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Polycyclic aromatic hydrocarbons

(PAHs) in surface sediments of Monastir
Bay (Tunisia, Central Mediterranean):
distribution, origin and seasonal
variations
a b c
Taoufik Nouira , Mohamed Ali Tagorti , Hélène Budzinski ,
d a
Henri Etchebert & Hamadi Boussetta
a
Laboratory of Biochemical and Environmental Toxicology, Higher
Institute of Agriculture, Chott-Mariem, 4042 Sousse, Tunisia
b
Department of Geology; High Institute of Biotechnology of
Monastir, 5000 Monastir, Tunisia
c
LPTC UMR-5472 CNRS, University of Bordeaux I, Bordeaux,
France
d
UMR 5805 EPOC, OASU, University of Bordeaux I, Bordeaux,
France
Published online: 19 Dec 2012.

To cite this article: International Journal of Environmental Analytical Chemistry (2012):

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments of Monastir Bay (Tunisia, Central
Mediterranean): distribution, origin and seasonal variations, International Journal of Environmental
Analytical Chemistry, DOI: 10.1080/03067319.2012.746325

To link to this article: http://dx.doi.org/10.1080/03067319.2012.746325

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 Intern. J. Environ. Anal. Chem.
2012, 1–14, iFirst

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments of

Monastir Bay (Tunisia, Central Mediterranean): distribution,
origin and seasonal variations
Taoufik Nouiraa*, Mohamed Ali Tagortib, Hélène Budzinskic, Henri Etchebertd
and Hamadi Boussettaa
a
Laboratory of Biochemical and Environmental Toxicology, Higher Institute of Agriculture,
Chott-Mariem, 4042 Sousse, Tunisia; bDepartment of Geology; High Institute of
Biotechnology of Monastir, 5000 Monastir, Tunisia; cLPTC UMR-5472
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CNRS, University of Bordeaux I, Bordeaux, France; dUMR 5805

EPOC, OASU, University of Bordeaux I, Bordeaux, France
(Received 2 June 2012; final version received 13 October 2012)

To assess PAH contamination state of Monastir Bay, surface sediments were

collected and analysed for 17 selected parent PAHs by GC/MS. Sediments were
sampled from five sites in wet and dry seasons. Total PAH concentrations were in
the range of 25.6 to 576.8 ng/g d.wt in winter and 44.9–395.8 ng/g d.wt in summer.
Comparison of results with Sediment Quality Guidelines suggested no
eco-toxicological risk for benthic organisms. The use of molecular indices has
shown that PAHs in surface sediments originate mainly from pyrolytic sources.
Total PAH concentrations in surface sediments showed no significant correla-
tions with organic matter content and pelite fraction. The analysis of spatial and
seasonal variations of PAHs in surface sediments has demonstrated that final
distribution of PAHs in surface sediments is mainly governed by hydrological
conditions.
Keywords: polycyclic aromatic hydrocarbons; surface sediments; Monastir Bay

1. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are one of the most widespread POPs
(persistent organic pollutants) in the environment. They are also ubiquitous contaminants
in aquatic environments mostly deriving from anthropogenic sources. Due to their
hydrophobic character (low aqueous solubility and high octanol-water partition coeffi-
cient), PAHs are quickly adsorbed onto suspended material and tend to be trapped in
sediment [1]. Hence, contaminated sediments constitute a real threat to associated biota
and to other organisms throughout the food web [2]. Being lipophylic compounds, PAHs
easily cross lipid membranes and tend to accumulate in organisms. They are known
to exhibit hazardous effects to aquatic organisms including reproductive toxicity,
photo-induced toxicity, mutagenicity and carcinogenicity [3].
PAHs detected in surface marine sediments usually reflect relative contributions from
different origins. They are commonly classified into three main groups according to

