Chemosphere 242 (2020) 125113

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Health risk assessment of heavy metals and pesticides: A case study in

the main drinking water source in Dalian, China
Wanwan Dong, Ying Zhang*, Xie Quan
Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Environmental Science and Technology, Dalian
University of Technology, Linggong Road 2, Dalian, 116024, China

h i g h l i g h t s

Only six target heavy metals were detected in water samples, and seven metals were detected in sediment and soil samples.

Only two of 65 target pesticides were detected in water, while five pesticides were detected in sediment and soil.

There is no apparent noncarcinogenic health risk associated with heavy metals and pesticides in our study area.

Hexachlorobenzene and arsenic in sediment and soil are the predominant contributors to potential human carcinogenic risks.

Figure Captions.

a r t i c l e i n f o a b s t r a c t

Article history: Health risk associated with drinking water has attracted increasing attention worldwide. Here, we
Received 22 August 2019 conducted a survey on the main drinking water sources of Dalian in China to clarify the local human
Received in revised form health risk associated with heavy metal and pesticide contaminants in the drinking water sources. The
12 October 2019
results showed that six heavy metals, namely, copper (Cu), zinc (Zn), cadmium (Cd), nickel (Ni), arsenic
Accepted 12 October 2019
Available online 25 October 2019
(As), and mercury (Hg), and two pesticides (atrazine and acetochlor) were detected in water samples,
where the highest concentration of Hg (0.0621 mg L1) exceeded the domestic standard only. In addition
Handling Editor: A. Gies to the above-mentioned metals, Cr was also detected in the sediment/soil samples. As to the pesticides,
atrazine, acetochlor, hexachlorobenzene, p,p’-DDE, and p,p’-DDD were detected in the sediment/soil
Keywords: samples at ng g1 levels, and atrazine and acetochlor were found in water samples at ng L1 levels. The
Heavy metal human health risk assessment showed no marked difference in carcinogenic and noncarcinogenic risks
Pesticide from drinking water. Our study approved that hexachlorobenzene and arsenic were the main contrib-
Carcinogenic risk utors to human carcinogenic risks, which were calculated at the level of 104. Furthermore, sediment and
Drinking water source
soil ingestion was considered as the major source of human health risk in our study area. This study
Health risk
revealed the current pollution status in the surrounding area of the drinking water source and the main
source associated with human health risk, which established a sound basis for further decision-making
to take necessary action on pollution control.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction happened on or around such rivers, lakes and reservoirs considered

as drinking water sources in China during 1986e2005 (Li et al.,
In recent decades, the accelerated urbanization and industrial- 2007). In recent decades, there has been illegal emission or acci-
ization, as well as the rapid economic development, have resulted dental leakage of wastewater containing heavy metals or other
in the increasing generation and discharge of pollutants into water organic substances either directly or indirectly into the watershed
bodies. In China, drinking water is commonly obtained from rivers, ecosystem or water supply source (Ali et al., 2014; Lan et al., 2017).
lakes, and artificial reservoirs. However, there were 86 incidents Therefore, the quality of drinking water source should be increas-
ingly focused because it is closely related to the health of local
inhabitants.
Heavy metals are frequently detected in drinking water source
* Corresponding author.
(i.e., rivers, reservoirs, or lakes), although their species and
E-mail address: yzhang@dlut.edu.cn (Y. Zhang).

https://doi.org/10.1016/j.chemosphere.2019.125113
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
2 W. Dong et al. / Chemosphere 242 (2020) 125113

