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POLYCYCLIC AROMATIC COMPOUNDS

https://doi.org/./..

Polycyclic Aromatic Hydrocarbons in Street Dust of Bushehr City,


Iran: Status, Source, and Human Health Risk Assessment
Behnam Keshavarzia , Sajjad Abbasi H.a , Farid Moorea , Hossein Delshabb , and Naghmeh Soltania
a
Department of Earth Sciences, College of Sciences, Shiraz University, Shiraz, Iran; b Bushehr Environmental Protection
Oce, Bushehr, Iran
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ABSTRACT ARTICLE HISTORY


This study identified concentrations, molecular distributions, toxicities, and Received August
sources of polycylic aromatic hydrocarbons (PAHs) in street dust from different Accepted July
land use of Bushehr city in southwest of Iran. For this purpose, 19 street dust
KEYWORDS
samples were collected from different land use of the city and analyzed using Bushehr; PAHs; risk
GCMS. !16PAHs (16 USEPA priority PAHs) concentrations ranged between 73.6 assessment; street dust
and 9491 g kg1 , with a mean of 1116.02 g kg1 . The high-molecular-weight
(HMW) PAHs (46 rings), that make 65.22% of the total, were the dominant
in almost all dust samples. In the northern part of the city, the concentration
of PAHs especially HMW is high, reflecting high traffic density. PAH sources
were identified statistically. It is demonstrated that the PAHs in Bushehr street
dust are mainly petrogenic derived from traffic emission. A significant posi-
tive correlation coefficient also exists between the !PAH concentration and
toxic equivalency concentration (TEQ). Estimated incremental lifetime cancer
risk (ILCR) results indicated that Bushehr residents are potentially exposed to a
high cancer risk, especially via dust ingestion and dermal contact.

Introduction
Rapid urbanization and continuous demand of land for infra-structural development in urban areas have
placed great stress on the local environment. As a consequence, there is a decline in the quality of urban
environment (14). Street dust, an accumulation of solid particles in the form of organic and inorganic
pollutants on outdoor ground surfaces, is a medium for characterizing urban environmental quality (6).
Polycyclic aromatic hydrocarbons (PAHs) are a group of ubiquitous environmental pollutants (7) hav-
ing low aqueous solubility, semi-volatility, high octanolwater partition coefficient (Kow ), and stability,
and their potential or proven carcinogenicity make them of considerable ecotoxicological concern (8).
They are distributed between the gaseous and particulate phases of the atmosphere according to their
vapor pressures. In the atmosphere, after formation, they get dispersed over large areas and transferred by
dry and wet deposition to soil or other environmental surfaces, such as water bodies and vegetation (9).
Many anthropogenic activities, such as transportation, industry, and commercial activities, contribute
to PAHs accumulation on street dust (10). PAHs in street dust have various origins: weathering of mate-
rials from street surfaces, automobile exhausts, tire particles, and atmospherically deposited materials
(11). They are released into the urban environment mainly through anthropogenic activities such as
vehicle emissions, coal and fossil fuel combustion for power generation, petroleum refining, straw and
firewood burning, industrial processing, chemical manufacturing, oil spills, and coal tars (12). Vehicular

CONTACT Sajjad Abbasi H. Sajjad.Abbasi@Shirazu.ac.ir Department of Earth Sciences, College of Science, Shiraz University,
Shiraz, Iran.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gpol.
Supplemental data for this article can be accessed on the publishers website.
Taylor & Francis Group, LLC
2 B. KESHAVARZI ET AL.

