This article was downloaded by: [Moskow State Univ Bibliote]On: 20 November 2013, At: 05:22Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Soil and Sediment Contamination: AnInternational JournalPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/bssc20

Distribution and Sources of PolycyclicAromatic Hydrocarbons Around aPetroleum Refinery Rejection Area inJarzouna-Bizerte (Coastal Tunisia)Ines Zrafi-Nouira a , Nimer M. D. Safi b , Raouf Bahri a , NadiaMzoughi c , Ameur Aissi d , Hassen Ben Abdennebi e & Dalila Saidane-Mosbahi aa Laboratoire d'Analyse , Traitement et Valorisation des Polluants del'Environnement et des Produits, Faculté de Pharmacie de Monastir ,Monastir, Tunisiab Institute of Chemistry and Biology of the Marine Environment , Carlvon Ossietzky University of Oldenburg , Oldenburg, Germanyc Institut National des Sciences et Technologie de la Mer , Tunis,Tunisiad Laboratoire de Pharmacognosie , Faculté de Pharmacie , Monastir,Tunisiae Laboratoire de Physiologie Humaine , Faculté de Pharmacie ,Monastir, TunisiaPublished online: 23 Apr 2010.

To cite this article: Ines Zrafi-Nouira , Nimer M. D. Safi , Raouf Bahri , Nadia Mzoughi , AmeurAissi , Hassen Ben Abdennebi & Dalila Saidane-Mosbahi (2010) Distribution and Sources of PolycyclicAromatic Hydrocarbons Around a Petroleum Refinery Rejection Area in Jarzouna-Bizerte (CoastalTunisia), Soil and Sediment Contamination: An International Journal, 19:3, 292-306

To link to this article: http://dx.doi.org/10.1080/15320381003695223

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the“Content”) contained in the publications on our platform. However, Taylor & Francis,our agents, and our licensors make no representations or warranties whatsoever as tothe accuracy, completeness, or suitability for any purpose of the Content. Any opinionsand views expressed in this publication are the opinions and views of the authors,and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content

should not be relied upon and should be independently verified with primary sourcesof information. Taylor and Francis shall not be liable for any losses, actions, claims,proceedings, demands, costs, expenses, damages, and other liabilities whatsoever orhowsoever caused arising directly or indirectly in connection with, in relation to or arisingout of the use of the Content.

This article may be used for research, teaching, and private study purposes. Anysubstantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &Conditions of access and use can be found at http://www.tandfonline.com/page/terms-and-conditions

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Soil and Sediment Contamination, 19:292–306, 2010Copyright © Taylor & Francis Group, LLCISSN: 1532-0383 print / 1549-7887 onlineDOI: 10.1080/15320381003695223

Distribution and Sources of Polycyclic AromaticHydrocarbons Around a Petroleum Refinery

Rejection Area in Jarzouna-Bizerte (Coastal Tunisia)

INES ZRAFI-NOUIRA,1 NIMER M. D. SAFI,2 RAOUF BAHRI,1

NADIA MZOUGHI,3 AMEUR AISSI,4

HASSEN BEN ABDENNEBI,5 ANDDALILA SAIDANE-MOSBAHI1

1Laboratoire d’Analyse, Traitement et Valorisation des Polluants del’Environnement et des Produits, Faculte de Pharmacie de Monastir, Monastir,Tunisia2Institute of Chemistry and Biology of the Marine Environment, Carl vonOssietzky University of Oldenburg, Oldenburg, Germany3Institut National des Sciences et Technologie de la Mer, Tunis, Tunisia4Laboratoire de Pharmacognosie, Faculte de Pharmacie, Monastir, Tunisia5Laboratoire de Physiologie Humaine, Faculte de Pharmacie, Monastir, Tunisia

Polycyclic aromatic hydrocarbons in the refinery rejection area of STIR, Tunisia’s uniqueoil refinery located on the Jarzouna coast, were investigated. Two depth layers from threesites beside the refinery and one site some distance away from it were considered. Thetotal concentration of 17 PAHs ranged from 916.42 ± 0.012 ng/g to 3146.2 ± 0.151ng/g in Layer-I and from 962 ± 0.003 ng/g to 4541.1 ± 0.009 ng/g in Layer-II. The PAHprofiles showed that the 4–5-ring compounds were the major PAHs detected in mostsampling sites. Characteristic ratios of anthracene (Anth)/(Anth + phenanthrene (Phe)),and fluoranthene (Flu)/(Flu + pyrene (Pyr)) indicated that the PAH pollutants couldoriginate from petrogenic and pyrolytic sources. Overall, our results indicate moderatecontamination of the Jarzouna sediments with PAHs. However, even at moderate levels,PAHs levels in this marine environment must be controlled and reduced due to theirpossible side-effects on the ecosystems and human safety.

