Particulate Polycyclic Aromatic Hydrocarbons (PAH)in the Atmosphere of Bizerte City, Tunisia

S. Ben Hassine • B. Hammami • W. Ben Ameur •

Y. El Megdiche • B. Barhoumi • M. R. Driss

Received: 22 January 2014 / Accepted: 21 May 2014

� Springer Science+Business Media New York 2014

Abstract The particle-phase concentrations of polycyclic

aromatic hydrocarbons (PAH) were determined in 13 air

samples collected in an urban area of Bizerte (Tunisia)

during 2009–2010. Atmospheric particulate samples were

extracted by ultrasonic bath and analyzed by high-perfor-

mance liquid chromatography with fluorescence detection.

PAH were found in all the analyzed air samples and the

most abundant compounds were pyrene, fluoranthene,

benzo[g,h,i]perylene, benzo[b]fluoranthene, chrysene and

benzo[a]pyrene.P

14-PAH concentrations ranging from

9.38 to 44.81 ng m-3 with mean value of 25.39 ng m-3.

PAH diagnostic ratio source analysis revealed gasoline and

diesel vehicular emissions as major sources. The mean total

benzo[a]pyrene toxicity equivalent calculated for samples

was 3.66 ng m-3 and the mean contribution of the car-

cinogenic potency of benzo[a]pyrene was determined to be

55.8 %. Concentrations of particulate PAH in Bizerte city

atmosphere were approximately eight times greater than

sampled at a nearby rural site.

Keywords Particle-associated polycyclic aromatic

hydrocarbons (PAH) � HPLC-FLD � Sources �Benzo(a)pyrene equivalent toxicity (BaP-TEQ) �Diagnostic ratios � Tunisia

Polycyclic aromatic hydrocarbons (PAH) are a large class of

over 100 organic compounds with 2–7 aromatic rings,

formed by incomplete combustion during burning or

pyrolysis of organic matter. Expose to atmospheric PAH

may cause respiratory problems, impair pulmonary function

and cause bronchitis (Kunzli et al. 2000; ATSDR 2009) and

also cause chronic effects, with several PAH having dem-

onstrated mutagenic and carcinogenic effects (Duran et al.

1999; Bostrom et al. 2002; IARC 2010). As a result of their

demonstrated health effects, the European Community and

the United States Environmental Protection Agency

(USEPA) have listed 16 ‘‘Priority PAH Pollutants’’.

While PAH originate from natural processes such as

biomass burning, volcanic eruptions and diagenesis (Wang

et al. 2007) a large portion of atmospheric releases of concern

to human health exposures are due to anthropogenic activity

such as coal and wood burning, petrol and diesel oil com-

bustion and industrial processes (Mostert et al. 2010).

Atmospheric PAH are semi-volatile organic compounds

(SVOC) and thus can be found in both vapour and particle

phase. Generally, lighter molecular weight and more volatile

species (2–3 ring structure) are predominantly found in

vapour phase while heavier molecular weight and less vol-

atile species ([5 ring structure) are predominantly found in

particle phase; medium molecular weight species (e.g.,

3-ring phenanthrene and 4-ring pyrene) have been shown to

partition between both phases (Venkataraman and Fried-

lander 1994; Ohura et al. 2004). PAH species classified as

carcinogens (e.g., benzo[a]pyrene, Group 1 ‘‘carcinogenic to

humans’’; dibenz(a,h)anthracene, Group 2 ‘‘probably car-

cinogenic to humans’’) have been shown to be largely

associated with smaller respirable particle size fractions

(Straif et al. 2005; Lu et al. 2008).