*Corresponding author. Email: nouira.taoufik@gmail.com

ISSN 0306–7319 print/ISSN 1029–0397 online

 2012 Taylor & Francis
http://dx.doi.org/10.1080/03067319.2012.746325
http://www.tandfonline.com
 2 T. Nouira et al.

processes they generate from: pyrogenic, petrogenic and biogenic PAHs. Pyrogenic PAHs
originate from an incomplete combustion of organic matter in high temperatures and are
mostly parent compounds with high molecular weight (HMW PAHs) with more than three
fused rings [4,5]. They are considered to be the major source of PAH inputs in aquatic
environments [6]. Petrogenic PAHs are formed during a slow maturation of organic matter
at low temperatures under geothermal gradient. They are characterized by the predom-
inance of alkylated compounds and have lower molecular weight (LMW PAHs) with two
to three fused rings. These PAHs can be released in marine environment by accidental or
operational spills produced during petroleum transportation or off-shore exploration.
On the other hand, biogenic PAHs generate from short-term degradation of diagenetic
precursors. Perylene, frequently detected in coastal marine sediments, derives mainly from
terrestrial precursors via diagenetic processes, but it could also be generated during
pyrolitic processes [7–8] or derive from aquatic organic matter and diatoms [9].
In aquatic environments, PAH distribution is controlled by multiple and
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inter-dependent parameters. Some of these parameters are linked to intrinsic physico-

chemical properties of these compounds, mainly hydrophobicity which controls
their partition between dissolved and particulate phases. Others are related to the
hydrological and geochemical characteristics of the environment including water agitation
and turbidity [10,11], sediment granulometry [12] and particulate or dissolved organic
matter content [13,14].
The littoral of Monastir-Tebulba (Monastir Bay) has been for many centuries a major
resource for people and marine species. In the last decades, it has known a significant
increase in urban density and a large extension of industrial, agriculture and fishing
activities which have progressively led to an advanced stage of degradation. Few
environmental studies have been carried out on this littoral and were mainly focused on
heavy metals pollution [15–17] and organic matter characterization [18]. To our
knowledge, there are no available data on POPs contamination in this area. This work
is the first investigation of the current PAH contamination state in Monastir Bay. It was
carried out in two seasons of the year and based on chemical analysis of surface sediments.
Fifteen parent PAHs recommended as priority pollutants by the US Environmental
Protection Agency (US-EPA) were identified and quantified. Two other PAHs (perylene
and benzo[e]pyrene) which are not included in the US-EPA list have also been studied
because of the additional information they could provide on PAH origin.

2. Experimental
2.1 Characteristics of the study area
The littoral of Monastir-Tebulba (Monastir Bay) lies on the Eastern shore of Tunisia
(Figure 1). This littoral fringe forms a reservoir of multiple wastewater effluents from
urban zones which are discharged in numerous points along the shoreline. The artificial
drain of Khniss is considered as the main source of terrestrial inputs in the region.
In addition to fluvial waters, this drain collects industrial and domestic wastewaters from
riverine agglomerations. It seems to play an important role in the evolution of the
environment state of the littoral. The sub-marine topography is irregular and extends in
the major part of the Bay as a shore-flat. A series of shoals, of very low depth and well
individualized opposite to Tebulba and Ksiba, isolate more or less the Bay from the open
sea. In the whole Bay, waters are generally characterized by a weak agitation and this is
 International Journal of Environmental Analytical Chemistry 3

Figure 1. Geographical location of the study area and sampling sites.

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due to certain factors. First, because of its geo-morphological form (about 20 m of altitude
and salient into the sea in the NE direction) (Figure 1), Monastir Cap acts as a screen
against Northern and especially NW winds. Second, swell, generated by the SE winds,
breaks on the shoals and arrives attenuated inside the Bay. The only winds likely to
generate agitations that can reach the coastline and affect the hydro-dynamics inside the
Bay are the Northern and NE winds blowing in winter and spring and also continental
Western and SW winds blowing in summer and autumn with a lower magnitude. In winter
and spring, water agitation creates beach-drift currents of NS and chiefly NE direction
resulting in sedimentary transport estimated at 12,000 m3/year [18].

