Environmental Pollution 268 (2021) 115926

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Chemical characteristics and sources of ambient PM2.5 in a harbor

area: Quantification of health risks to workers from source-specific
selected toxic elements*
Baoshuang Liu a, Jianhui Wu a, *, Jing Wang b, Laiyuan Shi b, He Meng b, Qili Dai a,
Jiao Wang c, Congbo Song d, Yufen Zhang a, Yinchang Feng a, Philip K. Hopke e, f
a
State Environmental Protection Key Laboratory of Urban Ambient Air Particulate Matter Pollution Prevention and Control & Tianjin Key Laboratory of
Urban Transport Emission Research, College of Environmental Science and Engineering, Nankai University, Tianjin, 300350, China
b
Qingdao Ecological and Environmental Monitoring Centre of Shandong Province, Qingdao, 266003, China
c
College of Environmental Science and Engineering, Key Laboratory of Marine Environmental Science and Ecology (Ministry of Education), Ocean University
of China, Qingdao, Shandong, 266100, China
d
School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, UK
e
Center for Air Resources Engineering and Science, Clarkson University, Potsdam, NY, 13699, USA
f
Department of Public Health Sciences, University of Rochester School of Medicine and Dentistry, Rochester, NY, 14642, USA

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

Article history: Samples of ambient PM2.5 were collected in the Qingdao harbor area between 21 March and May 25,
Received 21 July 2020 2016, and analyzed to investigate the compositions and sources of PM2.5 and to assess source-specific
Received in revised form selected toxic element health risks to workers via a combination of positive matrix factorization (PMF)
21 October 2020
and health risk (HR) assessment models. The mean concentration of PM2.5 in harbor area was 48 mg m
3
Accepted 22 October 2020
Available online 25 October 2020
with organic matter (OM) dominating its mass. Zn and V concentrations were significantly higher than
the other selected toxic elements. The hazard index (HI) and cancer risk (Ri) of all selected toxic elements
were lower than the United States Environmental Protection Agency (USEPA) limits. There were no non-
Keywords:
Cancer risks
cancer and cancer risks for workers in harbor area. The contributions from industrial emissions (IE), ship
Non-cancer risks emissions (SE), vehicle emissions (VE), and crustal dust and coal combustion (CDCC) to selected toxic
Source apportionment elements were 39.0%, 12.8%, 24.0%, and 23.0%, respectively. The HI values of selected toxic elements from
PSCF IE, CDCC, SE, and VE were 1.85  10
1, 7.08  10
2, 6.36  10
2, and 3.37  10
2, respectively; these are
lower than the USEPA limits. The total cancer risk (Rt) value from selected toxic elements in CDCC was
2.04  10
7, followed by IE (6.40  10
8), SE (2.26  10
8), and VE (2.18  10
8). CDCC and IE were the
likely sources of cancer risk in harbor area. The Bo Sea and coast were identified as the likely source areas
for health risks from IE via potential source contribution function (PSCF) analysis based on the results of
PMF-HR modelling. Although the source-specific health risks were below the recommended limit values,
this work illustrates how toxic species in PM2.5 health risks can be associated with sources such that
control measures could be undertaken if the risks warranted it.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction to multiple adverse human health outcomes (Kampa and Castanas,

Particulate matter (PM) with an aerodynamic diameter less than
or equal to 2.5 mm (PM2.5) has been recognized as an important
particulate air pollution (WHO, 2005), because it has been related
*
This paper has been recommended for acceptance by Admir C. Targino.
* Corresponding author. Nankai University, No.38 Tongyan Road, Jinnan District,
Tianjin, 300350, PR China.
E-mail address: envwujh@nankai.edu.cn (J. Wu).
2008; WHO, 2016; USEPA, 2019). PM2.5 has a relatively large surface
area to mass ratio making them potential carriers of biologically
available transition metals or metalloids (Pandey et al., 2013) that
can accumulate in the human body via inhalation, ingestion, and
dermal contact absorption (Fang et al., 2013; Xue et al., 2012; Zhang
et al., 2016). Hamad et al. (2016) and Huang et al. (2018) found that
the health effects of PM2.5 are strongly associated with its chemical
content. Health risk assessments of selected toxic elements in PM2.5
have recently received considerable attention worldwide (Chen

https://doi.org/10.1016/j.envpol.2020.115926
0269-7491/© 2020 Elsevier Ltd. All rights reserved.
B. Liu, J. Wu, J. Wang et al.
et al., 2014; Peng et al., 2017).
PM2.5 emission sources tend to be concentrated and diverse in
the large port areas with substantial quantities of PM2.5 being
emitted by various sources associated with the harbor activities
(Corbin et al., 2020; Healy et al., 2009; Pe
rez et al., 2016). Harbors
can result in environmental burdens with adverse effects on health
and climate (Cesari et al., 2014; Merico et al., 2016; USEPA, 2019). To
date, relevant studies on harbor areas have primarily focused on the
quantification of shipping emissions to air pollutants including
gaseous pollutants and PM (Merico et al., 2016; Lang et al., 2017;
Zhang et al., 2017, 2019; Nunes et al., 2017); source profiles of PM2.5
emitted from ships (Agrawal et al., 2008, 2010; Wen et al., 2018);
and the characteristics of chemical species and source apportion-
ment of PM (Bove et al., 2016; Tolis et al., 2015; Gao et al., 2002).
Agrawal et al. (2008) found that V, Ni, and Zn can be emitted from
the main and auxiliary engines of large ships. High exposure to
selected toxic elements emitted from sources in harbor areas can
affect the health of port workers who spend extensive periods in
the ambient environment. Thus, it is important to identify critical
sources of risks from selected toxic elements in harbor areas to be
able to effectively reduce occupational health risks. At present,
most studies are mainly focused on the analysis of health risks for
selected toxic elements emitted from specific sources (Chen et al.,
2014; Fang et al., 2013; Wen et al., 2018; Xu et al., 2016).
