Famiyeh 2024. Breathing in Danger PM2.5 Bound PAHs - STOTEN
Famiyeh 2024. Breathing in Danger PM2.5 Bound PAHs - STOTEN
Famiyeh 2024. Breathing in Danger PM2.5 Bound PAHs - STOTEN
H I G H L I G H T S G R A P H I C A L A B S T R A C T
A R T I C L E I N F O A B S T R A C T
Editor: Jianmin Chen Numerous studies have extensively examined the risk of lung cancer associated with polycyclic aromatic hy
drocarbons (PAHs), with particular emphasis on the 16 priority PAHs. However, this may underestimate the
actual risk. This study seeks to enhance the current risk assessment framework by integrating four additional
* Corresponding author.
** Correspondence to: J. He, Department of Chemical and Environmental Engineering, University of Nottingham Ningbo China, 199 Taikang E Rd, Ningbo 315100,
China.
E-mail addresses: [email protected] (Q. Guo), [email protected] (J. He).
https://doi.org/10.1016/j.scitotenv.2023.167762
Received 24 July 2023; Received in revised form 18 September 2023; Accepted 10 October 2023
Available online 16 October 2023
0048-9697/© 2023 Published by Elsevier B.V.
L. Famiyeh et al. Science of the Total Environment 907 (2024) 167762
Keywords:
parent PAHs such as Dibenzo[a,h]pyrene, Dibenzo[a,l]pyrene, Dibenzo[a,e]pyrene, 7H-benzo[c]fluorene with
Human exposure potentially high risk of causing cancer. By considering their physicochemical properties, metabolism, and
Breathing bioavailability, the study also examines the relationship between low molecular weight (LMW) - and high mo
PAHs lecular weight (HMW)-PAH doses and the risk of developing cancer in the human lungs. The study was con
Lung cancer ducted in Ningbo, China and identified five PAH sources: natural gas combustion (NGC), vehicular exhaust (VE),
Urban coal combustion (CC), biomass burning (BB), and volatilization of unburnt fuel (VUF). This study emphasizes the
Residential area elevated risk associated with highly carcinogenic PAHs, as they consistently exceed acceptable limits for lung
cancer risk throughout the year. Based on the study's estimation, approximately 324 out of every one million
individuals exposed to PAHs face an increased cancer risk over their lifetime. This research emphasizes the
importance of identifying source specific lung cancer risk in residential areas to protect the exposed population.
Moreover, while there is a moderate connection between LMW-PAH doses and lung cancer risk, a strong rela
tionship is observed with HMW-PAHs.
1. Introduction PAHs may vary in specific regions of the human lungs. This indicates
that by studying the dosage in these specific regions, valuable insights
Exposure to PAHs present in airborne particles can lead to mutagenic can be gained into the mechanisms of PAH adsorption and metabolism,
and carcinogenic effects in humans (Abdel-Shafy and Mansour, 2016). as well as the associated risk of lung cancer (Famiyeh et al., 2021; Liu
PAHs are mainly emitted more from anthropogenic sources, such as et al., 2020; Mo et al., 2019; Tong et al., 2019). To accurately estimate
vehicular exhaust, industrial emissions, coal combustion, natural gas PAH dosage in human exposure, realistic exposure scenarios were
combustion, and biomass burning (Nežiková et al., 2021). The PAHs employed based on parameters outlined in previous research in China
with high molecular weight are stable in the ambient air and can un (Li et al., 2016) and the Chinese Exposure Handbook (Duan et al., 2015).
dergo long-range transport to cause health hazards to the exposed The aim of this study is to assess the cumulative excess risk linked to
populations. The abundance, sources, and toxicity of cancer-causing lifetime exposure to PAHs and to investigate the potential association
PAHs in numerous outdoor urban residential areas vary tremendously. between the dose of PAHs deposited in the lungs and the risk of devel
Reports show that 1.6 % of documented lung cancer cases in China is a oping lung cancer. The specific objectives of the study are as follows: 1)
result of exposure to PAHs (Wang et al., 2018). Moreover, several studies investigate seasonal variations of PAHs in fine particles, 2) identify the
have demonstrated that PAHs are associated with lung cancer risk sources of PAHs using Positive Matrix Factorization (PMF)/Bivariate
(Zhang et al., 2019; Zhou et al., 2021). Therefore, it is crucial for re polar plots (BPPs), 3) assess the lifetime excess cancer risk (LECR)
searchers and local authorities to collaborate in evaluating the risk of through inhalation route, and 4) estimate the deposition doses of PAHs
developing lung cancer caused by PAHs and proposing strategic mea in human lungs. The integration of source apportionment data and lung
sures for mitigation. cancer risk assessment will provide reliable information in developing
Studies have shown that over 500 PAHs exist in ambient air (WHO, effective strategies for reducing PAH emissions in residential and com
2000), but researchers have primarily focused on the 16 priority PAHs mercial settings in Ningbo City.