2.2 Sampling and sample preparation for chemical analysis

Samples were collected from five sites of Monastir Bay namely Khniss (S1), Ksiba (S2),
Lamta (S3), Tebulba (S4) and Kuriat (S5) (Figure 1). General characteristics of the
sampling sites are presented in Table 1. Sampling has been undertaken during two periods:
from November 2007 to January 2008 then from June 2008 to August 2008, corresponding
respectively to wet and dry seasons of the year in Tunisia.
From each sampling site, about 2 kg of surface sediments were collected using a
stainless scoop then frozen on dry ice and transported in a dark container to the
laboratory for processing. In the laboratory, each sediment sample were lyophilized
and the fine fractions (silt þ clay having grain size 563 mm) was determined gravimet-
rically after dry sieving. Lyophilized samples were then stored at 20 C for further
analysis.

2.3 Extraction
Extraction was performed on a Dionex Accelerated Solvent system (ASE 200 Dionex,
voisins le Bertonneux, France). Approximately 0.5 g of lyophilized matrix was introduced
and mixed with glass pearls in each extraction cell (22 mL) then extracted under pressure
solvent (time: 8 min, cycle: 1, solvent: dichloromethane, pressure: 130 bars, heat time:
5 min, flush volume: 60%, purge time: 60 s).
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Table 1. General characteristics of the sampling sites.

Latitude Longitude Distance from the Depth Water temperature Sediment temperature
Sites (North) (East) shoreline (km) (m) Winter/Summer ( C) Winter/Summer ( C)

S1 (Khniss) 35 420 52.3500 10 490 19.0000 0.2 0.9 11/26 12/25.5
S2 (Ksiba) 35 420 09.6900 10 510 12.9200 2 0.5 11/25.5 12.5/24
S3 (Lamta) 35 410 04.4200 10 520 11.4300 0.2 1.4 11.5/26 13/24
S4 (Téboulba) 35 380 56.7100 10 590 09.5900 0.2 0.4 9/26.5 10/25.5
T. Nouira et al.

S5 (Kuriat) 35 450 48.5300 10 000 25.5000 12 0.8 12/27.5 12.5/23

Note: In sites S1, S3 and S4 sediments were brown to black coloured with a sulphurous smell. Dense herbarium of Cymodocea nodosa and abundant
vegetal debris were observed in S5.
 International Journal of Environmental Analytical Chemistry 5

2.4 Clean-up and fractionation

Organic extracts were collected then filtered on open columns (1 cm diameter, 25 cm
length). A first purification using columns of alumina (Merck, Aluminum oxide 150 basic
type T particle size 0.063–0.2 mm) was performed. Extracts were eluted three times with
5 mL of dichloromethane in order to eliminate macromolecules and polar compounds.
After replacing dichloromethane with isooctane, a second purification using columns of
silica gel (Merck, silica gel particle size 0.063–0.2 mm) was carried out to separate the
aliphatic and aromatic fractions. The aliphatic fraction was eluted with 2 mL of n-pentane
(pentane, nanograde, Mallinckrodt) followed by 5 mL of pentane/dichloromethane
mixture (65:35, v/v) to recover the aromatics. Then, the extracts were concentrated
under a nitrogen stream to a volume of nearly 100 mL. Just before analysis, two other
standards, called ‘‘syringe’’ standards, were gravimetrically added in order to calculate the
percentage of recovery of internal standards; it is about two perdeuterated PAHs: pyrene
d12 and benzofluoranthene d12.
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2.5 GC/MS analysis