emissions are one of the principal anthropogenic sources of PAHs (13). The former is characterized as
being mainly derived from vehicle exhaust and combustion of fossil fuel, whereas petrogenic sources are
usually derived from petroleum products and crude oil (14, 15). The presence of PAHs in street dust is of
great concern since they can be transported into water bodies through runoff, contaminating sediments
and, consequently, the aquatic food chain (16). Furthermore, street dust has become an important pollu-
tant source of PAHs to water and air because of the effects of run-off water and wind dispersion (1719).
Because of its increasing potential risk to the human health, an increased number of studies on
atmospheric PAH in urban areas have received a lot of attention in the last decade, especially in the last
years (20). They are human carcinogens and mutagens, toxic to all living organisms (82). Atmospheric
PAHs may cause respiratory problems, impair pulmonary function, and cause bronchitis (21). The
European Community and the U.S. Environmental Protection Agency (USEPA) have listed them as
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priority pollutants.
In terms of human health risk assessment, there are multiple pathways of human exposure to street
dust such as inhalation, ingestion, and dermal exposure (23, 24). The USEPA and European Union have
listed 16 PAHs compounds as priority pollutants (25). Several individual PAHs such as benzo[a]pyrene
(BaP), chrysene (Chr), indeno[1,2,3-c,d]pyrene, and benzo[b]fluoranthene (BbF) have produced car-
cinogenic, mutagenic, and genotoxic effects in animal experiments (26, 27). In particular, BaP or
dibenzo[a,h]anthracene (DbahA) shows strong inhalation and dermal carcinogenic risk (28). Human
cancer causes of skin, lungs, and bladder have always been associated with PAHs (29).
In developing countries like Iran, there are enormous problems associated with the pollution of sur-
face dust due to traffic load and industrial activities. The major objectives of the present study are (a) to
determine the concentration and distribution of PAH species in street dust of Bushehr, (b) to identify
potential PAH sources in urban surface dust, (c) to study what types of PAHs and under what conditions
can be concentrated, and (d) to examine the human health risks through PAH exposure to urban surface
dust via inhalation, ingestion, and dermal contact.

Materials and methods

Study area
Bushehr city is located southwest of Iran. This city is limited from north, south, and west by the Persian
Gulf and stands 18 m above sea level. This city can be divided into 2 parts, north and south, according
to PAH concentration in street dust, traffic load, and industries distribution. There are higher traffic
load and many industries in the northern part of the city, while the southern part mostly consists of
residential areas with lower traffic load. Therefore, Bushehr city clearly displays that traffic and industrial
activities can effect PAHs concentration. Bushehrs climate is semi-desert and warm with low annual
average precipitation of 268 mm occurring mainly in the winter. Annual average temperature and relative
humidity are 24.7C and 65%, respectively. The geological formations include alluvial deposits. Annual
average days of storm with dust are 76.6 days with wind direction predominantly from south to north.
According to the recent census in 2016, the population of Bushehr is 298,945 people.

Street dust sampling and sample extraction and instrumental analysis


In order to measure the concentration of the organic content in street dust, the collected samples were
immediately placed in dark glass bottles. The containers were previously washed with soapy water, rinsed
with distilled water, washed with n-hexane, and dried in an oven at 180C for 3 h, respectively. Finally,
screw aluminum foil caps were used to provide a gas-tight seal. In order to minimize microbial degra-
dation during transport to the laboratory, samples were stored below 4C in a cool box. A total of 19
street dust samples were collected under stable weather conditions in the dry season during September
2014 (summer time) (Figure 1). A sampling point within each land use (industrial, commercial, high
POLYCYCLIC AROMATIC COMPOUNDS 3
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Figure . Study area and sampling site locations in the city of Bushehr, south west Iran.

traffic, and residential) was selected. Samples were collected adjacent to the curb of the street. Approx-
imately 500 g of the dust particles accumulated on impervious surfaces (street, pavement) within a 5-
m radius circle around the selected sampling point were collected with a plastic dust pan and brush
then. Since the results show that the concentrations of dust-borne PAHs increased with the decreas-
ing particle size (30), street dusts were passed through a 2-mm sieve, and stored in an ice chest at
4C. The collected samples were transferred to the laboratory of Isfahan University of Technology and
were prepared for PAHs analysis using a HewlettPackard (HP) 1090 high-performance liquid chromato-
graph (HPLC) with an HP-1046 fluorescence detector. The 16 quantified PAHs in this study include
naphthalene (Nap), acenaphthene (Ace), fluorine (Fl), phenantheren (Phe), anthracene (Ant), fluoran-
thene (Flu), pyrene (Pyr), benzo[a]anthracene (BaA), Chrysene (Chr), Benzo[b]fluoranthene (BbF),
4 B. KESHAVARZI ET AL.

