Ecotoxicology and Environmental Safety 205 (2020) 111115

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Distribution patterns and sources of heavy metals in soils from an industry

undeveloped city in Southern China
Xiangyang Bi a, **, Mohai Zhang b, Yunjie Wu a, c, Zhongbiao Fu b, Guangyi Sun c, d, *, Lihai Shang c,
Zhonggen Li e, Pengcong Wang a
a
Hubei Key Laboratory of Critical Zone Evolution, School of Earth Sciences, China University of Geosciences, Wuhan, 430074, China
b
School of Environmental Studies, China University of Geosciences, Wuhan, 430074, China
c
State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, China
d
University of Chinese Academy of Sciences, Beijing, 100049, China
e
College of Resources and Environment, Zunyi Normal University, Zunyi, 563006, China

A R T I C L E I N F O A B S T R A C T

Keywords: The accumulations of heavy metals in urban soils are derived from natural parent materials and complex
Heavy metals anthropogenic emission sources. This paper investigated metal contamination in urban soils at an industry un­
Pb isotopes developed city (Haikou) in southern China, an ideal place to quantitatively assess the contribution of metals from
Urban soil
different sources. The concentrations of most heavy metals in the urban soils of Haikou were much lower than
Source discrimination
their guideline values and that of those from other big cities in China. In contrast, the chemical speciation of
metals in this study was similar to those from other cities. The spatial distributions of heavy metals and principal
component analysis (PCA) revealed that basaltic parent materials, traffic emissions, and coal combustion were
the main factors controlling the distribution of metals in the soils. The Pb isotope signatures of the Haikou soils
were greatly different from those of the Beijing and Shanghai soils, but similar to those of the Guangzhou soils,
suggesting the common sources of Pb in southern China cities. The results of ternary mixing model of Pb isotopes
showed that the contributions of Pb from natural background, coal combustion and traffic emission sources were
5.3–82.4% (mean: 39.7 ± 21.1%), 0–85.7% (mean: 25.5 ± 24.6%), and 1.9–64% (mean: 34.8 ± 22.9%),
respectively. This suggests that traffic emission is still the most important anthropogenic source of Pb in Haikou.

1. Introduction urban environmental quality.

Urbanization in China has unfold at an unprecedented rate in the
Heavy metal contamination in urban environments becomes a past three decades, resulting in substantial deterioration of urban en­
worldwide issue due to their persistence and high toxicity to humans vironments, including water, atmosphere, and soils (Kelly et al., 1996; Li
(Wei and Yang, 2010; Men et al., 2020; Jia et al., 2020; Liu et al., 2020a, et al., 2001; Manta et al., 2002; Chen et al., 2005; Duzgoren-Aydin et al.,
Liu et al., 2020b). Soil, an essential urban ecosystem component, serves 2006; Liu et al., 2019a, Liu et al., 2019b, Liu et al., 2020a,Liu et al.,
as not only a sink but also a source of urban metal pollutants. Metals 2020b; Liu et al., 2021). Wei and Yang (2010) and Luo et al. (2012)
retained by urban soils can be agitated and re-suspended into the at­ summarized the accumulation of heavy metals in soils from several
mosphere and may impair human health by inhalation, direct ingestion, typical China’s cities and found many of them were polluted by more
and dermal contact (Ljung et al., 2006; Yamamoto et al., 2006; Amato than one type of heavy metals. The occurrences and distribution patterns
et al., 2009; Bi et al., 2013; Han et al., 2020). Extensive studies have of heavy metals in urban soils are mainly controlled by the sources of
reported a strong correlation between blood lead levels (BLLs) of kids metals, and thus the source discrimination of metals is becoming a real
and Pb concentrations in urban soils (Laidlaw et al., 2005; Ren et al., necessity. In metropolises, metals in soils are originated from natural
2006; Laidlaw and Taylor, 2011; Li et al., 2020). Thus, heavy metals parent materials and anthropogenic sources, including traffic emissions,
caused soil contamination is an important assessment aspect of the coal combustion, and various industrial activities (Bi et al., 2007, 2009,

* Corresponding author. State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang, 550002, China.
** Corresponding author. Hubei Key Laboratory of Critical Zone Evolution, School of Earth Sciences, China University of Geosciences, Wuhan, 430074, China.
E-mail addresses: bixy@cug.edu.cn (X. Bi), sunguangyi@mail.gyig.ac.cn (G. Sun).

https://doi.org/10.1016/j.ecoenv.2020.111115
Received 23 February 2020; Received in revised form 12 July 2020; Accepted 31 July 2020
Available online 21 August 2020
0147-6513/© 2020 Elsevier Inc. All rights reserved.
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

