Ecotoxicology and Environmental Safety 191 (2020) 110157

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Ecotoxicology and Environmental Safety

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Health risk assessment and bioaccessibilities of heavy metals for children in T

soil and dust from urban parks and schools of Jiaozuo, China
Qiao Han1, Mingshi Wang∗,2, Jingli Cao3, Chenlu Gui3, Yanping Liu3, Xiangdong He1,
Yuchuan He3, Yang Liu1
College of Resource and Environment, Henan Polytechnic University, Jiaozuo, Henan, 454003, China

ARTICLE INFO ABSTRACT

Keywords: Urban parks and schools sever as the mainly activity areas for children, but risk assessment posed by heavy
Heavy metals metals (HMs) from soil and dust in these area has rarely been investigated. In this study, six urban parks and
Soil and dust seven schools in Jiaozuo, China, were taken as research objects to understand the contamination level and
Bioaccessibility bioaccessibility of HMs from soil and dust in urban parks and schools. The results indicated that Zn, Cu, Pb, Cd,
Risk assessment
As, Ni and Co from soil and dust were above the background values, especially Zn and Cd in dust, and As and Cd
Children
Jiaozuo
in soil. Serious Cd pollution was discovered, and respective Cd concentrations in soil and dust were 17.83 and
China 7.52 times the background value. Additionally, the average concentration and bioaccessibility of Zn, Mn, Pb, Cd,
Cr, Ni and Co in dust were both higher than in soil. High concentration and high bioaccessibility of HMs in dust
suggested that HMs contamination were serious and universal in Jiaozuo. The concentrations of most HMs were
higher in the gastric phase, except for Cu and Cd which remained higher in the intestinal phase. Both in the
gastric phase and intestinal phase, Mn, As and Cd in soil and dust both have high bioaccessibility which all
exceed 10%. The carcinogenic and non-carcinogenic risks base on the total HMs for children (soil: 7.93, 1.96E-
05; dust: 6.44, 3.58E-05) were greater than those for adults (soil: 6.35E-01, 1.32E-05; dust: 5.06E-01, 2.42E-05),
and urban parks and schools posed high potential risk for children. Therefore, assessment the risk posed by HMs
contamination of soil and dust in urban parks and schools is vital and urgent for children.

1. Introduction 2016). HMs are persistent, bio-accumulation and bio-magnification in

High-intensity industrialization and urbanisation were the key fac-
tors and integral parts of the economic growth (Jan et al., 2010; Antoci
et al., 2018), but numerous heavy metals (HMs) have entered si-
multaneously the urban environment (Yang et al., 2017; Zhang et al.,
2018a, 2018b; Yadav et al., 2019). Due to their non-degradable, urban
soil and dust serve gradually as the critical sinks and sources of HMs
contaminants in the urban ecosystem (Lu et al., 2010; Gu et al., 2016).
It is known that HMs, accumulated in urban soil and dust, are harmful
for human health through several pathways including ingestion, in-
halation, dermal contact and inadvertent ingestion (Bi et al., 2013; Liao
and Zhang, 2016; Han et al., 2016).
Additionally, HMs, such as Cd, Hg or Pb, can be acute or severely
detrimental to human health and the environment even at low con-
centrations (Duruibe et al., 2007; Li et al., 2013a; Noli and Tsamos,
the body tissues, and remains unclear for homeostasis mechanism of
them (Pandey et al., 2003; Han et al., 2016). Any high levels of HMs in
soil and dust entering the body tissues will threaten human health and
result in severe health risks, such as reduced intelligence for Children,
damaging central nervous system and immune systems, affecting in-
ternal organs etc. (Christoforidis and Stamatis, 2009; Chen et al., 2015;
Eqani et al., 2016). HMs in urban soil and dust are therefore an im-
portant indicator of environmental quality in the risk assessment of
contaminated sites (Nriagu and Pacyna, 1988; Li et al., 2013c).
In the last few decades, investigations concerning the urban soil and
dust contamination with HMs were numerous and mainly carried out in
the area close to industrial areas, urban street and road (Panagopoulos
et al., 2015; Lu et al., 2017; Alsbou and Al Khashman, 2018; Zhang
et al., 2019). Although many measures, such as banning leaded gasoline
and cleaner production, has been taken, HMs contamination was still

∗
Corresponding author. Henan Polytechnic University, Henan, China.
E-mail address: mingshiwang@hpu.edu.cn (M. Wang).
1
Address: Building 3, Lanyuan, Student Apartment, Henan Polytechnic University, Jiaozuo, Henan, China.
2
Address: Building 14, Jingyuan, Teachers Apartment, Henan Polytechnic University, Jiaozuo, Henan, China.
3
Address: Building 2, Lanyuan, Student Apartment, Henan Polytechnic University, Jiaozuo, Henan, China.