Benzo[a]pyrene (BaP) benzo[e]pyrene (BeP), Dibenzo[a,h]anthracene (DbahA), benzo[g,h,i]perylene


(BghiP), and indene (Ind). The samples were analyzed according to 3550B (extraction), EPA 3630C
(clean up), and 8310 (determination). Approximately 2 g of each freeze-dried and homogenized street
dust samples were mixed with 100 ml dichloromethane (CH2 Cl2 ) for 8 h. The extracts were concentrated
to 1 ml by a rotary vacuum evaporator. 20 l of this extract was then analyzed for PAHs. The mobile phase
was acetonitrile/water in gradient mode at a flow rate of 1 ml/min and the temperature was set at 35C.

Quality assurance and quality control


In order to vouch for the reliability of the results, appropriate quality assurance procedures and pre-
cautions were performed. Reagent blanks, analytical duplicates/replicates, and analysis of the standard
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reference material (Dr. Ehrenstorfer GmbH Alkanes-Mix 10, and Sigma-Aldrich Co. LLC EPA 525 PAH
Mix A and EPA 525 PAH Mix B) were processed. The average recoveries based on surrogate deuterated
PAHs in dust were approximately 8895% for the 16 measured PAHs. The detection limit (DL) of PAHs
for dust ranged from 0.05 to 0.4 g/kg and precision was 48%.

Statistical analyses source apportion


To identify the relationship among PAHs in street dust of Bushehr and their possible sources, Spearmans
correlation coefficients, principal component analysis (PCA), and cluster analysis (CA) were performed
using the commercial statistics software package SPSS version 19.0 for Windows. The sources of the
PAHs in the street dust were identified based on PAH inventories from available references. For example,
when PCA with varimax normalized rotation was performed, each principal component score contained
information on all PAHs combined into a single number, while the loadings indicated the relative con-
tribution for PAHs species made to that score (84, 32). The primary function of PCA was a reduction in
the number of variables while retaining as much as possible of the original information; therefore, vari-
ables with similar characteristics were grouped into factors (33). The correlation coefficient measures the
strength of inter-relationship between 2 parameters, and CA was performed to further classify PAHs of
different sources on the basis of the similarities of their chemical properties.

Toxic equivalency factor


The toxic equivalency factor (TEF) was developed to evaluate structurally related compounds, sharing
a common mechanism of action. The TEF was successfully developed to evaluate the potential toxicity
of PAHs in street dust, and the toxicity is expressed relative to BaP, the most toxic PAH and hence the
reference standard (34, 35). Other PAHs have their own TEF values based on their carcinogenic level in
comparison to that of BaP as reported by many authors (e.g., 36, 37):
!
TEQ = Cn TEFn (1)

where Cn is the concentration of PAHi , and TEFn is the TEF for PAHs. TEF for all PAHs is presented in
Table 2.

Risk assessment
The incremental lifetime cancer risk (ILCR) associated with exposures to PAHs in Bushehrs street
dust was evaluated using the USEPA standard models (residential scenario) (22, 38, 39). The following
assumptions underlie the model applied in this study: (a) Human beings are exposed to urban surface
dust through 3 main pathways: ingestion, inhalation, and dermal contact with dust particles; (b) Intake
rates and particle emission can be approximated by those developed for soil particles; (c) Some expo-
sure parameters of people in the observed areas are similar to those of reference populations; (d) The
total carcinogenic risk could be computed by summing the individual risks calculated for the 3 exposure
POLYCYCLIC AROMATIC COMPOUNDS 5

Table . Exposure factors for risk assessment models (residential scenario).