2017; Wang et al., 2020a). Heavy metals emitted from complex indus­ was then evaporated to near dryness at 90 ◦ C. Then, 3 mL of HNO3 and 2
trial processing generally have similar characteristics (e.g., similar mL of ultrapure water (2 ml, Milli-Q) were added to each residue, and
concentrations, compositions, isotope ratios) to those from traffic the closed Teflon tubes were kept at 150 ◦ C again for 6 h. After cooling
emissions and coal combustion, making them difficult to be distin­ down, the solution was diluted to 50 mL using ultrapure water (Bi et al.,
guished from each other by source apportionment models or isotope 2017). The speciation of heavy metals in urban soils was evaluated using
fingerprints (Huang et al., 2014; Bi et al., 2017; Wang et al., 2019b). In a sequential extraction procedure that was modified from Tessier et al.
order to assess the contamination by sole industrial activities, many (1979). This method divided the metals into six phases: F1, exchange­
researchers conducted field studies restricted to urban industrial areas, able fraction (2.5 g soil extracted by 25 ml of 1 M MgCl2, pH = 7.0, for
but this is still unable to totally exclude the impacts from traffic emis­ 20 min); F2, carbonate bound fraction (1 M NaOAc adjusted to pH = 5.0
sions and coal combustion (Zhu et al., 2013a, b; Wang et al., 2020b). with acetic acid, for 6 h); F3, humic acids (HA) bound fraction (0.1 M
Therefore, quantifying the contribution from traffic emissions and coal Na4P2O7, pH = 10.0, for 3 h); F4, Fe–Mn oxides bound fraction (0.04 M
combustion is essential to source discrimination of heavy metals in NH2OH⋅HCl in 25% (v/v) HOAc at 96 ◦ C, for 6 h); F5, organic matter and
urban environment. sulfides bound fraction (5 ml of 30% H2O2 and 3 ml of 0.02 M HNO3 for
Haikou, the capital of Hainan province in South China, is the in­ 2 h, a second 3 ml of 30% H2O2 for 3 h, at 85 ◦ C); F6, residual fraction
dustry least developed capital city in China after Lhasa. In 2019, the (total digestion with a concentrated mixture of HCl/HNO3/HF/HClO4)
whole industry output of Haikou is about 50 billion yuan, only 2.5% of (Fu et al., 2011).
those of Beijing (HMBS, 2019). Atmospheric emission inventories indi­ Major elements (Al, Fe, Mn, Ti and V) and heavy metals (As, Cd, Cr,
cated that heavy metal pollutants in the whole Hainan province are Cu, Ni, Pb, Sb and Zn) of the digested solutions were determined by ICP-
predominantly from traffic emissions and coal combustion, while the AES (Agilent 5100, Australia) and ICP-MS (Agilent 7500a, Australia),
contribution from industrial emissions (excluding coal emissions from respectively. The measurements were validated by method blanks, du­
industrial boilers) is quite limited (Li et al., 2012; Tian et al., 2012a, b, plicates, and certified reference materials (Chinese National Standard
2015). Thus, it is believed that heavy metals settled in urban soils of Soils GBW07423). The average recovery for the metals ranged from 85
Haikou are mainly derived from parent materials, traffic emissions, and to 110% (Wang et al., 2019b).
coal combustion. This makes Haikou an ideal place for quantitative The Pb isotopic composition of source-related samples and atmo­
assessment of the contribution of metals from different sources. In this spheric deposition particulate samples was measured by thermal ioni­
research, soil samples were collected from different urban regions of zation mass spectrometry (TIMS, Finnigan MAT 261). A standard
Haikou, and the total concentrations and chemical speciation of heavy reference material (NIST SRM 981) was used for calibration. Pb blanks
metals, as well as Pb isotope compositions were detected. The main during the study’s course are small than 1‰ of the total Pb that was
objectives of the study are 1) to address the occurrences and distribution analyzed in each sample. A mass fractionation correction was conducted
patterns of heavy metals in urban soils with a less industry impact and 2) based on the standard (NIST SRM 981). Analytic uncertainties (±2
to trace and quantify the specific sources (parent materials, traffic standard deviation) are as follows: 206Pb/204Pb < 0.0017, 207Pb/204Pb
emissions, and coal combustion) of heavy metals in the urban soils using < 0.0014, 208Pb/204Pb < 0.0038.
principal component analysis (PCA) and lead isotope compositions. The
results of this study may provide a useful reference for tracing the 2.3. Statistical analysis
sources and assessing the contamination degrees of heavy metals in
other cities. The data were statistically processed by the statistical package SPSS
v25.0 (SPSS Inc.). One-Way ANOVA analysis was performed to evaluate
2. Materials and methods the difference of metal concentrations between different urban areas.
The heavy metal concentrations were mapped based on the inverse
2.1. Sample collection and preparation distance method using ArcGIS 10.2 software (ESRI, Redlands, CA, USA)
to allow the spatial patterns to be assessed. Principal component analysis
Hainan Province is situated in the southern of China (18◦ 10′ - (PCA) was conducted using factor extraction with eigenvalues >1 after
20 10′ N, 108◦ 37′ -111◦ 03′ E) and the domain area is 33,920 km2.
◦
varimax rotation.
Climate in this region is tropical monsoon with a mean yearly rainfall of The pollution status of heavy metals in the soils was quantified using
1600–2500 mm and a mean yearly temperature of 23–25 ◦ C. Haikou the Nemerow pollution index (Lee et al., 2006), which is the most widely
city, the capital of Hainan province, is a world-famous resort, with an used method for soil metal pollution assessment in China (CEPA, 2004).
area of 2304 km2 and a population of 2.33 million by the end of 2019. It includes single factor pollution index (Pi) and integrated pollution
Geologically, the surface outcrops are Cenozoic mafic volcanic rocks and index (PN), which are defined as follows:
Quaternary unconsolidated sediments, and the major type of soil is
latosol. Pi = Ci /Ti (1)
Soil samples were collected from different urban areas of the Haikou √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
city, including industrial area, commercial area, residential area, resort 1 2
PN = ​ (Pi + ​ Pi2Ave ) (2)
area, street and suburban district (Fig. 1a). A sum of 70 surface soils 2 Max
(0–20 cm) were collected. Each sample comprised of 3–7 sub-samples /
from a 2 m × 2 m zone. The samples were air-dried at 25 ◦ C and dis­ ∑ ∑
n n
PiAve wi Pi wi (3)
aggregated and sieved by a 1 mm polyethylene sieve to get rid of stones, i=1 i=1
coarse substances, and other debris. Subsequently, the dried soil was
ground to fine powder for geochemical analysis. where Ci is the concentration of a given metal in soil samples, and Ti is
the corresponding target concentration. Here we chose the Dutch soil
2.2. Analytical methods guidelines (VROM, 2000) as the target values due to their universality
and rigor (Luo et al., 2012). Pi Max and Pi Ave are the maximum and
For the analysis of major elements and heavy metal concentrations of weighted average values of Pi of the considered metals, respectively. wi
the soils, the collected samples were digested using the following pro­ is the weighting factor of the metals, which is 3 for As, Cd, and Pb, and 2
cedures: the samples (about 50 mg) were accurately weighed into a for Cu, Cr, and Ni, respectively. According to PN, the soil quality is
Teflon tube with 3 mL of Nitric acid and 0.5 mL of Hydrofluoric acid classified as five degrees: clean (PN ≤ 0.7), precautionary (0.7 < PN ≤
added. The tubes were digested for 48 h at 150 ◦ C. Each digest solution 1.0), slightly polluted (1.0 < PN ≤ 2.0), moderately polluted (2.0 < PN ≤