From each sample, 1 mL was injected and analysed by GC/MS on a HP Agilent
Technologies 7890 Gas Chromatograph (GC) coupled to a HP Agilent 5975 mass selective
detector (MSD). The GC was equipped with a split/splitless injector (splitless time: 1 min;
flow: 60 mL/min); injector temperature was maintained at 270 C. Columns were:
30 m  0.25 mm i.d.  0.25 mm Elm thickness. The carrier gas was helium at a constant
Fow rate of 1 mL/min. Column temperature was from 50 C (for 2 min) to 300 C (for
20 min) at a rate of 10 C/min. Mass spectrometer was operated in Selected Ion Monitoring
(SIM) mode in the electron impact mode at 70 eV.
Analysed PAHs range from di- (naphthalene) to hexa- hexacyclic PAHs (indeno[1,2,3-c
d]pyrene, benzo[ghi]perylene). Used abbreviations are: Naphthalene: Naph,
Acenaphthylene: Acty, Acenaphtene: Acte, Fluorene: Fe, Phenanthrene: Phe,
Anthracene: An, Fluoranthene: Fluo, Pyrene: Pyr, Benz[a]anthracene: BaA,
Triphenylene: Triph, Chrysene: Chry, Benzo[b]fluoranthene: BbF, Benzo[j]fluoranthene:
BjF, Benzo[k]fluoranthene: BkF, Benzo[e]pyrene: BeP, Benzo[a]pyrene: BaP, Perylene
(Per), Dibenz[a,h]anthracene: DahA, Dibenz[a,c]anthracene: DacA, Indeno[1,2,3-c
d]pyrene: IP, Benzo[ghi]perylene: BPer.
Some co-elutions between structural isomers have to be noted: (i) Triph with chry; (ii)
BbF with BkF and BjF; (iii) DahA with DacA.
For all samples, PAH quantifications were performed relative to perdeuterated PAHs
(Naph-d8, Phe-d10, An-d10, DBT-d8, Fluo-d10, Chry-d12, BeP-d12, BaP-d12, BPer-d12)
used as internal standards [19–21]. They were added directly to the collected aromatic
extracts to avoid contamination of ASE cells and memory effects [22]. Response factors of
the selected PAHs were regularly measured by the use of the Standard Reference Material,
SRM 2260 (NIST, Gaithersburg, Maryland, USA). Average recovery values for the
perdeuterated PAHs ranged between 66% and 96%.

2.6 Determination of organic matter content

Organic matter in surface sediments was quantified by the determination of the total
organic carbon (TOC) which has been measured in the fine fraction of each sediment
sample using the carbon analyser LECO CS 125 according to the method of Cauwet [23].
 6 T. Nouira et al.

Table 2. Percentage of TOC (total organic carbon), percentage of finer grain size fraction, PAH
concentrations (ng/g dry wt) and selected molecular ratios in surface sediments of Monastir Bay.

Winter Summer

PAHs S1 S2 S3 S4 S5 S1 S2 S3 S4 S5

TOC (%) 2.6 6.25 2.3 3.35 3.8 3 4.65 2.65 1.65 6.8
563 m (%) 8 0.1 1.5 5 0.45 4 0.3 0.8 3 0.6
Naph 54.5 nd 11.6 3.6 nd 25.5 17.4 6.9 0.6 50.5
Acty 1.7 0.3 50.1 0.2 nd 0.2 50.1 0.1 50.1 50.1
Acte 0.8 50.1 2.0 1.4 1.2 3.9 0.5 1.9 0.1 1.1
Fe 0.9 50.1 0.1 2.5 0.3 0.4 0.6 0.2 0.9 0.5
Phe 5.8 3.6 2.6 42.2 1.3 1.6 2.1 2.3 14.5 6.5
An 0.7 0.4 0.3 6.6 0.2 0.2 0.3 0.2 2.2 0.9
Fluo 13.4 5.2 4.3 72.4 2.2 4.3 5.6 4.6 42.4 14.9
Pyr 11.7 4.9 4.5 72.9 2.1 3.6 4.5 5.7 38.3 11.2
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BaA 8.5 2.4 1.9 42.5 1.9 3.0 2.8 1.7 31.7 8.4
Triph þ Chrys 8.0 3.2 2.6 47.6 1.0 1.8 2.5 2.5 24.5 7.1
BbF þ BkF þ BjF 55.5 7.1 6.7 95.1 8.2 4.2 14.6 10.0 122.4 34.1
BeP 7.6 2.5 2.2 40.7 1.6 1.2 1.9 1.3 19.4 5.3
BaP 13.3 3.9 3.7 47.7 2.7 0.9 3.3 1.9 28.3 7.1
Per 2.5 1.2 0.7 13.8 0.4 50.1 0.6 0.4 5.5 1.3
DahA þ DacA 1.1 0.2 0.2 4.6 1.9 0.5 50.1 0.5 3.1 0.7
IP 15.2 3.3 2.3 45.8 nd 2.2 2.1 2.5 42.7 7.5
BPer 7.6 3.2 3.1 37.2 0.7 3.6 1.5 2.0 19.3 4.5
Total PAHs 208.7 41.5 48.8 576.8 25.6 57.0 60.3 44.9 395.8 161.3
Phe/An 8.27 10.25 8.63 6.4 5.41 9.35 8.22 12.12 6.7 7.43
Fluo/Pyr 1.14 1.07 0.95 0.99 1.05 1.2 1.23 0.8 1.1 1.32
Fluo/FluoþPyr 0.53 0.51 0.48 0.49 0.51 0.54 0.53 0.44 0.52 0.56
BeP/BaP 0.57 0.65 0.58 0.85 0.57 1.26 0.56 0.7 0.68 0.74
LMW/HMW 0.44 0.11 0.51 0.1 0.13 1.25 0.53 0.35 0.04 0.58
% (Per/penta-) 3.02 7.4 4.76 6.4 3.1 nc 2.8 3.05 2.3 2.64