Value
Residential
Factor Definition Unit Children Adults

IRIngestion Ingestion rate mg day a a


IRInhalation Inhalation rate m day .c c
PEF Particle emission factor m kg . f,#
SA Exposed skin area cm ,a, ,a,
SL Skin adherence factor mg cm day .d .d
ABS Dermal absorption factor for PAHs .d
ED Exposure duration year d d
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EF Exposure frequency day year f f


BW Average body weight kg .a a
AT Average life span for PAHs day ,e ,e
a ().
b ().
c (, ).
d ().
e ().
f Site specific.
Mean value for years old children.
Mean value for years old people.
# Calculated based on Cowherd et al. ()

ways; (e) The cancer risk is assessed based on exposure under a type of land use pattern over the entire
lifetime. The ILCR (unit less) in terms of direct ingestion, dermal contact, and inhalation are as follows:
" # $
CS CSFIngestion 3 BW 70
IRIngestion EF ED
ILCRsIngestion = (2)
BW AT 106
" # $
CS CSFDermal 3 BW 70
SA AF ABS EF ED
ILCRsDermal = (3)
BW AT 106
" # $
CS CSFInhalation 3 BW 70
IRInhalation EF ED
ILCRsInhalation = (4)
BW AT PEF
where CS is the PAH concentration of dust (g kg1 ) based on toxic equivalents of BaP using the TEF
listed in Table 2 (77), CSF is carcinogenic slope factor (mg kg1 day1 )1 , BW is body weight (kg), AT
is the average life span (day), EF is the exposure frequency (day year1 ), ED is the exposure duration
(year), IRInhalation is the inhalation rate (m3 day1 ), IRIngestion is the dust intake rate (mg day1 ), SA is the
dermal surface exposure (cm2 day1 ), AF is the dermal adherence factor (mg cm2 ), ABS is the dermal
adsorption fraction, and PEF is the particle emission factor (m3 kg1 ). The determination of carcinogenic
slope factor is based on the cancer-causing ability of BaP; CSFIngestion , CSFDermal , and CSFInhalation of BaP
are 7.3, 25, and 3.85 (mg kg1 day1 )1 , respectively (83, 75, 39). Other parameters referred in the model
for children (16 years old) and adults (731 years old) are based on the Risk Assessment Guidance of
USEPA and related publications (Table 1).

Results and discussion


Table 2 shows the averages, standard deviations, maximum, minimum, and skewness of the PAH con-
centrations in street dust from different land use of Bushehr. Concentrations of !PAHs (sum of the 26
ring PAHs in Table 2) in urban surface dust varied from 73.60 (B3) to 9491 (B13) g kg1 with an average
of 1116.02 g kg1 . This result indicated that PAHs tend to accumulate in dust particles, which could
6 B. KESHAVARZI ET AL.

Table . PAHs concentrations (g kg ) in street dust collected from Bushehr city.

Aromatic ring TEF Minimum Maximum Mean Std. deviation Skewness

Naphthalene (Nap) . . . . . .
Acenaphthene (Ace) . . . . . .
Fluorine (Fl) . . . . .
Phenanthrene (Phe) . . . . .
Anthracene (Ant) . . . .
Fluoranthene (Flu) . . . . . .
Pyrene (Pyr) . . . . . .
Benzo[a]anthracene (BaA) . . . . . .
Chrysene (Chr) . . . . .
Benzo[b]fluoranthene (BbF) . . . . . .
Benzo[k]fluoranthene (BkF) . . . . .
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Benzo[a]pyrene (BaP) . . . .
Benzo[e]pyrene (BeP) . . . . .
Dibenzo[a,h]anthracene (DbahA) . . . . .
Benzo[g,h,i]perylene (BghiP) . . . . . .
Indene (Ind) . . . . . .
!PAH . . . .
ring (%) . . . . .
ring (%) . . . . .
ring (%) . . . . -.
and ring (%) . . . . .
LMW . . . . .
HMW . . . . .
ComPAHs/!PAH . . . . .
CANPAHs/!PAH . . . . .
NCANPAHs/!PAH . . . . -.
TEQ . . . . .
TEQ/!PAH . . . . .