Keywords hydrocarbons, PAHs, sediments, petroleum refinery

Introduction

Hydrocarbons are one of the most important pollutants that can persist for years (Burnsand Teal, 1979) and have dangerous effects on coastal environments (DeLaune et al.,1990). Polycyclic aromatic hydrocarbons (PAHs) are contaminants widespread through-out the marine environment. Contamination by PAHs is very harmful to the environment

Address correspondence to Ines Zrafi-Nouira, Laboratoire d’Analyse, Traitement et Valorisationdes Polluants de l’Environnement et des Produits, Faculte de Pharmacie de Monastir, Rue Avicenne5000, Monastir, Tunisia. E-mail: Zrafi ines@yahoo.fr

292

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Distribution and Sources of PAHs 293

(Fernandes et al., 1997). Polycyclic aromatic hydrocarbons (PAHs) in the environment areattracting increasing attention for their widespread occurrence and their toxic, mutagenic,and carcinogenic potential (Freitag et al., 1985). They belong to a class of hundreds of indi-vidual compounds composed of two or more fused aromatic rings originating mainly frompetrogenic or pyrolytic sources. Petrogenic PAHs are associated with direct deposition ofpetroleum (ballasting/de-ballasting operations of tankers, oily bilge-water discharges, tankwashing, refinery effluents, municipal waste, discarded lubricant oils, chronic or acciden-tal petroleum inputs, natural seepages. . .) (Mille et al., 2007), whereas pyrolytic sourcesare associated with natural combustion (forest fires, burning land, plants), anthropogeniccombustion (fossil products), and atmospheric deposition (Mille et al., 2007). In Tunisia,there has been little interest in hydrocarbon pollution, especially in open seawater. In fact,very few studies have evaluated hydrocarbon pollution in the city of Bizerte (Yoshida et al.,2002; Trabelsi and Driss, 2005; Zrafi-Nouira et al., 2008), and in Sfax (Louati et al., 2001;Zaghden et al., 2005, 2007; Elloumi et al., 2008). The area of interest is in one of the mosthighly populated and industrialized zones. Industrial activities in this area include metalindustries, naval construction, and tire production (Trabelsi and Driss, 2005). Also in thiszone there are many local wastewater discharges, a Tunisian military naval base, extensivenautical traffic and other harbor activities, as well as solid landfill and the unique petroleumrefinery of the country, “STIR” (“Tunisian Society of the Refining Industries”). Previousstudies along the Jarzouna coast of Bizerte, especially in the region of “STIR” rejectionarea, showed the presence of anthropogenic hydrocarbons in several locations (Zrafi-Nouiraet al., 2008). Created in 1961, the STIR refinery (latitude 37◦.25 N and longitude 9◦.88E) has a capacity of one million cubic meters and uses seawater in the treatment of thepetroleum effluents in the refining process and in the cleaning of its oil reservoirs. Thetreatment consists of successive decantation basins to recover the oil, with the used seawa-ter rejected into the sampling area, which can produce liquid, solid and gaseous pollutants.To our knowledge, no information on PAH levels and origins in this region is available.Therefore, the identification and quantification of these compounds in this refinery rejectionarea will be of the utmost interest. To complement information on hydrocarbon pollutionaround the STIR refinery, concentration, spatial distribution, compound profiles, and pos-sible sources of PAHs were examined and evaluated in this paper. The differences of PAHbetween two depth layers from superficial sediment were compared. Our study is significantto understand the regional background in PAH levels, to differentiate the various types ofanthropogenic input, and evaluate the contribution of the STIR refinery’s effluent in PAHpollution.

Material and Methods

Study Area and Sample Collection

The sampling region is located at 37◦17′ 57.10′′ N, 9◦51′ 53.61′′E in northern Tunisia usingthe Global Positioning System (GPS). Sample collection was carried out in March 2002from different sites along the Jarzouna seacoast in Bizerte, as shown in Figure 1. Threesampling sites were located in the vicinity of the rejection area of seawater used in thetreatment of the petroleum effluent of the “STIR” refinery respectively, at 0.59 and 107 m.One site was about 2380 m distant from the rejection area of the refinery. This site waschosen in order to determine the extent of the refinery’s impact on the region, and toinvestigate other possible sources of pollution. The characteristics of water under samplingoperations are reported in Table 1. The detailed sampling locations are shown in Figure 1.

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

294 I. Zrafi-Nouira et al.

Figure 1. Map of the area of Bizerte showing STIR refinery and sampling location. ◦ ndicates themost industrialized zone; ♦ indicates the localization of the petroleum refinery (STIR). Sites areindicated using arrows.