https://doi.org/10.1016/j.ecoenv.2019.110157
Received 26 August 2019; Received in revised form 30 December 2019; Accepted 31 December 2019
0147-6513/ © 2020 Elsevier Inc. All rights reserved.
Q. Han, et al.
very serious in street soil and dust, and HMs in dust posed more risks for
human health than that in urban soil (Christoforidis and Stamatis,
2009; Dehghani et al., 2017; Yadav et al., 2019; Maeaba et al., 2019;
Khademi et al., 2019). Additionally, due to the behavior of repetitive
hand/finger sucking, children are more likely to ingest significant
quantities of soil and dust than adults (Bargagli, 1998). However, urban
parks and schools, as the mainly activity areas for children, may re-
present a more probable exposure source than the above area because
residents mainly dwell in high-rise buildings in China (Jin et al., 2019).
Data concerning the conditions of soils and dusts contaminated by HMs
in urban parks and schools is limited. Therefore, it is vital and urgent
for children to assess the risk posed by the contamination of soils and
dusts HMs in urban parks and schools.
At the same time, due to that HMs entering the human body cannot
be absorbed completely (Mingot et al., 2011; Luo et al., 2012; Hong
et al., 2016), in vitro bioaccessibility of HMs were taken into con-
sideration as well as the concentration of HMs. In recent years, several
in vitro digestion models, especially the physiologically-based extrac-
tion test (PBET), have been widely applied to evaluate the harm caused
by HMs to human health (Sialelli et al., 2010; Zhuang et al., 2016; Gu
and Gao, 2018; Li et al., 2018). Moreover, because of high in the ab-
sorption rate of HMs from digestion system and hemoglobin sensitivity
to HMs for children (Chisolm and O'Hara, 1982), risk assessment results
based on the bioaccessibility of HMs would be more comparable and
accurate.
This study area was located in the region of Jiaozuo (Henan
Province, China) which has boomed through coal mining and utiliza-
tion (Wang et al., 2018a). Six urban parks and severe schools were
selected as the research object in this paper. According to the Chinese
urban statistical yearly report (2018), the total population of children
(0–14 years) in Jiaozuo is approximately 243,900. The main objectives
of the present study were to determine total concentrations of HMs in
the surface soil and dust of urban parks and schools, discriminate the
anthropogenic sources of highly concentrated HMs in the surface soil
and dust, explore the bioavailability of HMs and to assess health risk of
HMs for children and adults via different exposure pathways. The re-
sults of this work can supply a more accurate assessment of the en-
vironmental quality in urban parks and schools on children and are
helpful for pollution control and urban planning.
2. Materials and methods
2.1. Study area
Jiaozuo (35°10′-35°21′N, 113°4′-113°26′E), as it is shown in Fig. 1,
is located at the northwest of Henan Province, and the south of the
Yellow River. The climate of the study area is warm temperate con-
tinental monsoon with average temperatures between 12.8 and 14.9 °C,
annual precipitation of 603.5 mm, frost-free period of 231days, and
average relative humidity of 62% (Wang et al., 2018b). The prevailing
wind directions reveal northeastern and southwestern fluctuations
(Wang et al., 2019), and the average wind speed 2.9 m/s. Jiaozuo
covers an area of 424,000 square kilometers, including Jiefang district,
Zhongzhan district, Macun district and Shanyang district (Li et al.,
2014). Several industrial enterprises of different sizes are located in
Jiaozuo, among which, WanFang Aluminium Plant and WanFang
Power Plant were around urban area. Aeolus Tire Company, China
Resources Power Plant, Shanxi Cooking Coal Power Plant, Gaoxin
Thermal Power Plant and Power Plant existed in the urban area.
2.2. Sampling and sample preparation
A total of 41 soil samples and 41 dust samples were collected from
seven schools and six parks in December 2016 in Jiaozuo, Henan
Province in this work (Fig. 1). During this period, precipitation was
relatively scarce and heating has been started in Jiaozuo. In sampling
2
Ecotoxicology and Environmental Safety 191 (2020) 110157
area, most regions, except for the concrete structure, are covered by
vegetation basically. Dust samples were collected mainly from the
edges around the flower beds, followed by windowsills and staircases,
and the structures were near the soil samples. The edges are about
0.3–0.8 m above the ground, 20–40 cm wide, and the windowsills and
staircases are about 1–1.5 m above the ground, and 10–30 cm wide.
The number of top-soil (0–10 cm depth) and dust samples collected
for each park or school were determined according to their area. Each
soil sample was a composite of five sub-samples taken from an area of
1 m2. Each dust sample was carefully collected by brush and dustpan at
least five days after raining incidents so that enough dust was de-
posited, and sampling tools were cleaned between sampling sites to
avoid cross contamination.
Before the experiment, extraneous materials, such as rhizomes, hair,
sand and gravel, were removed from samples. Then all samples were
dried in an oven at 40 °C until constant weight. Soil samples and dust
samples were sieved through 200 μm mesh nylon sieves, in which the
soil sample was grounded firstly with an agate pestle and mortar.
Finally, samples were put into self-sealing polyethylene bags, labeled
and taken to the laboratory.
2.3. Physiologically-based extraction test (PBET) analysis
PBET analytical methods were modified from previously described
studies (Ruby et al., 1996; Intawongse and Dean, 2006). PBET was
widely used to estimate uptake and oral HMs Bioaccessibility in gastric
and intestinal physiological compartment (Gu and Gao, 2018).
The simulated gastric juice contained 2.5 g pepsin (Shanghai
Yuanye Bio-Technology Co.), 1.0 g citric acid (Tianjin Hongyan
Chemical Reagent Factory), 1.0 g malic acid (Shanghai Yuanye Bio-
Technology Co.), 0.84 mL lactic acid (Shanghai Yuanye Bio-Technology
Co.), 1 ml glacial acetic acid (Guangdong Xilong Science Co.), and
0.15 mol L−1 NaCl (Tianjin Kemiou Chemical Reagent Co.). pH was
adjusted consistently to 1.5 with concentrated HCl (Zhengzhou Paini
Chemical Reagent Factory). The simulated gastric juice was poured into
the cone bottles containing 2 g samples, and each 200 mL was put into
the constant temperature concussion box. Argon was injected into the
simulated liquid at 1 L/min. After shaking at 100 r·min−1 in a ther-
mostatic bath (maintained at 37 °C) for 1 h, the supernatant 30 mL was
extracted and filtered through a 0.45 μm filter disk for analysis. In the
intestinal stage, saturated NaHCO3 (Tianjin Hongyan Chemical Reagent
Factory) solution was added until the pH of the solution was 8. Then,
0.12 g trypsin (Shanghai Yuanye Bio-Technology Co.) and 0.4 g bile salt
(Shanghai Yuanye Bio-Technology Co.) were added into the constant
temperature concussion box, for 4 h in the same condition. The su-
pernatant 30 mL was then collected and filtered. Gastric and intestinal
extracts were stored at 4 °C in the refrigerator for analysis.
Bioaccessibility in the gastric or intestinal stages could be calculated
in the following form (Ai et al., 2018; Tang et al., 2004).
Ci Vi
BA = × 100%
Cs ms
where BA is the Bioaccessibility of HMs in soil (%); Ci is the soluble
state content (mg·L−1) of HMs in the reaction phase of PBET experi-
ment; Vi (L) is the reaction liquid in each reactor; Cs (mg/kg) is the total
amount of HMs in samples; ms (kg) is the mass of the sample.
2.4. Sample analysis and quality control
For soil sample and dust sample, electro-thermal plate digestion and
inductively coupled plasma mass spectroscopy (ICP-MS, PE NEXION
300) was used for the determination of HMs with the analysis details as
described in Wang et al. (2019). Reagent blanks and parallel samples
were carried out throughout the analysis to correct the analytical re-
sults. National standard soil samples (GBW07401, Geophysical Stan-
dard Reference Sample Soil) were used and the deviation between the
Q. Han, et al. Ecotoxicology and Environmental Safety 191 (2020) 110157