!PAHs: total PAH concentration, sum of individual mass concentration of PAH congeners.
LMW PAHs: low molecular weight ring PAHs.
HMW PAHs: high molecular weight ring PAHs.
COMPAHs: combustion derived PAH concentration.
CANPAHS: carcinogenetic PAHs.
NCANPAHs: non-carcinogenetic PAHs.
TEF: PAHs toxic equivalency factor with respect to BaP (, ).

be used as an indicator of urban environmental pollution (42). It is worth mentioning that Sadra boule-
vard sampling site (B13) is the place where a petroleum supporter tank is installed. PAHs having 4 rings
were the primary components (Figure 2) and accounted for 31.90% of the total 16 PAHs on average.
Figure 2 and Table 2 show that the low-molecular-weight (LMW) PAHs (23 rings) ranged from 13.48%
to 58.34% (mean, 34.77%) with the mean of 322.25 g kg1 . The HMW PAHs (46 rings) ranged from
41.65% to 86.52% with mean being 793.76 g kg1 . HMW compounds were dominant in almost all dust
samples.
Combustion PAHs (the sum of Flu, Pyr, BaA, Chr, B(b+k)F, and BaP (43, 44)) make up a significant
proportion of the total concentration of PAHs in Bushehr street dust, ranging from 0.42 to 0.84 g kg1 .

Figure . Percentage of dierent ring PAHs in street dust of Bushehr.


POLYCYCLIC AROMATIC COMPOUNDS 7

Carcinogenetic PAHs contains Nap, BaA, Chr, BeP, BbF, BkF, BaP, DbahA, and Ind. The mean
ratio of carcinogenic PAHs to total PAHs (CANPAHs/!PAHs) is greater than the mean ratio of non-
carcinogenic PAHs to total PAHs (NCANPAHs/!PAHs) indicating that carcinogenetic PAHs are more
abundant than non-carcinogenetic PAHs in this area (Table 2 and Figure S1).
Some PAHs reflect their sources, and thus can be used as indicators. For example, Flu, Chr, B(b+k)F,
Phe, Ind, and BghiP indicate combustion source (45). Ace represents vehicle emissions, and Ant is the
main indicator of petroleum source (46), while Fl is the signature PAHs coming from coking ovens (41).
Furthermore, Fl, Flu, Pyr, BbF, and Ind are indicators of oil combustion (47). In general, of combustion-
derived PAHs, the LMW (3 rings) species are abundant at low to moderate temperatures, such as wood
and coal combustion (42). On the contrary, HMW (4 rings and above) are generated at high temperature,
such as vehicle emission (25).
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As shown in Figure 2, PAHs with 3 and 4 rings were dominant in Bushehr samples. Moreover, the
concentration of HMW PAHs was higher than that of LMW ones. This might be due to the tendency of
HMW compounds to adhere to street dust (42). Also, the high fraction of HMW PAHs in total PAHs
indicates that they mostly come from petroleum fuels combustion (48); in other words, PAHs with more
than 4 rings generally come from pyrogenic sources (49). The results of PAHs concentration in Bushehr
street dust showed that this city can be divided into 2 parts, northern and southern, where in the north-
ern part, the concentration of PAHs, and in particular HMW PAHs species are high and reflects high
traffic density, because HMW PAHs mainly originate from combustion of fuels (for example in vehicle
emissions) (Figure S1 and Figures 2 and 3) (10, 50, 48, 51, 40, 11).

Figure . Distribution of !PAHs and proportion of LMW and HMW in sampling site.
8 B. KESHAVARZI ET AL.