due to their well-known toxicity, high concentrations, persistence, and
greater exposure chances for the general population (Mo et al., 2019). 2. Materials and methods
Among these priority PAHs, benzo[a]pyrene is the most carcinogenic
and becomes the widely used surrogate of PAH exposure. However, 2.1. Study area and sample collection
many highly carcinogenic PAHs, such as 7H-benzo[c]fluorene and
various dibenzopyrene derivatives, have been largely left out of lung The research was carried out in an urban residential area located in
cancer risk assessments. While the ambient concentrations of these four University of Nottingham Ningbo China (UNNC), Ningbo, China. A
PAHs are low, they have been found to be more likely to cause lung comprehensive depiction of the study area can be found in the supple
cancer compared to BaP though they were more scarcely monitored. mentary materials. This sampling campaign of fine particle (≤2.5 μm)
This exclusion can create an inaccurate measurement of the real risk of samples lasted for one year. PM2.5 samples were collected on 8 × 10-inch
lung cancer linked to PAH exposure. As revealed by recent research quartz fiber filters (PALL Co., USA). To prepare for sampling, the quartz
(Iakovides et al., 2021), including these highly carcinogenic PAHs in the filters were covered with aluminum foil and baked at 550 ◦ C in a muffle
risk assessment model can increase the lung cancer risk in several-folds furnace (Carbolite Ltd., Hope Valley, England) for 6 h to remove im
(Famiyeh et al., 2021). These findings highlight the importance of purities. The filters were equilibrated at 23 ± 2 ◦ C and 30 ± 6 % relative
considering a broader range of PAHs in environmental risk assessment humidity for 24 h before sampling. In the field, PM2.5 samples were
efforts. collected using a high-volume aerosol sampler (TH-150C111, Tianhong
PAHs can be found in both the particulate phase and the gaseous Instrument Co. Ltd., Wuhan, China) operated at a flow rate of 1.05 m3
vapor phase. However, the vapor phase typically contains LMW-PAHs, min− 1 for 24 h. A total of 120 samples were collected between 22
which are generally less carcinogenic, except for naphthalene September 2020 and 18 August 2021. Out of these 120 samples, 30
(Famiyeh et al., 2021). The particle phase consists of HMW PAHs that samples were collected in each of the four seasons. On average, samples
pose a high cancer risk. Moreover, LMW-PAHs are less lipophilic and can were collected every three days every week during each season.
readily be adsorbed into the lower respiratory system and removed from Furthermore, out of the 120 samples collected, 80 were collected on
the body. In contrast, HMW-PAHs are highly lipophilic and can linger in weekdays and 40 on weekends.
the body for a longer time (Ewing et al., 2006; Famiyeh et al., 2021). The The electronic balance (Model: AL 104, Mettler Toledo, precision 0.1
presence of carcinogenic LMW PAHs in the vapor phase can lead to a mg) was utilized to measure the masses of the aerosol samples. The
slight underestimation of the true risk levels when estimating lung weight of the sample was measured by subtracting the weight of the
cancer risk based solely on the particulate phase. filters prior to collecting the aerosol from the weight of the filters after
Our recent comprehensive review proposed the need for precise PAH aerosol collection. By dividing the sample mass by the air volume, the
risk assessment utilizing practical and appropriate exposure scenarios mass concentration was determined. The aerosol samples were wrapped
(Famiyeh et al., 2021). The conventional approach to risk assessment with aluminum foil and sealed in a zip-lock bag upon the collection at
often relies solely on ambient concentrations as the measure of exposure the sampling site, which were then immediately transferred to the
(Wang et al., 2020). However, it has been suggested that the levels of analytical lab and stored at − 20 ◦ C until PAH analysis to prevent any
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volatilization. The sampling site and the analytical lab are in the same 2.5. Health risk of PAH exposure
building at University of Nottingham Ningbo China, hence the transport
of the samples between both sites would have negligible effect on the 2.5.1. Lung deposition doses of PAHs
loss of the volatile fractions. To predict the doses of PM2.5-bound PAHs in the extrathoracic (ET),
tracheobronchial (TB), and pulmonary (PL) regions of the human lungs,
we first employed the Multiple-Path Particle Dosimetry Model (MPPD, v.
2.2. Extraction and analysis of PAHs 3.04) to predict the deposition fraction (DF). The lung deposition dose
was calculated according to Eq. (1) (Deepthi et al., 2019; Famiyeh et al.,
A small part of the sample filter was cut to extract PAHs using a 2023).
hexane and dichloromethane (1:1, v/v) mix in an accelerated solvent ( )
Dose D, μg day− 1 = DF × C × TV × BF × ET (1)
extractor (Dionex ASE 350, ThermoFisher Scientific). The extracts were
then concentrated to 1 mL using a rotatory evaporator (Biotage Turbo
where DF: Deposition Fraction, C: Exposure Concentration (μg m− 3), TV:
Vap II). A 1-μl aliquot of the final extract was injected to a gas chro
Tidal Volume (m3 breath− 1), BF: Breathing Frequency (breaths min− 1),
matography/mass spectrometry (GC/MS) system (Agilent 7890B/
ET: Exposure Time (min day− 1).