Fig. 1. Sampling points and map of the study area in Jiaozuo, Henan province, China.

measured and standard values was kept to < 15% for quality control. c × CF × EF IRgadult EDadult IRchild EDchild
CDIing = × +
AT BWadult BWchild (4)
2.5. Data analysis
c × EF × FSPO × CF × PLAF × PM10
CDIinh =
Processing of the data were carried out by SPSS (IBM, USA). AT
Correlation analysis and principal component analysis (PCA) have been IRhadult EDadult IRhchild EDchild
× +
widely used in the study of HMs in dust and soil by domestic and for- BWadult BWchild (5)
eign scholars (Borůvka et al., 2005; Wang et al., 2015; Zhang et al.,
c × CF × EF × AF × ABS
2018a; Peng et al., 2019). High correlations between specific HMs in CDIderm =
AT
sediments may reflect similar levels of contamination and/or release
SAadult EDadult SAchild EDchild
from the same sources of pollution (Håkanson and Jansson, 1983; Li × +
et al., 2009a). Combined with other information, PCA was conducted BWadult BWchild (6)
with quartimax rotation to identify latent factors (Hou et al., 2014). The potential carcinogenic (CRs) and non-carcinogenic risks (NCRs;
Hazard Quotient, HQ) for metals were estimated using the following
2.6. Human health risk model based on total heavy metals equations (USEPA, 2007; Gu et al., 2016):

Total carcinogenic risk (TCR) = CR = CDI · SF (7)

Human health risk model could quantify the daily metal intake from
contaminated soil and dust, carcinogenic risk (CRs) and non-carcino-
genic risk (NCRs; hazard quotients; HQ) for both children and adults.
CRs and HQ were determined using the cancer slope factor (SF) and
reference dose (RfD) values from US EPA, respectively (Gu and Gao,
2018). In this study, Zn, Cu, Mn, As, Pb, Cd, Cr, Ni and Co exerted
chronic NCRs on human, and some of them (As, Cd, Co, Cr, Ni) also had
CRs. For the exposure assessment model, contamination could occur via
three main pathways: (a) direct oral ingestion of substrate particles
(CDIing), (b) inhalation of suspended particles through the mouth and
nose (CDIinh) and (c) dermal adsorption of trace elements in particles
adhered to exposed skin (CDIderm) (Miguel et al., 2007; Na et al., 2010).
Based on the exposure factors handbook, chemical daily intake (CDI,
mg kg−1day−1) of metals through each of the path from soil and dust
ware calculated using the following equations (1)–(6).
For adults:
c×IRg × CF × EF×ED
CDIing = determined (Table 1), including minimum, maximum, median, mean,
BW × AT
c×CF × SA × AF × ABS × EF × ED
CDIderm =
BW × AT
c × IRh × CF × EF × ED × FSPO × PLAF × PM10
CDIinh =
BW × AT
For child:
1
Hazard index (HI ) = HQ = CDI ·RfD (8)
When HQ < 1 or HI < 1, no adverse health effects are observed,
and the NCR is within the acceptable range. When HQ > 1 or HI > 1,
NCR exists in the region. When CR < 10−6, no cancer risk exists.
When 10−6 < CR < 10−4, the risk is within the acceptable range.
When CRN > 10−4, human tolerance is exceeded. All HMs risk re-
ference SFs and RfDs used in the models are presented in Appendix
(Table S1) (USEPA, 1991; USEPA, 2007; USEPA, 2008; USEPA, 2011).
3. Results and discussion
3.1. Total metal concentration
The concentration of HMs (Zn, Cu, Mn, As, Pb, Cd, Cr, Ni and Co) in
37 soil and 40 dust samples from the urban parks and schools were
(1)
standard deviation, kurtosis, skewness, coefficient of variation (CV),
and background values. All HMs (except Mn and Cr) from dust and soil
(2) were above the background values. Among the HMs surveyed, dust Zn
and Cd concentrations exceeded the background value by 6.05 and
17.83 times respectively; Soil As and Cd concentrations exceeded the
(3)
background value by 5.29, 7.52 times respectively. The concentrations
of Zn, Cu, Pb, Cd, Cr, Ni and Co from dust were higher than that from