Although some work has identified major sources of risk using a
combination of positive matrix factorization (PMF) and a health risk
assessment model (Peng et al., 2017; Tsai et al., 2020), such studies
are still limited. Tsai et al. (2020) analyzed health risks and major
sources of toxic elements risk at a suburban site on the west coast of
Taiwan and found that greatest cancer risk comes from the As and
Cr(VI), which are closely related to emissions from a coal-fired
power plant. Furthermore, regional transport can also have an
important impact on the concentration of ambient selected toxic
elements in harbor areas. However, there have been no related
studies on the potential source -areas for health risks from toxic
elements from this perspective.
The main ports of Qingdao are located in Jiaozhou Bay and on
the west coast of the city. They are both important maritime
transport hubs (Li et al., 2017). In recent years, Qingdao has
implemented a relocation and transformation project for busi-
nesses from the old city to the port area. Industrial enterprises such
as iron and steel industries have been relocated to form a port in-
dustrial complex. These industries, ships in port, and the related
vehicles emit PM and selected toxic elements into the air in this
area (Zhang et al., 2017; Li et al., 2017). Chen et al. (2017) found that
the annual emissions of PM10 and PM2.5 from ships across the
Qingdao port area were up to 4.54  103 and 4.18  103 tons,
respectively. Some studies reported that approximately 70% of ship
emissions occurred within 400 km of the coastal regions (Chen
et al., 2019; Contini et al., 2015; Eyring et al., 2010). Near-shore
emissions can negatively affect public health in coastal areas,
especially at the ports (Chen et al., 2016, 2017; Poplawski et al.,
2011). However, the health risks to workers from selected toxic
elements discharged from PM sources and potential source -areas
for these risks have not been assessed in the Qingdao harbors.
The objectives of this study were to: (1) Collect PM2.5 samples
and analyze their chemical composition and identify the PM2.5
sources in the harbor area; (2) Conduct an assessment of health
risks of selected toxic elements in PM2.5 to harbor workers; (3)
Evaluate the health risks of selected toxic elements emitted from
different sources by combining PMF and risk assessment models;
and (4) Analyze potential source -areas for health risks of selected
toxic elements from different sources by developing a combined
positive matrix factorizationehealth risksepotential source
2
Environmental Pollution 268 (2021) 115926
contribution function (PMFeHRePSCF) method.
2. Methods and materials
2.1. Site description
Qingdao is situated on the Shandong Peninsula in eastern China
(Fig. 1) and has a temperate marine monsoon climate. The urban
area is 3293 km2, with a population of more than 9 million in 2016.
There were more than 2.3 million vehicles in the city in 2016. The
coastline is approximately 730 km in length. The total cargo
throughput of the Qingdao port was 500 million tons in 2016, the
seventh greatest globally in that year. In this study, PM2.5 sampling
campaigns were conducted at three harbor sitese Dongjiakou
(DJK), Huangdao (HD), and Jiaonan (JN) (Fig. 1). DJK was surrounded
by industrial parks (Table S1), HD was near the hub for large cargo
ships, and JN was close to a part of harbor where freighters often
passed. The meteorological parameters and data on atmospheric
pollutants were obtained from China National Air Quality Moni-
toring Stations within 1 km of the PM samplers during the sam-
pling campaign (Fig. S1). Southerly and South-easterly winds
prevailed in Qingdao during the study period (Fig. S2).
2.2. Sampling and chemical analysis
2.2.1. Sampling
PM2.5 samples were collected at the three sites from 21 March to
5 April and 16 to 25 May, 2016 using a six-channel sampler
(ZR3930, Qingdao Junray Intelligent Instrument Co., Ltd, Qingdao)
with a flow rate of 16.7 L min
1. Three channels of the sampler were
loaded with quartz filters while the other three were loaded with
polypropylene filters for PM2.5 sampling. The samples were
collected for 22 h, from 11:00 to 09:00 the following day. The total
number of ambient PM2.5 samples taken during the sampling
period was 78. The sampling sites were set on building rooftops
~10e15 m above ground level. Field blanks and parallel samples
were collected synchronously at each site. Before sampling, quartz
filters (47 mm in diameter; Munktell, Sweden) and polypropylene
filters (47 mm in diameter; Munktell, Sweden) were baked in an
oven at 500  C and 60  C, respectively. After sampling, all the filters
were stored at 4  C before gravimetric and chemical analysis.
2.2.2. Gravimetric and chemical analysis
Prior to gravimetric analysis, the filters were equilibrated for
48 h at constant temperature (20 ± 1  C) and humidity (45%e55%)
conditions. The sample filters collected on 23 May were equili-
brated for 72 h due to high relatively humidity (89%) on that day. All
filters were weighed three times on a microbalance with a reso-
lution of 0.01 mg (XS105DU, Mettler Toledo) before and after
sampling. The differences in replicate weights were less than 40 mg
for each sample. After gravimetric analysis, a 0.536 cm2 punch was
taken for organic carbon (OC) and elemental carbon (EC) analysis.
OC and EC were measured using a Desert Research Institute Model
2001 thermal/optical carbon analyzer, according to the IMPROVE_A
thermal/optical reflectance (TOR) protocol. The remainder of the
quartz filters were analyzed for water-soluble ion content using ion
chromatography (Metrohm, 940 Professional IC Vario). The
elemental content of the polypropylene filters was measured by
inductively coupled plasmaemass spectrometry (ICP-MS; Agilent
7500a). The selected toxic elements measured in this study were Cr,
V, Cd, Mn, Pb, As, Co, Zn, Ni, and Cu. Further details of the mea-
surement and quality control of elements, water-soluble inorganic
ions and carbon species (OC and EC) are given in the Supplemen-
tary Material.