concentrations are generally region specific (Gao et al., 2008; Niu Biliuhe Reservoir is the main drinking water source in Dalian
et al., 2015; Wang et al., 2013; Yang et al., 2018). In Dongting Lake and is considered a highly valued water resource. Its annual water
of China, several heavy metals (especially Cd, Zn, and Hg) were supply accounts for approximately 80% of the total annual water
detected higher than their corresponding background values in supply in the urban area, which benefits a population of more than
both surface water and sediment (Bi et al., 2018). Further, many 4 million. The reservoir is located near a densely populated area
kinds of heavy metals were observed in the surface water of Lake and a farmland or former mining area along its inflow rivers.
Pontchartrain Basin and its inflows in the USA, and their concen- Contaminants including heavy metals and pesticides that are
trations exceeded the standards (Zhang et al., 2016). This indicates introduced into the reservoir by anthropogenic terrestrial dis-
that heavy metals have been detected in drinking water sources charges result in relevant human health risk. To ensure the safety of
worldwide. The risk associated with heavy metals has drawn drinking water source and avoid human health risks, we conduct a
elevated attention owing to their environmental stability, difficult survey on the heavy metals and pesticides surrounding Biliuhe
degradation, easy accumulation, and tendency to translate to more Reservoir. Our primary objective is to clarify the current contami-
toxic organic forms (Liu et al., 2017; Ma et al., 2016). It has been well nation status in the surface water and sediment of the reservoir,
known that long-term exposure of heavy metals may lead to followed by human health risk assessment. Our results will estab-
adverse effects on the immune, nervous, and endocrine systems (Li lish a sound basis for further decision-making to take necessary
et al., 2014b) or cause cancer or impairments to both adults and action on pollution control to maintain the safety and quality of
children (Patlolla et al., 2012; Wu et al., 2018). It was also reported drinking water and avoid human health risk from the drinking
that metals could translocate into humans through the food chain water source.
and pose potential risk to the human residents (Liu et al., 2010;
Zhuang et al., 2014). Health risk assessments showed that the over- 2. Method and materials
standard concentrations of Fe, Pb, and Cd in river water source did
pose potential risk to the human population in India (Singh and 2.1. Study area
Kumar, 2017).
Pesticides are also chemicals of concern in drinking water Biliuhe Reservoir is the main drinking water source, located in
source, as they have been used increasingly to obtain more agri- northern Dalian, Liaoning Province, northeastern China. Its catch-
cultural yields in the past decades (Li et al., 2014a). Twenty-eight ment area is approximately 1800 km2, with a normal storage of 70
pesticides were detected in Lebanon’s water resources (drinking million m3, including three major inflow rivers (namely, the Biliuhe
water included), where the concentration of individual pesticide in River, Gelihe River, and Bajiahe River). Our sampling sites covered
surface water was up to 220 ng L1 (Kouzayha et al., 2013). In China, Biliuhe Reservoir and its three inflow rivers, as well as the
pesticides were also detected at high concentration in water, Wolongquan River (a main branch of the Biliuhe River, one inflow
sediment, and soil. For example, the highest pesticide concentra- river) and the bay area of the Bajiahe River. The locations of the
tions were found exceeding 250 ng L1 in water and 4900 ng g1 in sampling sites are given in Fig. 1. Sample collection was conducted
sediment and soil (Grung et al., 2015). It was also reported that the during August 2014 to April 2015, and a total of 102 water samples
pesticide concentration in the suburban area of Shenyang was at and 101 sediment/soil samples were collected.
the maximum of 51.32 ng g1 (Shi et al., 2011). A recent study
showed that 11 pesticides were detected in the rural rivers of 2.2. Sample collection and chemical analysis
Guangzhou, five of which at concentrations above 100 ng L1 (Tang
et al., 2019). Current research shows that high levels of pesticide The heavy metals investigated in this study were Cu, Zn, Cd, Cr,
residues could enter the food chain and ultimately endanger hu- Ni, Hg, and As, which were chosen on the basis of their toxicities
man health, which has turned to be one of the most urgent safety and potential environmental risks from the viewpoint of water
concerns (Chen et al., 2018; Cui et al., 2011; Wan et al., 2008). pollution as well as their wide application and detection in recent
Both heavy metals and pesticides are detected in water source years. Sixty-five pesticides from various chemical classes were
and intensify threat to water quality and safety (Ab Razak et al., analyzed as targets in this study (Table S1), including 23 triazine
2015; Derbalah et al., 2019; Gao et al., 2019; Taiwo, 2019). and amide herbicides, 18 organophosphorous pesticides (OPPs),
Further, they would cause damage to the ecological environment and 24 organochlorine pesticides (OCPs). These chosen pesticides
and health risk to humans, although the over-standard concen- were listed as targets because of their wide use in recent years or
tration did not mean ecological or health risk. There have been during the past few decades in our study area as well as their
some reports on the noncarcinogenic and carcinogenic risks of toxicity, persistence, and potential widespread application. Water
heavy metals and pesticides through ingestion, inhalation, and samples were collected in glass bottles at each sampling site and
dermal contact. Singh and Kumar (2017) found that the high con- filtrated through a glass fiber filter (GF/F, Whatman, prebaked at
centration of Fe, Pb, and Cd in Ajay River Basin, which were beyond 450  C for 4 h) before further analysis. Top sediments/soils were
the permissible limit for the drinking water quality, could cause collected using a stainless steel shovel or grab from the sampling
potential health risks through oral consumption and dermal ab- sites at a depth of 0e20 cm and then stored in polythene zip bags.
sorption. It was reported in Nigeria that river sediments were All the water samples were stored at 4  C before analysis within a
heavily contaminated by organochlorine pesticides due to both week, and sediment/soil samples were stored at 20  C before
historical and recent use, and the related health assessment analysis. Reagent blanks and standard reference materials were
showed that the carcinogenic and noncarcinogenic risks were used in the analysis for quality assurance and control. The purity of
relatively high through ingestion (Ogbeide et al., 2016). Accord- all chemicals during the pretreatment and analysis of heavy metals
ingly, particular focus should be given to the health risk associated and pesticides was >98%. All solutions were prepared using Milli-Q
with heavy metals and pesticides in water or sediments. These water (Millipore, Billerica, MA, USA). All samples were analyzed in
contaminant-associated risks are region specific, and the survey on triplicate, and relative standard deviations were within ±20%.
drinking water source should be conducted on a case-by-case basis.
As we know, heavy metals and pesticides in the drinking water 2.2.1. Heavy metals
source of Dalian have been barely reported, which resulted in an For heavy metal detection, the water sample was acidified and
urge to drive the relevant survey. kept in a cleaned polyethylene bottle for further analysis. Sediment/
 W. Dong et al. / Chemosphere 242 (2020) 125113 3

Fig. 1. The sampling sites of study areas.

soil samples were oven-dried at 105  C and ground to pass through tetrachloro-m-xylene (TCMX) were used as the recovery stan-
a 100-mesh nylon sieve. The sediment sample (0.2 g) was digested dards for OCPs, and tributyl phosphate (TBP) was added as the
in a digestion vessel by adding 3 mL hydrochloric acid, 9 mL nitric recovery standard for OPPs. Pentachloronitrobenzene (PCNB) was
acid, 2 mL hydrofluoric acid, and 1 mL perchloric acid. The digestion added as the internal standard for OCP analysis, while triphenyl
program was as follows: 100  C for 30 min, increasing to 130  C for phosphate (TPP) was the internal standard for OPPs and herbicides.
60 min, then 150  C for 60 min, and 180  C for 30 min. The soil An Agilent 6890 gas chromatograph-5975 mass spectrometer
sample (0.2 g) was first added to the digestion vessel containing (GC-MS) system in the electron impact ionization (EI) mode was
10 mL hydrochloric acid and digested at 100  C for 30 min. After used to detect the pesticides. A DB-5MS GC column (30 m  0.25
cooling, 5 mL nitric acid, 5 mL hydrofluoric acid, and 1 mL mm  0.25 mm) was used to separate the analytes. The oven tem-
perchloric acid were added simultaneously before increasing the perature for OPPs was programmed as follows: 60  C for 1 min,
temperature to 150  C for 30 min. After filtering the digested so- increasing to 120  C at a rate of 30  C/min, followed by 4  C/min to
lution, Hg concentration was measured with an atomic fluores- 180  C, 5  C/min to 260  C, and then 15  C/min to 290  C for 5 min.
cence spectrometer (AFS-9770, Beijing Haiguang Instrument Co. The oven temperature for OCPs was programmed as follows: 70  C
Ltd., China). An inductively coupled plasma mass spectrometer for 0.5 min, increasing to 160  C at a rate of 30  C/min, followed by
(ICP-MS, NexION 300D, PerkinElmer Inc., Waltham, MA, USA) was 4  C/min to 240  C and then 10  C/min to 290  C for 5 min. The oven
applied to determine the concentration of the other heavy metals. temperature for herbicides was as follows: 70  C for 1 min,
increasing to 130  C at a rate of 30  C/min, followed by 5  C/min to
250  C and then 15  C/min to 280  C for 5 min.
2.2.2. Pesticides
The preconcentrated and cleanup process was performed on a
C18 solid phase extraction (SPE, 6 mL, 1000 mg) cartridge. First, the 2.3. Human health risk assessment
SPE cartridge was conditioned with 10 mL MeOH and 10 mL Milli-Q
water. Then 1 L water sample, spiked with recovery standards, was Here, human health risk associated with a specific chemical was
passed through the cartridges at a flow rate of 4 mL/min, followed classified into two categories: carcinogenic and noncarcinogenic
by vacuum drying for 1 h. The cartridges were eluted with 5 mL risk. It was considered that direct ingestion of drinking water and
ethyl acetate and 5  2 mL dichloromethane, and the eluents were dermal absorption of contaminants in water by adhering to the
then evaporated and solvent-exchanged to hexane. exposed skin are the most common routes for contaminants in
The sediment/soil samples were first dried and then ground to water (Li and Zhang, 2010; Wu et al., 2009), and the pollutants in
pass through a 60-mesh sieve. The sediment/soil samples were first sediment and soil are exposed to the human body mainly through
added to recovery standards and then extracted with acetone/ the ingestion absorption pathway. The slope factors for carcino-
dichloromethane (1/1, v/v) using an accelerated solvent extractor genic contaminants and reference doses for noncarcinogenic
(ASE, Dionex ASE 350, Thermo Fisher Scientific, Sunnyvale, CA, chemicals were extracted from Integrated Risk Information System
USA) at 100  C and 1500 psi for two cycles. The extracts were (IRIS, US EPA) and other databases, as given in Table S2. Following
concentrated to near dryness, reconstituted in 1 mL hexane, and the recommended acceptable risks provided by the US EPA (2000),
purified with Florisil® SPE cartridge (6 mL, 1000 mg) by eluting here 1  106 was applied as the acceptable critical threshold of
with 10 mL acetone/hexane (20/80, v/v). PCB209 and 2,4,5,6- lifetime risk of cancer for adults in our health risk assessment.
4 W. Dong et al. / Chemosphere 242 (2020) 125113