3
Q. Han, et al. Ecotoxicology and Environmental Safety 191 (2020) 110157

Table 1
Concentrations of heavy metals (mg/kg) in surface soil and dust.
Element Sample type Minimum Maximum Median Mean ± SD Kurtosis Skewness C.V. (%) Background valuea

Zn Soil 28.24 365.00 84.00 99.51 ± 65.01 2.63 8.23 64 61.9

dust 16.84 1717.26 303.34 374.30 ± 324.90 2.49 7.49 86
Cu Soil 12.00 38.00 20.19 20.88 ± 5.19 0.99 1.90 24 19.9
dust 3.36 82.88 52.59 49.85 ± 20.92 −0.35 −0.71 41
Mn Soil 238.22 1302.81 485.20 487.57 ± 182.86 2.39 10.16 37 570
dust 285.63 891.79 441.11 473.77 ± 159.92 0.89 0.07 33
As Soil 17.61 258.47 40.92 57.68 ± 46.92 2.79 9.02 80 10.9
dust 15.51 36.57 21.67 23.08 ± 4.50 0.86 0.86 19
Pb Soil 7.13 104.70 30.83 30.87 ± 18.30 1.97 6.51 58 25.4
dust 12.89 203.97 29.70 55.26 ± 48.46 1.28 0.97 87
Cd Soil 0.12 2.35 0.37 0.53 ± 0.44 2.59 8.04 82 0.07
dust 0.39 6.66 0.87 1.25 ± 1.11 3.35 14.44 88
Cr Soil 12.51 113.62 60.40 58.53 ± 27.18 0.05 −0.94 46 65.7
dust 41.66 551.61 98.71 112.07 ± 82.99 3.94 20.46 73
Ni Soil 26.13 62.28 35.63 35.79 ± 7.54 1.21 2.68 21 30
dust 32.03 191.23 44.56 51.70 ± 25.80 4.29 22.51 49
Co Soil 10.41 39.99 15.32 17.88 ± 7.61 1.54 1.50 42 10.8
dust 3.58 107.54 15.45 25.27 ± 22.04 1.74 3.50 86

a
The background values of the heavy metals in the table are selected from the background values of soil in Henan Province; SD: standard deviation.