B. Liu, J. Wu, J. Wang et al.
Fig. 1. Map of sampling sites in the harbor area. HD represents Huangdao site, JN represents Jiaonan site, and DJK represents Dongjiakou site.
2.3. Mass reconstruction
The reconstruction of PM2.5 mass was conducted by summing
the concentrations of secondary organic aerosols (SOA), primary
organic aerosols (POA), EC, crustal material, trace elements, sulfate,
nitrate, ammonium, sea salt, and other materials. Further details
are provided in the Supplementary Material.
2.4. Positive matrix factorization (PMF) and risk assessment model
PMF decomposes a matrix of sample composition data (X) into
two matrices, the source profiles (F) and source contributions (G)
(Paatero and Tapper, 1994; Hopke, 2016). The principles of PMF are
described in the Supplementary Material. Bootstrap (BS) and
displacement (DISP) analysis were used to investigate the effects of
measurement error and rotation ambiguity on the resulting solu-
tions. The measured concentrations of selected toxic elements and
the health risk assessment model developed by the United States
Environmental Protection Agency (USEPA) (USEPA, 1996) were
used to analyze the non-cancer risk (NCR) factors (Hazard Quotient:
HQ, Hazard Index: HI) and cancer risk (CR) (Ri) factors. In this study,
the selected toxic elements pose health risks to workers in the
harbor area through the exposure pathways of inhalation and
dermal contact (Chen et al., 2014; Ferreira-Baptista and De Miguel,
2005) but the ingestion pathway was not considered given the
actual intake situations since workers ate and drank under condi-
tions that were unlikely to provide exposures to ambient pollut-
ants. Further details are provided in the Supplementary Material.
3
Environmental Pollution 268 (2021) 115926
2.5. Positive matrix factorizationetoxic element health risks (PMF-
HR) model
In order to quantify the HR from sources, a PMF-HR model was
developed by combining the PMF model with the health risk
assessment model.
Step 1: Using PMF to estimate source contributions to selected
toxic elements in PM2.5
Cijk ¼ gik *fjk (1)
Cijk *103
Pijk ¼ (2)
Si
where Ckij represents the calculated contribution (ng m
3) of the jth
toxic element from kth source in the ith sample, Pkij represents the
ratio mass contribution (mg kg
1) of the jth toxic element from kth
source in the ith sample, and Si is the PM2.5 mass concentration (mg
m
3) of the ith sample. The gki is the calculated contribution from
kth source in the ith sample, and the fkj is the fraction of the jth toxic
element from kth source.
Step 2: Quantifying the HR from sources.
(1) Source apportionment for NCR. The daily dose of the jth toxic
element through inhalation (Dkij,inh, mg kg
1 d
1) and dermal
contact (Dkij,der, mg kg
1 day
1) in the ith sample from the
kth source are calculated using the following:
B. Liu, J. Wu, J. Wang et al. Environmental Pollution 268 (2021) 115926

2.6. Backward trajectory and the potential source contribution

function (PSCF)
Pijk *InhR*EF*ED
Dkij;inh ¼ (3)
PEF*BW*AT Air parcel trajectories at the Qingdao harbor (35.82 N, 119.96
E) were calculated backwards in time at 1 h intervals for 72 h using
the Hybrid Single Particle Lagrangian Integrated Trajectory (HYS-
Pijk *SA*SL*ABF*EF*ED*10
6 PLIT) model, and the starting height was set at 100 m above the
Dkij;der ¼ (4) ground. PSCF analysis were used to identify the likely source -areas
BW*AT
based on the results of the HYSPLIT analysis. The study region was
where the inhalation rate of air, InhR, is assumed to be 20 m3 d
1 divided into equal-sized grid cells i  j. The HYSPLIT trajectory
(Ferreira-Baptista and De Miguel, 2005). The exposure frequency clustering and PSCF were run using the GIS-based software TrajStat
(EF) is assumed to be 350 d year
1, and the exposure duration (ED) (Wang et al., 2009). In this study, the results of the PMF-HR model
is given as 30 years for adults (USEPA, 2004). The PEF the particle were used to determine the potential source -areas of health risks
emission factor, and its value is set to 1.36  109 m3 kg
1 in this from selected toxic elements with the PSCF model. Further details
study (USEPA, 2001). The mean body weight (BW) is 70 kg for of backward trajectory and PSCF analysis are presented in the
adults, and the mean exposure time (AT) is 25,550 (70*365) days Supplementary Material.
(Ferreira-Baptista and De Miguel, 2005; USEPA, 2004). The exposed
skin area (SA) is assumed as 5700 cm2 for adults, the SL is the skin 3. Results and discussion
adherence factor, taken as 0.07 mg cm
2 d
1, and the dermal ab-
sorption factor (ABF) is set to 0.001 while that for As and Cr (VI) is 3.1. Characteristics of PM2.5 and chemical species
0.03 and 0.04 (Ferreira-Baptista and De Miguel, 2005; Wang et al.,
2020). The plots of the time series of PM and PM2.5/PM10 during the
The corresponding HQ is estimated as below: sampling period are shown in Fig. 2. The mean and standard de-
viation of the PM2.5 concentration in the harbor area was
48 ± 30 mg m
3, which exceeds the limit for air quality standards in
Dkij;inh China (GB3095-2012 Grade II, 35 mg m
3) by 137%. A Kruskal-Wallis
k
HQij;inh ¼ (5)
RfDinh ANOVA on ranks (KW-ANOVA) for the three sites showed that the
results were significant (p < 0.01). The Dunn-Bonferroni (DB) was
performed for all possible post-hoc pairwise comparisons. The
Dkij;der mean PM2.5 concentrations at DJK (59 ± 37 mg m
3) were signifi-
k
HQij;der ¼ (6) cantly higher (p < 0.01) than at the other sites (HD: 35 ± 20 mg m
3;
RfDder
JN: 48 ± 25 mg m
3). The mean and standard deviation for PM2.5/
where HQkij,inh, HQkij,der are the HQ of the jth toxic element in the ith PM10 at the harbor were 0.6 ± 0.2 and all site ratios exceeded 0.5.