For these reasons, the study of the occurrence of par-

ticulate PAH and the processes governing their fate is of

great importance and efforts have been made in recent

years to determine ambient concentrations of particulate

PAH in many urban and rural environments around the

S. Ben Hassine � B. Hammami � W. Ben Ameur �Y. El Megdiche � B. Barhoumi � M. R. Driss (&)

Laboratory of Environmental Analytical Chemistry (05/UR/12-03),

Department of Chemistry, Faculty of Sciences of Bizerte,

University of Carthage, 7021 Zarzouna, Bizerte, Tunisia

e-mail: mr.driss@fsb.rnu.tn

123

Bull Environ Contam Toxicol

DOI 10.1007/s00128-014-1303-9

world. To our knowledge, however, analysis of PAH in

Tunisia has been investigated only in sediment samples

(Trabelsi and Driss 2005; Zaghden et al. 2007; Ben Ameur

et al. 2010; Barhoumi et al. 2014) and in airborne diesel

exhaust particulates (Dridi et al. 1998). Information on

background levels of PAH in the atmosphere of Tunisia is

not available. To expand this limited literature and also

provide information on background levels of particulate

PAH in Tunisia, the aims of this study were to: investigate

PAH associated with the particle phase in an urban atmo-

sphere (Bizerte, Tunisia) in winter; identify the major

emission source types using PAH diagnostic ratios; and,

provide context for the current sampled ambient PAH

levels with those in other international urban centres.’’

Materials and Methods

The urban atmospheric particulate samples (n = 13) were

collected during winter (December 2009 to February 2010)

in Bizerte city, located in northern Tunisia near the Med-

iterranean coast (Fig. 1). The city lies between latitude

37�1602800N and longitude 9�5202600E and has a population

of approximately 127,000 (2012 Census, National Institute

of Statistics Tunisia). The economic activity in this region

consists primarily of agriculture (food crops, livestock,

dairy), fishing, and operations by light and heavy industries

(i.e., cement manufacture, plastic, textile, mechanic and

electronic, iron and steel metallurgy, petroleum refining

and lubricants). The sampler was located adjacent to a busy

roadway intersection, that sees frequent traffic congestion

during commuting hours. Sampling site is surrounded by

residential areas and business district and situated

approximately 1 km from petroleum refining and cement

manufacture. Meteorological conditions (average temper-

ature, relative humidity and wind speed, provided by the

national institute of meteorology) in Bizerte City during

sampling dates are given in Table 1. The background PAH

samples (n = 4) were collected during winter (December

2013) from a rural site approximately 20 km from the

urban site (i.e., El Alia region, latitude 37�1007.6700N and

longitude 10�200.3700E; Fig. 1).

Air particles at the TSP size fraction were collected on

glass fiber filters (37 mm diameter, 1 lm pore size, pro-

vided by Supelco) previously baked at 450�C for 12 h, by

means of a low-volume sampling apparatus operating at a

constant flow rate of 2.5 Lmin-1 (ESCORT ELF� Pump,

MSA). Samples were collected over 10 h periods yielding

sampled air volumes of *1.5 m3. The sampler inlet was

located approximately 1 m above the ground. Collected

samples were wrapped in aluminum foil and promptly

transported to the laboratory for immediate analysis, min-

imizing potential sample loss due to prolonged storage.

Three blanks filters, which accompanied samples to the

Fig. 1 Map showing urban

(Bizerte City) and background

(El Alia) sampling locations for

Bizerte region, Tunisia

Bull Environ Contam Toxicol

123

sampling site, were used to determine any background

contamination attributed to handling, storage and

transportation.

The solvents used in this study (acetone, methanol, ace-

tonitrile and dichloromethane) were pesticide quality and

were obtained from Fluka (Buchs. Switzerland). PAH stan-

dards purchased from Supelco USA were: naphthalene

(Naph), acenaphthene (Ace), fluorene (Fl), phenanthrene

(Phe), anthracene (An), fluoranthene (Ft), pyrene (Py),

benzo[a]anthracene (B[a]an), chrysene (Chy), benzo[b]flu-

oranthene (B[b]ft), benzo[k]fluoranthene (B[k]ft), ben-

zo[a]pyrene (B[a]py), dibenzo[a,h]anthracene (D[a,h]an),

benzo[g,h,i]perylene (B[g,h,i]pe), Standard solutions of

each PAH were prepared in dichloromethane and were

further diluted in methanol to obtain mixed fortifying and

HPLC calibration standard solutions.

The extraction of filters was carried out as per modified

Colombini et al. (1998) method. Briefly, the filters were

extracted with 20 mL of dichloromethane:acetone mixture

(70:30) in an ultrasonic bath for three cycles of 20 min.