In sampling sites, seawater is of 1 meter depth. In order to study the depth effecton the fate of hydrocarbon compounds on superficial sediment, two sediment layers wereconsidered. Layer-I refers to the upper sediment (0–15 cm in thickness), while Layer-IIrefers to the deeper part of the sediment (15–30 cm in thickness). At each site, threesamples, separated by 1 m from each other, were taken in sediment from the two depthlayers. Sediment samples were then placed in pre-cleaned aluminum boxes and then storedin a freezer at −4◦C until transported to the laboratory (with no exposure to light). Inour laboratory, the three sediment samples of the same site and same layer were mixed inorder to increase the size of the samples and to recover the surface of sampling, manuallyhomogenized, lyophilized, passed through a stainless steel sieve (200 and 100 µm) andfinally stored at 4◦C until analysis. All the results were reported as dry weight.

Hydrocarbon Extraction

The analytical procedure for hydrocarbons extraction, summarized below, has been previ-ously described in detail (Zrafi-Nouira et al., 2008). Briefly, 50 g of dry sediment sampleswere Soxhlet-extracted with chloroform (1:2 m/v) for a period of 8 hours at 40◦C. The ex-tracts were then concentrated using rotary evaporation. Following chloroform evaporation,the extract was fractionated into non-aromatic hydrocarbons (NAH) and total aromatic hy-drocarbons (TArom) by adsorption liquid chromatography using a column of alumina andsilica-gel, and gradient solvents as eluent: n-hexane and 2:1 n-hexane/chloroform for NAHand TArom fractions, respectively. The polar fraction (PF) was not eluted. Fractionation was

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Tabl

e1

Loc

atio

nsan

dch

arac

teri

stic

sof

sam

plin

gsi

tes

Type

ofSe

awat

erSe

awat

erL

ayer

Site

Cod

eL

atitu

de(N

)L

ongi

tude

(E)

Sedi

men

tSiz

ebo

ttom

tem

pera

ture

(◦ C)

Salin

ity(�

)

SMT

B-1

-C1

37◦ 1

5′ 37.

12′′ N

9◦ 53′ 4

4.61

′′ EFi

negr

aine

dsa

nd<

100

µm

Sand

with

out

seag

rass

2035

Lay

er-I

SMT

B-2

-C1

37◦ 1

5′ 37.

12′′ N

9◦ 53′ 5

5.25

′′ EFi

negr

aine

dsa

nd<

100

µm

Sand

with

out

seag

rass

1534

(0–1

5cm

)SM

TB

-3-C

137

◦ 15′ 3

1.81

′′ N9◦ 5

4′ 07.

09′′ E

Fine

grai

ned

sand

<10

0µ

mSa

ndw

ithou

tse

agra

ss14

35

SMT

B-4

-C1

37◦ 1

5′ 18.

74′′ N

9◦ 55′ 1

3.62

′′ EM

ediu

mgr

aine

dsa

nd(1

00–2

00µ

m)

Mea

dow

ofse

agra

sses

1435

SMT

B-1

-C2

37◦ 1

5′ 37.

12′′ N

9◦ 53′ 4

4.61

′′ EFi

negr

aine

dsa

nd<

100

µm

Sand

with

out

seag

rass

2035

Lay

er-I

ISM

TB

-2-C

237

◦ 15′ 3

7.12

′′ N9◦ 5

3′ 55.

25′′ E

Fine

grai

ned

sand

<10

0µ

mSa

ndw

ithou

tse

agra

ss15

34

(15–

30cm

)SM

TB

-3-C

237

◦ 15′ 3

1.81

′′ N9◦ 5

4′ 07.

09′′ E

Fine

grai

ned

sand

<10

0µ

mSa

ndw

ithou

tse

agra

ss14

35

SMT

B-4

-C2

37◦ 1

5′ 18.

74′′ N

9◦ 55′ 1

3.62

′′ EM

ediu

mgr

aine

dsa

nd(1

00–2

00µ

m)

Mea

dow

ofse

agra

sses

1435

C1:

sam

ple

com

esfr

omse

dim

ento

fL

ayer

-I(0

–15

cm);

C2:

sam

ple

com

esfr

omse

dim

ento

fL

ayer

-II

(15–

30cm

).

295

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

296 I. Zrafi-Nouira et al.

performed in a silica microcolumn. Following solvent evaporation, the total hydrocarbonsTH and TArom were weighed.

Chromatography Analysis

The (TArom) fraction that contains the total PAHs was analyzed with a Hewlett-Packard5890 gas chromatograph equipped with a temperature controlled injector, a flame ionizationdetector (GC/FID), and a capillary column HP5: 5% diphenyl, 95% dimethylpolisiloxane(25 m × 0.32 mm × 0.52 µm). The oven temperature program was as follows: 1 minat 80◦C, from 80 to 280◦C at 4◦C/min and 10 min at 280◦C. The injector and detectortemperatures were 250◦C and 280◦C, respectively. The samples were solubilized in 1 mlcyclohexane and an aliquot of 1 µl of each extract was injected following the addition ofan external standard (n-eicosene).