sample from the kth source, related to inhalation and dermal The PM2.5/PM10 at DJK (0.7 ± 0.1) was significantly higher than at
contact, respectively. The reference dose (RfD) values of ten the other sites according to the results of the KW-ANOVA and DB
selected toxic elements are shown in Table 1. tests (p < 0.05) (HD: 0.5 ± 0.2; JN: 0.6 ± 0.2). The lowest PM2.5/PM10
(2) Source apportionment for CR. The cancer risk of the jth toxic at HD implied the occurrence of higher dust pollution.
element in the ith sample from the kth source (Rkij) is esti- Good correlations (r2 > 0.98) were found between the recon-
mated as follows: structed and observed PM2.5 concentrations (Fig. S3). The recon-
structed PM2.5 explained 94%e96% of the PM2.5 mass across all the
sites. The mean concentration of OM (POA þ SOA) was
Rkij ¼ Dkij;inh *SFIj (7) 16.7 ± 5.8 mg m
3 and dominated the PM2.5 mass. The OC con-
centration (10.5 ± 3.6 mg m
3) was highest, followed by sulfate
(9.7 ± 5.5 mg m
3), nitrate (8.8 ± 7.8 mg m
3), ammonium
X (6.5 ± 3.7 mg m
3) and EC (3.8 ± 1.8 mg m
3). In addition to emis-
Rt ¼ Rkij (8)
sions from motor vehicles and coal combustion, high concentra-
tions of OC might be related to the high emissions from ship
where Dkij,inh is obtained using Eq. (3). The inhalation slope factor
engines and ancillary vehicles in the harbor (i.e. diesel trucks and
(SFI) values of the ten selected toxic elements are listed in Table 1. Rt
forklifts) (Fig. S4) (Corbin et al., 2020; Wen et al., 2018). Primary OC
is the total risk of cancer from toxic element exposures.
(POC) and EC showed similar spatial distributions across all sites,
with the highest concentrations at DJK (6.7 ± 3.2 and
Table 1 4.3 ± 2.2 mg m
3) and lowest at JN (5.6 ± 2.3 and 3.5 ± 1.4 mg m
3);
The reference doses and slope factors of selected toxic elements. secondary OC (SOC) followed a different spatial distribution, its
Element RfDinh RfDder SFI concentration followed the order HD (5.6 ± 2.9 mg m
3) > JN
(4.3 ± 1.8 mg m
3) > DJK (3.9 ± 2.9 mg m
3). A higher SOC con-
Cr(VI) 1.00E-04 7.50E-05 5.00E-01
Mn 1.43E-05 1.84E-03
centration at HD may have caused the low correlation between OC
Co 5.71E-06 1.60E-02 9.80Eþ00 and EC at that site (r2 ¼ 0.29, p ¼ 0.006), which was noticeably
Ni 2.06E-02 5.40E-03 8.40E-01 lower than at the other sites (r2 ¼ 0.64e0.67, p ¼ 0.000) (Fig. S5).
Cu 4.02E-02 1.20E-02 The OC/EC ratio at DJK (2.7 ± 0.8) was significantly lower than at the
Zn 3.00E-01 6.00E-02
other sites (JN: 3.0 ± 0.7; HD: 3.5 ± 1.1), likely due to the influence
As 3.01E-04 1.23E-04 1.51Eþ01
Cd 1.00E-03 1.00E-05 6.30Eþ00 of diesel trucks, forklifts, and diesel-powered cranes (Table S1 and
Pb 3.52E-03 5.25E-04 Fig. S4). The concentrations of sulfateenitrateeammonium (SNA)
V 7.00E-03 7.00E-05 at DJK (mean: 30.9 ± 16.2 mg m
3) were significantly higher (KW-
The reference values were obtained from Alves et al. (2019), Chen et al. (2014), ANOVA and DB tests, p < 0.01) than at the other sites (JN:
Wang et al. (2020), and Ferreira-Baptista and De Miguel (2005). 22.0 ± 12.1 mg m
3; HD: 22.9 ± 15.1 mg m
3); this was likely related
4
B. Liu, J. Wu, J. Wang et al.
Fig. 2. Time series of concentrations of (a) PM and PM2.5/PM10, and mass (b) concentrations and (c) fractions of PM2.5 species. SNA denotes the sum of sulfate, nitrate and
ammonium. Mass reconstruction is described in the Supplementary Material.
to the complex industrial sources around DJK (Fig. S4). Previous
studies have found that desulphurization of emissions from coal-
fired boilers-achieved via wet processing and residential coal
combustion in traditional household stoves (Dai et al., 2019; Li
et al., 2019) can discharge substantial quantities of sulfate parti-
cles into the air (Liu et al., 2017; Ma et al., 2015). These sources may
explain why concentrations of sulfate were higher at DJK
(12.4 ± 5.7 mg m
3) than at the other sites (HD: 8.4 ± 5.4 mg m
3; JN:
8.8 ± 4.5 mg m
3), while the concentrations of gaseous precursors
(SO2) were lower at DJK (18 ± 6 mg m
3) than at near HD
(26 ± 10 mg m
3) (Table S1). In addition, Wen et al. (2018) found
that the amount of SO2
4 emitted directly by ships should not be
ignored. The NO
2

3 /SO4 ratio has been used to indicate the impor-
tance of stationary versus mobile emissions (Arimoto et al., 1996).