Both extracts were combined and then concentrated to

1 mL. The concentrated solution was redissolved in ace-

tonitrile and then reduced to 0.5 mL in a micro-Kuderna-

Danish evaporator under a gentle stream of nitrogen at

room temperature. The final extract was filtered with

0.45 lm pore size Teflon membrane before being subjected

to high-performance liquid chromatography with fluores-

cence detection (HPLC-FLD) analysis.

Separation and identification of PAH were performed on a

HPLC unit (Jasco, Japan) equipped with a HPLC pump

(PU-2089, Jasco), an type 7125 Rheodyne injector (20 lL

loop) and a fluorescence detector (FP-2020, Jasco) with

variable excitation and emission wavelengths. The opti-

mized parameters of the fluorescence detector for the

determination of each PAH compound are illustrated in

Table 2. Chromatographic separation and resolution was

best achieved by using a Supelcosil LC-PAH (Supelco, Inc.

Bellefonte, PA) reverse-phase C18 column (4.6 9 250 mm,

5 lm particle size). Data acquisition and processing was

controlled by Chrom NAV (Jasco) software. The mobile

phase was methanol/water in gradient mode at a flow rate of

1 mL min-1. The gradient elution program started with an

initial mobile phase at 20:80 MeOH:water (v/v) for 5 min,

changing linearly to 100 % MeOH in 15 min and, after

30 min, changing back to initial phase (20:80).

Six calibration standards were prepared by diluting

the standard solution (10 lg mL-1 each PAH) to a

Table 1 Meteorological conditions in Bizerte City during sampling

dates

Sampling

dates

Ambient

temperature (�C)

Wind speed

(m/s)

Relative

humidity (%)

13/12/2009 14.4 3.2 68

26/12/2009 17.0 3.0 80

29/12/2009 17.1 3.0 43

31/12/2009 14.7 1.2 63

15/01/2010 12.5 3.7 83

18/01/2010 13.1 2.7 82

20/01/2010 13.6 4.0 87

05/02/2010 17.7 5.7 68

12/02/2010 8.0 5.5 73

17/02/2010 14.3 2.6 75

19/02/2010 20.9 4.7 53

20/02/2010 13.4 5.3 70

25/02/2010 15.9 2.6 69

Table 2 Retention time (Rt), excitation and emission wavelengths (kex, kem), recoveries with relative standard deviation (RSD), regression

coefficient (R2) and limit of detection (LOD)

Compoound name Abbreviation Rt (min) kex (nm) kem (nm) Recovery (%) (RSD) R2 LOD (ng m-3)

Naphtalene Naph 6.10 220 335 31.5 (15) 0.996 0.23

Acenaphthene Ace 9.94 220 335 49.0 (14) 0.999 0.06

Fluorene Fl 11.12 220 335 51.4 (15) 0.997 1.06

Phenanthrene Phe 12.09 252 370 53.7 (14) 0.999 0.08

Anthracene An 13.33 252 370 60.0 (14) 0.998 0.08

Fluoranthene Ft 14.34 235 420 76.2 (13) 0.995 0.39

Pyrene Py 14.98 235 420 63.1 (13) 0.999 0.34

Benzo[a]anthracene B[a]an 19.23 270 392 73.3 (4.0) 0.998 0.09

Chrysene Chy 21.54 270 392 75.2 (6.0) 0.999 0.13

Benzo[b]fluoranthene B[b]ft 27.32 295 430 75.4 (10) 0.992 0.15

Benzo[k]fluoranthene B[k]ft 33.50 295 430 81.0 (10) 0.999 0.03

Benzo[a]pyrene B[a]py 36.18 295 430 91.8 (11) 0.998 0.12

Dibenzo[a,h]anthracene D[a.h]an 49.03 300 416 99.0 (4.0) 0.999 0.28

Benzo[ghi]perylene B[g,h.i]pe 52.66 300 416 100 (5.0) 0.999 0.25

Bull Environ Contam Toxicol

123

concentration range of 1–40 ng mL-1 (Ace, An, B[a]an,

B[k]ft),10–50 ng mL-1 (Naph, Phe, Chy, B[b]ft, B[a]py)

