and processing plants, such as copper mills, copper
and scrap metal processing plants. Therefore, it was inferred that PC3 was a mining and
demolition plants, copper rice plants, and scrap metal processing plants. Therefore, it was
metallurgical source. PC4 mainly reflected the composition information of As, and the
inferred that PC3 was a mining and metallurgical source. PC4 mainly reflected the
explained variance accounted for 11.443%. The accumulation characteristics of As in the
composition information of As, and the explained variance accounted for 11.443%. The
study were quite special. Its correlation with other metal elements was low. In the study
accumulation characteristics of As in the study were quite special. Its correlation with
area, the pollution level of As was low in the north but high in the south. The highest
other metal elements was low. In the study area, the pollution level of As was low in the
concentration points were concentrated in the Binhai New Area. As is also a diagenetic
element, and its accumulation in the soil comes from both natural and anthropogenic
sources. The anthropogenic sources were mainly the application of agrochemical products,
mining, and industry. Studies have shown that the spatial distribution of As in Tianjin’s soil
Int. J. Environ. Res. Public Health 2022, 19, 10013 14 of 15

was related to the distribution of arsenic emission enterprises in Tianjin and the irrigation
of farmland [30].

4. Conclusions
In this paper, we collected the surface soil in Tianjin at high density, combined with
land use types, and used multiple data analysis and multivariate statistics to study the
distribution characteristics and pollution sources of heavy metals in soil, and evaluated
the pollution levels by various indices. The results showed that the accumulation of
heavy metals was highest in grassland, and the coefficient of variation of heavy metal
content was higher in garden land, industrial and mining storage land, residential land
and transportation land, indicating that the soil heavy metal content under these land
use types was more obviously disturbed by human factors. The evaluation results of
the ground accumulation index method show that the soil in Tianjin is free of pollution
except for Cd which is free of pollution to moderate pollution level. Cd, Pb and Zn are
the main contributors to pollution by anthropogenic factors, such as traffic and industry;
Cr and Ni are the main contributors to pollution by soil parent material; Cu is the main
contributor to pollution by mining and metal smelting; As is presumed to be the main
contributor by agriculture and surface runoff. The results can provide reference significance
for agricultural environmental protection in urban development.

Supplementary Materials: The following supporting information can be downloaded at:

https://www.mdpi.com/article/10.3390/ijerph191610013/s1, Table S1: Land use types at sam-
pling sites; Table S2: Background values and risk screening values of seven heavy metals in soils
(mg/kg); Table S3: Classification of geo-accumulation index; Table S4: Classification of the evaluation
using Nemerow comprehensive index; Table S5: Classification of pollution load index; Table S6:
Principal component analysis and total variance explained content for heavy metal contents in soils
and Table S7: Component, rotated component and loading matrix of heavy metal contents in soils of
Tianjin based on principal component analysis.
Author Contributions: T.M. and Y.Z. (Youwen Zhang): Samples collection, Methodology, Visu-
alization, Writing—original draft preparation, Project administration. Q.H.: Samples collection,
Methodology, Visualization. M.H. and Z.L.: Samples collection, Methodology. X.L.: Writing—review
& editing, Visualization. Y.Z. (Youjun Zhang): Samples collection, Methodology. R.S.: Samples
collection, Writing—review & editing, Funding acquisition. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by Key R & D plan project of Ningxia Hui Autonomous
Region—Research on key technologies and product development for restoration and cultivation
of barrier farmland in Yellow River Irrigation Area (2021BEG02002) and Funds for Science and
Technology Innovation Project from the Chinese Academy of Agricultural Sciences.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: Thanks for the hard work of relevant staff in the process of sample collection.
Conflicts of Interest: The authors declare that they have no known competing financial interest or
personal relationships that could appear to influence the work reported in this paper.

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