The exposure doses through ingestion and dermal absorption implemented with Crystal Ball (Oracle Inc., USA), embedded in
pathways were calculated with Eq. (1) and Eq. (2), respectively, Microsoft Office Excel. The parameters used in health risk calcula-
which were adapted from the USEPA (US EPA, 1989). The noncar- tion with Monte Carlo simulation are shown in Table S3. To deter-
cinogenic health risk of single pollutant was calculated with Eq. (3), mine the concentration of each contaminant, the distribution was
and the sum of the risk was calculated with Eq. (4). fitted with our survey data, and then the fitting parameters were
used to assign the distribution in Monte Carlo simulation. The
C  IR  EF  ED default distribution for concentration was assigned to be logarith-
ADDingestion ¼ (1)
BW  AT mic normal distribution, where the parameters of geometric mean
and geometric standard deviation were the characterization pa-
C  SA  AF  ABS  EF  ED rameters. After assigning each parameter, Monte Carlo simulation
ADDdermal ¼ (2)
BW  AT was performed as 10,000 iterations to achieve the confidence in-
terval of outputs we set.
Rni ¼ ½ADD = ðRfDi  70Þ  106 (3)
3. Results and discussion
X
n
R¼ Rni (4) 3.1. Occurrence and distribution of target pollutants in the study
i¼1 area

where Rni refers to the noncarcinogenic health risk, ADD is the According to the presurvey on the utilization of pesticides in the
average daily dose (mg kg1 d1); C represents the concentration of study area, we targeted 7 heavy metals (Cu, Zn, Cd, Cr, Ni, As, and
the target pollutants; IR is the intake rate (kg d1 or L d1); EF Hg) and 65 pesticides within the list of chemical detection for the
denotes the exposure frequency (365 d y1); ED is the exposure surface water, sediment, and soil samples. All the target heavy
duration (years), which is 30 years for adult according to the US EPA metals except Cr were detected in surface water, and a total of 7
(2011); BW is the body weight (kg); AT is the average exposure time heavy metals were detected in the sediment and soil of the study
(days); SA is the skin exposure area (cm2); AF is the adherence area, whereas only two pesticides (atrazine and acetochlor) were
factor (kg cm2 d1); ABS is the dermal absorption factor, which is detected in surface water, and five target pesticides (atrazine,
dimensionless; in this study, i is a heavy metal or a pesticide. RfD is acetochlor, hexachlorobenzene, p,p’-DDE, and p,p’-DDD) were
the reference dose of each pollutant. The average lifetime of adults detected in sediment and soil samples (Table 1).
assumed in this study is 70 years.
Carcinogenic risk, here, indicates the lifetime probability of an 3.1.1. Heavy metals
individual to develop cancer from exposure to heavy metal and The concentrations of heavy metals in each sampling region are
pesticide pollution. Carcinogenic risk was calculated using Eq. (5) shown in Table 1. The maximum concentrations of each heavy
(US EPA, 1991); when the result was above 0.01, the formula metal detected in the surface water were 163 mg L1 for Zn,
would be refined as Eq. (6). The total risk was calculated using Eq. 81.0 mg L1 for Cu, and 4.10 mg L1 for Ni. The mean concentrations
(7). of Zn and Cu were approximately 20.0 mg L1, and those of Ni and As
 were approximately 1.00 mg L1, while the mean concentrations of
Rci ¼ ADD  SFi 70 (5) Hg and Cd were only approximately 0.0300e0.0400 mg L1. In
sediment and soil samples, there were no marked differences in