5977A) and analyzed for 20 target PAHs (Nap, Acy, Ace, Flu, Phe, Ant,
The model takes into consideration:
Flt, 7H-BcF, Pyr, BaA, Chr, BbF, BkF, BaP, InPyr, DahA, BghiP, DBahPyr,
DBalPyr, and DBaePyr) following a well-established method (Iakovides
(1) Characteristics of the particles (size, shape, and density)
et al., 2021). The samples obtained from the filters and the standard PAH
(2) Aerodynamic behaviors of the particle (inertia impaction, diffu
were spiked with internal standards such as d10-pyrene and d10-phen
sion, and sedimentation).
anthrene. The capillary column (HP-5MS, 0.25 μm × 0.25 mm × 30 m)
(3) Anatomical structure (symmetric and asymmetric) of the respi
helped in the separation of PAHs with a flow rate of 1 mL min− 1 using
ratory system (head, extrathoracic, and alveoli). The model takes
ultrahigh purity grade helium gas as a carrier gas. The GC inlet was set in
into account: functional residual capacity (FRC), and upper res
the splitless mode at 290 ◦ C. The GC oven program started at 80 ◦ C, held
piratory tract volume (URT) of the respiratory system.
for 1 min, increased at a rate of 10 ◦ C min− 1 to 240 ◦ C, held for 10 min,
(4) Exposure scenarios (aerosol concentration, exposure time,
and increased at a rate of 5 ◦ C min− 1 to 300 ◦ C, held for 2 min. The MS
breathing frequency, tidal volume).
was operated in the selected-ion-monitoring (SIM) mode to detect the
parent and daughter ions. The identification of PAHs was based on m/z
The MPPD model utilizes mathematical equations and computa
and retention time and their quantification through internal calibration
tional algorithms to account for the interaction among particle charac
of authentic standards of PAH congeners.
teristics, aerodynamic behavior, and anatomical factors, and exposure
scenarios in order to estimate particle deposition efficiency (Man
ojkumar et al., 2019).
2.3. Quality control/quality assurance (QC/QA)
The present study used the same parameters as a study conducted in
Beijing, China (Li et al., 2016) and parameters in Chinese Exposure
For each season, ten field blanks were collected, and five laboratory
Handbook to determine the dose of inhaled particles in the lungs of
blank samples spiked with 20 μL mixed standard solution containing 20
adults (Duan et al., 2015). These parameters include a functional re
PAHs were prepared. Both types of blank samples were subject to the
sidual capacity (FRC, mL) of 2950, upper respiratory tract volume (URT,
same extraction and analytical procedure for the measurement of PAHs.
mL) of 44.7, breathing frequency (BF, breath min− 1) of 16, and tidal
To account for any field background contamination, all analytical results
volume (TV, mL) of 537.5. The density of PM2.5 (1.13 g cm− 3) was
of field samples were corrected by subtracting the values obtained from
adopted from previous studies (Li et al., 2016; Yin et al., 2015). In the
the field blank samples. The lab blank samples were analyzed to deter
MPPD model, we considered a constant value for TV, BF, and ET. The
mine the recoveries of all 20 PAHs, which were found to vary between
key factors that determine the lung deposition dose for individuals of the
87.3 % for Ant and BkF for 105.8 %, which are in the range of the As
same age group are the particle deposition efficiency and the concen
sociation of Analytical Communities (AOAC) allowable interval (AOAC)
tration in the ambient air. The exposure time used in the MPPD is based
(85–115 %) (He and Balasubramanian, 2009; He et al., 2009). The limit
on data provided in the Chinese Exposure Handbook (Duan et al., 2015),
of detection (LOD) was determined as three times the mean standard
that recommends an average ET value of 221 min per day for adult
deviation of the blank sampling values, ranging from 0.001 to 0.009 ng
population in China.
m− 3. Besides, both the PAH standards and samples were spiked with
internal standards (d10-pyrene and d10-phenanthrene) in order to ac
2.5.2. Lifetime excess lung cancer risk (LECR)
count for potential variation or drift in the instrument response.
To determine the toxicity potency of various PAH congeners in
comparison to BaP, the BaP-toxicity equivalent (BaPeq) was computed.
This was achieved by multiplying the concentration and toxicity
2.4. Positive matrix factorization model
equivalent factor of each PAH congener. The TEF of the 20 PAHs
examined are shown in supplementary material (Table S1). The overall
In this study, the PMF dataset consisted of 120 samples, with 30
carcinogenic potency of 20 PAHs was calculated by computing the sum
representative samples from each season. The dataset also included 20
of the BaPeq, which is represented as the toxicity equivalent quotient
PAH congeners. Details on the PMF model are provided in the supple
(BaPTEQ) as shown in Eq. (2) (Ali-Taleshi et al., 2021; Hong et al., 2016).