The mean NO
2

3 /SO4 ratio at DJK (0.6 ± 0.4) was lower than that at
HD (0.8 ± 0.5) and JN (1.0 ± 0.6), suggesting that the influence of
stationary emissions near DJK was relatively higher than at the
other sites.
The mean concentration of crustal material across the three sites
was 6.7 ± 2.6 mg m
3, with the concentration at DJK
(7.5 ± 3.4 mg m
3) noticeably higher than that at the other sites (JN:
6.1 ± 1.6 mg m
3; HD: 6.4 ± 2.4 mg m
3). Fe had the highest con-
centration (0.8 ± 0.6 mg m
3), followed by Ca (0.7 ± 0.3 mg m
3), Al
(0.6 ± 0.6 mg m
3), and Si (0.5 ± 0.2 mg m
3); there were smaller
spatial differences in the concentrations of trace elements. The
mean concentrations of the ten selected toxic elements at the three
sites were in the order Zn > V > Pb > Mn > Cr >
Cu > Ni > As > Cd > Co (Table S3). The concentrations of Zn and V
were likely higher than those of other toxic elements due to the
influence of vehicle and ship emissions (Agrawal et al., 2008; Bove
et al., 2016; Tao et al., 2017; Leung et al., 2008). The mean con-
centration of V at HD (168 ± 143 ng m
3) was markedly higher than
that of DJK (105 ± 91 ng m
3) and JN (99.1 ± 68.8 ng m
3), likely
because of the emissions from ships (Fig. S4). The measured mean
concentrations of As and Cr exceeded the limits of air quality
standards in China by 1.43 and 1544 times, respectively, while
those for Pb and Cd were lower than the corresponding limits. The
mean concentrations of V and Cr in the Qingdao harbor area were
5
Environmental Pollution 268 (2021) 115926
higher than those in other port cities (Table S4), while the value for
Ni was close to those in Nanjing and Dalian but significantly lower
than those at Huzhou and Thessaloniki. The mean concentration of
Cd in the Qingdao harbor area was lower than those in the other
cities (Table S4). Fig. S6 shows the Pearson correlation coefficients
for the ten selected toxic elements in the harbor area; Mn, Zn, Pb,
As, Cd, Ni, and Cu showed significant correlations with each other,
with r2 values ranging from 0.45 to 0.94, implying that their sources
and transport mechanisms were related. The correlations between
V and other selected toxic elements were not significant; this
suggests that V was likely derived from a different source, such as
ship emissions (Bove et al., 2016; Tao et al., 2017). The poor corre-
lation between V and Ni (r2 ¼ 0.06) is unusual for a port; however, it
does indicate that the Ni primarily originated from industrial, not
marine sources. The correlation between Co and As was moderately
high (r2 ¼ 0.59), while those of Co and other selected toxic elements
were poor (0.01 < r2 < 0.03).
3.2. HR assessment for selected toxic elements in PM2.5
Table S5 summarizes the results of estimations of the daily
doses, HQs, and HIs for Cr(VI), Co, Ni, As, Mn, Cu, Cd, Zn, and Pb
(Fig. 3, Tables S6eS7). Prior studies have suggested that Cr(VI) is
generally only a small fraction of the total concentration of Cr (Park
et al., 2008; Rowbotham et al., 2000). It is assumed that 14.2% of the
Cr was Cr (VI), based on studies by Hieu and Lee (2010), Xu et al.
(2016), and Tsai et al. (2020). For inhalation, the total HQinh was
3.68  10
3; the HQinh values for Mn and Co were higher than those
for all other selected toxic elements at 3.34  10
3 and 1.87  10
4,
respectively. The HQinh values of Mn and Co at HD were relatively
high at 3.70  10
3 and 2.22  10
4, respectively, while that of
Cr(VI) (1.01  10
4) was relatively high at JN. For dermal contact,
the total HQder was 0.19; the HQder values of Cr(VI) and V were 0.11
and 0.07, respectively; significantly higher than other toxic ele-
ments. The HQder value of Cr(VI) was relatively high at JN (0.15)
while that of V was relatively high at HD (9.24  10
2). Dermal
contact is a major pathway for selected toxic elements in terms of
their total HQ; this observation is distinct from the results in related
B. Liu, J. Wu, J. Wang et al.
Fig. 3. Daily doses, hazard quotients (HQ), hazard indices (HI) and cancer risks of selected toxic elements in the harbor area.
studies (Fang et al., 2013; Chen et al., 2014; Peng et al., 2017). For a
HQ value less than 1, non-cancer effects are believed to be
improbable (Leung et al., 2008). Therefore, as the HQ values
calculated for the exposure routes of inhalation and dermal contact
were all less than 1, there is likely no significant risk of non-cancer
effects from these in the harbor area.
The HI values for selected toxic elements in the harbor area are
shown in Fig. 3 and Table S7. The HI values were ranked in the order
Cr(VI) > V > Cd > Mn > Pb > As > Co >Zn > Ni > Cu, and the total HI
value of all the selected toxic elements was 0.20 and less than the
acceptability limit of 1 (USEPA, 1989). Of the ten selected toxic el-
ements, Cr(VI) and V were the major contaminants that could cause
any non-cancer risks. The mean HI values of Cr(VI) at DJK (0.13) and
JN (0.15) were higher than that at HD (0.06), while that of V was
higher at HD (0.09) than at JN (0.06) and DJK (0.05) (Table S7).
These results suggest a greater non-cancer risk at JN although it
dose not exceed the USEPA limits.