Rci ¼ ½1  expð  ADD , SFi Þ 70 (6) heavy metal concentrations in sediment and soil samples, and
hence, they would be taken into account together in the following
X
n section. Among all the heavy metals detected in the sediment/soil
R¼ Rci (7) samples, the maximum concentrations were 144 mg g1 for Zn, with
i¼1 a mean value of 73.3 mg g1; 82.0 mg g1 for Cu, with a mean value of
24.7 mg g1; 21.6 mg g1 for As, with a mean value of 7.61 mg g1; and
where Rci refers to the carcinogenic health risk; ADD is the average 0.312 mg g1 for Hg, with a mean value of 0.0621 mg g1. It is worthy
daily dose (mg kg1 d1); SF is the slope factor; for adults, 70 years to notice that the mean concentrations of Cd and Hg were of 2e3
of lifetime was assumed in this study, equivalent to the average orders lower than that of Zn in both water and sediment/soil
lifetime. samples. Compared with the second-grade state standard (MEP,
The reference values of exposure factors used to estimate the 2002), no metals in the water samples exceeded the domestic
intake values and risks of target heavy metals and pesticides are standard level, with an exception of the highest concentration of Hg
provided in Table S2. The RfD and SF values were mainly collected (0.0621 mg L1), which was 1.2 times greater than the standard
from RAIS and IRIS databases (IRIS, 2019; RAIS, 2019). To reduce the level. For sediment and soil samples, all heavy metal concentrations
uncertainty, most of the exposure parameters, for example, the were under the acceptable limits of the domestic standards (MEE,
values of the skin surface area and body weight, were obtained 2018) but beyond the corresponding local background values (see
from the Exposure Factors Handbook of Chinese Population (MEP, Table S4). However, it remains unclear whether they present po-
2014). Further, data for exposure parameters were used from in- tential human health risks or not, as the long-term exposure of low-
ternational studies if the localized values were unavailable. level contaminants could still impact human health.
The concentrations of heavy metals were also depicted in spatial
2.4. Monte Carlo simulation distributions for surface water and sediment/soil samples. From the
perspective of risk control, we present the maximum concentra-
Monte Carlo simulation is a random sampling method based on tions of heavy metals in Fig. 2 during three sampling seasons (flood,
mathematical statistics and the probability theory, which has been normal, and dry seasons). Among all water samples, the concen-
commonly used in health risk calculation, as recommended by the trations of Ni, As, and Hg were found to be higher in the northern
National Academy of Sciences and the USEPA (NRC, 1994; US EPA, area rivers than in the reservoir, while Cu and Zn presented higher
1997; US EPA, 2014). In this study, Monte Carlo simulation was concentration in the reservoir. In the case of Cd, its concentration in
 W. Dong et al. / Chemosphere 242 (2020) 125113 5

the Biliuhe River was higher than that in other regions. As shown in

N.D.~2.33
p,p’-DDD
Fig. 2, the concentrations of Cu, Zn, Cd, Cr, and Ni in sediment and
soil samples collected from inflow rivers were lower than that in

N.D.

N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
N.D.
the reservoir area. In contrast, As and Hg were present at high
concentrations in sediment and soil in all sampling sites across the

N.D.~15.7

N.D.~25.1

N.D.~15.7

N.D.~18.8
p,p’-DDE
study area. For the reason that most of our target metals were the
accessory elements of ore, the detected concentrations of metals

12.6
N.D.

N.D.

N.D.

N.D.

N.D.
N.D.
N.D.
might be attributed to both natural release and anthropogenic ac-
tivities. Comparing the spatial patterns, it was obvious that the
Hexachalorobenzene

same metal exhibited heterogeneous spatial patterns in water and

sediment/soil, which may be attributed to the residues of mining
plants in the upper reaches of the Biliuhe Reservoir even when they
N.D.~2.39

N.D.~15.5

N.D.~2.76
are far from our study area. Heavy metals tended to migrate from
water to sediments and accumulated in the sediments of rivers,
N.D.

N.D.
N.D.
N.D.
N.D.
N.D.

N.D.
N.D.
N.D.
which could be washed downstream by the water scour and
Concentrations of pesticides

deposited in the reservoir (Sun, 2002). Historical accumulation led

c. Considering that the contents of target pollutants were not very different in sediment and soil samples, so the two types of samples are discussed together in this table.
b. The unit of heavy metal concentration is mg L1 in water and mg g1 in sediment/soil, the unit of pesticide concentration is ng L1 in water and ng g1 in sediment/soil.
Acetochlor

N.D. ~37.2
20.4e61.9

29.3e34.0

to the spatial pattern of higher heavy metal concentrations in the

N.D.~46.2

N.D.~34.0

N.D.~32.2

N.D.~98.6
N.D.~239

sediment of the reservoir than in the sediments of other regions.

N.D.

N.D.

N.D.

N.D.

The relatively lower heavy metal concentrations in water might be

attributed to the fact that China has implemented drinking water
source protection policies during the past two decades, which had
94.5e323

73.4e202
N.D.~11.8

N.D.~54.5

N.D.~17.4

N.D.~18.0

N.D.~26.8
170e196

132e304
Atrazine

restricted on ore mining and discharge of industrial effluents into

N.D.

N.D.

N.D.

drinking water sources.

Our study gave the case-study of heavy metals and pesticides
survey of a valued drinking water resource in northeast of China. As
0.0100e0.0500

0.0500e0.0900
0.0400e0.0600

0.0210e0.123

0.0130e0.115
N.D.~0.0710

shown in Table 2, Cu and Zn concentrations in the water sample of

N.D.~0.220

N.D.~0.312

a. K ¼ Biliuhe Reservoir; S ¼ Bay area of Bajiahe River; B ¼ Biliuhe River; G ¼ Gelihe River; J ¼ Bajiahe River; W ¼ Wolongquan River.

our survey area were relatively higher than those in other lakes and
0.0200

0.0600

rivers, while they were not higher in the sediment and soil samples
N.D.

N.D.
Hg

than those in other reports in China or foreign countries. It is worth

mentioning that the concentration of Cr in water and sediment/soil
0.400e1.26

0.600e1.10

0.490e1.86
0.790e21.6
0.400e2.30
0.770e13.6

6.35e11.2

7.40e12.0

is relatively lower than those in other rivers and lakes we listed

N.D.~18.6

worldwide.
0.950

N.D.

N.D.
As

3.1.2. Pesticides
Among the 65 pesticides we analyzed, only 5 pesticides were
0.250e4.10

0.700e3.80
1.25e2.10
18.0e49.0
1.21e1.60
33.0e42.0

10.0e37.0

13.0e30.0

15.0e27.0

11.0e35.0

detected in water and sediment/soil at least for one time or in one

sampling region, which are summarized in Table 1. As shown in
Occurrence of heavy metals and pesticides in water, sediment and soil of different sampling areas.

N.D.