2
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

Fig. 1. The map of study area. a: sampling location, b: geochemical maps of Pb, Zn, Cd, Cu, As, and Sb in soils from urban areas of Haikou city.

3
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

3.0), and heavily polluted (PN > 3.0).

3. Results

3.1. Major elements and heavy metal concentrations

The concentrations of major elements and heavy metals in the soils

are listed in Table 1. The major element concentrations varied widely,
ranging from 0.01 to 15.4 g/kg for Al, 2.94 to 148 for Fe, 0.05–1.19 g/kg
for Mn, 0.31–30.2 g/kg for Ti, and 0.18 to 13.2 for V, respectively. The
ranges of As, Cd, Cr, Cu, Ni, Pb, Sb and Zn concentrations in the soils
were 0.74–9.87 mg/kg, 0.01–1.34 mg/kg, 8.1–376 mg/kg, 0.61–98.7
mg/kg, 1.46–190 mg/kg, 1.47–69.4 mg/kg, 0.11–1.68 mg/kg and
13.8–208 mg/kg, respectively (Table 1). The mean concentrations of
heavy metals were generally higher than their corresponding median
Fig. 2. Concentrations and pollution index (PN) of heavy metals in soils among
values, indicating that the dispersion of the data depended on the high
different functional areas of Haikou.
values. In comparison with the background values of China’s soils, the
Cd, Cr and Ni concentrations were higher, while other metal concen­
trations were lower or comparable in the collected soils. In addition, the 3.3. Pb isotopic compositions
concentrations of most the metals in this study were lower than their
guideline values (Table 1), indicating a limited anthropogenic impact in The Pb isotopic compositions of the soil samples, as well as the po­
tential Pb sources, are presented in a three-isotope graph (206Pb/207Pb
this city.
The trace metal concentrations in soils from different functional vs. 208Pb/207Pb) (Fig. 4). Generally, the natural sources, including ma­
rine sand, bedrock, and natural soils, had more radiogenic Pb compo­
areas are showed in Fig. 2. The significantly high (p < 0.05) concen­
trations of Pb (mean 41.8 ± 19.2 mg/kg) and As (mean 5.6 ± 2.7 mg/kg) sitions with 206Pb/207Pb and 208Pb/206Pb ratios of 1.19–1.22 and
2.039–2.085, respectively. In contrast, Pb from the anthropogenic
were found in samples from the street district and industrial areas,
respectively. However, the significantly high (p < 0.01) concentrations sources exhibited a less radiogenic signature. Pb from the coal com­
of Cd, Cr, Cu, and Ni were unexpectedly found in those samples from the bustion dust in Haikou had 206Pb/207Pb and 208Pb/206Pb ratios of
1.162–1.171 and 2.103–2.113, respectively; and Pb from the vehicle
suburban district. In addition, the soils of the suburban district had
significantly low (p < 0.05) concentrations of Sb. exhaust had 206Pb/207Pb and 208Pb/206Pb ratios of 1.149–1.171 and
2.099–2.126, respectively. The soils from Haikou had intermediate Pb
isotopic compositions (206Pb/207Pb, 1.172–1.195; 208Pb/206Pb,
3.2. The speciation of heavy metals 2.076–2.104) and fell between the natural and anthropogenic sources on
the plot of 206Pb/207Pb vs. 208Pb/206Pb.
The sequential chemical fractions of trace metals in the selected soil
samples are shown in Fig. 3. Cd in the soils was mainly associated with 4. Discussion
exchangeable (7.6–34.7%), Fe–Mn oxides (5.6–47.2%) and residual
(8.4–55.9%) fractions, while the carbonate (8.9–22.3%), HA 4.1. Distribution patterns of heavy metals in urban soils
(2.8–19.6%), and OM and sulfides (6.2–21.8%) bound fractions were
less important. Pb was mainly controlled by the Fe–Mn oxides bound Compared with other big cities in China, Haikou had obvious lower
fraction (25.8–81.0%), and the residual fraction (3.1–58.9%) was the As, Cu, Pb, and Zn concentrations in the soils, which were attributed to
second dominant. For Cu and Zn, the residual form was the most the undeveloped industry (Fig. 5). However, the concentrations of Cr
important chemical fraction (Cu, 34.1–88.6%; Zn, 28.8–74.2%), fol­ and Ni were much higher than that of those from most cities, revealing a
lowed by the Fe–Mn oxides bound (Cu, 4.5–31.5%; Zn, 6.7–37.8%) and high geological background of these metals in Haikou. The distribution
HA bound (Cu, 4.6–30.5%; Zn, 3.3–19.5%) fractions. Cr and Ni in the patterns of heavy metals among different functional areas of Haikou
soils were present predominantly in the residual fraction (Cr, further supported this statement. Significantly high (p < 0.01) concen­
84.2–96.8%; Ni, 71.7–95.6%), while the portions of the other fractions trations of Cd, Cr, Cu, and Ni were simultaneously observed in suburban
were generally less than 5%.