soil, especially Zn and Cd, which indicated that the degree of dust
contamination was greater than that of soil in terms of HMs con-
centration. According to our analysis, As concentrations in soil and dust
generally decreased from southwest to northeast (Table 1), consistent
with the prevailing wind directions in Jiaozuo and in agreement with
Mingshi Wang and T.J. Keegan's study results (Keegan et al., 2006;
Wang et al., 2019). As is a proven human carcinogen and could po-
tentially damage ecological communities (Sadiq et al., 2003). Coal-fired
power plants were the main pollutant (Meng et al., 2016; Huang et al.,
2017), which was in keeping with the fact that the variance of As in
dust was much smaller than that in soil.
The coefficient of variation (CV) reflects the average variation of
HM concentrations, with CV > 35% reflecting high variation,
15% < CV < 35% reflecting moderate variation and CV ≤ 15%
reflecting low variation. Table 1 showed that the CVs of Zn, Pb, Cd, Cr
and Co in dust and soil samples all show a high level of spatial variation
(CV > 35%) and a relatively no-uniform spatial distribution, which
reveals that the concentration of HMs is obviously disturbed by human
activities (Wang et al., 2019). Additionally, the CVs of HMs (expect Mn
and Zn), in dust samples were higher than that in soil samples. This
result suggests that considerable variability exists in the HMs data, and
that the spatial distribution of HMs in this area is not homogeneous (Xu
et al., 2014). Besides the high concentrations and high CVs, the Kurtosis
and Skewness of Zn and Cd from dust and soil samples were still rela-
tively high, which might been caused by distinct anthropogenic sources
(Jin et al., 2019).
3.2. Sources of heavy metals
3.2.1. Correlation analysis
Table 2 shows the results of the Pearson correlation analysis. It is
obvious that the correlations between the metals in soil are stronger
than that in dust (Table 2). For soil HMs, significant correlations
(p < 0.05) were found between Zn, Pb, Ni and Cd, between Mn, Pb, Cr
and Ni, and between Pb, Cd, Cr and Ni. Strong correlations between the
concentrations of elements in samples might reflect that the elements
have similar contamination levels and they may originate from
common sources (Wang et al., 2016). Zn, Mn, Pb, Cr and Ni in soil were
grouped together, thus indicating that the anthropogenic sources of
these HMs are closely related in the sediments of the study area
(Facchinelli et al., 2001; Ali et al., 2016). On the other hand, correla-
tions among the HMs in dust were generally weaker than that in soil,
which was in agreement with Jin's study results (Jin et al., 2019). That
suggested that the dust HMs were more likely to have been influenced
by anthropogenic and anthropogenic pollution. The correlations among
Cr, Zn and Mn are statistically significant (**p < 0.01), which sug-
gested that they might share a common source, such as traffic emission,
parts and tyre wear (Wang et al., 2007). As, Cu and Co did not show
significant correlations with other metals in soil or dust (Table 2),
which indicated that the pollution sources of As, Co and Cu differ from
those of the other metals (Wang et al., 2019).
3.2.2. Principal component analysis (PCA)
Soil and dust data are conducted firstly by KMO and Bartlett tests
because these tests (KMO > 0.05; Sig < 0.05) can indicate whether
PCA is useful for dimensionality reduction (Wang et al., 2015). The
KMO of sampling adequacy for the above variables were 0.68 and 0.53,
and Bartlett tests meet the requirements, which suggested that there are
compact correlations and the PCA should yield distinct and reliable
factors (Field, 2009). The PCA factor loadings (varimax rotation mode)
are presented in Table 3.
For HMs in soil, three principal components accounted 74.62% of
the variance. As, Pb, Cd, and Ni had relatively high first component
(PC1a) values, which result was consistent with the results of Pearson's
correlation analysis (Table 2) and indicated that the sources of these
elements were attributed to anthropogenic pollution. Zn and Pb pol-
lutants in soil originated particularly from leaded gasoline, wear of
parts and tyre, and other traffic pollution (Zhang, 2006). On PC2a,
which explained 20.3% of the total variance, Co and Cu showed posi-
tive loadings of 65.0% and 34.7% respectively. PC3a explained 11.83%
of the total variance, and the loadings of Mn, As and Cr were 60.3%,
88.3% and 38.0%, respectively. The distribution of As was greatly af-
fected by coal-fired power plants (Keegan et al., 2006) and smelting
(Duan and Tan, 2013).
For HMs in dust, there are also three principal components ac-
counting 61.96% of the variance, with the first, second, and third
components explaining 32.18%, 16.16%, and 12.99%, respectively. On
PC1b, As and Ni showed strongly positive loadings of 41.4% and 44.3%,
respectively; On PC2b, Zn, Mn and Cr showed strongly positive loadings
of 65.4%, 55.0% and 66.9%; On PC3b, Cu, Pb, and Cd showed strongly
positive loadings of 45.5%, 72.0% and 81.2%, respectively. Three
principal components suggested that the pollution sources of the dust
are composite sources, including transportation, coal-firing, mining,
industry and paint (Chen et al., 1997; Zhang et al., 1998; Xu et al.,
2001; Liu et al., 2006; Li et al., 2009b). Additionally, whether on PC2a
or PC3b, Co all showed weak or negative loadings with other HMs. It
furtherly suggested that the pollution sources of Co differ from those of
the other metals and could be the chemical plant and electroplating

4
Q. Han, et al. Ecotoxicology and Environmental Safety 191 (2020) 110157

Table 2
Results of correlation analysis of heavy metal concentrations in soil and dust, Jiaozuo.
Type Zn Cu Mn As Pb Cd Cr Ni Co

Soil Zn 1
Cu 0.378* 1
Mn 0.093 −0.12 1
As −0.034 0.033 0.339* 1
Pb 0.664** −0.016 0.421** 0.091 1
Cd 0.482** 0.19 0.183 −0.023 0.761** 1
Cr 0.19 −0.283 0.697** 0.198 0.628** 0.347* 1
Ni 0.548** 0.22 0.535** 0.101 0.772** 0.645** 0.609** 1
Co −0.224 0.274 −0.272 −0.324 −0.456 −0.137 −0.406 −0.212 1
Dust Zn 1
Cu −0.219 1
Mn 0.256 −0.525** 1
As 0.141 −0.354* 0.334* 1
Pb −0.038 0.312* −0.237 −0.114 1
Cd 0.076 0.391* 0.051 −0.215 0.446** 1
Cr 0.450** −0.336* 0.578** 0.239 −0.228 −0.097 1
Ni 0.04 −0.353* 0.195 0.326* −0.021 0.066 0.164 1
Co −0.06 0.311 −0.313* −0.334* 0.179 0.03 −0.251 −0.146 1

*p < 0.05; **p < 0.01; coefficients (**) are in bold.