mentary material. PMF analysis was conducted for factors ranging from
two to eight. During the selection process for the number of factors, ∑
N ∑
N
priority was given to strong bootstrap mapping and avoiding unmapped BaPTEQ = BaPeq = (Ci × TEFi ) (2)
bootstrap results. After analyzing the bootstrap summary, the optimal
i=1 i=1
solution for PAHs during the one-year study period was determined to where BaPTEQ, N, Ci, and TEFi represent BaP toxicity equivalent quo
be five factors. Bivariate polar plots were used to provide additional tient, number of PAH congeners, concentration of ith PAH congener, and
information about the transport of PAHs from identified sources to our toxicity equivalent factor of the ith PAH congener, respectively.
study site. These plots took into account the direction and speed of the
wind recorded hourly at a monitoring station (29.83◦ N, 121.56◦ E), LECRinh = BaPTEQ × URBaP (3)
located <500 m from the sampling site (29.8022◦ N, 121.5592◦ E).
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L. Famiyeh et al. Science of the Total Environment 907 (2024) 167762
The use of BaPeq can help evaluate the likelihood of an individual reactions generate oxygenated and nitrated PAHs. Additionally, higher
developing lung cancer in their lifespan (70 years) by examining the temperatures enhance the degradation of LMW-PAHs by accelerating
carcinogenic effects caused by exposure to PAHs. To determine the reaction rates. Consequently, the combined effect of solar radiation and
lifetime excess cancer risk (LECR) from inhaling PM2.5-bound PAHs, Eq. high temperatures during summer provides optimal conditions for the
(3) was used. The BaPeq of each PAH was multiplied by the BaP unit risk evaporation and degradation of LMW-PAHs. Moreover, frequent rainfall
established by the WHO for individuals working with coke ovens (URBaP in summer also contributes to the low PAH concentration (Chen et al.,
= 8.70 × 10− 5 per ng m− 3) (Hong et al., 2016). This unit risk was applied 2022). A significant concentration of NaP (17.3 % of total PAH) during
to represent the estimated increase in the probability of developing lung summer is likely caused by unburnt fuel vaporizing in high temperatures
cancer over a lifetime of exposure to a concentration of 1 ng m− 3 of BaP. and solar radiation. In Table S1, it can be seen that the PAH/PM2.5 ratio
The URBaP method has been extensively employed for assessing the lung is lower during the warm season, which suggests the occurrence of
cancer risk of PAHs present in atmospheric particles (Wang et al., 2012; photochemical aging of PAHs (Lv et al., 2016). For instance, increased
Zhang et al., 2019; Zhu et al., 2022). levels of atmospheric oxidants (O3), higher ambient temperatures, and
solar radiation during warmer seasons could potentially result in the
3. Results and discussions photochemical oxidation of NaP into naphthoquinone derivatives.
The seasonal variation of PAH concentration based on aromatic rings
3.1. Seasonal variations of PAHs is presented in Fig. 1. During autumn, winter, spring, and summer, the
most prevalent PAHs had five-aromatic rings, four-aromatic rings, six-
The mean levels of individual PAHs showed significant seasonal aromatic rings, and four and five-aromatic rings, respectively. The
variation (ANOVA, p ≤ 0.05). All the 20 PAHs exhibited significant dominance of five-aromatic rings PAHs in concentration suggests that
seasonal variability (as shown in Table S1). The total mean concentra fossil fuel combustion has a significant contribution (Elzein et al., 2020).
tion of the 16 priority PAHs was highest in autumn (9.43 ± 4.67 ng During the winter season, the high level of four-ring PAHs was caused by
m− 3), followed by winter (9.26 ± 6.02 ng m− 3), spring (4.35 ± 2.10 ng the use of wood for domestic heating and the increased need for coal by
m− 3), and summer (1.83 ± 0.94 ng m− 3). Similar trends were observed coal-powered plants to generate electricity. Furthermore, the consistent
in the overall concentrations of LMW-PAHs and HMW-PAHs, with high concentrations of five and six-aromatic ring PAHs throughout the
autumn and winter levels exceeding the annual mean concentration and field campaign signify that vehicular exhaust emissions have a sub
spring and summer levels being lower. This order is in contrast with stantial contribution to the PAH pollution at the study site.
previous studies in Ashan city (Wang et al., 2020) and Nanjing (He et al.,
2014), where the highest concentrations were observed in winter, fol 3.2. PMF-bivariate polar plots
lowed by spring, autumn, and summer. The annual mean concentration
of the 16 priority PAHs (6.21 ± 5.11 ng m− 3) was lower than in other The quality of input data depends on the signal-to-noise (S/N) of the
areas like Anshan (Wang et al., 2020), Wuhan (Zhang et al., 2019), PAHs derived from the PMF model. PAHs with S/N > 2.0 and <0.2 were
Nanjing (He et al., 2014), Shanghai (Liu et al., 2018), Taiwan (Chen labeled as “strong” and “weak”, respectively (Chen et al., 2021). The S/
et al., 2016), and Beijing (Liu et al., 2019), but higher than in São Paulo, N ratios of the 20 PAHs ranged from 2.4 to 10 and were all included in
Brazil (Callén et al., 2014), and Bangi, Malaysia (Khan et al., 2015). the PMF analysis due to their ratios being >2.0. Through a year-round
These results indicate that the levels of PAH exposure vary significantly field campaign, vehicular exhaust, coal combustion, natural gas com
across different regions worldwide. bustion, biomass burning, and volatilization of unburnt fuel were opti
The HMW-PAHs, excluding 7H-BcF and dibenzopyrene derivatives mized as the five sources associated with PAHs (as represented in Fig. 2).