Table 1
The concentrations of major elements and heavy metals in urban soils of Haikou.
Mean SD Min Median Max National soil background of Chinaa Chinese soil quality standard (II)b Target value of Dutch soil guidelinesc

Al (g/kg) 27.5 13.7 3.86 27.4 63.4

Fe (g/kg) 46.5 34.4 2.94 37.8 148
Mn (g/kg) 0.28 0.24 0.05 0.19 1.19
Ti (g/kg) 6.28 5.40 0.31 4.79 30.2
V (g/kg) 3.56 2.81 0.18 2.77 13.2
As (mg/kg) 3.83 2.08 0.74 3.42 9.87 11.2 30 29
Cd (mg/kg) 0.25 0.22 0.01 0.19 1.34 0.097 0.3 0.8
Cr (mg/kg) 89.5 75.9 8.10 65.7 376 61 200 100
Cu (mg/kg) 19.1 21.6 0.61 11.1 98.7 23 100 36
Ni (mg/kg) 50.0 45.9 1.46 31.9 190 27 50 35
Pb (mg/kg) 29.2 16.8 1.47 25.7 69.4 27 300 85
Sb (mg/kg) 0.66 0.35 0.11 0.60 1.68 1.21
Zn (mg/kg) 84.7 46.6 13.8 73.7 208 74 250 140
a
The national background soil values (NBSVs) (Chen et al., 1991).
b
The guideline value for the Environmental Quality Standard for Soils (II) in China (CEPA, 1995).
c
Values for soil remediation proposed by Dutch Ministry of Housing, Spatial Planning and Environment (VROM, 2000).

4
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

Fig. 3. Chemical speciation (%) of heavy metals in soils of Haikou. Sample 1 and 2 from industrial area, 3 from commercial area, 4 and 5 from residential area, 6 and
7 from resort area, 8 and 9 from street and 10 from suburban district.

districts where no industrial factories were distributed. These high levels the industrial area. On the other hand, As showed an inverse pattern
of metals in soils had also been reported by Wang et al. (2019a), which with the highest concentrations in the industrial area and second high
were most likely to be derived from the basaltic parent materials, since concentrations in the street district. For Cu, Cd and Zn, high concen­
basalts in Hainan province had similar high concentrations of Cr (254 trations could be found in both the street district and the industrial area.
mg/kg), Cu (53 mg/kg), and Ni (130 mg/kg) (Li et al., 2014). On the For Sb, however, high concentrations were mainly distributed in the
contrary, the significantly high concentrations of Pb observed in the industrial area, revealing their coal combustion origin, which was
street district should be associated with traffic emissions. The pillar in­ comparable to the emission inventory of Sb in this region (Tian et al.,
dustries in Haikou are food processing and pharmaceutical industries 2012b).
(HMBS, 2019), none of which belongs to metal pollution sources. The single factor pollution indexes (Pi) of Ni (mean 1.5) and Cr (0.92)
Therefore, the relative high levels of As in soils from the industrial area were either higher than or approximately 1, which were again attributed
might be associated with coal combustion emission from coal fired to their high background concentrations. While the other metals had a Pi
power plant (CFPP) and industrial boilers (Zhu et al., 2013). In addition, (As: 0.13, Cd: 0.31, Cu: 0.61, Pb: 0.34, Zn: 0.60) of far lower than 1. The
the soils from different urban functional areas of Haikou had similar integrated pollution indexes (PN) indicated that the suburban area was
concentrations of Sb, which were about twice of those in the suburban moderately polluted (PN = 2.68) and the industrial area was slightly
district (Fig. 2). This suggests that Sb accumulated in the urban envi­ polluted (PN = 1.22) by the heavy metals, while the other urban areas
ronment of Haikou is derived from similar anthropogenic area pollution. belonged to the degree of clean to precautionary situation (PN =
A previous study demonstrated that the main emission sources of Sb in 0.63–0.91) (Fig. 2). The pollution delineated for the suburban area was
Hainan province were coal combustion (67%), municipal solid waste mainly dependent on their high Ni and Cr concentrations as mentioned
incineration (16.5%) and brake wear (16.5%) (Tian et al., 2012b). above.
The spatial distributions of heavy metals in soils from urban areas
further confirmed the constraints of anthropogenic activities (Fig. 1b).
4.2. Heavy metal mobility in urban soils
The highest concentrations of Pb were found in samples from the street
district, and the second high concentrations were found in those from
The chemical speciation of metals was usually used to evaluate their

5
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

which showed a high mobility in the urban soils. Based on the portions
of exchangeable and carbonate fractions, the mobility of trace metals in
the urban soils of Haikou was in the decreasing order: Cd > Zn > Pb >
Cu > Ni > Cr, which was in good agreement with previously studies
conducted in big cities (Lu et al., 2007; Luo et al., 2012), suggesting the
common characteristics of metal speciation in urban soils. Besides, it is
noteworthy that substantial portions (about 10%) of Cd, Cu, and Zn
remained in the HA fraction, which might be available to soil organisms.
The high portion of Fe–Mn oxides bound Pb in the soils suggested that Pb
in the urban environment should be emitted as oxides through high
temperature combustions, such as coal combustions and traffic emis­
sions. Compared with other metals, Cr and Ni showed a higher stability
in the soils and thus were not easily leachable and bioavailable.