Table 3 results (Andrew and Ip, 2007; Li, 2013d). PH in gastric stage was lower
Principal components (PC) of dust and soil samples. than that in intestinal stage, which could increase the activity of en-
Element Soil Dust
zymes. HMs could be more likely to release in the condition of acidic,
which leaded to the high bioaccessibility in the gastric stage. However,
PC1a PC2a PC3a PC1b PC2b PC3b after entering the intestinal stage, HMs were easily precipitated, and
absorbed, so that HMs would be fixed and passivate again (Aurélie
Zn 0.405 0.181 0.011 −0.033 0.654 0.075
Cu 0.154 0.650 0.105 −0.337 −0.264 0.425
et al., 2011; Zheng et al., 2013). Due to the complexation with digestive
Mn 0.162 −0.299 0.603 0.260 0.550 −0.091 enzymes (pepsin, bile salt and pancreatin), the bioaccessibility of Cu in
As −0.051 0.062 0.883 0.414 0.086 −0.142 gastric phase could be less than that in corresponding intestinal phase
Pb 0.458 −0.220 0.151 −0.033 −0.142 0.720 (Williams et al., 1998; Sialelli et al., 2010; Luo et al., 2012).
Cd 0.428 −0.015 −0.056 −0.031 0.106 0.812
All HMs in the gastric phase and intestinal phase of dust samples
Cr 0.251 −0.468 0.380 0.120 0.669 −0.142
Ni 0.435 −0.067 0.257 0.443 −0.032 0.161 were higher bioaccessibility than that in soil samples. For example, the
Co −0.115 0.347 −0.403 −0.323 −0.147 0.103 average bioaccessibility of Zn, Pb, Cr, Ni and Co in the dust samples was
Eigenvalue 3.824 1.827 1.064 2.953 1.455 1.169 about 3.2, 1.8, 1.9, 1.9 and 2.6 times that in soil samples in gastric
Cumulative of 42.49 62.79 74.62 32.81 48.97 61.96 phase and 2.6, 14.9, 2.7, 2.3 and 4.1 times that in soil sample in in-
variation (%)
testinal phase. High concentrations and high bioaccessibilities of HMs
in dust suggested the universal and serious pollution of these HMs in
industry (Suh et al., 2019). Jiaozuo. Additionally, with low concentration, some HMs (Mn, Pb, Zn
and Ni) had high bioaccessibility (Tables 1 and 4), which indicated that
bioaccessibility might be related to the metal speciation and soil
3.3. Bioaccessibility of heavy metails in soil and dust
characteristics such as conductivity, pH, texture and organic matter
content may influence metal bioavailability (Wu et al., 2015; Zhao,
Percent bioaccessibilities (gastric and intestinal phases) of Zn, Cu,
2018; Xing et al., 2019). It suggested that bioaccessibilities of HMs
Mn, As, Pb, Cd, Cr, Ni and Co are presented in Fig. 2. Both bioaccessible
based on the PBET was closer to the actual harm of HMs than other
and residual concentrations of HMs in the soil and dust are summarized
method based on the concentration of HMs.
in Table 4. The difference between the bioaccessible concentrations of
HMs in soil and dust samples was much less than the total concentra-
tions (Tables 1 and 4), which indicated that the total amount of HMs 3.4. Health risk assessment of heavy metals based on total heavy metals
had no significant effect on its bioaccessibility. For soil samples,
average of metal bioaccessibilities were as follows: Mn > Pb > Cd > Results of NCR and CR human health risk assessment for children
As > Zn > Ni > Cu > Co > Cr for gastric phase and Cd > and adults of HMs from the soil and dust through possible exposure
Mn > As > Cu > Zn > Ni > Co > Cr > Pb for intestinal phase. pathways (ingestion, inhalation, and dermal contact) were shown in
For dust samples, the average of metal bioaccessibilities were as fol- Table 5. For NCR effects of soil and dust, As, Cr and Mn posed the
lows: Zn > Mn > Pb > As > Cd > Ni > Cu > Co > Cr for greatest NCR to adults and children, followed by Pb and Co, and then
gastric phase and Pb > Cd > Mn > As > Zn > Ni > Cu > Co > Ni, Cd, Zn and Cu. The HQ values of all HMs from soil and dust for
Cr for intestinal phase (Table 4). The elements (Zn, Mn, As and Cd) adults were lower than 1, indicating that the NCRs of HMs in urban
showed higher bioaccessibility than other metals, and Zn demonstrated parks and schools of Jiazouo were acceptable. However, the NCRs of
the highest bioaccessibility (36.77%) in the gastric phase of dust sam- Mn, As (soil and dust) and Cr (dust) for children exceeded the threshold
ples. Cr demonstrated the lowest bioaccessibility (2.87%) in the in- of 1, which suggested that these HMs posed NCR heath risk to children,
testinal phase of soil samples. In gastric and intestinal phase, Cr was especially As in soil (3.83) and dust (1.53). Thought the concentration
mainly in the form of residue and not easily digested by human gas- of Cd and Zn were above the background values, the NCR and CR of
trointestinal fluid (Li et al., 2013b; Piggio et al., 2009). them for adults and children were under the safety threshold. For the
For soil and dust samples, the bioaccessibility of Zn, Mn, As, Ni and CR effects of soil and dust, the order of CR of HMs for both children and
Co (except for Cu) in the gastric stage were higher than that in the adults were Cr > Co > As > Ni > Cd in soil, while in dust were
intestinal stage, which was in agreement with Li yi and Andraw's study Cr > Co > Ni > As > Cd (Table 5). The CR probabilities for all

5
Q. Han, et al. Ecotoxicology and Environmental Safety 191 (2020) 110157

Fig. 2. Spatial variations of heavy metals in total concentrations and percentage bioaccessibility of heavy metals in soil and dust from schools and parks of Jiaozuo,
China.