Note: nd: not determined (below detection limit), nc: not calculated due to concentrations below
detection limits, 50.1 : below blank concentration. LMW (low molecular weight PAHs): 2–3 ring
PAHs (Naph, Acty, Acte, Fe, Phe and An). HMW (high molecular weight PAHs): 4–6 ring PAHs
(Fluo, Pyr, BaA, Triph, Chrys, BFs, BeP, BaP, Per, DA, IP and BP).

2.7 Statistical treatment

Statistical treatment of data was performed with SPSS 10,0 for Windows. The Pearson
correlation was used to analyse relationships between different PAHs on one hand and
between PAHs and sediment characteristics on the other.

3. Results and discussion

3.1 PAH levels
PAH concentrations (dry weight basis) obtained at each site for each individual PAH and
during wet and dry seasons of the year are presented in Table 2. Total PAH concentrations
ranged from 25.6 to 576.8 ng/g with a mean value of 162 ng/g.
A global comparison of PAH levels in surface sediments of Monastir Bay with other
Mediterranean areas (Table 3) indicates low contamination. Baumard et al. [7] proposed
four levels of sediment contamination in PAHs: low, moderate, high and very high when 
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Table 3. Sediment PAH concentrations (ng/g dry wt) recorded in several Mediterranean areas.

Location Sampling period PAH concentration range Sum of analysed PAH compounds Reference

France October 1995 45.1–13,010 14 [7]

Venice lagoon(Italy) – 1.3–4800 7 [24]
Genova (Italy) September 1996 24–501 16 [25]
Genova harbour (Italy) 1998 5201–26,247 16 [26]
Napoli harbour (Italy) November 2004 9–31,774 16 [27]
Corsica October 1995 1.18–20,440 14 [7]
Sardinia October 1995 1.47–919 14 [7]
Greece (Ionian sea) March 1998 25–6582 17 [28]
Greece (Adriatic sea) March 1998 11–6544 17 [28]
Crete (Greece) – 14.6–158.5 28 [29]
Izmit Bay(Turkey) June and September 1999 2500–25,000 14 [30]
Gemlik Bay (Turkey) – 50.8–13,482 13 [31]
Egypt June and July 2003 13.5–22,600 39 [32]
Western harbour of Alexandria (Egypt) November 2006 8–131,150 43 [33]
Gabes Gulf (Sfax,Tunisia) Winter 2007 113–10,720 17 [34]
Ghar El Melh lagoon (Tunisia) – 39.59–655.28 17 [35]
Monastir Bay (Tunisia) Summer 2008 25.6–576.8 17 Present study
International Journal of Environmental Analytical Chemistry
7
 8 T. Nouira et al.