Table S1 compares the concentration of PAHs measured in street dusts of Bushehr city with other
major cities in the world. The mean of PAHs in street dusts samples in Bushehr (this work) is higher
than Esfehan and Tehran (Iran), Beijing and Guangzhou (China), United Kingdom, Norway, Canada,
Australia, and Egypt, and lower than Tamale (Ghana), Chang-Zhu-Tan (China), Brimngham, Taiwan,
Ulsan (Korea), and United Kingdom (Table S1). These differences can be due to the degree of industri-
alization, traffic density, population, the amount of street washing, weather, size of street dust, and many
others. For example, intense rains can remove the signature of contaminants from street dust (52).
ShapiroWilk test, skewness, and standard deviation showed that the data is non-normaly distributed
(Table S2). Table S3 presents the correlation coefficients matrix among PAH compounds based on Spear-
mans correlation analysis. It is obvious that PAHs are significantly positively correlated, suggesting a
common origin. The LMW (23 rings) group does not display a strong positive correlation with the
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HMW (45 rings) group. There is also a strong positive correlation between members of each group. The
poor correlation reflects different origins for the 2 groups. The LMW PAHs mainly originate from oil
leak and were easier to be evaporated and degradated, while the HMW PAHs mainly originate from com-
bustion of fuels and were hardly to be evaporated and degraded (48). Furthermore, the poor correlation
between HMW and LMW could be explained by the high atmospheric mobility of LMW compounds,
which may have been transported from remote sites via atmospheric transportation (according to volatil-
ity and Kow ) (73). Also, the HMW PAHs are more likely associated with airborne particulate and have a
lower relation in the gas-phase than the LMW PAHs, so they can be moved in shorter distance (53).
Toxic equivalency concentration (TEQ) calculated for street dust of Bushehr along with TEF values
is shown in Table 2. In calculating TEF, BaP was taken as reference and hence was assigned a value of
1. Other PAHs displayed their own TEF values based on their carcinogenic level compared to BaP (54,
36). High correlation coefficients between HMW and TEQs in Bushehr street dust suggest that HMW
have much higher TEF values than LMW species (5). PAHs measured in north of Bushehr displayed
higher TEQ compared to those in south of Bushehr (Figure S3). There is also a significant positive
correlation coefficient between the !PAH concentration and TEQ (Figure S2), which suggest that total
PAH concentration could be effect on TEQ. This is evident, because in TEQ formula, concentration and
TEF play a role. Of these, HMW PAHs, which are released from fuel combustion, have higher TEF than
LMW PAHs and mostly affect TEQ.
To assess the source of PAHs, PCA was employed, and it provided a means of reducing the complexity
of the total PAH data set. PCA was conducted with Varimax rotation using SPSS software. In addition,
the KMO and Bartletts test were performed to test the adaptability of PCA. PCA of the PAHs for Bushehr
dusts resulted in 3 factors of 44.66%, 29.89%, and 17.96%, respectively, accounting for 92.51% of the total
variability (Table 3). Factor 1 was heavily weighted by Phe, Flu, Pyr, BaA, Chr, BeP, BbF, BkF, and DbahA
consistent with emitted HMW from vehicle (5557). Nap, Ace, and Fl in factor 2 are LMW and have
23 rings and originate from straw and firewood burning (58, 37). Also, Nap could be designated as
petroleum since Nap is the signal for incomplete combustion-related sources (58, 37). BaP, BghiP, and
Ind stay on factor 3 and were HMW having similar chemical and physical properties. BghiP and Ind are
6-ring PAHs, and BaP maybe produced with BghiP and Ind.
CA was performed according to cases, with Wards method using standardize range 0 to 1, as calcu-
lated by software of SPSS 19. Two diagrams from analytical results are shown in Figure 4. Samples were
classified into 2 cluster groups based on sampling locations: a cluster of samples collected from northern
part of the city (G1) and another cluster taken from the southern (G2) parts. The PAH contents in the
subgroup G1 were significantly higher than those in samples in subgroup G2. Sampling sites B1, B4, B6,
and B8, which were taken from residential area, also stay on subgroup 2, as the concentration of PAHs in
this sampling site is also low, because residential area is far away from the city center and it has relatively
low traffic transport and private car occupancy, which show less source contribution of PAH pollution
from human activities (30).
PAH ratios are commonly used to determine PAH sources, clarify samples by location, and estimate
the importance of combustion- and petroleum-derived PAHs (31). For example, of combustion-derived
PAHs, HMW-PAHs were abundantly generated at high temperature, while the petroleum-derived
residues contain relatively high abundances of LMW-PAHs (59). Then, the ratio of LMW/HMW could
POLYCYCLIC AROMATIC COMPOUNDS 9

Table . The results of principal component analysis (PCA) for PAHs.