The Ri from inhalation exposure was calculated using the Dinh
and SFI (Fig. 3). Mn, Cu, Zn, Pb, and V were eliminated from the
evaluation of cancer risk because of the absence of corresponding
SFI values. The Ri values for As, Ni, Co, Cd, and Cr(VI) were
1.58  10
7, 1.53  10
8, 1.04  10
8, 9.68  10
9, and 3.88  10
9,
respectively, indicating that As is the critical toxic element in terms
of cancer risks to workers. This result differs from that of Peng et al.
(2017). The total Ri value of these five selected toxic elements was
1.98  10
7; this is below the acceptable limit (1.00  10
6) (Betha
et al., 2014). The Ri values of As at DJK was 1.94  10
7, which is
higher than that at HD (1.41  10
7) and JN (1.41  10
7). Thus, this
study shows that workers in the harbor area are not at risk from
cancer although they are exposed to selected toxic elements. In
contrast, Tsai et al. (2020) found that As and Cr(VI) contribute the
majority of the cancer risk at one site near the western coast of
Taiwan.
6
Environmental Pollution 268 (2021) 115926
3.3. Source apportionment for PM2.5
The EPA PMF V5.0 was used to identify PM2.5 sources in the
Qingdao harbor area. Seven factors were chosen in PMF analysis
(Fig. S7). The estimated Q value from PMF was close to the theo-
retical value. The observed PM2.5 concentrations and those calcu-
lated from the PMF had a high correlation (r2 ¼ 0.98) (Fig. S8) and
the scaled residual distributions demonstrated good fits to the
included species. Based on a base model BS error estimation of the
PMF model, we found that the calculated results were stable and all
factors were mapped in over 90% of BS runs when the seven factors
were selected. The first factor was denoted industrial emissions (IE)
because it featured by high Cr, Mn, Fe, Co, Ni, Cu, and Zn explained
variances and relatively high concentrations of Cl
, SO2
4 and OC.
These species mainly originated from industrial emissions related
with steel and metallurgy (Ali et al., 2019; Liu et al., 2018; Zhao
et al., 2019; Zhang et al., 2020), and have relatively narrow DISP
intervals.
The ship emissions (SE) factor is characterized by high V and Ni
explained variances with associated narrow DISP bands, and rela-
tively high concentrations of OC and EC (Bove et al., 2016; Tao et al.,
2017; Wen et al., 2018). The third factor is dominated by OC and EC
and relative high Cu and Zn explained variances with small DISP
bounds. OC and EC are generally derived from vehicle exhaust (Liu
et al., 2018; Shirmohammadi et al., 2017). Zn is widely used as an
additive in lubricating oil that is combusted in engines resulting in
emitted Zn (Pulles et al., 2012; Amirante et al., 2017). Cu is related to
brake wear (Liu et al., 2017; Canha et al., 2012; Zhang et al., 2020).
Thus, this factor was classified as vehicle emissions (VE).
The fourth factor is dominated by high Si, Ca, Mg, and Al
explained variances with narrow DISP bounds and relatively high
concentrations of As, Cl
, SO2
4 , and OC. Si, Ca, Mg, and Al originate
mainly from crustal dust (Liu et al., 2018, 2020; Wang et al., 2015),
B. Liu, J. Wu, J. Wang et al.
while As, Cl
, SO2

4 , and OC are related to coal combustion (Liu et al.,
2017; Park et al., 2020; Zhang et al., 2011; Dai et al., 2018). Thus, this
factor was a mixed source of crustal dust and coal combustion
(CDCC). The factor characterized by high Na and Cl
with narrow
DISP bounds was identified as sea salt (SS) (Bove et al., 2016; Tian
et al., 2018). Secondary nitrate (SN) is composed primarily of NO

and NHþ 4 with tight DISP intervals (Liu et al., 2018; Uranishi et al.,
2017; Zhao et al., 2019). The final factor featured high concentra-
tions of SO2
4 and NHþ 4 , and some OC (Park et al., 2020;
Srimuruganandam and Nagendra, 2012; Tian et al., 2020); those
species have smaller DISP ranges than the others. Therefore, it was
classified as secondary sulfate and SOC (SSSC).
The industrial emissions, ship emissions, vehicle emissions,
crustal dust and coal combustion, sea salt, secondary nitrate, and
secondary sulfate and SOC were identified as major contributors to
PM2.5 in the harbor area, contributing 7.7% (4.5 mg m
3), 6.0%
(3.5 mg m
3), 16.8% (9.8 mg m
3), 29.6% (17.2 mg m
3), 3.4%
(1.9 mg m
3), 15.1% (8.6 mg m
3), and 16.8% (9.6 mg m
3), respec-
tively (Fig. 4 and Fig. S9). The contribution of industrial emissions to
PM2.5 at Dongjiakou (8.6%; 5.6 mg m
3) was higher than that at
Huangdao (7.6%; 4.4 mg m
3) and Jiaonan (6.9%; 3.6 mg m
3); this is
probably because there is an industrial park around Dongjiakou
(Table S2). The contribution of ship emissions to PM2.5 was higher
at Huangdao (6.9%; 4.0 mg m
3) than at Dongjiakou (5.6%;
3.6 mg m
3) and Jiaonan (5.5%; 2.8 mg m
3), likely due to frequent
shipping activity at Huangdao port. For vehicle emissions, the
contribution to PM2.5 was higher at Dongjiakou (18.1%; 11.7 mg m
3)
than at Huangdao (16.5%; 9.4 mg m
3) and Jiaonan (15.9%;
8.2 mg m
3). The contribution of crustal dust and coal combustion
to PM2.5 at Dongjiakou (32.5%; 21.0 mg m
3) was significantly
higher than at Huangdao (30.0%; 17.1 mg m
3) and Jiaonan (26.3%;
13.5 mg m
3). The higher contributions of vehicle emissions and
crustal dust and coal combustion at Dongjiakou were associated
with frequent industrial activities and freight transport (Table S2).