and 50–100 ng mL-1 (Fl, Ft, Py, D[a,h]an, B[g,h,i]pe). Each

calibration level was analyzed by HPLC-FLD in triplicate

and regression analysis was used to construct calibration

curves. PAH were found to be linear in the tested ranges with

correlation coefficients (R2) from 0.992 to 0.999. The limits

of detection (LOD) calculated by a signal-to-noise ratio of

three were in the range of 0.03 to 1.06 ng m-3. In order to

obtain PAH recovery efficiencies the glass fiber filters were

spiked with a known amount of standard PAH solutions and

were subjected to the same analytical procedure used for the

samples. The obtained recoveries are summarized in Table 2

(average percentages of five replicates). Relative standard

deviations of the method (n = 5) were in the range of 4 %–

15 % indicating acceptable repeatability of the method.

Quantitative and qualitative analyses were performed by

comparison with external standard. Procedural blanks were

periodically analysed to check for interference and con-

tamination and no significant background interferences were

observed. Field blank samples were analysed in the same

manner as the real samples and concentration of individual

compounds on the blank glass fiber filters were below

detection limits and in most case not detectable. The

recoveries of PAHs for overall procedure with relative

standard deviation (RSD), correlation coefficients (R2) and

limits of detection (LOD) are shown in Table 2.

Results and Discussion

Table 3 shows the arithmetic mean, median, minimum and

maximum concentration values and number of samples

above LOD for the PAH identified in urban and rural sites

from Bizerte. Results obtained for Bizerte city atmosphere

are discussed in the following section. Naphthalene and

fluorene were not analysed as above LOD in any sample;

this result is expected for particle phase sampling, as

naphthalene is highly volatile and fluorene is relatively

volatile and also not very fluorescent. Overall, analysed

samples were most enriched in 4-ring (Ft, Py, B[a]an,

Chy,), 5-ring (B[b]ft, B[k]ft, B[a]py and D[a,h]an) and

6-ring (B[g,h,i]pe) PAH while 3-ring species (Ace, Phe,

An) contributed relatively little to sampled mass concen-

trations. This result is in good agreement with the findings

of studies focused on gas–particle partitioning whereby

high ring PAH are predominantly attached to particles

while low ring PAH tend to exist in the gas phase (Ohura

et al. 2004). Total PAH concentrations were in the ranges

of 9.38–44.81 ng m-3 with a mean and median value of

25.39 and 26.97 ng m-3 respectively. The PAH contribu-

tions to total sampled PAH were summarized over the

urban samples (average species concentrations of n = 13)

and presented as a profile in Fig. 2. Pyrene and fluoranth-

ene were the most abundant compound and accounted for

about 20.9 % and 16.7 % of total sampled PAH concen-

tration (P

14-PAH), followed by B[g,h,i]pe (11.6 %),

B[b]ft (10.3 %), Chy (9.8 %), B[a]py (8 %), Phe (4.6 %),

B[a]an (4.5 %), D[a,h]an (4.2 %), B[k]ft (4.1 %), An

(3.7 %) and Ace (1.6 %).

For the rural site, Naph, Ace, Fl were not detected in any

of the analysed samples while An, Ft, B[a]an, B[b]ft,

B[a]py, D[a,h]an and B[g,h,i]pe were found under LOD

(Table 3). Only four compounds were detected and quan-

tified at concentrations above LOD: Phe, Py, Chy and

B[k]ft. The mean and median levels of total sampled PAH

concentrations (P

14-PAH) were 3.08 and 3.18 ng m-3

respectively. Comparing the results of the urban and rural

sampling campaigns, total ambient particulate PAH levels

(P

14-PAH) at Bizerte city were found to be approxi-

mately eight times greater than at the rural site, this dif-

ference was expected due to proximity of PAH sources to

the urban site (e.g., road traffic).