4.3. Source attributions of trace metals in urban soils

4.3.1. Deducing from PCA analysis

The distribution of heavy metals, together with major elements, in
the urban soils of Haikou was determined by three principal components
(PCs) that explained 75.3% of the total variances (Fig. 6). PC1 explained
53.7% of the total variances with higher loadings of Cd, Cu, Cr, Ni, Fe,
Mn, Ti and V. PC2 was related to Pb, Zn and Al, accounting for 12.6% of
the variances. Arsenic and Sb were associated in PC3, accounting for
9.0% of the variances. The accumulations of Cd and Cu in the urban
environment are usually derived from anthropogenic emissions (Duz­
goren-Aydin et al., 2006; Gong et al., 2010). However, Cd and Cu in this
study showed close relationships with the basaltic parent materials
related elements (Cr, Ni, Fe, Mn, Ti and V) (Wang et al., 2019a). This
suggested that a substantial amount of Cd and Cu in the soils might be
derived from natural sources. The spatial distribution patterns of Pb, As,
and Sb within urban areas indicated that PC2 should be related to traffic
emissions, and PC3 might be associated with coal combustion emissions.
Fig. 4. Diagram of 206Pb/207 Pb vs 208Pb/206 Pb in soils of Haikou and
comparison with other sources. The data of Beijing, Shanghai, and Guangzhou 4.3.2. Deducing from Pb isotopic composition
soils are from Yu et al. (2016), Li et al. (2011), and Liang et al. (2019), The Pb isotopic compositions of urban soils depended largely on the
respectively. Other data are from Bi et al. (2017). sources of Pb. The signatures of Pb isotopes of the Haikou urban soils
differed greatly from those of the Beijing and Shanghai soils, indicating a
clear difference of Pb sources between Haikou and these two big cities
(Fig. 4a). However, the Pb isotope ratios of Haikou soils distributed
within the range of those of Guangzhou (Fig. 4a), which suggested that
Pb in urban soils from southern China cities may have common sources.
Coal combustion, traffic emissions and nonferrous metal mining and
smelting are the most common anthropogenic sources of Pb in the urban

Fig. 5. The comparison of heavy metal concentrations in urban soils between

Haikou and other capital cities in China (data of Wuhan from Yang et al., 2007;
data of Changchun from Yang et al., 2011; data of Shanghai from Li et al., 2011
and Wang et al., 2018; data of Xi’an from Chen and Lu, 2018; data of
Guangzhou from Liang et al., 2019; data of Beijing from Liu et al., 2020a,Liu
et al., 2020b; data of the other cities from Luo et al., 2012).

mobility and availability in soils. Exchangeable and carbonate adsorbed

fractions are regarded as weakly bonded metals which may equilibrate
with aqueous phase and thus turn into more quickly bioavailable (Pardo
et al., 1990; Wang et al., 2019b), whereas the residual fraction of metals
was strongly bonded in mineral lattices and thus difficult to be moved.
The results of chemical sequential extraction revealed that more than
30% of Cd was associated with exchangeable and carbonate fractions,
Fig. 6. PCA result of the soils in the three-dimensional space.