(DBahPyr, DBalPy, and DBaePyr), are the most prevalent PAHs in The time-series of the concentration of PAHs associated with the five
ambient particles and display significant seasonal fluctuations. During sources derived from the PMF model are shown in Fig. 3. The bivariate
the cold season, the levels of Chr, BbF, BkF, BaP, IPyr, and BghiP were polar plots depict the concentration profiles of these five sources, illus
high, indicating a substantial contribution from coal combustion (Fang trating the dispersion patterns and transportation of PAHs to our study
et al., 2020) and gasoline exhaust emissions (Galvão et al., 2023). The site (as shown in Fig. 4).
consistent presence of elevated concentrations of BghiP throughout the Factor 1 is composed of high levels of certain types of PAHs,
field campaign suggests that vehicular emissions are a consistent including 3–4 aromatic ring PAHs like Acy, Ace, and Flu (with loadings
contributor to PAH pollution (Wang et al., 2020). The levels of BaP were of 70.4 %, 23.7 %, and 28.9 % respectively), which are indicative of
highest during autumn (0.68 ± 0.56 ng m− 3), followed by winter (0.48 diesel engine emissions, and 5–6 aromatic ring PAHs like BbF, BkF,
± 0.46 ng m− 3), spring (0.19 ± 0.15 ng m− 3), and summer (0.08 ± 0.07 BghiP, IPyr, and DBahA (with loadings of 51.9 %, 36.7 %, 60.4 %, 59.5
n gm− 3). The yearly concentration of BaP (0.36 ± 0.44 ng m− 3) fell %, and 75.3 % respectively), which suggest PAH emission from gasoline
below the acceptable limit (1.0 ng m− 3) (Xing et al., 2020), and the exhaust engines (Galvão et al., 2023; Wang et al., 2020). The elevated
primary sources for its high levels in winter were most likely from levels of DBahPyr, DBaePyr, and DBalPyr in the sample strongly suggest
vehicular exhaust, wood burning, and coal combustion. The decrease in PAH emission from vehicular tire wear (Sadiktsis et al., 2012). As a
BaP levels in China in recent years can be attributed to the prohibition of result, factor 1, which accounts for 25 % of the total PAH, is attributed to
open coal combustion for heating and cooking in homes, as well as ad vehicular emissions (as shown in Fig. 2a). The data on the sources of
vancements in domestic and industrial heating systems and the use of PAHs over time demonstrates a consistent vehicular exhaust emissions
alternative fuels with minimal PAH emissions (WHO, 2000). throughout all seasons. However, there has been a decline in emissions
In cold seasons, the high PAH levels are partly caused by the lower during the later days of the warm season (as depicted in Fig. 3a). The
mixing layer and periodic temperature inversion (Wang et al., 2020). poor air-to-fuel mixing during the cold season exacerbates PAH emis
The cold weather (9.83 ± 4.99 ◦ C in winter, 14.8 ± 4.77 ◦ C in autumn) sions from vehicular exhaust. The bivariate polar plot reveals that there
increases the accumulation and adsorption of PAH in ambient particles. is a presence of PAHs emitted from road traffic nearby, particularly in
The decrease of PAH concentration in summer is due to the reduced use low wind speed background conditions. The transportation of high PAH
of fossil fuels (Ye et al., 2017). The warm seasons have a high ambient concentrations from vehicular exhaust occurs from both the southwest
temperature (spring: 19.7 ± 4.91 ◦ C, summer: 27.9 ± 3.12 ◦ C) that can and northwest, whereas low concentrations are transported from the
cause PAH degradation and increase the mixing layer height, resulting southeast, as indicated in Fig. 4(a).
in a low PAH concentration. Intense solar radiation during the summer The second factor exhibited significant loading for Flt, Pyr, Phe, 7H-
season leads to the evaporation and degradation of LMW-PAHs through BcF, Chr, BkF, and Ace, with Flt, Pyr, Phe, Chr, and Ace known to be
photochemical reactions (Famiyeh et al., 2021; He et al., 2014). These markers of coal combustion (Fang et al., 2020; Wang et al., 2013). Coal
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L. Famiyeh et al. Science of the Total Environment 907 (2024) 167762
4-rings: Flt,
5-rings: Pyr, BaA,
5-rings: BbF,
Chr, 7H-BcF, 4-rings: Flt,
BbF, BkF, BkF, BaP,
BaP, DahA, 2.64 Pyr, BaA, Chr,
DahA, 2.99
3.16 Autumn Winter 7H-BcF, 3.13
5-rings:
BbF, BkF,
BaP, DahA, 4-rings: Flt, Pyr,
5-rings: BbF, 4-rings: Flt, 0.76 BaA, Chr, 7H-
BkF, BaP, Pyr, BaA, BcF, 0.76
DahA, 1.28 Chr, 7H-BcF,
Spring 0.98
Summer
2-rings: NaP,
0.36 3-rings:Acy,
6-rings: IPy, BghiP,
DBahPy, DBaePyr, Ace, Flu, Phe,
DBalPyr, 1.99 Ant, 0.5
4-rings: Flt,
Pyr, BaA, Chr,
5-rings: BbF, 7H-BcF, 1.78
BkF, BaP, DahA,
1.99
Annual
Fig. 1. Comparisons of seasonal average PAHs concentration (ng m− 3) based on aromatic ring.