6
Q. Han, et al. Ecotoxicology and Environmental Safety 191 (2020) 110157

Fig. 2. (continued)

7
Q. Han, et al. Ecotoxicology and Environmental Safety 191 (2020) 110157

Table 4 in dust were higher than that in soil, indicating that the potential risk
Bioaccessiblity of heavy metals in the gastric phase and intestinal phase of soil posed by dust still deserve public attention. As the greening rate of
and dust. urban soil and the hardening rate of cement keep increasing, HMs in
HMs Type Gastric (%) Intestinal (%) Residual (%) dust may represent a more probable exposure source for people than
that in soil. Additionally, ingestion of soil and dust appeared to be the
Range Mean Range Mean Range Mean main exposure pathway for HMs to children and adult, followed by
dermal contact and inhalation routes, respectively. This result is con-
Zn Soil 5.07–18.71 11.35 1.96–10.82 5.95 73.39–89.24 82.70
dust 22.41–47.84 36.17 5.77–22.87 15.34 30.79–71.82 48.50 sistent with other studies (Yeganeh et al., 2013; Chabukdhara and
Cu Soil 2.43–27.55 8.69 3.13–32.88 10.76 39.57–94.44 80.55 Nema, 2013; Qing et al., 2015; Shahab A et al., 2018). Therefore, it is
dust 1.42–14.93 5.61 1.83–29.15 8.43 55.92–96.56 85.96 necessary for children to keep the hand and mouth clean and avoiding
Mn Soil 16.46–40.80 26.31 10.50–30.31 18.16 28.89–72.23 55.54
“hand eating” when they went out to play in urban parks and schools.
dust 17.79–44.95 29.63 14.13–39.89 24.34 15.17–66.08 46.04
As Soil 5.97–27.77 15.78 5.59–21.87 13.19 50.85–88.45 71.04
dust 12.62–27.37 21.12 14.20–26.93 19.17 47.75–68.47 59.71
4. Conclusion
Pb Soil 7.49–41.48 20.48 0.30–3.69 1.23 56.17–91.55 78.29
dust 18.02–78.04 35.76 1.85–36.79 18.32 5.11–77.30 45.92
Cd Soil 0.98–11.84 13.26 1.19–36.64 15.30 37.45–89.58 71.43 The concentration, bioaccessibilities and health risk assessment of
dust 12.02–35.81 20.57 7.78–36.54 21.00 35.83–74.89 58.43 Zn, Cu, Mn, As, Pb, Cd, Cr, Ni and Co from soil and dust in six urban
Cr Soil 0.90–11.84 3.55 1.15–5.68 2.89 83.15–97.95 93.56
parks and seven schools in Jiaozuo were investigated in this study.
dust 3.09–10.69 6.57 3.72–15.71 7.84 76.46–93.19 85.59
Ni Soil 4.93–13.40 8.69 4.04–10.92 6.73 76.69–91.02 84.58
However, the results indicated that: (1) High concentration and high
dust 10.20–26.09 16.82 10.61–23.23 15.44 50.68–79.18 67.74 coefficient of variation suggested that HMs contamination from soil and
Co Soil 3.38–10.85 6.74 1.77–5.47 3.63 83.68–94.84 89.63 dust were very serious in urban parks and schools of Jiaozuo and ob-
dust 3.46–38.64 17.39 2.90–29.02 14.66 35.13–93.32 67.95 viously disturbed by human activities. Among the HMs surveyed, Cd
concentrations in soil and dust exceeded the background value by
17.83, 7.52 times respectively. (2) Subsequently, Pearson's correlation
HMs to children and adults were under the acceptable level
analysis and principal component analysis were conducted to identify
(< 1 × 10−4). Hazard quotients and hazard indices indicated no sig-
the potential sources of HMs in soil and dust. HMs in soil with strong
nificant risk of CR effects to children and adults exposed to soil and dust
correlations reflected that the elements might have originate from
in the urban parks and schools studied.
common sources, which HMs in dust with weak correlations and PC1b,
Additionally, the NCR and CR effects of HMs (expect for Mn and As)
PC2b and PC3b both suggested that the pollution sources of the dust are

Table 5
Health risk assessment of heavy metals based on total heavy metals in soil and dust for adults and children.
Sample type Heavy metals Adults Children