The GC identification and quantification of PAHs was carried out as described byTrabelsi and Driss (2005) based on the comparison with known standards injected underthe same conditions. A certified standard reference (National Institute of Standards andTechnology, USA) was used. Sixteen un-substituted PAHs have been listed by the US En-vironmental Protection Agency (EPA) as priority pollutants. The PAHs investigated in thisstudy were: naphthalene (Naph), 1-methyl-naphthalene (1menaph), 1-ethyl-naphthalene(1enaph), ace-naphthylene (Ac), acenaphthene (Ace), 2,3,6-trimethyl-naphthalene (2,3,6-trimenaph), fluorene (Flu), phenanthrene (Phe), 2-methyl-phenanthrene (2-mephe), 1-methyl-phenanthrene (1-mephe), 3,6-dimethyl-phenanthrene (3,6-dimephe), fluoranthene(Fluo), pyrene (Pyr), 1-methyl-pyrene (1-mepyr), anthracene (Anth), chrysene (Chr), andperylene (Pery).

When the peaks were not identified by GC, an analysis was carried out using a coupledGC/MS. The mass spectrometer was of type HP 9572 II (Agilent, California) (GC-MS)equipped with a Splitless injection system. The capillary column (30 m × 0.25 mm,0.25 µm), the carrier gas was nitrogen. The GC conditions were the same as described forCG/FID analysis. For the MS analysis, the conditions were: electron ionization of 70 eV andlinear scanning over the mass range 35–500 Da were used. Compound identification wasbased on individual mass spectra and GC retention times in comparison to the literature,library data, and standards. To ensure an appropriate quality of analyses, standards andblanks were analyzed under the same conditions as the samples. All analyses were done intriplicate.

Statistical Analyses

Data of the individual and total polycyclic aromatic hydrocarbon concentrations werestatistically analyzed. For each PAH compound, standard errors were calculated betweenthree repetitions of the chromatography analysis (n = 3). Results are expressed as mean± SE (standard error). Comparisons among multiple groups of samples, for each site andeach depth, were achieved by one-way ANOVA followed by Tukey’s Multiple ComparisonTest. Statistical significance was defined as P < 0.05.

Results and Discussions

Spatial Distributions of PAH Contamination in Jarzouna (Coastal Tunisia)

In our previous study in the same region, we demonstrated that (TH) and (TArom) ab-sorption occurred upon discharge from the refinery. We noted that the (TH) and (TArom)concentrations were greater in the Layers-II than in Layers-I (Zrafi-Nouira et al., 2008). In

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Distribution and Sources of PAHs 297

Table 2Individual PAH levels (ng/g ± SE dry weight) in different sites from sediment of Layer-I