combustion is known as the second source of PAH and contributes to (Sakizadeh, 2020). Such emissions account for 9.66 % of the total PAH.
about 21.1 % of the total PAH concentration, as shown in Fig. 2(b). The The increase in PAH linked to burning of biomass in the colder season
concentration of PAH related to coal combustion was highest during suggests that the peak concentration in winter may be caused by wood
winter (as shown in Fig. 3b) due to the surge in demand for coal by coal- burning (as shown in Fig. 3d) Moreover, PAHs originating from the
fired power plants for electricity generation. The polar plots displayed in burning of crop residues in northwest regions got conveyed to UNNC
Fig. 4(b) demonstrate that the PAHs that result from coal combustion due to high wind velocity (as shown in Fig. 4d).
originate from industrial facilities located in the northwest region and Factor 5 was found to have a high concentrations of NaP, DBaePyr
are carried to the campus of the UNNC by strong winds (Chen et al., and Flu with percentages of 71.6 %, 36.0 % and 28.8 % respectively. The
2022). high concentration of NaP and Flu indicates that unburnt fuel is being
According to Callén et al. (2014), the presence of high loadings of evaporated, which is more prominent during warmer seasons. The
BaA, Chr, DBahPyr, BaP, BkF, DBaePyr, IPyr, and Ace in factor 3 in contribution of vaporization of unburnt fuel to the total PAH is at 9.61 %
dicates PAH emissions from natural gas combustion. BaA, BaP, and Chr (Fig. 2e). Low wind speeds facilitated the arrival of these LMW-PAHs,
serve as identifiable indicators of natural gas combustion. The third emitted from marine vessels at East China Sea and Ningbo-Zhoushan
factor, which represent PAH emission from natural gas combustion, port, to UNNC, as shown in Fig. 4(e).
constitute 33.6 % of the total PAH. The highest concentration of PAH
associated with natural gas combustion occurred more frequently during
the cold season (as shown in Fig. 3c). These PAHs were conveyed to 3.3. Health risk assessment
UNNC from the northwest and southwest areas at high wind speeds
(Fig. 4c). Additionally, the background PAHs associated with natural gas 3.3.1. BaPeq concentration and lifetime excess lung cancer risk
combustion were linked to local emissions caused by domestic heating The BaPeq of the LMW-PAHs dominated by Ant (as shown in Fig. S1
and cooking activities. a) were found to be lower compared to the BaPeq of the HMW-PAHs (as
Factor 4 comprises high loadings of Ant (71.3 %), Phe (34.8 %), Flu shown in Fig. S1 b). The annual total BaPeq of HMW-PAHs was 1725
(28.4 %), Ace (25.1 %), and Acy (22.7 %). The high loadings of Ant, Phe, times greater than the total BaP of LMW-PAHs. LMW-PAHs have a
Flu, and Ace suggest the release of PAHs from burning biomass higher tendency to partition in the gaseous phase, whereas HMW-PAHs
tend to partition in the particle phase. This difference in partitioning
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Fig. 3. Time series source concentrations (ng m− 3) derived from PMF model: (a) vehicular exhaust (VE), (b) coal combustion (CC), (c) natural gas combustion (NGC),
(d) biomass burning (BB), and (e) volatilization of unburnt fuel (VUF).
vehicular exhaust and coal combustion to the 20 PAHs, compared to the Coal is extensively utilized in China for electricity generation and
16 PAHs, suggests that the four additional PAHs are emitted more from industrial purposes. To reduce PAH emissions from coal combustion,
these sources rather than other sources. 7H-Benzo[c]fluorene and various strategies can be implemented including improving combustion
Dibenzopyrene derivatives are emitted primary from coal combustion technologies, enforcing strict emission standards, promoting renewable
and vehicular exhaust and tire wear (Bergvall and Westerholm, 2007; energy sources, and investing in cleaner coal technologies like dedus
Richter-Brockmann and Achten, 2018; Sadiktsis et al., 2012). ters, electrostatic precipitation, and fabric filters (Scott et al., 2021).