PAH concentrations have been reported for many dif-

ferent urban areas throughout the world. It has been

reported that PAH levels in urban environment could be

significantly affected by several factors such as location of

the sampling site and its proximity to emission sources

(Harrison et al. 1996), sampling methodology (Tsapakis

and Stephanou 2005), meteorological conditions (rainfall,

wind speed, relative humidity, temperature) (Mastral et al.

2003; Dallarosa et al. 2005; Tham et al. 2008), concen-

tration of other ambient air pollutants such as ozone (O3);

carbon monoxide (CO); and sulfur dioxide (SO2) (Tsapakis

and Stephanou 2005; Tham et al. 2008) as well as the

variety of methods used for clean-up analysis and the

varying analytical uncertainties contained within, as well

as the time of the year during which sampling was con-

ducted. Therefore direct comparison of PAH concentra-

tions between various urban environments should be done

with caution. Particulate PAH concentrations observed in

this study were compared with published data to provide an

overall picture of PM-associated PAH in different urban

regions (Table 4). Comparative studies were chosen based

on comparable duration and season (winter) and a summed

PAH suite reasonably comparable to the current study.

Comparative studies were largely limited to respirable fine

fraction (PM2.5) data because of its greater associated

health risk; comparison with the TSP sampling data in this

study is reasonable because particle-associated PAH have

been shown be largely associated with the respirable PM2.5

size fraction (Venkataram and Friedlander, 1994). Total

sampled particulate PAH concentration (P

14-PAH) in

Bizerte city atmosphere were found to be approximately

(Table 4): 16 times lower than found for Beijing in China

(Wang et al. 2008); about 6, 4, 3 and 2 orders of magnitude

Bull Environ Contam Toxicol

123

lower, respectively, than those reported for Zonguldak in

Turkey (Akyuz and Cabuk 2008), Delhi in India (Singh et al.

2011), Chennai (Egmore) in India (Mohanraj et al. 2011) and

Urumqi in China (Da Limu et al. 2012); approximately 2

times higher than sampled in Tuscany (Florence, FIG site) in

Italy (Martellini et al. 2012) and Virolahti in Finland

(Makkonen et al. 2010); and, much higher than sampled in

Madrid in Spain (Mirante et al. 2013).

Diagnostic ratios have been used (Yunker et al. 2002;

Katsoyiannis et al. 2011) to characterize and identify major

PAH source types in different environmental media. While it

is recognized that PAH have inherent source-receptor con-

servation issues (e.g., gas/particle partitioning changes,

reactivity, particle washout, etc.; Galarneau et al. 2008), a

diagnostic ratio analysis can usefully provide an initial

identification of probable source types. Published ratios can

help distinguish PAH emissions originating from various

sources such as petroleum products, petroleum combustion,

biomass combustion, or coal combustion. It has been

reported that Ft/(Ft ? Py) ratios below 0.40 imply the

prominence of unburned petroleum (petrogenic sources),

ratios from 0.40 to 0.50 suggest the combustion of liquid

fossil fuels (vehicle and crude oil), whereas ratios larger than

0.50 are characteristic for grass, wood, or coal combustion

(Yunker et al. 2002; De La Torre-Roche et al. 2009). In this

study, the mean Ft/(Ft ? Py) was 0.44 consistent with the

combustion of liquid fossil fuels. The significant contribu-

tion of pyrogenic sources was also indicated by other PAH

member diagnostic concentration ratios such as indeno

[1,2,3-cd]pyrene to indeno[1,2,3-cd]pyrene plus benzo

[g,h,i]perylene (Ind/(Ind ? B[g,h,i]pe), benzo[a]anthracene

to benzo[a]anthracene plus chrysene B[a]an/(B[a]an ? Chr),

(Yunker et al. 2002). In the present study the mean value of

B[a]an/(B[a]an ? Chy) was 0.32 pointing out the importance

of vehicular emissions other possible emission sources (Yunker

et al. 2002). In addition, the mean B[a]py/B[g,h,i]pe was 0.69,

remain within the range of typical values found for traffic

emissions ([0.6) (Katsoyiannis et al. 2011).