HQing HQinh HQdermal HI Risk HQing HQinh HQdermal HI Risk

Soil Zn 5.69E-04 2.32E-05 1.73E-06 5.94E-04 6.52E-03 1.38E-04 2.66E-05 6.68E-03

Cu 8.96E-04 2.44E-05 2.73E-06 9.23E-04 1.03E-02 1.44E-04 4.18E-05 1.04E-02
Mn 1.82E-02 3.71E-03 1.78E-01 2.00E-01 2.08E-01 2.20E-02 2.73E + 00 2.96E + 00
As-non-cancer 3.30E-01 6.56E-03 1.00E-03 3.37E-01 3.78E + 00 3.89E-02 1.54E-02 3.83E + 00
As-cancer 4.15E-07 4.15E-07 6.15E-07 6.15E-07
Pb 1.51E-02 8.23E-05 4.58E-05 1.53E-02 1.73E-01 4.88E-04 7.03E-04 1.74E-01
Cd-non-cancer 9.03E-04 7.37E-04 2.75E-06 1.64E-03 1.03E-02 4.37E-03 4.22E-05 1.48E-02
Cd-cancer 1.78E-08 1.78E-08 2.64E-08 2.64E-08
Cr-non-cancer 3.35E-02 1.36E-02 1.07E-02 5.78E-02 3.83E-01 8.09E-02 1.64E-01 6.28E-01
Cr-cancer 1.18E-05 1.18E-05 1.75E-05 1.75E-05
Ni-non-cancer 3.07E-03 9.27E-05 9.07E-06 3.17E-03 3.52E-02 5.50E-04 1.39E-04 3.58E-02
Ni-cancer 1.44E-07 1.44E-07 2.14E-07 2.14E-07
Co-non-cancer 1.53E-03 1.56E-05 1.64E-02 1.79E-02 1.76E-02 9.27E-05 2.51E-01 2.69E-01
Co-cancer 8.40E-07 8.40E-07 1.25E-06 1.25E-06
Dust Zn 2.14E-03 8.73E-05 6.52E-06 2.23E-03 2.45E-02 5.17E-04 1.00E-04 2.51E-02
Cu 2.14E-03 5.81E-05 6.51E-06 2.20E-03 2.45E-02 3.45E-04 9.99E-05 2.49E-02
Mn 1.77E-02 3.60E-03 1.73E-01 1.94E-01 2.02E-01 2.14E-02 2.66E + 00 2.88E + 00
As-non-cancer 1.32E-01 2.63E-03 4.01E-04 1.35E-01 1.51E + 00 1.56E-02 6.15E-03 1.53E + 00
As-cancer 1.66E-07 1.66E-07 2.46E-07 2.46E-07
Pb 2.71E-02 1.47E-04 8.20E-05 2.73E-02 3.10E-01 8.73E-04 1.26E-03 3.12E-01
Cd-non-cancer 2.14E-03 1.75E-03 6.52E-06 3.89E-03 2.45E-02 1.03E-02 1.00E-04 3.50E-02
Cd-cancer 4.22E-08 4.22E-08 6.25E-08 6.25E-08
Cr-non-cancer 6.41E-02 2.61E-02 2.05E-02 1.11E-01 7.34E-01 1.55E-01 3.14E-01 1.20E + 00
Cr-cancer 2.26E-05 2.26E-05 3.35E-05 3.35E-05
Ni-non-cancer 4.43E-03 1.34E-04 1.31E-05 4.58E-03 5.08E-02 7.94E-04 2.01E-04 5.18E-02
Ni-cancer 2.08E-07 2.08E-07 3.09E-07 3.09E-07
Co-non-cancer 2.17E-03 2.21E-05 2.31E-02 2.53E-02 2.48E-02 1.31E-04 3.55E-01 3.80E-01
Co-cancer 1.19E-06 1.19E-06 1.76E-06 1.76E-06

Sample type Type Adults Children

HQing HQinh HQdermal HI Risk HQing HQinh HQdermal HI Risk

Soil Non-cancer 4.04E-01 2.49E-02 2.06E-01 6.35E-01 4.62 E+00 1.48E-01 3.16 E+00 7.93 E+00
Cancer 1.32E-05 1.96E-05
Dust Non-cancer 2.54E-01 3.46E-02 2.17E-01 5.06E-01 2.91 E+00 2.05E-01 3.33 E+00 6.44 E+00
Cancer 2.42E-05 3.58E-05

8
Q. Han, et al.
composite sources, including transportation, coal-firing, mining, in-
dustry and paint. (3) The concentration and bioaccessibility of HMs
from dust were higher than that from soil. It suggested that dust posed
higher health risk for children than soil, which was in agreement with
the result of health risks assessment based on total concentration and
bioaccessibility of HMs. This study demonstrates that assessing the
environment quality of urban parks and school for children is necessary
and can help implement more reasonable risk management of metals in
urban environment.
CRediT authorship contribution statement
Qiao Han: Investigation, Conceptualization, Writing - original
draft, Formal analysis, Data curation, Writing - review & editing.
Mingshi Wang: Conceptualization, Methodology, Supervision, Project
administration, Writing - review & editing. Jingli Cao: Investigation,
Formal analysis, Data curation, Writing - original draft, Writing - review
& editing. Chenlu Gui: Investigation, Formal analysis, Data curation,
Writing - original draft, Writing - review & editing. Yanping Liu:
Formal analysis, Data curation. Xiangdong He: Formal analysis, Data
curation. Yuchuan He: Formal analysis, Data curation. Yang Liu:
Investigation, Formal analysis.
Declaration of competing interest
None.
Acknowledgments
This work was supported by the Foundation of Henan Educational
Committee (16A170001), the Excellent Youth Foundation of Henan
Polytechnic University, the Fundamental Research Funds for the
Universities of Henan Province (NSFRF1631) and Foundation of Key
scientific research project of colleges and universities in Henan pro-
vince (20A170009).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ecoenv.2019.110157.
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