In order to effectively decrease PAH concentrations and mitigate the
associated risk of lung cancer, the primary focus should be placed on 3.3.3. Association of deposition doses and LECR
addressing three major sources: combustion of natural gas, combustion The doses of LMW-PAHs were lower than those of HMW-PAHs due to
of coal, and emissions from vehicular exhaust. To achieve this, alter their low ambient concentrations. HMW-PAHs possess a strong ability to
native fuels, such as biofuels, hydrogen, methanol, propane, and electric partition into particulate phases due to their low vapor pressure,
power, can be promoted as replacements for natural gas combustion due whereas LMW-PAHs, with their high vapor pressure, tend to preferen
to their minimal emissions of PAHs (Osman et al., 2022). The use of tially partition into the gaseous phase. This disparity leads to higher
biofuels presents several advantages as they are environmentally concentrations of HMW-PAHs in PM2.5 compared to LMW-PAHs
friendly, economically viable, and sustainable. When hydrogen is (Famiyeh et al., 2021). Consequently, when individuals inhale PM2.5-
burned, it only produces water as a by-product. Moreover, methanol is a bound PAHs, there are higher doses of HMW-PAHs in the human res
clean fuel that is affordable. Propane offers cost-effectiveness, high en piratory system, as compared to LMW-PAHs. Furthermore, regardless of
ergy output, and is widely available. Furthermore, the promotion of the molecular weight, the ET region displayed higher doses of PAH
renewable sources of electric power, such as solar, wind, hydropower, compared to the TB and PL regions. This suggests that factors other than
and geothermal energy, is warranted given their absence of PAH molecular weight contribute to the higher PAH doses observed in the ET
emissions. region. The relationship between dose and lung cancer for LMW-PAHs
To reduce vehicle exhaust PAH emissions, various strategies can be and HMW-PAHs is depicted in figures (a) and (b) respectively. It
adopted. These strategies include using alternative fuels with lower PAH should be noted that the relationship between doses and LECR varies
levels, such as electric power, biofuels, natural gas, and hydrogen depending on the molecular weight of PAHs, with a moderate rela
(Sandaka and Kumar, 2023). In addition, there are several other effec tionship for LMW-PAHs and a strong relationship for HMW-PAHs. The
tive measures to reduce PAH emissions from vehicle exhaust. These diversity in the relationship between low- and high molecular weight
include regular vehicle maintenance, the installation of three-way cat PAHs can be attributed to several factors. These include differences in
alytic converters (TWC), optimizing combustion and fuel injection physicochemical properties, metabolism, and bioavailability (Famiyeh
processes, promoting sustainable transportation options, and enhancing et al., 2021).
environmental regulations and policies (Famiyeh et al., 2021; IARC, Low molecular weight PAHs are generally more volatile and easily
2010). Specifically, raising awareness and promoting the use of electric absorbed and eliminated by the body compared to their high molecular
public transportation can significantly contribute to reducing PAH weight counterparts. The discrepancy in clearance rates can result in
emissions. variations in the association between the dosage of PAHs and the risk of
7
L. Famiyeh et al. Science of the Total Environment 907 (2024) 167762
(a) (b)
(c) (d)
(e)
Fig. 4. Bivariate polar plots (BPPs) of five sources associated with annual PM2.5-PAHs concentration (ng m− 3) derived from PMF model (a) Vehicular exhaust (b) coal
combustion, (c) natural gas combustion, (d) biomass burning, and (e) volatilization of unburnt fuel.
developing lung cancer. The efficient clearance of LMW-PAHs by the cancer. On the other hand, HMW-PAHs with low clearance rates can
body may prevent significant harm from occurring. Consequently, this pose a higher risk of lung cancer when exposed to higher doses. This
efficient clearance process can potentially result in a reduced association association between dose and lung cancer risk is notably stronger for
between the dosage of LMW-PAHs and the risk of developing lung HMW-PAHs found in human lungs, as shown in Fig. 8(b).
8
L. Famiyeh et al. Science of the Total Environment 907 (2024) 167762
4. Conclusions
5. Environmental implications
The metabolism of low and high molecular weight PAHs differs CRediT authorship contribution statement
significantly. Low molecular weight PAHs are generally not easily
metabolized, resulting in the formation of less harmful metabolites that Lord Famiyeh: Investigation, Data curation, Writing – original draft,
can be rapidly eliminated (Famiyeh et al., 2021). On the other hand, Writing – review & editing. Honghui Xu: Investigation, Methodology,
Data curation. Ke Chen: Investigation, Methodology, Data curation. Yu-
9
L. Famiyeh et al. Science of the Total Environment 907 (2024) 167762
Fig. 8. Association of doses and LECR: (a) LMW-PAHs and (b) HMW-PAHs.
Ting Tang: Methodology, Writing – review & editing. Dongsheng Ji: Bergvall, C., Westerholm, R., 2007. Identification and determination of highly
carcinogenic dibenzopyrene isomers in air particulate samples from a street canyon,
Methodology, Writing – review & editing. Hang Xiao: Investigation,
a rooftop, and a subway station in Stockholm. Environ. Sci. Technol. 41 (3),
Methodology, Data curation. Lei Tong: Investigation, Methodology, 731–737. https://doi.org/10.1021/es062232p.