PAH concentrations are 0–100, 100–1000, 1000–5000 and 45000 ng/g respectively. Based
on this classification, surface sediments of Monastir Bay can be considered low to
moderately polluted with PAHs.
The comparison of sediment PAH levels with other sites is delicate. In fact, certain
parameters should be taken into consideration such as the number and the type of
individual species determined in each study, the analysed sediment fraction and the
adopted analytic protocol [31].
Values of total organic carbon (TOC) and fine fraction percentages in surface
sediments are listed in Table 2. TOC contents were generally high, ranging between 1.65%
and 6.8%. Sassi et al. [18] reported similar TOC values (2-6%) in surface sediments from
the littoral of Monastir-Ksiba (Northern part of Monastir Bay).
Statistical analysis showed no significant correlation between TOC levels in both
seasons (R ¼ 0.19), which indicates anthropogenic organic matter contribution in addition
to natural marine and continental organic matter. The highest TOC values were recorded
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in S1 and S2 in winter (6.25%) and S5 in summer (6.8%). High TOC contents recorded in
S1 and S2 can be mainly related to their proximity to Khniss drain which rejects large
amounts of terrestrial organic matter especially in rainy seasons, whereas, the high TOC
concentrations recorded in S5 would be mainly due to the abundance of marine organic
matter resulting from the decomposition of marine algae and phanerogams (Cymodocea
nodosa) which form a dense herbarium on the Western side of Kuriat Islands (S5).
No significant correlations were found between total PAH levels and %TOC. This
suggests that distribution and concentrations of PAHs are more influenced by direct inputs
rather than by organic matter content in sediments. Several other studies recorded similar
results indicating no significant correlation between PAHs and %TOC [32,33,35] brushing
aside the hypothesis of PAHs-organic matter dependence.
In all sampled sediments, pelite fraction did not exceed 8% (Table 2) with a mean value
of 2.3%. According to Ibouily classification [36], pelite fraction below 10% characterize
pure sands. Homogenous grain size composition made difficult the study of correlation
between fine fraction and PAH concentrations. Otherwise, the predominance of the sandy
sediments, characterized by poor adsorbability, in the whole Bay of Monastir could
explain low levels of PAHs in surface sediments.

3.2 Ecotoxicological assessment

To estimate the potential eco-toxicological risk of sediments to benthic organisms, we have
compared the determined PAH concentrations with Sediment Quality Guidelines (SQG)
commonly used in sediment quality assessment. Several methods and approaches have
been used to develop these guidelines and each of them has its advantages and its limits
which certainly influence their application in the evaluation of sediment toxicity. Several
SQG are cited in the literature. For example, ERL/ERM (Effect Range low/Effect Range
Medium) and TEL/PEL (Threshold Effect Level/Probable Effect Level) recommenda-
tions, established respectively by Long et al. [37] and Macdonald et al. [38] according to
empirical and effects-based approaches, are the most used to assess quality of marine and
estuarine sediments. These guidelines are sediment toxicity thresholds and define for each
chemical two values which identifies sediments that are rarely (5ERL, 5TEL), frequently
(4ERM, 4PEL), or occasionally (4ERL, 5ERM and 4TEL, 5PEL) associated with
adverse biological effects. Except for naphthalene, individual PAH concentrations found
 International Journal of Environmental Analytical Chemistry 9

Table 4. Comparison of PAH concentrations in surface sediments of Monastir Bay with sediment
guidelines.

Sediment Guidelines (ng/g) Present study

ERL ERM TEL PEL Winter Summer

PAHs Min Max Min Max

Naph 160 2100 35 391 0 54.5 0.6 50.5

Acty 44 640 6 128 0 1.7 0 0.2
Acte 16 500 7 89 0 2 0.1 3.9
Fe 19 540 21 144 0 2.5 0.2 0.9
Phe 240 1500 87 544 1.3 42.2 1.6 14.5
An 85 1100 47 245 0.2 6.6 0.2 2.2
Fluo 600 5100 113 1494 2.2 72.4 4.3 42.4
Pyr 665 2600 153 1398 2.1 72.9 3.6 38.3
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BaA 261 1600 75 693 1.9 42.5 1.7 31.7

Chrys þ Tryph Na Na na na 1 47.6 1.8 24.5
B(b þ k þ j)F Na Na na na 6.7 95.1 4.2 122.4
BeP Na Na na na 1.6 40.7 1.2 19.4
BaP 430 1600 89 763 2.7 47.7 0.9 28.3
Per Na Na na na 0.4 13.8 0 5.5
DaA þ DaC Na Na na na 0 4.6 0 3.1
IP 240 950 na na 1.9 45.8 2.1 42.7
BPer 85 330 na na 0.7 37.2 1.5 19.3

Note: na : not available

in all prospected sites were below ERL and PEL values (Table 4) which indicates a
relatively clean environment. The highest concentrations of naphthalene found in S1 in
winter (54.5 ng/g) and in S5 in summer (50.5 ng/g) slightly exceed TEL value. However, if
we take into account losses occurring to LMW PAHs during sample handling because of
their relatively higher volatility [39], the concentrations of the lower molecular weight
PAHs might be underestimated. Hence, toxic biological effects on benthic organisms could
be expected in S1 and S5 due to naphthalene.