The contribution of sea salt to PM2.5 at Jiaonan (5.3%; 2.7 mg m
3)
was markedly higher than at Dongjiakou (2.6%; 1.7 mg m
3) and
Huangdao (2.1%; 1.2 mg m
3). For secondary nitrate, secondary
sulfate and SOC, their contributions to PM2.5 at Jiaonan were higher
than at other sites. Figs. S10eS11 show the time series of source
contributions at different sites; of these contributions, those from
crustal dust and coal combustion and secondary sources were
relatively higher than those from other sources monitored during
the study period.
Fig. 4. Source contributions of PM2.5 at three sites in the harbor area. IE represents industrial emissions, SE represents ship emissions, VE represents vehicle emissions, CDCC
represents crustal dust and coal combustion, SS represents sea salt, SN represents secondary nitrate, SSSC represents secondary sulfate and SOC, and US represents unresolved
sources.
Environmental Pollution 268 (2021) 115926
Source apportionment results from other global port -cities
show that secondary sources, coal/industrial emissions, crustal
dust, and vehicle emissions were major sources of PM2.5, while the
contributions of ship emissions were relatively low (Jeong et al.,
2017; Cesari et al., 2014; Choi et al., 2013). Zhou et al. (2017)
3 found that coal combustion and biomass burning, in winter and
autumn, respectively, could increase their contributions to emis-
sions but led to lower contributions of shipping emissions. Zhao
et al. (2013) found that the primary PM2.5 from shipping accoun-
ted for only 4.23% of the PM2.5 measured at Yangshan Port in
Shanghai. However, the contribution of ship emissions to PM2.5 in
the harbor area in Qingdao, at 6.0%, was higher than in other port
cities (Lang et al., 2017; Zhao et al., 2013; Zhang et al., 2014).
3.4. Quantifying the HR from each source
Source contributions to selected toxic elements were calculated
based on the PMF results (Figs. S12eS15). The contributions of IE,
SE, VE, and CDCC to selected toxic elements were 39.0%, 12.8%,
24.0%, and 23.0%, respectively; these were significantly higher than
the contributions of other sources. IE made the highest contribu-
tion to each toxic element in the harbor area; its contribution to Cr
was 82.0%. The contributions of VE to Zn and Cd were 51.3% and
66.2%, respectively, and the contribution of CDCC to As was 71.7%.
The contribution of IE to selected toxic elements at DJK was 40.2%,
which was significantly higher than at HD (38.2%) and JN (38.2%).
The contribution of SE to selected toxic elements at HD (14.4%) was
significantly higher than at JN (12.9%) and DJK (11.4%). However,
there were no significant spatial differences in the contributions of
VE and CDCC to selected toxic elements.
The Dder and Dinh for selected toxic elements from different
sources were estimated based on the results of the PMF model
(Tables S8eS9). The HQ and HI values of selected toxic elements
from different sources were then calculated (Fig. S16;
Tables S10eS12). The source contributions to Cr(VI) were estimated
based on 14.2% of the total Cr contributions. The total HQder values
of selected toxic elements from IE, CDCC, SE, and VE were
1.80  10
1, 6.94  10
2, 6.31  10
2 and 3.10  10
2, respectively;
these were all higher than the other sources. The HQder value of
Cr(VI) from IE was up to 1.38  10
1, which was significantly higher
than those of selected toxic elements from other sources. The HQder
values of V from CDCC (6.47  10
2), SE (6.15  10
2), and IE
(3.70  10
2) were also relatively high. The total HQinh values of
7
B. Liu, J. Wu, J. Wang et al.
selected toxic elements from IE, VE, and CDCC were 5.15  10
3,
2.78  10
3, and 1.45  10
3, respectively; these values are higher
than those of the other selected toxic elements. The HQinh values of
Mn from IE, VE, and CDCC were 4.91  10
3, 2.74  10
3, and
1.27  10
3, respectively; these are significantly higher than those
of other selected toxic elements from other sources. If HQ < 1, non-
cancer effects are thought to be improbable (Leung et al., 2008). In
this study, the total HQder and HQinh values of selected toxic ele-
ments from all the sources in the harbor area were 0.35 and 0.01,
respectively, indicating that there is no significant risk of non-
cancer effects on workers via inhalation and dermal contact in
that setting. The HI values of the ten selected toxic elements pre-
sent in IE, CDCC, SE, and VE were 1.85  10
1, 7.08  10
2,
6.36  10
2, and 3.37  10
2, respectively; these are significantly
higher than the values for other sources (Fig. S16 and Table S12).
The HI value of Cr(VI) from IE (1.38  10
1) was higher than those of
other selected toxic elements from other sources. Furthermore, the
HI values of from SE (6.15  10
2) and CDCC (6.47  10
2) were also
relatively high. However, the HI value for each toxic element was
much less than 1.0 in the harbor area, and the total HI value of
selected toxic elements from all sources was 0.36, which is lower
than the acceptable limit of 1. According to the USEPA (1989), this
suggests that there were no non-cancer risks overall in the Qingdao
harbor area.