Benzo[a]pyrene has been regarded by the World Health

Organization (WHO 2001) as a good index for total PAH

carcinogenicity (De Martinis et al. 2002). The concentrations

of B[a]py in winter ranged between 0.63 and 3.87 ng m-3 in

Bizerte air, with a mean value of 2.04 ± 1.06 ng m-3. This

indicates that B[a]py contamination may exceed the

Fig. 2 Special PAH profile for ambient particulate sampled at

Bizerte City urban site (average of n = 13 samples)

Table 3 Concentrations (ng m-3) of particulate PAH in urban and rural sites in Bizerte atmosphere (Tunisia)

Compounds Urban site (n = 13) Rural site (n = 4)

n [ LOD Meana ± SD Median Range Meana ± SD Median Range

Naph 0 ND ND ND ND ND ND

Ace 3 0.40 ± 0.85 ND 0.73–2.60 ND ND ND

Fl 0 ND ND ND ND ND ND

Phe 6 1.17 ± 1.71 ND 0.95–4.82 0.73 ± 0.30 0.62 0.5–1.07

An 4 0.93 ± 1.83 ND 2.66–4.86 \LOD \LOD ND–0.17

Ft 13 4.23 ± 1.27 ND 2.49–6.53 \LOD \LOD ND–0.43

Py 13 5.30 ± 2.78 4.42 0.89–10.12 1.16 ± 0.42 1.14 0.76–1.59

B[a]an 12 1.06 ± 1.29 6.20 0.28–4.65 \LOD \LOD ND–0.12

Chy 13 2.49 ± 2.86 0.62 0.64–11.48 0.74 ± 1.04 0.29 ND–1.92

B[b]ft 13 2.62 ± 1.53 1.56 0.73–5.24 \LOD \LOD ND–0.19

B[k]ft 13 1.04 ± 0.52 2.05 0.32–2.27 0.13 ± 0.11 0.07 0.06–0.26

B[a]py 13 2.04 ± 1.06 0.92 0.63–3.87 \LOD \LOD ND–0.20

D[a.h]an 13 1.07 ± 1.16 1.90 0.76–3.59 \LOD \LOD ND–0.30

B[g.h.i]pe 13 2.95 ± 0.61 0.98 2.26–4.05 \LOD \LOD ND– \LODP

14-PAH 25.39 ± 9.31 2.77 9.38–44.81 3.08 ± 0.94 3.18 2.09–3.97

SD standard deviation, ND not detecteda The concentration below detection limit was treated as zero for calculation of arithmetic mean

Bull Environ Contam Toxicol

123

permissible risk level of 1 ng m3 in ambient air during winter

times, based on the carcinogenic potential of inhaled par-

ticulate PAH (Slooff et al. 1989) and the European Union

requirements about ambient air quality assessment and

monitoring (96/62/CE directive). Another method used to

characterize more precisely the carcinogenic properties of

PAH mixtures is the toxic equivalence factors (TEFs)

approach, whereby Benzo(a)pyrene equivalent toxicity

(BaP-TEQ) for each PAH are calculated by multiplying the

individual PAH concentration by its corresponding TEF

value (Nisbet and La Goy 1992). Speciated and total sampled

(P

14-PAH) values of BaP-TEQ for the average sampled

urban concentrations are tabulated alongside reference TEF

values in Table 5. Using this approach, the average total

BaP-TEQ found was 3.66 ng m-3 and the mean contribution

of the carcinogenic potency of B[a]py to the Bizerte air

samples was determined to be 55.8 % of the activity of all

PAH measured (Table 5). This result shows the importance

of B[a]py as a surrogate compound for total PAH in air.

Similar contributions such as 51 %–64 % in indoor air,

50 %–67 % in ambient air and 53 %–70 % in vehicular

exhausts have been reported (Ohura et al. 2004; Tsai et al.

2004). However, other PAH including the D[a,h]an, benzo-

fluoranthenes also play a role in the total carcinogenicity of

PAHs in Bizerte air contributing 29.1 % and 10 % respec-

tively. Moreover, new findings indicate that D[a,h]an has a

carcinogenic potency ten or more times greater than B[a]py

(Okona-Mensah et al. 2005). Therefore, the total BaP-TEQ

calculated for Bizerte urban air samples likely represents a

lower estimate of its carcinogenic character.