SMTB1-C1 SMTB2-C1 SMTB3-C1 SMTB4-C1

naph <LD§� <LD§� 0.5 ± 0.009∗#� 0.1 ± 0.000∗#§

1-menaph <LD§ <LD§ 1.5 ± 0.006∗#� <LD§

1-enaph 4.1 ± 0.012#§� <LD∗ <LD∗ <LD∗

Ac 5.3 ± 0.015#§� <LD∗§� 2.2 ± 0.007∗# 2.3 ± 0.016∗#

Ace 2.8 ± 0.017#§� 31.4 ± 0.009∗§� 13.3 ± 0.010∗# 13.5 ± 0.009∗#

2,3,6-trimenaph 16.6 ± 0.049#§� 159.2 ± 0.011∗§� 44.8 ± 0.012∗#� 24.6 ± 0.003∗#§

Flu 30.0 ± 0.044#§� 36.5 ± 0.013∗§� 19.1 ± 0.003∗#� 29.9 ± 0.009∗#§

Phe 16.8 ± 0.009#§� 189.0 ± 0.003∗§� 16.5 ± 0.014∗#� 31.8 ± 0.012∗#§

Anth 14.6 ± 0.009#§� 42.1 ± 0.009∗§� 46.8 ± 0.013∗#� 28.9 ± 0.007∗#§

2-mephe 34.5 ± 0.018#§� 164.2 ± 0.003∗§� 17.0 ± 0.554∗#� 63.2 ± 0.003∗#§

1-mephe 39.4 ± 0.003#§� 147.3 ± 0.012∗§� 102.9 ± 0.003∗#� 60.2 ± 0.012∗#§

3,6-dimephe 36.7 ± 0.009#§� 195.1 ± 0.006∗§� 42.6 ± 0.003∗#� 77.6 ± 0.022∗#§

Fluo 70.8 ± 0.012#§� 109.0 ± 0.003∗§� 142.0 ± 0.003∗#� 140.8 ± 0.013∗#§

Pyr 2567.8 ± 0.009#§� 458.3 ± 0.006∗§� 413.0 ± 0.03∗#� 170.6 ± 0.012∗#§

1-mepyr 71.0 ± 0.062#§� 112.0 ± 0.003∗§� 185.5 ± 0.007∗#� 73.4 ± 0.0145∗#§

Chr 150.7 ± 0.009#§� 115.4 ± 0.000∗§� 347.5 ± 0.014∗#� 114.2 ± 0.012∗#§

Pery 85.0 ± 0.080#§� 255.4 ± 0.003∗§� 387.5 ± 0.012∗#� 85.3 ± 0.009∗#§

Total PAHs 3146.2 ± 0.151#§� 2014.8 ± 0.003∗§� 1782.8 ± 0.003∗#� 916.4 ± 0.012∗#§

LD: limit of detection; SE: Standard Error.C1: sample comes from sediment of Layer-I (0–15 cm); PAHs: polycyclic aromatic hydrocarbon;.

∗: p < 0.05 vs SMTB1; #: p < 0.05 vs SMTB2; §: p < 0.05 vs SMTB3; �: p < 0.05 vs SMTB4.naphthalene (Naph), 1methyl-naphthalene (1menaph), 1ethyl-naphthalene (1enaph), ace-

naphthylene (Ac), acenaphthene (Ace), 2,3,6 trimethyl-naphthalene (2,3,6 trimenaph), fluorene(Flu), phenanthrene (Phe), 2-methyl-phenanthrene (2-mephe), 1-methyl phenanthrene (1-mephe),3.6-dimethyl-phenanthrene (3,6-dimephe), fluoranthene (Fluo), pyrene (Pyr), 1-methyl-pyrene (1-mepyr), anthracene (Anth), chrysene (Chr), and perylene (Pery): these are expressed as ng/g ± SE ofsediment by using GC analyses.

this article we focused on the distribution of Total PAHs within the aromatic hydrocarbonfraction. Tables 2 and 3 show the spatial distribution of total PAH concentrations in Layer-Iand Layer-II, respectively. Those concentrations were significantly different in Layer-IIthan in Layer-I for all the sites except for SMTB3, where we found relatively similar lev-els of PAHs (Tables 2 and 3). The concentration of total PAHs in Layer-I shows a widevariation range of 916.4 ± 0.012 ng/g to 3146.2 ± 0.151 ng/g dry weight (dw), whereasin Layer-II the wide variation ranges from 962.0 ± 0.003 ng/g to 4541.1 ± 0.009 ng/g dw.Inter-station comparisons of the total PAHs showed that the SMTB1 site, located closest tothe refinery rejection point, had the highest concentration of these chemicals, wile SMTB4contained the lowest concentration. Levels of the total PAHs decrease progressively fromSMTB1 to SMTB4. The concentrations of PAHs registered in the sole site located far fromthe refinery (SMTB4) were also relatively high. This can be explained either by the extentthe refinery’s pollution has reached or that STIR is not the only source of PAHs in thisregion and that there are other possible sources of hydrocarbons, such as the presence of alarge number of factories, various types of industrial activities which are the major factorof the consumption of energy sources. Jarzouna is located in a highly populated area andsubject to hydrocarbon pollution by sewage, industrial and aquacultural waste, agriculturerun-off, and other human activities (Trabelsi and Driss, 2005). Another possibility for the

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

298 I. Zrafi-Nouira et al.

Table 3Individual PAH levels (ng/g ± SE dry weight) in different sites from sediment of Layer-II