Rotated Component Matrixa


Component

Naphthalene . 0.94 .
Acenaphthene . 0.90 .
Fluorine . 0.96 .
Phenanthrene 0.69 . .
Anthracene 0.96 . .
Fluoranthene 0.88 . .
Pyrene 0.78 . .
Benzo[a]anthracene 0.95 . .
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chrysene 0.67 . .
Benzo[e]pyrene 0.75 . .
Benzo[b]fluoranthene 0.82 . .
Benzo[k]fluoranthene 0.90 . .
Benzo[a]pyrene . . 0.82
Dibenzo[a,h]anthracene 0.63 . .
Benzo[ghi]perylene . . 0.63
Indene . . 0.62
% of Variance . . .
Cumulative % . . .

Extraction Method: Principal Component Analysis.


Rotation Method: Varimax with Kaiser Normalization.
a. Rotation converged in iterations.

be used as an index for apportioning the anthropogenic sources of PAHs (60). Figure 5 shows that
the ratio of LMW/HMW in Bushehr street dusts is lower than 1. The ratio of Ant/(Ant + Phe) <0.1
suggests a petroleum source, while a ratio >0.1 reflects combustion. Similarly, Flu/(Flu + Pyr) <0.4
indicates a petroleum source and a liquid fossil fuel combustion source between 0.4 and 0.5, and if >
0.5, it characterizes biomass and coal combustion (31). IcdP/(IcdP + BghiP) and BaA/(BaA + Chr)
may characterize the nature of potential PAH emission sources as IcdP/(IcdP + BghiP) is <0.2 and
BaA/(BaA + Chr) is <0.2, indicating petroleum and petrogenic sources, respectively. When BaA/(BaA
+ Chr) falls between 0.2 and 0.35 and IcdP/(IcdP + BghiP) between 0.2 and 0.5, the PAHs are assumed
to originate from petroleum combustion (liquid fossil fuel, vehicle, and crude oil combustion). However,
when IcdP/(IcdP + BghiP) >0.5 and BaA/(BaA + Chr) >0.5, it strongly indicates contribution from
coal, grass, and wood (31). Table 4 shows other calculated isomer ratios. The isomer ratio indicates a
pyrogenic source for the majority of the samples. Furthermore, Flu/(Flu + Pyr), BaA/(BaA + Chr), and
BaP/(BaP + Chr) indicate pyrogenic PAHs origin from gasoline automobiles in Bushehr city and fossil
fuel combustion as one of the sources of PAHs.

Figure . Dendrogram resulting from the Wards method of hierarchical cluster analysis for PAHs (G: cluster group).
10 B. KESHAVARZI ET AL.
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Figure . Source (petrogenic or pyrogenic) PAHs in dust samples. (A) Ant/(Ant + Phe); (B) Phe/Ant; (C) BaP/(BaP + Chr) and (D)
LMW/HMW.

Human health risk assessment was based on the assumption that adults and children may be exposed
to PAHs (according to residential scenario). The aim of this risk assessment was to investigate the pos-
sibility of cancer development among local residents in Bushehr as a result of exposure to PAHs via
inhalation, ingestion, and dermal exposure routes. Average concentration of each of the 16 investigated
individual PAHs was used in the calculations of risk assessments.
The cancer risk levels via dermal contact and ingestion pathway ranged from 103 to 105 with a
mean of 104 in all the dust samples, while mean cancer risk via inhalation was 1010 1012 , about
105 109 times less than that of ingestion and dermal contact (Table 5). Therefore, dermal contact is the

Table . Diagnostic ratios used in identification of PAHs pollution sources in the street dust of Bushehr.