The Ri values of Cr(VI), Co, Ni, As and Cd from different sources in
the harbor area are shown in Table S13. The Rt value of these five
selected toxic elements from CDCC was 2.04  10
7, which was
significantly higher than IE (6.40  10
8), SE (2.26  10
8) and VE
(2.18  10
8). This result was markedly different from those
showing the contributions of emission sources to selected toxic
elements (Fig. S12), and the results of Peng et al. (2017). For Cr(VI),
Co, and Ni, IE was the main source of cancer risk; the Ri values of the
three selected toxic elements were 4.75  10
9, 5.82  10
9 and
7.74  10
9, respectively. For As, CDCC was the main source of
cancer risk and its Ri value was 1.96  10
7, while the contributions
from IE, SE, and VE were relatively low and their Ri values were
4.34  10
8, 1.66  10
8, and 1.30  10
8, respectively. For the risk
of cancer from Cd exposure, VE was the main source and its Ri value
was 6.62  10
9, followed by IE (2.27  10
9) and SE (1.51  10
9).
In summary, CDCC and IE can be regarded as the primary sources of
CR in the harbor area, with Ri values of selected toxic elements from
different sources varying significantly.
3.5. Backward trajectory and PSCF analysis
The HYSPLIT model was used to identify the air mass transport
pathways during the study period. The trajectories were divided
into six groups according to direction and area of travel (Fig. S17).
Trajectory clusters 1 and 4, respectively accounting for 20.6% and
7.6% of the total trajectories, originated in Russia and passed over
Inner Mongolia, eastern Hebei, and the Bo Sea before arriving at
Qingdao harbor. Trajectory cluster 2, accounting for 19.6% of the
total, began at the Bo Sea and passed through eastern Shandong
and over the East China Sea before reaching the harbor area. Tra-
jectory cluster 5 accounted for 18.5% of the total and originated
from over the East China Sea. Trajectory cluster 3 originated in
Inner Mongolia and passed over western Hebei, southern Anhui,
and Jiangsu before arriving at the Qingdao harbor; it accounted for
10.9% of the total. Trajectory cluster 6 accounted for 22.8% of total
and originated in southern Anhui, crossing northern Jiangsu before
reaching the harbor area.
Potential source -areas for the HI and Ri of selected toxic ele-
ments from different sources were analyzed via PSCF based on the
results of PMFeHR modelling. The methodology and results are
shown in Figs. S18eS20. Weighted PSCF (WPSCF) values for the HI
8
Environmental Pollution 268 (2021) 115926
of selected toxic elements from IE were higher along the bay and
coast of the Bo Sea, where there are a large number of industrial
enterprises. Higher WPSCF values for HI of selected toxic elements
from VE were also observed in northern Jiangsu and Anhui, and
south-eastern Shandong. The WPSCF values for the HI of Co, As, and
V from CDCC were higher in north-eastern Shandong, along the bay
and coast of the Bo Sea, and eastern Inner Mongolia. The highest
WPSCF values for HI of Ni and V from SE were measured over the
East China Sea, south-eastern Shandong, northern Jiangsu and
Anhui; this was probably due to freight transport on inland rivers.
The WPSCF values for Ri of Cr(VI), Co, Ni, As, and Cd from IE were
highest in north-eastern Shandong, Dalian, and the bay of the Bo
Sea. The Bo Sea Bay may be a composite region for pollutant
transport. Xu et al. (2016) found high concentrations of toxic ele-
ments in the Bo Sea and considerable toxic element pollution in the
area. The WPSCF values for Ri of Cr(VI) and Cd from VE were high in
southern Shandong, northern Jiangsu, and Anhui. There were high
WPSCF values for Ri of Ni from SE over the East China Sea, in
southern Shandong and the north of Anhui and Jiangsu. The WPSCF
values for Ri of Co and As from CDCC were high in north-eastern
Shandong, the bay and coast of the Bo Sea, and eastern Inner
Mongolia.
4. Conclusions
This study investigated the characteristics of chemical species
and sources of PM2.5 in Qingdao harbor, and assessed the HR to
workers there. The mean PM2.5 concentration in the harbor area
was 48 ± 30 mg m
3, OM dominated the mass of PM in the harbor
area, and concentrations of trace elements were relatively low. The
concentrations of Zn and V were significantly higher than those of
other selected toxic elements, while the HI and Ri of all the selected
toxic elements were lower than the USEPA limits. There were no
non-cancer and cancer risks for workers in the harbor area. The
contributions of IE, SE, VE, and CDCC to selected toxic elements
were 39.0%, 12.8%, 24.0%, and 23.0%, respectively. The HI values of
selected toxic elements from IE, CDCC, SE, and VE were 1.85  10
1,
7.08  10
2, 6.36  10
2, and 3.37  10
2, respectively; these are far
lower than the USEPA limits. The total risk of cancer (Rt) from
selected toxic elements in CDCC was 2.04  10
7, followed by IE
(6.40  10
8), SE (2.26  10
8), and VE (2.18  10
8). CDCC and IE
were the likely sources of CR in the harbor area. Finally, a PSCF
analysis based on the results of the PMF-HR modelling indicated
that the bay and coast of the Bo Sea were identified as the most
probable source -areas for both non-cancer and cancer risks from
selected toxic elements associated with IE.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This study was financially supported by the Tianjin Science and
Technology Plan Program (18ZXSZSF00160), and the China Post-
doctoral Science Foundation (2019M660986). The authors thank
the Qingdao Ecological and Environmental Monitoring Centre of
Shandong Province for their participations in the sampling
campaign and the China National Environmental Monitoring
Centre for their participations in chemical analysis for samples.
B. Liu, J. Wu, J. Wang et al.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.envpol.2020.115926.
Author statement
Baoshuang Liu: Data curation, Writing-Original draft prepara-
tion and Reviewing. Jianhui Wu: Writing-Reviewing and Editing.
Philip K. Hopke, Yufen Zhang and Yinchang Feng: Supervision
and Reviewing. Congbo Song and Qili Dai: Reviewing and Revision.
Jing Wang, Laiyuan Shi, He Meng and Jiao Wang: Data collection
and Investigation.
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