Data curation. Chunrong Jia: Writing – review & editing. Qingjun Callén, M.S., Iturmendi, A., López, J.M., 2014. Source apportionment of atmospheric
Guo: Supervision, Writing – review & editing, Funding acquisition. Jun PM2.5-bound polycyclic aromatic hydrocarbons by a PMF receptor model.
Assessment of potential risk for human health. Environ. Pollut. 195, 167–177.
He: Funding acquisition, Supervision, Project administration, Writing – https://doi.org/10.1016/j.envpol.2014.08.025.
review & editing. Chen, Y.C., Chiang, H.C., Hsu, C.Y., Yang, T.T., Lin, T.Y., Chen, M.J., Chen, N.T., Wu, Y.
S., 2016. Ambient PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) in
Changhua County, central Taiwan: seasonal variation, source apportionment and
Declaration of competing interest cancer risk assessment. Environ. Pollut. 218, 372–382. https://doi.org/10.1016/j.
envpol.2016.07.016.
Chen, T., Liu, J., Ma, Q., Chu, B., Zhang, P., Ma, J., Liu, Y., Zhong, C., Liu, P., Wang, Y.,
The authors declare the following financial interests/personal re Mu, Y., He, H., 2021. Measurement report: effects of photochemical aging on the
lationships which may be considered as potential competing interests: formation and evolution of summertime secondary aerosol in Beijing. Atmos. Chem.
Jun He reports financial support was provided by Ningbo Municipal Phys. 21 (2), 1341–1356. https://doi.org/10.5194/acp-21-1341-2021.
Chen, K., Xu, J., Famiyeh, Lord, Sun, Y., Ji, D., Xu, H., Wang, C., Metcalfe, S.E., Betha, R.,
Bureau of Science and Technology. Qingjun Guo reports financial sup Behera, S.N., Jia, C., Xiao, H., He, J., 2022. Chemical constituents, driving factors,
port was provided by National Natural Science Foundation of China. and source apportionment of oxidative potential of ambient fine particulate matter
in a Port City in East China. J. Hazard. Mater. 440 (May), 129864 https://doi.org/
10.1016/j.jhazmat.2022.129864.
Data availability Deepthi, Y., Shiva Nagendra, S.M., Gummadi, S.N., 2019. Characteristics of indoor air
pollution and estimation of respiratory dosage under varied fuel-type and kitchen-
Data will be made available on request. type in the rural areas of Telangana state in India. Sci. Total Environ. 650, 616–625.
https://doi.org/10.1016/j.scitotenv.2018.08.381.
Duan, Xiaoli, Xiuge, Zhao, Wang, Beibei, Chen Yiting, C.S., 2015. Highlights of the
Acknowledgement Chinese Exposure Factors Handbook (Adults). https://doi.org/10.1016/c2014-0-
03838-5.
Elzein, A., Stewart, G.J., Swift, S.J., Nelson, B.S., Crilley, L.R., Alam, M.S., Reyes-
The authors acknowledge the financial supports from Ningbo Science
Villegas, E., Gadi, R., Harrison, R.M., Hamilton, J.F., Lewis, A.C., 2020.
and Technology Innovation 2025 Key Project (2022Z028), Ningbo A comparison of PM2.5-bound polycyclic aromatic hydrocarbons in summer Beijing
Natural Science Foundation Key Project (2023J024), Ningbo (China) and Delhi (India). Atmos. Chem. Phys. 20 (22), 14303–14319. https://doi.
org/10.5194/acp-20-14303-2020.
Commonwealth Programme Key Project (2023S038), National Natural
Ewing, P., Blomgren, B., Ryrfeldt, A., Gerde, P., 2006. Increasing exposure levels cause
Science Foundation of China (41975831, 41625006, 41761144066, an abrupt change in the absorption and metabolism of acutely inhaled benzo(a)
41625006, and 41561144005), National Key Research and Develop pyrene in the isolated, ventilated, and perfused lung of the rat. Toxicol. Sci. 91 (2),
ment Program of China (2017YFC0212703). 332–340. https://doi.org/10.1093/toxsci/kfj104.
Famiyeh, Lord, Chen, K., Xu, J., Sun, Y., Guo, Q., Wang, C., Lv, J., Tang, Y.-T., Yu, H.,
Snape, C., He, J., 2021. A review on analysis methods, source identification, and
Appendix A. Supplementary data cancer risk evaluation of atmospheric polycyclic aromatic hydrocarbons. Sci. Total
Environ. 789, 147741 https://doi.org/10.1016/j.scitotenv.2021.147741.
Famiyeh, L., Jia, C., Chen, K., Tang, Y.T., Ji, D.S., He, J., Guo, Q.J., 2023. Size
Supplementary data to this article can be found online at https://doi. distribution and lung-deposition of ambient particulate matter oxidative potential: a
org/10.1016/j.scitotenv.2023.167762. contrast between dithiothreitol and ascorbin acid assays. Environ. Pollut. 336,
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