PAH ratio Value range Source This work Reference

!LMW/!HMW < Pyrogenic . ()


> Petrogenic ()
Phe/Ant > Petrogenic ()
< Pyrogenic . ()
Ant/(Ant + Phe) <. Petrogenic ()
>. Pyrogenic . ()
Flu/(Flu + Pyr) <. Petrogenic ()
.. Gasoline emissions . ()
.. Diesel emissions ()
BaA/(BaA + Chr) <. Petrogenic ()
.. Gasoline emissions . ()
.. Diesel emissions ()
.. Petrogenic origin ()
BaP/(BaP + Chr) . Automobiles . ()
. Gasoline emissions ()
. Diesel engines ()
Ind/Ind + BghiP <. Petroleum and . ()
petrogenic source
>.<. Petroleum combustion ()
(liquid fossil fuel,
vehicle, and crude oil
combustion)

>. Coal, grass, and wood ()


POLYCYCLIC AROMATIC COMPOUNDS 11

Table . Incremental lifetime cancer risk (ILCR) for children and adults in Bushehr street dust (according to residential scenario).

Child Adult
Exposure pathways ILCRsIngestion ILCRsDermal ILCRsInhalation Cancer risk ILCRsIngestion ILCRsDermal ILCRsInhalation Cancer risk

Mean .E .E .E .E .E .E .E .E
Max .E .E .E .E .E .E .E .E
Min .E .E .E .E .E .E .E .E
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Figure . Scatter plot of cancer risk for street dust collected from the northern and southern parts of the Bushehr city. The cancer risk in
samples collected in the northern part is higher than that in the southern part.

main pathway for exposure to PAHs and bears a high risk. Also, other study shows similar results that
both ingestion and dermal contact greatly contribute to the cancer (61). The mean cancer risk is higher
than 104 , indicating that carcinogenic risk is high and worrying. It is worth to mention that cancer
risk for children is higher than for adults. The most sensitive subpopulation is young children because
of their hand-to-mouth activity, whereby contaminated dust can be readily ingested (62). In addition,
considering the lower body weight of children, the PAHs intake (mg/kg body weight/day) of a child is
believed to be greater than that of an adult (42).
Cancer risk in northern part of the Bushehr city is above 104 , compared with 104 106 in the south-
ern part of the city, which represents potential cancer risk (ILCR). Higher cancer risk in the northern
part of Bushehr is apparently due to higher traffic load (Figure 6). Although industrial activities are also
effective on PAHs concentration, but in fact in the Bushehr city, the prevailing activity is traffic. However,
the presence of oil reservoirs at station of 13 causes to increase mean of ILCR and cancer risk, but it is
necessary to note that all of the sites in northern part of the city (with high traffic load) indicate high
cancer risk individually (above 104 ). On the other hand, as already mentioned, fuel combustion due to
vehicle engine can release HMW PAHs, which have usually higher TEF than LMW PAHs.

Conclusions
!PAHs concentration ranges from 73.6 to 9491 g kg1 with an average of 1116.02 g kg1 in the
street dust of Bushehr. Almost 41.6586.52% of PAH mass is contributed by HMW PAHs, suggesting
a combustion origin. Based on the PAH distribution pattern, the northern part of the city has a higher
concentration of PAHs than the southern part, which is consistent with the greater traffic load in this part
of the city. PAHs in northern part of the city also display higher TEQs and higher correlation coefficients
between the total PAH concentration and TEQ. Diagnostic ratios and PCA analysis indicated vehicle
emission as the major source, with minor contributions from oil. The estimated ILCR associated with
exposure to street dust revealed that both children and adults are exposed to high potential cancer risk
via both dust ingestion and dermal contact pathways and need immediate attention. It is clear from the
results of this study that street users (for example vendor, street-sweeper, shopkeeper, etc.) in Bushehr
are exposed to the harmful PAHs in street dust. PAH contamination in dust can be reduced by means
of reducing the traffic load, prohibiting straw burning, as well as planning residential areas away from
industrial and traffic zones. Finally, the study of relationship between meteorological parameters (such as
season, precipitation, and direction/speed winds) and PAHs concentration and distribution is suggested.
12 B. KESHAVARZI ET AL.

Acknowledgments
The authors wish to express their most sincere gratitude to Shiraz University Research Committee and medical geology
research center of Shiraz University for supporting this research.

Funding
This research was financially supported by Bushehr Environmental Protection Office.

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