6
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

environments (Bi et al., 2017). The contribution of Pb from nonferrous emissions, the contributions of which were 5.3–82.4% (mean: 39.7 ±
metal mining and smelting activities in Haikou may be neglected since 21.1%), 0–85.7% (mean: 25.5 ± 24.6%), and 1.9–64% (mean: 34.8 ±
no such industries were present in this city. The vehicle exhausts and 22.9%), respectively, according to the analysis of the ternary isotope
street dusts collected from Haikou had similar ranges of Pb isotope ratios mixing models. This result suggested that traffic emission is still the most
(Fig. 4a), which were comparable to the data from other cities in China important anthropogenic source of Pb in Haikou.
(Bi et al., 2017). We thus took their average value (206Pb/207Pb: 1.160 ±
0.007, 208Pb/206Pb: 2.109 ± 0.008) as the end member of the traffic Credit author statement
emission source in Haikou. The two fall dust samples collected near the
Haikou CFPP had isotope ratios (206Pb/207Pb: 1.162–1.171, Xiangyang Bi: Data curation, Writing - original draft, Supervision,
208
Pb/206Pb: 2.103–2.113) similar to those of the traffic emissions, but Writing- Reviewing and Editing. Mohai Zhang: Visualization, Investi­
different from those of coals in China (Fig. 4a). Furthermore, their Pb gation, Validation. Yunjie Wu: Visualization, Investigation. Guangyi
isotope compositions were also different from that of the soil Sun: Conceptualization, Methodology, Software, Data curation, Writing
(206Pb/207Pb: 1.183, 208Pb/206Pb: 2.099) collected near this CFPP. - original draft, Supervision, Writing- Reviewing and Editing. Lihai
Therefore, we speculate that these two fall dust samples may have been Shang: Visualization, Investigation. Zhonggen Li: Software, Validation.
contaminated by traffic emissions. Coals used in Haikou were imported Pengcong Wang: Visualization, Investigation.
from various coal mines within China. In addition, the environment of
Haikou might be impacted by coal emissions from surrounding cities.
Declaration of competing interest
Thus, we used the average ratio of Pb isotopes of China’s coals
(206Pb/207Pb: 1.180 ± 0.001, 208Pb/206Pb: 2.103 ± 0.002) to represent
The authors declare that they have no known competing financial
the end member of coal emission source in this study. The average value
interests or personal relationships that could have appeared to influence
of Pb isotopes of the natural background was calculated from uncon­
the work reported in this paper.
taminated natural soils, marine sands, and bedrocks, which was 1.205 ±
0.01 for 206Pb/207Pb and 2.066 ± 0.016 for 208Pb/206Pb, respectively. In
Acknowledgements
the graph of 206Pb/207Pb vs. 208Pb/206Pb, the data of the Haikou soils
were distributed approximately within a triangular area with natural
This work was supported by the National Key Research and Devel­
background, coal combustion and traffic emission as the three vertices
opment Program of China (No. 2018YFC1802701), the National Natural
(Fig. 4b). This implied that Pb in the soils was derived mainly from these
Science Foundation of China (No. 41773146) and China Postdoctoral
three sources. The soils from the street district (except one sample) had
Science Foundation (No. 2018M640939). The authors gratefully
Pb isotope ratios closer to the side of traffic emissions and natural
acknowledge the support of all the persons involved in the project.
background, compared with the other soil samples (Fig. 4b). This con­
firms the reliability of the Pb isotope tracing results.
References
According to the above discussion, the relative contribution (%) of
natural background (a), coal combustion (b) and traffic emission (c) to Amato, F., Pandolfi, M., Viana, M., Querol, X., Alastuey, A., Moreno, T., 2009. Spatial
the soil Pb can be calculated by a ternary mixing model as shown below: and chemical patterns of PM10 in road dust deposited in urban environment. Atmos.
( 206 ) ( ) ( ) Environ. 43, 1650–1659.
Pb/207 Pb sample = a ​ 206 Pb/207 Pb background + ​ b 206 Pb/207 Pb coal Bi, X.Y., Feng, X.B., Yang, Y.G., Li, X.D., Shin, G.P.Y., Li, F.L., Qiu, G.L., Li, G.H., Liu, T.Z.,
( 206 ) Fu, Z.Y., 2007. Heavy metals in an impacted wetland system: a typical case from
+ c Pb/207 Pb traffic (4) southwestern China. Sci. Total Environ. 387, 257–268.
Bi, X.Y., Feng, X.B., Yang, Y.G., Li, X.D., Shin, G.P.Y., Li, F.L., Qiu, G.L., Li, G.H., Liu, T.Z.,
( 208 ) ( ) ( ) Fu, Z.Y., 2009. Allocation and source attribution of lead and cadmium in maize (Zea
Pb/206 Pb sample = a ​ 208 Pb/206 Pb background + ​ b 208 Pb/206 Pb coal mays L.) impacted by smelting emissions. Environ. Pollut. 157, 834–839.
( 208 ) Bi, X.Y., Liang, S.Y., Li, X.D., 2013. A novel in situ method for sampling urban soil dust:
+ c Pb/206 Pb traffic (5)
particle size distribution, trace metal concentrations, and stable lead isotopes.
Environ. Pollut. 177, 48–57.
a+b + c = 1 (6) Bi, X.Y., Li, Z.G., Wang, S.X., Zhang, L., Xu, R., Liu, J.L., Yang, H.M., Guo, M.Z., 2017.
Lead isotopic compositions of selected coals, Pb/Zn ores and fuels in China and the
The calculated results showed that the contributions of Pb from application for source tracing. Environ. Sci. Technol. 51 (22), 13502–13508.
natural background, coal combustion and traffic emission sources were CEPA, 1995. Environmental Quality Standards for Soil (GB15618-1995). Chinese
Environmental Protection Administration.
5.3–82.4% (mean: 39.7 ± 21.1%), 0–85.7% (mean: 25.5 ± 24.6%), and CEPA, 2004. The Technical Specification for Soil Environmental Monitoring. Chinese
1.9–64% (mean: 34.8 ± 22.9%), respectively. This suggests that traffic Environmental Protection Administration.
emissions are still the most important anthropogenic source of Pb in Chen, J., Wei, F., Zheng, C., Wu, Y., Adriano, D.C., 1991. Background concentrations of
elements in soils of China. Water, Air. Soil Pollut 57–58 (1), 699–712.
Haikou. In contrast, in other cities of China, the contribution of traffic Chen, T., Zheng, Y., Lei, M., Huang, Z., Wu, H., Chen, H., Fan, K., Yu, K., Wu, X., Tian, Q.,
emission related Pb was reduced significantly due to the removed leaded 2005. Assessment of heavy metal pollution in surface soils of urban parks in Beijing,
gasoline as well as the increased emissions of Pb from coal combustions China. Chemosphere 60, 542–551.
Chen, X., Lu, X., 2018. Contamination characteristics and source apportionment of heavy
(Li et al., 2012; Bi et al., 2017). Overall, the relatively low contribution metals in topsoil from an area in Xi’an city, China. Ecotoxicol. Environ. Saf. 151,
of coal Pb in Haikou highlights the underdevelopment of industries in 153–160.
this city. Duzgoren-Aydin, N.S., Wong, C.S.C., Aydin, A., Song, Z., You, M., Li, X.D., 2006. Heavy
metal contamination and distribution in the urban environment of Guangzhou, SE
China. Environ. Geochem. Health 28, 375–391.
5. Conclusions Fu, Y., Chen, M., Bi, X., He, Y., Ren, L., Xiang, W., Qiao, S., Yan, S., Li, Z., Ma, Z., 2011.
Occurrence of arsenic in brown rice and its relationship to soil properties from
Hainan Island, China. Environ. Pollut. 159, 1757–1762.
The concentrations of heavy metals in urban soils of Haikou were Gong, M., Wu, L., Bi, X., Ren, L., Wang, L., Ma, Z., Bao, Z., Li, Z., 2010. Assessing heavy-
much lower than those of other big cities in China. In contrast, their metal contamination and sources by GIS-based approach and multivariate analysis of
chemical speciation showed similar characteristics. The significantly urban–rural topsoils in Wuhan, central China. Environ. Geochem. Health 32, 59–72.
Haikou Municipal Bureau Statistics (HMBS), 2019. Haikou Statistical Yearbook. China
high concentrations of Pb and As were found in the samples from the
Statistics Press.
street district and industrial areas, respectively. But significantly high Han, Q., Wang, M., Cao, J., Gui, C., Liu, Y., He, X., He, Y., Liu, Y., 2020. Health risk
concentrations of Cd, Cr, Cu, and Ni simultaneously occurred in those assessment and bioaccessibilities of heavy metals for children in soil and dust from
samples from the suburban district. The results of PCA and Pb isotope urban parks and schools of Jiaozuo, China. Ecotoxicol. Environ. Saf. 191, 110157.
Huang, R.J., Zhang, Y., Bozzetti, C., Ho, K.F., Cao, J.J., Han, Y., Daellenbach, K.R.,
composition suggested that heavy metals in the urban soils were mainly Slowik, J.G., Platt, S.M., Canonaco, F., Zotter, P., Wolf, R., Pieber, S.M., Bruns, E.A.,
derived from natural parent materials, coal combustion and traffic Crippa, M., Ciarelli, G., Piazzalunga, A., Schwikowski, M., Abbaszade, G., Schnelle-