The present study provides for the first time information on

background levels of particulate PAH in the atmosphere of

Tunisia. Since sampling in this study was restricted to particle-

associated PAH, total ambient concentrations (sum of vapour

phase and particle phase PAH) will necessarily be higher. In

addition, urban and rural sampling campaigns were not carried

out at the same time (separated by several years), sampling

period was limited to winter months and no seasonal variation

was studied, as well as limitation of the sampling apparatus

(lower sampling volume, TSP rather than size-fractioned

PM). Therefore, additional investigations of the occurrence of

these pollutants in Tunisian atmosphere are warranted to

expand upon this preliminary study.

Conclusions

In this study, concentrations of 14 USEPA priority PAH

associated with the atmospheric solid phase were measured

in Bizerte city during winter periods of 2009–2010 using

reversed phase high-performance liquid chromatography

Table 4 Comparison of particulate PAH concentration (ng m-3) measured at urban areas around the world

Study area city/country Period Size fraction PAH summed RPAH (ng m-3) References

Bizerte/Tunisia Dec 2009–Feb 2010 TSPP

14-PAH 25.39 This study

Zonguldak/Turkey Winter times 2007 PM2.5P

14-PAH 152.60 Akyuz and Cabuk (2008)

Chennai/India Winter 2009–2010 PM2.5P

11-PAH 82.30 Mohanraj et al. (2011)

Delhi/India Winter 2007–2008 PM2.5P

16-PAH 96 Singh et al. (2011)

Virolahti/Finland February 2006 PM2.5P

11-PAH 14.42 Makkonen et al. (2010)

Madrid/Spain February 2010 PM1–2.5P

16-PAH 0.035 Mirante et al. (2013)

Urumqi/China Winter 2010–2011 PM2.5P

15-PAH 54.11 Da Limu et al. (2012)

Tuscany/Italy Cold period 2009–2010 PM2.5P

16-PAH 13 Martellini et al. (2012)

Beijing/China Dec 2005–Jan 2006 PM2.5P

16-PAH 407.55 Wang et al. (2008)

Table 5 Average sampled concentration, toxic equivalence factors,

and calculated B[a]py equivalent toxicity (BaP-TEQ) concentrations

for Bizerte City urban air samples

Average

concentration

(ng m-3)

Factor (TEF)

of Nisbet and

LaGoy

BaP-

TEQ

(ng m-3)

Ace 0.40 0.001 0.0004

Phe 1.17 0.001 0.001

An 0.93 0.01 0.009

Ft 4.23 0.001 0.004

Py 5.30 0.001 0.005

B[a]an 1.06 0.1 0.11

Chy 2.49 0.01 0.02

B[b]ft 2.62 0.1 0.26

B[k]ft 1.04 0.1 0.10

B[a]py 2.04 1 2.04

D[a.h]an 1.07 1 1.06

B[g.h.i]pe 2.95 0.01 0.03

Sum

carcinogenicity

activity

3.66

Contribution

of B[a]py to

the total

carcinogenicity

activity (%)

55.8

Bull Environ Contam Toxicol

123

with fluorescence detection. PAH composition pattern was

dominated by the presence of 4-ring PAH (51.5 %) fol-

lowed from 5-ring (26.7 %) and 6-ring PAH (11.6 %)

while 3-ring PAH gave the least contribution (9.8 %). The

total concentrations of 14 particulate PAH were 9.38-

44.81 ng m-3. Particulate PAH in samples taken at Bizerte

city were found to be present in greater concentrations than

at the selected rural site by a factor of approximately eight.

The results of diagnostic ratios analysis indicated vehicle

emissions as a dominant source type contributing to urban

particle-associated PAH. Using the TEFs approach, the

average total BaP-TEQ calculated for the Bizerte City

urban samples was 3.66 ng m-3 with B[a]py contributing

approximately 56 % of sampled carcinogenic activity.

Acknowledgments The authors want to express their thanks to all

those who were contributed in this work and acknowledge the Editors

and anonymous referees for valuable comments and suggestions that

greatly improved the manuscript.

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