N.D.
Ni

Table 1, only two herbicides occurred in surface water, whose

maximum concentrations were 323 ng L1 for atrazine and
22.0e73.0

46.0e72.0

12.0e53.0

18.0e61.0

12.0e39.0

14.0e33.0

61.9 ng L1 for acetochlor, with mean concentrations of 157 ng L1

and 26.6 ng L1, respectively, whereas in the sediment and soil
N.D.

N.D.

N.D.

N.D.

N.D.

N.D.
Cr

samples, all of the five target pesticides were detected, with the
maximum concentrations ranging from 2.33 ng g1 for p,p’-DDD to
0.0500e0.0860

239 ng g1 for acetochlor, and 54.5 ng g1, 15.5 ng g1, and
0.0120e0.260

0.0580e0.239

0.0670e0.220

0.0690e0.140
0.120e0.160
N.D.~0.0400

N.D.~0.0300

N.D.~0.0900

25.1 ng g1 for atrazine, hexachlorobenzene, and p,p’-DDE,

respectively. The mean concentrations were according to the
(9.62 ng g1) > p,p’-DDE
N.D.

N.D.

N.D.

following sequence: acetochlor

Concentrations of heavy metals

Cd

1
(4.98 ng g ) > atrazine (4.61 ng g1) > p,p’-DDD
(0.951 ng g1) > hexachlorobenzene (0.897 ng g1). The high p,p’-
29.0e97.0

32.0e70.0

37.0e81.0
49.0e144

84.0e141

37.0e107
N.D.~163

N.D.~116

DDE concentrations and detect frequencies in sediment and soil

d. N.D.: Not detected or below the detection limits.
N.D.

N.D.

N.D.

N.D.

indicated the historical usage of DDT pesticide in our study area.

Zn

The OPPs were not detected in the study area, which may be
attributed to the fact that organophosphorus pesticides could be
10.0e50.0

32.0e35.0

11.0e31.0

6.00e82.0

9.00e16.0

14.0e36.0
N.D.~81.0

N.D.~78.5

N.D.~72.0

degraded rapidly under natural conditions (Shi et al., 2011).

Comparing with the domestic standards presented in Table S4,
N.D.

N.D.

N.D.
Cu

even the maximum pesticide concentration monitored in surface

water was still far below the standards regulated by the Chinese
sediment/soil

sediment/soil

sediment/soil

sediment/soil

sediment/soil

sediment/soil
sample type

government (MEP, 2002). Despite low pesticide concentrations

contained in our samples, their health risks still should be drawn
water

water

water

water

water

water

attention because their hazard might be critical to humans.

The spatial distributions of pesticide concentrations in water
and sediment/soil are presented in Fig. 2. Here, we focused the
Location

maximum concentrations of pesticides collected during different

Table 1

sampling periods from the viewpoint of potential human health

W
G
K

B
S

risk. As shown in Fig. 2, pesticides occurred in the reservoir, the

6 W. Dong et al. / Chemosphere 242 (2020) 125113

Fig. 2. The spatial distributions of heavy metals and pesticides in surface water and sediment/soil (Based on the maximum concentration of each sampling site).

Biliuhe River, the Gelihe River, and the bay area of the Bajiahe River. Bajiahe River and the Wolongquan River. It can be seen that higher
No detectable concentrations of pesticides were encountered in the concentrations of atrazine and acetochlor in surface water were
 W. Dong et al. / Chemosphere 242 (2020) 125113 7

found in the northern area of our study region, where many or- two Spanish rivers (Ccanccapa et al., 2016). For acetochlor, the
chards and farmland are distributed. This result may be attributed maximum concentration in surface water in our study (61.9 ng L1)
to the increasing utilization of herbicides for crop cultivation (Wang was comparable to that of 71.15 ng L1 reported by Ccanccapa et al.
et al., 2017). Moreover, agricultural and irrigation runoff is (2016) but much lower than that reported previously (116 ng L1) in
considered one of the main sources of pesticides in our study area. the rivers of Guangzhou, China (Tang et al., 2019). The maximum
From the spatial distributions of pesticide concentration in sedi- and mean concentrations of hexachlorobenzene in our study
ment and soil, it can be seen that atrazine and acetochlor concen- (15.5 ng g1; 0.897 ng g1) were nearly twice higher than those in
trations in the upper rivers were higher than those in the reservoir, farmland soil samples (6.47 ng g1; 0.59 ng g1, respectively)
while higher concentrations of hexachlorobenzene were found collected from suburban areas in south Shenyang (Shi et al., 2011).
mainly in the northern part of the reservoir, and p,p’-DDD was As compared to other regions globally, the higher p,p’-DDE con-
observed only at several sites in the reservoir. It is to be noted that centration in the sediment and soil samples of our study area
p,p’-DDE was the most frequently detected substance and mostly indicated that the historical pollution in this area was of particular
found in the reservoir. p,p’-DDE was recorded to be the highest significance.
component among DDT metabolites (CCME, 1999), a kind of OCP
that had been banned for decades in China. The spatial distribution
of p,p’-DDE suggested that DDT might have ever been used in large 3.2. Health risk assessment
quantities as an OCP in this catchment historically, and an
increasing amount of residual pesticides in soils might have been 3.2.1. Carcinogenic risk assessment
carried into the reservoir by land runoff. Carcinogenic risks were estimated for the heavy metals and
Compared with other lakes and rivers worldwide (Table 2), the pesticides (i.e., Cd, As, atrazine, hexachlorobenzene, p,p’-DDE, and
atrazine concentrations were found to be higher in our study area p,p’-DDD), and their carcinogenic slope factors are available. To
than in the Miami River, USA (Fernandez and Gardinali, 2016), and represent the worst case for exposure, the highest concentration in
each sampling region (obtained from Table 1) and the values for

Fig. 2. (continued).
8 W. Dong et al. / Chemosphere 242 (2020) 125113
Table 2
Heavy metal and pesticide levels in water, sediment and soil from different countries/regions.

Locations Cu Zn Cd Cr Ni As Hg Sample types Ref.