3.3 PAH spatial and seasonal variation

Globally, spatial and seasonal variations of PAH levels were observed. The highest total
PAH concentration was recorded in S4 in both wet and dry periods (576.8 and 395.8 ng/g
respectively), followed by S1 where total PAHs are 4 times higher in the rainy season
(208.7–57.0 ng/g in winter and summer respectively).
The distribution pattern of PAHs per class of aromaticity (Figures 2a and 2b) shows
relative prevalence of tetra- and penta-cyclic compounds (PAHs of high molecular weight)
in both wet and dry seasons. Their highest concentrations were recorded in S4 in winter
(235.4 ng/g and 201.9 ng/g for tetra- and penta-cyclic PAHs respectively); penta-cyclic
PAHs were mainly represented by the benzo-fluoranthene isomers (BbF, BkF, BjF).
Analysis of spatial and temporal variations of PAH levels should already include two
types of parameters. On one hand, intrinsic parameters mainly related to the physico-
chemical properties of the contaminant (e.g. water solubility, hydrophobicity, sorption
 10 T. Nouira et al.
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Figure 2. PAH distribution per class of aromaticity: (a) summer, (b) winter.

and desorption enthalpies. . .) and, on the other hand, extrinsic ones linked to various
abiotic and biotic factors (e.g. temperature, currentology, sediment characteristics,
bioturbation. . .).
Observed variations of PAH concentrations in surface sediment of all studied sites
seem to be simultaneously related to multiple parameters including temporal variability of
terrestrial pollutant inputs and also to transport and reshuffle of surface sedimentary
material mainly due to hydrological conditions.
To interpret the PAH distributions, an, statistical approach was followed. Analysis of
correlation factors were used to detect possible co-variability of PAH contamination
between sites. Correlation factors are presented in Table 5. Because of the low
concentrations of LMW PAHs in surface sediments, we have subtracted them from the
correlations, hence, only HMW PAHs were considered.
Most correlations between all sites were positive and significant in both winter and
summer. This co-variability in PAH contamination indicates that pollution circulation
proceeds in the same way in the whole Bay. Except for sites whose correlations were tested
 International Journal of Environmental Analytical Chemistry 11

Table 5. Inter-site PAH correlations.

Couple of sites Winter Summer

S1/S2 0.81**, n ¼ 11 0.54, n ¼ 9

S1/S3 0.82**, n ¼ 11 0.71*, n ¼ 10
S1/S4 0.78**, n ¼ 11 0.6*, n ¼ 10
S1/S5 0.96**, n ¼ 10 0.65*, n ¼ 10
S2/S3 0.98**, n ¼ 11 0.94**, n ¼ 10
S2/S4 0.98**, n ¼ 11 0.97**, n ¼ 10
S2/S5 0.74**, n ¼ 10 0.99**, n ¼ 10
S3/S4 0.95**, n ¼ 11 0.93**, n ¼ 11
S3/S5 0.74**, n ¼ 10 0.95**, n ¼ 10
S4/S5 0.69**, n ¼ 10 0.98**, n ¼ 11

Note: Values flagged with a single asterisk are significant at the 0.05 level,
with two asterisks are significant at the 0.01 level.
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Table 6. Ranges of some molecular indices used to characterize PAH origin.