SMTB1-C2 SMTB2-C2 SMTB3-C2 SMTB4-C2

naph <LD# 8.9 ± 0.011∗§� <LD# <LD#

1-menaph <LD#§ 13.4 ± 0.016∗§� 0.7 ± 0.011∗#� <LD#§

1-enaph <LD <LD <LD <LDAc <LD#§� 14.6 ± 0.003∗§� 3.2 ± 0.003∗#� 5.0 ± 0.024∗#�

Ace 37.6 ± 0.007#§� 28.9 ± 0.011∗§� 9.8 ± 0.003∗#� 5.8 ± 0.003∗#�

2,3,6-trimenaph 149.4 ± 0.006#§� 59.0 ± 0.044∗§� 29.6 ± 0.003∗#� 16.4 ± 0.009∗#�

Flu <LD #§� 29.7 ± 0.003∗§� 70.0 ± 0.003∗#� 75.9 ± 0.006∗#�

Phe 36.9 ± 0.009#§� 38.5 ± 0.003∗§� 20.5 ± 0.003∗#� 20.1 ± 0.005∗#�

Anth 69.5 ± 0.018#§� 62.9 ± 0.009∗§� 18.5 ± 0.003∗#� 9.0 ± 0.045∗#�

2-mephe 80.4 ± 0.014#§� 127.1 ± 0.003∗§� 35.4 ± 0.006∗#� 13.5 ± 0.003∗#�

1-mephe 113.6 ± 0.011#§� 223.6 ± 0.003∗§� 82.1 ± 0.003∗#� 76.0 ± 0.006∗#�

3,6-dimephe 220.3 ± 0.011#§� 126.9 ± 0.006∗§� 34.0 ± 0.003∗#� 31.7 ± 0.013∗#�

Fluo 303.9 ± 0.007#§� 188.6 ± 0.009∗§� 110.4 ± 0.003∗#� 105.4 ± 0.018∗#�

Pyr 1330.5 ± 0.018#§� 814.4 ± 0.007∗§� 240.2 ± 0.009∗#� 200.6 ± 0.012∗#�

1-mepyr 547.2 ± 0.009#§� 196.9 ± 0.003∗§� 504.4 ± 0.012∗#� 152.5 ± 0.003∗#�

Chr 603.3 ± 0.000#§� 411.3 ± 0.003∗§� 134.7 ± 0.015∗#� 204.0 ± 0.007∗#�

Pery 1048.5 ± 0.015#§� 570.8 ± 0.007∗§� 463.4 ± 0.009∗#� 46.2 ± 0.003∗#�

Total PAHs 4541.1 ± 0.009#§� 2915.5 ± 0.003∗§� 1756.7 ± 0.011∗#� 962.0 ± 0.003∗#�

LD: limit of detection; SE: Standard Error.C2: sample comes from sediment of Layer-II (15–30 cm); PAHs: polycyclic aromatic hydrocarbon;

∗: p < 0.05 vs SMTB1; #: p < 0.05 vs SMTB2; §: p < 0.05 vs SMTB3; �: p < 0.05 vs SMTB4.naphthalene (Naph), 1methyl-naphthalene (1menaph), 1ethyl-naphthalene (1enaph), ace-

naphthylene (Ac), acenaphthene (Ace), 2,3,6 trimethyl-naphthalene (2,3,6 trimenaph), fluorene(Flu), phenanthrene (Phe), 2-methyl-phenanthrene (2-mephe), 1-methyl phenanthrene (1-mephe),3.6-dimethyl-phenanthrene (3,6-dimephe), fluoranthene (Fluo), pyrene (Pyr), 1-methyl-pyrene (1-mepyr), anthracene (Anth), chrysene (Chr), and perylene (Pery): these are expressed as ng/g ± SE ofsediment by using GC analyses.

presence of PAH in the site SMTB4 is the possible amount of waste gas particles with PAHsfrom incomplete combustion of fossils in industrial activities emitted into the atmosphere,and then transferred to the soil via dry/wet deposition. Given the presence of a correlationbetween the amount of PAHs in the soil and in the air (Trapido, 1999), the PAH level in theair in this region should also be investigated.

An understanding of the local and global extent and severity of marine environmentcontamination by fossil fuel hydrocarbons from various sources requires measuring thecompounds of interest and comparing them in different regions. The comparison of PAHconcentration found in this study and other regions is shown in Table 4. Compared with ourfindings in the Jarzouna area, national comparisons revealed elevated PAH concentrations inthe northern coast of Sfax, Tunisia (Zaghden et al., 2007), but this comparison also showedthat the region examined in this paper presented significantly higher sedimentary concen-trations of PAHs compared with those found in Bizerte’s lagoon (Table 4). A similar orderof magnitude of PAH average concentrations were found on other Mediterranean coasts(France, Spain, and Italy) (Table 4). Indeed, some aquatic systems have reached higherlevels of PAH input than those registered in Tunisia’s Jarzouna coastal area (West Mediter-ranean Sea). Moreover, in comparison with other ecosystems (Crete, Greece, Egypt), PAHlevels in Jarzouna are relatively higher. In a broader comparison with worldwide aquatic

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Distribution and Sources of PAHs 299

Table 4Comparison of sediment PAH concentration (ng/g dry weight) of Jarzouna coastal with

those in others regions

Location Range (ng/g) References

Jarzouna-Bizerte, Tunisia (Layer-I),Mediterranean Sea

916.4–3146.2 This Study

Jarzouna-Bizerte, Tunisia (Layer-II),Mediterranean Sea

962–4541.1 This Study

Bizerte lagoon, Tunisia, MediterraneanSea

83.3–447.08 Trabelsi and Driss (2005)