The Biliuhe Reservoir area. China N.D.~81.0 N.D.~163 N.D.~0.0900 N.D. N.D.~4.10 N.D.~2.30 N.D.~0.06 water This study
(24.2) (29.8) (0.0268) (1.59) (0.966) (0.0364)
6.00e82.0 29.0e144 0.0120 12.0e73.0 10.0e49.0 N.D.~21.6 N.D.~0.312 sediment
(24.7) (73.3) e0.260 (38.0) (26.9) (7.61) (0.0621)
(0.120)
The Liaohe River protected 7.9e41.1 26.67e93.4 0.4e0.7 18.23e57.2 9.23e35.27 3.43e17.63 sediment Ke et al. (2017)
areas，China (17.82) (50.24) (1.20) (35.06) (17.73) (9.88)
The Taihu Lake area, China 80.59e391.85 109.02 40.98e502.22 13.98 Sediment of Niu et al. (2015)
(154.22) e639.84 (142.35) e102.91 inflow rivers
(272.22) (42.12)
27.2 99.5 86.7 40.6 Sediment of
Taihu lake
The Dongting Lake, China 0.7e7.65 (2.5) 2.81e71.24 N.D.~0.15 0.15e1.03 0.29e5.11 1.77e6.91 N.D. water Bi et al. (2018)
(20.91) (0.05) (0.62) (1.51) (3.62)
34.93e73.43 226.98 0.66e7.89 53.52e116.03 23.03e54.89 16.04 0.05e0.47 sediment
(45.46) e463.38 (2.87) (88.97) (41.65) e64.28 (0.18)
(322.6) (29.22)
The Yellow River area, China 14.1e30.3 39.9e74.6 0.1e0.3 61.3e139.5 19.3e34.6 sediment Ma et al. (2016)
The Gunga River area, India 19.42e43.72 31.73e71.37 11.41e39.24 41.8e70.16 31.28e61.11 water Pandey et al.
15.3e70.7 185.15 30.01 133.75 18.38e97.1 sediment (2015)
e278.61 e128.13 e247.05
The Louisiana’s Lake 2.15e4.2 24.7e528 0.05e0.35 5.57e7.3 1.3e3.05 water Zhang et al.
Pontchartrain Basin, USA (2016)
Drinking water system of the 7.41e104.77 N.D.~1.00 0.39e10.76 0.10e39.31 drinking water Ghaderpoori
Khorramabad city, Iran (47.01) (0.42) (5.08) (6.79) et al. (2018)

Locations Atrazine Acetochlor Hexachalorobenzene p,p’-DDE p,p’-DDD Sample types Refs.

The Biliuhe Reservoir area, China N.D.~323 N.D.~61.9 N.D. N.D. N.D. water This study
(157) (26.6)
N.D.~54.5 N.D.~239 N.D.~15.5 (0.897) N.D.~25.1 N.D.~2.33 sediment
(4.61) (9.62) (4.98) (0.951)
The rural rivers in Guangzhou, China N.D.~116 (10) water Tang et al. (2019)
N.D.~223 (36) sediment
The suburban areas in south Shenyang, N.D.~6.47 (0.59) N.D.~15.57 N.D.~33.48 soil Shi et al. (2011)
China, (3.35) (3.55)
The drinking water system in Nanjing, N.D.~38.73 (4.06) drinking Wu et al. (2010)
China water
The East Lake, Wuhan, China N.D. ~ 4.89 N.D. ~ 5.06 (1) surface Yang et al. (2014)
(1.03) water
The water sources, Lebanon surface Kouzayha et al. (2013)
water
1.2e1.6 (1.5) ground
water
N.D.~4.5 (1.7) drinking
water
The Miami River, USA 11-21 (16) water Fernandez and Gardinali,
2016
The Júcar River and Turia River, Spain N.D. ~19.8 N.D. ~71.15 water Ccanccapa et al. (2016)
The Cau Hai lagoon, Vietnam 0.2e1.2 0.5e4.8 sediment Tran et al. (2019)

a. The unit of heavy metals in water sample is mg L1, and in sediment/soil sample is mg g1; the unit of pesticides in water sample is ng L1, and in sediment/soil sample is ng
g1.

adult females were used in carcinogenic risk calculation. Generally, associated with heavy metals and pesticides ranged from
a risk value exceeding 104 indicates unacceptable carcinogenic 9.91  106 to 2.01  104 and 3.00  108 to 7.01  104, respec-
health risk, while a risk value of 106 could be considered as the tively. That suggested sediment and soil could be considered the
maximum acceptable level. When the risk value is between 106 major sources of carcinogenic risks in our study area, and heavy
and 104, the health risk is considered acceptable or tolerable (US metals and pesticides were the main contaminants associated with
EPA, 2001) and that between 108 and 107 was considered as carcinogenic risk. For the individual contaminant (Table 3), the
negligible (Wang et al., 2018). Accordingly, we considered 106 as maximum carcinogenic risk of hexachlorobenzene and arsenic was
an acceptable critical threshold for adults. Our results on carcino- higher than 104, while that for other contaminants (Cd, p,p’-DDE,
genic risks associated with heavy metals (Cd and As) and pesticides p,p’-DDD, and atrazine) were at the level of 107. The contributions
(atrazine, hexachlorobenzene, p,p’-DDE, and p,p’-DDD) through of individual target contaminant to carcinogenic risks are shown in
different exposure pathways are summarized in Table 3. According Fig. 3A, which illustrated that hexachlorobenzene (83%) and arsenic
to Table 3, carcinogenic risks associated with heavy metals and (17%) presented the main contributors to carcinogenic risks in our
pesticides in surface water were all within the maximum accept- study area.
able level (106). On the contrary, the carcinogenic risks associated
with heavy metals and pesticides in sediment and soil were
3.2.2. Noncarcinogenic risk assessment
9.40  106-2.01  104 and 3.00  108-7.01  104, respectively.
Considering the worst case of noncarcinogenic health risk, we
From the view of overall risk from different environmental media
calculated noncarcinogenic risk with the highest observed con-
(i.e., surface water, sediment, and soil), the total carcinogenic risk
centrations of Cu, Zn, Cd, Cr, Ni, As, Hg, atrazine, acetochlor, and
 W. Dong et al. / Chemosphere 242 (2020) 125113 9

Table 3
Carcinogenic and non-carcinogenic risks from heavy metals and pesticides of the study area.