LMW PAHs/
Index P/A Fluo/Pyr Fluo/Fluo þ Pyr BeP/BaP IP/IP þ BPer HMW PAHs

Pyrolytic origin 1–10 41 40.5 52 40.2 51

Petrogenic origin 425 51 50.5 45 50.2 41
References [40] [41,42] [43,44] [45] [44] [46]

with S5, correlation factors showed higher values in winter than in summer, which
indicates that PAH distribution is closely related to meteorological factors and water
circulation system. In fact, dominant winds blowing in winter from the North and NE
create beach-drift currents which come inside Monastir Bay carrying with them
sedimentary material and therefore, associated pollution. These currents create water
circulation along the shoreline towards the South. Relatively higher levels of PAHs
recorded in S4 could also be explained by an accumulation of sedimentary material in the
Southern part of the Bay due to low depths at the shoal of Tebulba, in addition to
pollution from local inputs. This hypothesis is in accordance with what Sassi et al. [17]
described on sedimentary dynamics in Monastir Bay. The latter reported that deposition
of sedimentary material is favored by the damping of waves within shoals.
Besides, correlation factors calculated between sites (Table 5) showed that S2, S3 and
S4 are more highly correlated with S5 in summer than in winter, which suggests that a
pollution circulation also occurs in summer, but in the opposite direction to that of the
winter. Indeed, SW dominant winds of summer create outgoing currents from inside the
bay to the NE direction, which may cause transport of sediment material and associated
pollution from the nearshore sites towards the open sea.

3.4 Origin of contamination

Several molecular indices are commonly used to assess and identify origins of PAHs in
sediments (Table 6). LMW/HMW ratio (sum of LMW PAH concentrations versus sum of
 12 T. Nouira et al.
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Figure 3. Plot of the isomeric ratios P/A versus Fluo/Pyr.

HMW PAH concentrations) was preliminary applied. It allowed a global estimation of

contamination origin. Table 2 shows values of this index determined in each site and
season. Except in S1 and only in summer, all calculated values were inferior to 1. This
indicates relative predominance of HMW PAHs, generated by incomplete combustion of
organic matter at high temperatures (pyrolytic origin). In S1 (Khniss), the value of LMW/
HMW ratio varies from 1.25 in summer to 0.44 in winter. The predominance of HMW
PAHs relative to light PAHs in rainy season can be due to a larger reception of pyrolytic
compounds when effluents are abundantly discharged during floods. The artificial drain of
Khniss represents the main source of pollution of surrounding waters.
Other molecular indices have been used to better characterize the distribution of PAHs
according to the processes they were generated from. They are Phe/An [40], Fluo/Pyr
[41,42], Fluo/Fluo þ Pyr [43,44], BeP/BaP [45] and IP/IP þ BPer [44] ratios. Relative
concentration of perylene among the penta-aromatics has also been examined. Being a
diagenetic precursor, perylene could indicate eventual diagenetic fingerprint [9]. The values
of the molecular indices used are presented in Table 2.
A comparative analysis of these indices reveals a global pyrolytic sign in all surveyed
sites. According to Yunker et al. [44], values of IP/IP þ BP ratio superior to 0.5 indicate
combustion of coal, grasses and wood which is the case in all sites except in S1 in summer
and S3 in winter (Table 2). In the latter sites, values of IP/IP þ BPer ratio were between 0.2
and 0.5 indicating rather petroleum combustion [44].
The plot of P/A versus Fluo/Pyr ratios (Figure 3) brings to light a petrogenic
contribution in sediments of Lamta (S3) which is more apparent in summer. Hence, it is
remarkable in this site, that a superposition of both pyrolytic and petrogenic sources exists,
although, the petrogenic pattern is hidden by the greater pyrolytic profile in rainy season
because of larger wastewater inputs.
For all sediment samples, concentrations of perylene relative to penta-cyclic isomers
ranged from 0% to 7.4% (Table 2) and were clearly larger in rainy season. According to
Baumard et al. [7], perylene concentrations higher than 10% indicate a probable diagenetic
origin of the compound whereas those less than 10% indicate a probable pyrolytic input.
 International Journal of Environmental Analytical Chemistry 13

On the other hand, relative concentrations of perylene recorded in S2 and S4 in rainy

season (7.4% and 6.4% respectively) were low but not negligible, which supposes a
diagenetic origin for a slight fraction of perylene present in sediments. These low amounts
of perylene would derive from biogenic precursors introduced with terrestrial organic
matter via river discharges and flooding.

Acknowledgements
We would like to thank Dr Oussama Ayara and Dr Yosra Belaı̈d-Nouira for proofreading the article
and Mr Faissal Ghachem for his assistance in sampling.

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