7
X. Bi et al. Ecotoxicology and Environmental Safety 205 (2020) 111115

Kreis, J., Zimmermann, R., An, Z., Szidat, S., Baltensperger, U., Haddad, I.E., Men, C., Liu, R.M., Xu, L.B., Wang, Q.R., Guo, L.J., Miao, Y.X., Shen, Z.Y., 2020. Source-
Prevot, A.S.H., 2014. High secondary aerosol contribution to particulate pollution specific ecological risk analysis and critical source identification of heavy metals in
during haze events in China. Nature 514, 218–222. road dust in Beijing, China. J. Hazard Mater. 388, 121763.
Jia, Z.Y., Wang, J.X., Zhou, X.D., Zhou, Y.J., 2020. Identification of the sources and Pardo, R., Barrado, E., Perez, L., Vega, M., 1990. Determining and association of heavy
influencing factors of potentially toxic elements accumulation in the soil from a metals in sediments of the Pisucrga River. Water Res. 24, 373–379.
typical karst region in Guangxi, Southwest China. Environ. Pollut. 256, 113505. Ren, H., Wang, J., Zhang, X., 2006. Assessment of soil lead exposure in children in
Kelly, J., Thornton, I., Simpson, P.R., 1996. Urban Geochemistry: a study of the influence Shenyang, China. Environ. Pollut. 144, 327–335.
of anthropogenic activity on the heavy metal content of soils in traditionally Tessier, A., Campbell, P.G.C., Blsson, M., 1979. Sequential extraction procedure for the
industrial and non-industrial areas of Britain. Appl. Geochem. 11, 363–370. speciation of particulate trace metals. Anal. Chem. 51, 844–851.
Laidlaw, M.A.S., Mielke, H.W., Filippelli, G.M., Johnson, D.L., Gonzales, C.R., 2005. Tian, H., Cheng, K., Wang, Y., Zhao, D., Lu, L., Jia, W., Hao, J., 2012a. Temporal and
Seasonality and children’s blood lead levels: developing a predictive model using spatial variation characteristics of atmospheric emissions of Cd, Cr, and Pb from coal
climatic variables and blood lead data from Indianapolis, Indiana, Syracuse, New in China. Atmos. Environ. 50, 157–163.
York, and New Orleans, Louisiana (USA). Environ. Health Perspect. 113, 793–800. Tian, H., Zhao, D., Cheng, K., Lu, L., He, M., Hao, J., 2012b. Anthropogenic atmospheric
Laidlaw, M.A.S., Taylor, M.P., 2011. Potential for childhood lead poisoning in the inner emissions of antimony and its spatial distribution characteristics in China. Environ.
cities of Australia due to exposure to lead in soil dust. Environ. Pollut. 159, 1–9. Sci. Technol. 46, 3973–3980.
Lee, C.S., Li, X.D., Shi, W.Z., Cheung, S.C., Thornton, I., 2006. Metal contamination in Tian, H., Zhu, C., Gao, J., Cheng, K., Hao, J., Wang, K., Hua, S., Wang, Y., Zhou, J., 2015.
urban, suburban, and country park soils of Hong Kong: a study based on GIS and Quantitative assessment of atmospheric emissions of toxic heavy metals from
multivariate statistics. Sci. Total Environ. 356, 45–61. anthropogenic sources in China: historical trend, spatial distribution, uncertainties,
Li, H., Yu, S., Li, G., Deng, H., Luo, X., 2011. Contamination and source differentiation of and control policies. Atmos. Chem. Phys. 15, 10127–10147.
Pb in park soils along an urban-rural gradient in Shanghai. Environ. Pollut. 159, VROM, 2000. Circular on Target Values and Intervention Values for Soil Remediation
3536–3544. Annex A: Target Values, Soil Remediation Intervention Values and Indicative Levels
Li, J., Zhang, G., Gong, Z., 2014. Mobilization and redistribution of elements in soils for Serious Contamination. Dutch Ministry of Housing, Spatial Planning and
developed from extreme weathering basalt on Hainan Island. Chin. J. Geochem. 33, Environment (VROM).
262–271. Wang, A.T., Wang, Q., Li, J., Yuan, G.L., Albanese, S., Petrik, A., 2019b. Geo-statistical
Li, M., Gao, Z., Dong, C., Wu, M., Yan, J., Cao, J., Ma, W., Wang, J., Gong, Y., Xu, J., and multivariate analyses of potentially toxic elements’ distribution in the soil of
2020. Contemporary blood lead levels of children aged 0-84 months in China: a Hainan Island (China): a comparison between the topsoil and subsoil at a regional
national cross-sectional study. Environ. Int. 134, 105288. scale. J. Geochem. Explor. 197, 48–59.
Li, Q., Cheng, H., Zhou, T., Lin, C., Guo, S., 2012. The estimated atmospheric lead Wang, J., Zhou, Y., Don, X., Yin, M., Tsang, D., Sun, J., Liu, J., Song, G., Liu, Y., 2020a.
emissions in China, 1990-2009. Atmos. Environ. 60, 1–8. Temporal sedimentary record of thallium pollution in an urban lake: an emerging