Substances Sample type Exposure Carcinogenic risks in each sampling region

pathways
K S B G J W

Cd water drinking 4.00E- 3.00E- 1.00E- e e e

09 09 08
dermal 5.00E- 3.00E- 1.00E- e e e
10 10 09
∑water 4.50E- 3.30E- 1.10E- e e e
09 09 08
sediment/soil ingestion 7.00E- 4.00E- 6.00E- 6.00E- 2.00E-07 4.00E-
07 07 07 07 07
P
Cd 7.05E- 4.03E- 6.11E- 6.00E- 2.00E-07 4.00E-
07 07 07 07 07
As water drinking 5.00E- 5.00E- 8.00E- 1.00E- e e
07 07 07 06
dermal 3.00E- 3.00E- 5.00E- 6.00E- e e
09 09 09 09
∑water 5.03E- 5.03E- 8.05E- 1.01E- e e
07 07 07 06
sediment/soil ingestion 2.00E- 9.00E- 2.00E- 1.00E- 1.00E-04 1.00E-
04 06 04 04 04
P
As 2.01E- 9.50E- 2.01E- 1.01E- 1.00E-04 1.00E-
04 06 04 04 04
Atrazine water drinking 2.00E- 1.00E- 1.00E- 2.00E- e e
08 08 08 08
dermal 1.00E- 8.00E- 9.00E- 1.00E- e e
10 11 11 08
∑water 2.01E- 1.01E- 1.01E- 3.00E- e e
08 08 08 08
sediment/soil ingestion 1.00E- 2.00E- 2.00E- 2.00E- 3.00E-08 2.00E-
08 08 08 08 08
P
Atrazine 3.01E- 3.01E- 3.01E- 5.00E- 3.00E-08 2.00E-
08 08 08 08 08
Hexachalo- water drinking e e e e e e
robenzene dermal e e e e e e
∑water e e e e e e
sediment/soil ingestion 7.00E- e e 7.00E- e 7.00E-
04 04 04
P
Hexachalorobenzene 7.00E- e e 7.00E- e 7.00E-
HexachalorobenzeneHexachalorobenzeneHexachalorobenzene 04 04 04
p,p’-DDE water drinking e e e e e e
dermal e e e e e e
∑water e e e e e e
sediment/soil ingestion 6.00E- 4.00E- 5.00E- 5.00E- e 3.00E-
07 07 07 07 07
P
p,p’-DDE 6.00E- 4.00E- 5.00E- 5.00E- e 3.00E-
07 07 07 07 07
p, p’-DDD water drinking e e e e e e
dermal e e e e e e
∑water e e e e e e
sediment/soil ingestion 4.00E- e e e e e
07
P
p,p’-DDD 4.00E- e e e e e
07

Heavy metals water 5.08E- 5.06E- 8.16E- 1.01E- 0.00Eþ00 3.00E-

07 07 07 06 07
sediment/soil 2.01E- 9.40E- 2.01E- 1.01E- 1.00E-04 1.00E-
04 06 04 04 04
P
heavy metals 2.01E- 9.91E- 2.01E- 1.02E- 1.00E-04 1.00E-
04 06 04 04 04
Pesticides water 2.01E- 1.01E- 1.01E- 3.00E- 0.00Eþ00 3.00E-
08 08 08 08 07
sediment/soil 7.01E- 4.20E- 5.20E- 7.01E- 3.00E-08 7.00E-
04 07 07 04 04
P
pesticides 7.01E- 4.30E- 5.30E- 7.01E- 3.00E-08 7.01E-
04 07 07 04 04

Substances Sample type Exposure pathways Non-carcinogenic risks in each sampling region

K S B G J W

Cu water drinking 1.00E-09 e 1.00E-09 1.00E-09 e e

dermal 4.00E-12 e 4.00E-12 3.00E-12 e e
∑water 1.00E-09 e 1.00E-09 1.00E-09 e e
sediment/soil ingestion 2.00E-08 1.00E-08 1.00E-08 3.00E-08 7.00E-09 2.00E-08
P
Cu 2.10E-08 1.00E-08 1.10E-08 3.10E-08 7.00E-09 2.00E-08
(continued on next page)
10 W. Dong et al. / Chemosphere 242 (2020) 125113
Table 3 (continued )

Substances Sample type Exposure pathways Non-carcinogenic risks in each sampling region

K S B G J W

Zn water drinking 4.00E-10 e 3.00E-10 e e e

dermal 1.00E-12 e 7.00E-13 e e e
∑water 4.01E-10 e 3.01E-10 e e e
sediment/soil ingestion 7.00E-09 7.00E-09 5.00E-09 5.00E-09 4.00E-09 4.00E-09
P
Zn 7.40E-09 7.00E-09 5.30E-09 5.00E-09 4.00E-09 4.00E-09
Cd water drinking 5.00E-11 4.00E-11 1.00E-10 e e e
dermal 1.00E-13 1.00E-13 3.00E-13 e e e
∑water 5.01E-11 4.01E-11 1.00E-10 e e e
sediment/soil ingestion 8.00E-09 5.00E-09 7.00E-09 7.00E-09 3.00E-09 4.00E-09
P
Cd 8.05E-09 5.04E-09 7.10E-09 7.00E-09 3.00E-09 4.00E-09
Cr water drinking e e e e e e
dermal e e e e e e
∑water e e e e e e
sediment/soil ingestion 1.00E-09 1.00E-09 1.00E-09 1.00E-09 7.00E-10 8.00E-10
P
Cr 1.00E-09 1.00E-09 1.00E-09 1.00E-09 7.00E-10 8.00E-10
Ni water drinking 7.00E-11 5.00E-11 1.00E-10 1.00E-10 e e
dermal 2.00E-13 1.00E-13 4.00E-13 4.00E-13 e e
∑water 7.02E-11 5.01E-11 1.00E-10 1.00E-10 e e
sediment/soil ingestion 4.00E-08 3.00E-08 3.00E-08 2.00E-08 2.00E-08 3.00E-08
P
Ni 4.01E-08 3.01E-08 3.01E-08 2.01E-08 2.00E-08 3.00E-08
Hg water drinking 1.00E-10 4.00E-11 1.00E-10 1.00E-10 e e
dermal 3.00E-13 1.00E-13 4.00E-13 4.00E-13 e e
∑water 1.00E-10 4.01E-11 1.00E-10 1.00E-10 e e
sediment/soil ingestion 1.00E-08 2.00E-09 2.00E-08 6.00E-09 4.00E-09 6.00E-09
P
Hg 1.01E-08 2.04E-09 2.01E-08 6.10E-09 4.00E-09 6.00E-09