Sfax Coast, Tunisia, Mediterranean Sea 113–8902 Zaghden et al. (2007)Moroccan Coast, Mediterranean Sea 15–551 Pavoni et al. (2003)Egyptian Coast, Mediterranean Sea 6.338–88 El Nemr et al. (2007)Gulf of Fos area, France, Mediterranean

Sea34–13780 Mille et al. (2007)

Crete, Greece, Mediterranean Sea 14.7–161.5 Gogou et al. (2000)Northern Sardinia, Italy, Mediterranean

Sea160–770 De Luca et al. (2005)

Barcelona, Spain, Mediterranean Sea 1740–8420 Baumard et al. (1998a)West Mediterranean Sea 1.5–20440 Baumard et al. (1998b)Western Mediterranean Sea 180–3200 Lipiatou and Saliot (1991)Baltic Sea 720–1900 Witt (1995)Adriatic Sea 18–580 Caricchia et al. (1993)Washington Coast, USA 29–460 Prahl and Carpenter (1983)

ecosystems, PAH levels registered in this study are in the range encountered in open seaor coastal areas with moderate contamination in terms of levels, but certainly not in termsof risk. In fact, PAHs are known to have dangerous effects on the ecosystems and humansafety. The accumulation of contaminants in marine sediments can cause death, reproduc-tive failure, growth impairment, or other detrimental changes in the organisms exposed tothese contaminants. Such changes can affect not only individuals but also entire benthicpopulations and communities. It will result in a degraded marine community, changes topredator-prey relationships through a possible decrease in the palatability of prey andtoxicity (Tuvikene, 1995). Toxicity, persistence, bio-accumulation and bioamplification ofhydrocarbons in the food chain are currently shown (Papagiannis et al., 2004). In general,PAHs may be readily metabolized by enzymatic systems in higher aquatic organisms suchas fish, although there is uncertainty about whether they are detoxified. Some invertebrates,such as bivalve mollusks, have only a limited ability to metabolize PAHs and tend to accu-mulate them to higher concentrations and retain them more (Khedir-Ghenim et al., 2009).Therefore, consumption of these animals may be a source of human exposure. Humanhealth effects include carcinogenesis, localized skin effects, pulmonary and respiratoryproblems, genetic reproduction and development effects, behavioral neurotoxic and otherorgan system effects and increased risk of bladder, skin and lung cancers (Mastrangeloet al., 1996; Boffetta et al., 1997). In the environment, a significant correlation betweenPAH concentration and cancers was established (Denissenko et al., 1996). Therefore theEnvironmental Protection Agency (EPA) has already added PAHs into the list of the priority

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

300 I. Zrafi-Nouira et al.

pollutants in the environment. The maximum allowable concentrations (MAC) for somePAH were set up and recommended whereas MAC for other PAHs are still to be set up,and according to the World Health Organization WHO (1998) no safe level can be recom-mended for some PAH due to their carcinogenicity. Therefore measurement of PAHs inthe Jarzouna coast is helpful in assessing the existing level of PAHs in source emissions,effluents, and sediment. This will help in the development of data bank of PAHs levelsin environmental compartments and development of standards for sediment quality andeffluents, granting consent based on PAHs to the relevant sources, identification and recordof sources of PAHs, and formulations of abatement and control strategies of PAHs in theenvironment.

Individual PAH Compound Profiles and Characteristics in Sediment from Jarzouna

The mean individual PAH concentrations, standard error (SE), and significance of proba-bility estimation are listed in Tables 2 and 3. Crude oil and refined products from differentsources can have different PAH distributions. PAHs are one of the most valuable fingerprint-ing classes of hydrocarbons for oil identification. Even differences between the same typesof products are discernible through an examination of the PAH distribution. In sedimentfrom Jarzouna, 17 individual PAHs were detected in all the sediment samples, with theexception of naphthalene and its derivatives (naph, 1-menaph, 1-enaph, Ac,), which in themajority of cases were below the limit of detection. These PAH compounds are known tobe extremely volatile, which can explain their absence in the sediment. Wang and Fingas(2003) reported, however, that a pronounced decrease in naphthalene compared with otheralkylated PAH series is a result of chemical compositional changes due to weathering.When crude oil or petroleum products are accidentally released into the environment, theyare in fact immediately subject to a wide variety of weathering processes (Jordan andPayne, 1980). These weathering processes can include: evaporation, dissolution, microbialdegradation, and other processes such as dispersion and water–oil emulsification, photo-oxidation, adsorption onto suspended particulate materials, and oil-mineral aggregation.Weathering causes considerable changes in the chemical and physical properties of spilledoils. Major chemical compositional changes due to weathering were previously reported(Page et al., 1995; Wang et al., 1999).