Li, X.D., Poon, C.S., Liu, P.S., 2001. Heavy metal contamination of urban soils and street thallium pollution source from copper metallurgy. Chemosphere 242, 125172.
dusts in Hong Kong. Appl. Geochem. 216, 1361–1368. Wang, L., Chang, J., Zheng, X., Liu, J., Yu, M., Liu, L., Yang, Y., Zhang, H., 2018. Survey
Liang, S., Cui, J., Bi, X., Luo, X., Li, X., 2019. Deciphering source contribution of trace of ecological environmental conditions and influential factors for public parks in
metal contamination in urban soil, road dust, and foliar dust of Guangzhou, southern Shanghai. Chemosphere 190, 9–16.
China. Sci. Total Environ. 695, 133596. Wang, P., Li, Z., Liu, J., Bi, X., Ning, Y., Yang, S., Yang, X., 2019a. Apportionment of
Liu, L., Liu, Q., Ma, J., Wu, H., Qu, Y., Gong, Y., Yang, S., An, Y., Zhou, Y., 2020b. Heavy sources of heavy metals to agricultural soils using isotope fingerprints and
metal(loid)s in the topsoil urban parks in Beijing, China: concentrations, potential multivariate statistical analyses. Environ. Pollut. 249, 208–216.
sources, and risk assessment. Environ. Pollut. 260, 114083. Wang, Y., Duan, X., Wang, L., 2020b. Spatial distribution and source analysis of heavy
Liu, J., Luo, X., Sun, Y., Tsang, D., Qi, J., Zhang, W., Li, N., Yin, M., Wang, J., Lippold, H., metals in soils influenced by industrial enterprise distribution: case study in Jiangsu
Chen, Y., Sheng, G., 2019b. Thallium pollution in China and removal technologies province. Sci. Total Environ. 710, 134953.
for waters: a review. Environ. Int. 126, 771–790. Wei, B., Yang, L., 2010. A review of heavy metal contaminations in urban soils, urban
Liu, J., Rem, S., Zhou, Y., Tsang, D., Lippoid, H., Wang, J., Yin, M., Xiao, T., Luo, X., road dusts and agricultural soils from China. Microchem. J. 94, 99–107.
Chen, Y., 2019a. High contamination risks of thallium and associated metal(loid)s in Yamamoto, N., Takahashi, Y., Yoshinaga, J., Tanaka, A., Shibata, Y., 2006. Size
fluvial sediments from a steel-making area and implications for environmental distributions of soil particles adhered to children’s hands. Arch. Environ. Contam.
management. J. Environ. Manag. 250, 109513. Toxicol. 51, 157–163.
Liu, J, Ren, S, Cao, J, Tsang, D, Beiyuan, J, Peng, Y, Fang, F, She, J, Yin, M, Shen, N, Yang, T., Liu, Q., Chan, L., Cao, G., 2007. Magnetic investigation of heavy metals
Wang, J, 2021. Highly efficient removal of thallium in wastewater by MnFe2O4- contamination in urban topsoils around the East Lake, Wuhan, China. Geophys. J.
biochar composite. J. Hazard. Mater. 401, 123311. Int. 171, 603–612.
Liu, J., Yin, M., Xiao, T., Zhang, C., Tsang, D., Bao, Z., Zhou, Y., Chen, Y., Luo, X., Yang, Z., Lu, W., Long, Y., Bao, X., Yang, Q., 2011. Assessment of heavy metals
Yuan, W., Wang, J., 2020a. Thallium isotopic fractionation in industrial process of contamination in urban topsoil from Changchun city, China. J. Geochem. Explor.
pyrite smelting and environmental implications. J. Hazard Mater. 384, 121378. 108, 27–38.
Ljung, K., Selinus, O., Otabbong, E., Berglund, M., 2006. Metal and arsenic distribution in Zhu, Z.M., Sun, G.Y., Bi, X.Y., Li, Z.G., Yu, G.H., 2013a. Identification of trace metal
soil particle sizes relevant to soil ingestion by children. Appl. Geochem. 21, pollution in urban dust from kindergartens using magnetic, geochemical and lead
1613–1624. isotope analyses. Atmos. Environ. 77, 9–15.
Lu, Y., Zhu, F., Chen, J., Gan, H.H., Guo, Y.B., 2007. Chemical fractionation of heavy Yu, Y, Li, Y, Shen, Z, Stenstrom, M.K., 2016. Metal enrichment and lead isotope analysis
metals in urban soils of Guangzhou, China. Environ. Monit. Assess. 134, 429–439. for source apportionment in the urban dust and rural surface soil. Environ. Pollut.
Luo, X.S., Yu, S., Zhu, Y.G., Li, X.D., 2012. Trace metal contamination in urban soils of 216, 764–772.
China. Sci. Total Environ. 421–422, 17–30. Zhu, Z.M., Li, Z.G., Bi, X.Y., Han, Z.X., Yu, G.H., 2013b. Response of magnetic properties
Manta, D.S., Angelone, M., Bellanca, A., Neri, R., Sprovieri, M., 2002. Heavy metals in to heavy metal pollution in dust from three industrial cities in China. J. Hazard
urban soils: a case study from the city of Palermo (Sicily). Italy. Sci. Total Environ. Mater. 246–247, 189–198.
300, 229–243.