Substances Sample type Exposure pathways Non-carcinogenic risks in each sampling region

K S B G J W

Atrazine water drinking 6.00E-12 4.00E-12 4.00E-12 6.00E-12 e e

dermal 2.00E-14 1.00E-14 1.00E-14 2.00E-14 e e
∑water 6.02E-12 4.01E-12 4.01E-12 6.02E-12 e e
sediment/soil ingestion 3.00E-08 5.00E-12 3.00E-08 3.00E-08 8.00E-12 3.00E-08
P
Atrazine 3.00E-08 9.01E-12 3.00E-08 3.00E-08 8.00E-12 3.00E-08
Acetochlor water drinking 2.00E-12 1.00E-12 1.00E-12 e e e
dermal 6.00E-15 3.00E-15 3.00E-15 e e e
∑water 2.01E-12 1.00E-12 1.00E-12 e e e
sediment/soil ingestion 7.00E-12 2.00E-10 9.00E-12 9.00E-12 3.00E-11 8.00E-11
P
Acetochlor 9.01E-12 2.01E-10 1.00E-11 9.00E-12 3.00E-11 8.00E-11
Hexachaloro-benzene water drinking e e e e e e
dermal e e e e e e
∑water e e e e e e
sediment/soil ingestion 3.00E-06 e e 3.00E-06 e 3.00E-06
P
Hexachalorobenzene 3.00E-06 0.00Eþ00 0.00Eþ00 3.00E-06 0.00Eþ00 3.00E-06
P
Heavy metals p,p-DDD water 1.63E-09 1.30E-10 1.61E-09 1.20E-09 0.00Eþ00 0.00Eþ00
sediment/soil 8.60E-08 5.50E-08 7.30E-08 6.90E-08 3.87E-08 6.48E-08
P
heavy metals 8.76E-08 5.51E-08 7.46E-08 7.02E-08 3.87E-08 6.48E-08
pesticides water 8.03E-12 5.01E-12 5.01E-12 6.02E-12 0.00Eþ00 0.00Eþ00
sediment/soil 3.03E-06 1.21E-09 3.10E-08 3.03E-06 7.38E-10 3.03E-06
P
pesticides 3.03E-06 1.22E-09 3.10E-08 3.03E-06 7.38E-10 3.03E-06

Fig. 3. Contributions of target substances to carcinogenic risks (A) and non-carcinogenic risks (B).

hexachlorobenzene because their doseeresponse factors are noncarcinogenic risk to adult females was chosen to be the worst
available. Similar to the carcinogenic risk assessment, the population for exposure (see Table 3). We can see that the total
 W. Dong et al. / Chemosphere 242 (2020) 125113 11

noncarcinogenic risk associated with both heavy metals and pes- risks in our study area. Fig. 4 shows that each inflow river and the
ticides ranged from 5.01  1012 to 3.03  106, suggesting that reservoir had almost similar contribution to the carcinogenic risks.
there were no apparent noncarcinogenic health risks in our study The inflow river, located on the northern part of the reservoir (i.e.,
area. Fig. 3B shows the noncarcinogenic risks of each target sub- Biliuhe River, Gelihe River, and Wolongquan River), contributed
stance and its contribution. It can be seen that hexachlorobenzene more to carcinogenic risks than the reservoir, while the bay area of
contributed 95% of the total noncarcinogenic risk; Ni contributed the Bajiahe River showed lower carcinogenic risks than the reser-
2%; and Cu, Hg, and atrazine contributed 1%. Although the voir. These results might be related to the watershed area of the
noncarcinogenic risks posed by the target heavy metals and pes- inflow river, the local gross population, the livestock and poultry
ticides were currently low in our study area, some potential mea- braising farm scale, and mining activities in our study area. The
surements for further control of pesticide utilization should be orchards and farmlands were grown in a large area in the northern
taken into consideration. part of our study area, for which pesticides were widely used by
To clarify the contribution of heavy metals and pesticides to local residents; consequently, a large amount of pesticide-
human health risks in each sampling region, we prepared a bar containing agricultural runoff from farmland discharged directly
chart (Fig. 4) to show the risk values (Fig. 4A and B) and proportion into the water environment and rivers. Furthermore, the residues of
(Fig. 4C and D) of carcinogenic risks and noncarcinogenic risks from the mining plant near the inflow rivers located on the northern part
surface water and sediment/soil in each sampling region. As shown of the reservoir also discharged industrial effluents to the rivers
in Fig. 4, heavy metals and pesticides in the sediment and soil were historically, so that the inflow rivers on the north of the reservoir
the dominant contributors to both carcinogenic risk and noncar- showed higher potential human health risks than other parts of our
cinogenic risk in the reservoir and its inflow rivers. Fig. 4 also shows study area.
the total human health risks in each sampling region. In general,
the carcinogenic risks were more critical than the noncarcinogenic

Fig. 4. Health risk and contributions of heavy metals and pesticides from water and sediment/soil to carcinogenic risks and non-carcinogenic risks in each sampling region.
12 W. Dong et al. / Chemosphere 242 (2020) 125113

4. Conclusion assessment and source identification for heavy metals in surface sediment from
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Our research presents ample information on the presence and 2013. Occurrence of pesticide residues in Lebanon’s water resources. Bull. En-
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Declaration of competing interest regions of the Yellow River using metal chemical fractions and multivariate
analysis techniques. Chemosphere 144, 264e272.
MEP, 2002. Ministry of Environmental Protection of the People’s Republic of China,
The authors have declared that no competing interests exist. Chinese National Environmental Quality Standard for Surface Water GB3838-
2002. China Environmental Science Press, Beijing (in Chinese).
Appendix A. Supplementary data MEP, 2014. Ministry of Environmental Protection of the People’s Republic of China,
Exposure Factors Handbook of Chinese Population (Adults). China Environ-
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Supplementary data to this article can be found online at MEE, 2018. Ministry of Ecology and Environment of the People’s Republic of China,
https://doi.org/10.1016/j.chemosphere.2019.125113. Chinese National Soil Environmental Quality Risk Control Standard for Soil
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