A (Flu) was not detected only in the (SMTB1-C2) site (Tables 2 and 3). The concentra-tion of individual detected PAH varied from 0.1 ± 0.00 ng/g for naphthalene to 2567.8 ±0.009 ng/g for pyrene, in Layer-I, and from 3.2 ± 0.003 ng/g for acenaphthylene to 1330.5± 0.018 ng/g for pyrene. Pyrene is the most important representative toxic PAH, in Layer-Iwith a mean value ranging from 170.6 ± 0.012 to 2567.8 ± 0.009 ng/g, while both pyreneand perylene presented higher concentrations in Layer-II (Table 3). The higher concentra-tions of perylene could result from terrigenous precursors whose diagenetic degradationcould lead to the formation of perylene (Venkatesan, 1988). Chrysene concentrations werebetween 114.2 ± 0.012 ng/g and 347.5 ± 0.014 ng/g in Layer-I and between 134.7 ± 0.015ng/g and 603.3 ±0.00 ng/g in Layer-II. High concentrations of chrysene can be associatedwith the weathering effect in crude oil’s chemical composition change. Chrysene is consid-ered as a “conservative” PAH and selected to be a good biomarker of petroleum compounddue to its resistance to weathering and bacterial degradation (Wang and Fingas, 2003).

In some cases, qualitative chemical analysis and individual PAH characteristics com-parison enable the detection of the possible sources. The analysis of the number of PAHrings has historically been used by petroleum geochemists in the characterization of marinepollution and an interpretational advantage in fingerprinting sources of spilled oils and for

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Distribution and Sources of PAHs 301

Figure 2. Distribution of total PAHs, 2–3-rings PAHs and 4–5-rings PAHs in Layers I and Layer II indifferent sites. Individual PAH in sediment were obtained following total aromatic fractionation in acapillary column and quantified referring to external standard. Total PAHs (17PAHs), the (2–3 PAHSrings) and the (4–6 PAHs rings) were quantified and statistically compared. (#): for each comparedgroups p < 0.01. Layer-I: the upper layer (0–15 cm); Layer-II: the deeper layer (15–30 cm).

providing additional diagnostic information. Analysis of individual PAH sediment charac-teristics from Jarzouna showed the predominance of high weight compounds (Figure 2).The amount of 2–3ring PAHs (�2–3ring PAHs) ranged from 200.9 ± 0.009 ng/g to 964.7± 0.012 ng/g, whereas the amount of 4–5 ring PAHs (�4–5ring PAHs) varied from 584.2± 0.033 ng/g to 2945.3 ± 0.006 ng/g (Figure 2). PAHs were predominant by the 4–5 ringPAHs. This might be related to the fact that PAHs with higher rings tend to be stronglyadsorbed by the soil, and lower molecular PAHs are apt to be depleted preferentially. It canalso be related to the effect of biodegradation selectivity. It is in fact recognized that thesecompounds are less degraded by indigenous bacteria and, compared to low-weight PAHs,are more resistant. On the other hand, the petroleum source in general contains relativelyhigher concentrations of individual 2–3 ring PAH compounds (Tolosa et al., 1996), whilea large proportion of high-molecular weight parent PAHs is a typical characteristic of acombustion origin (Budzinski et al., 1997). The PAHs with 4–5 rings have been recog-nized as directly carcinogenic and evidence suggests that the environmental persistenceand genotoxicity of PAHs increase as the molecular size of the PAHs increases up to fouror five fused benzene rings (Cerniglia, 1992).

Sources of PAHs from Jarzouna Coastal Sediment

The various sources of PAHs in the environment have been well discussed (Youngblood andBlumer, 1975; Laflamme and Hites, 1978 and Hites et al., 1980). A number of diagnosticratios of target alkylated PAH species have been successfully used as indicators for oilspill identification. Ratios between individual compounds have been calculated for theidentification of PAH origin. These ratios are based on the formation temperature of thecompounds. The formation of fossil fuels requires low temperatures, and the thermalalteration of organic matter results in PAHs with a 2–3 rings. High-temperature combustion

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

302 I. Zrafi-Nouira et al.

0.00

5.00

10.00

15.00

20.00

25.00

30.00

0.00 1.00 2.00 3.00 4.00 5.00

Pyrolytic origin

Phe/Anth

Fluo/Pyr

Pet

roge

nic

orig

in

SMTB1-C1

SMTB2-C1

SM

TB

3-C

1

SMTB 4-C1

SM

TB

1-C

2

SMT

B2-

C2

SMTB3-C2SMTB4-C2

Mixed

origin

Figure 3. Plot of (Phe/Anth) versus (Fluo/Pyr). • indicates sediment from different sampling sites.Fluo/Pyr: ratio of Fluorene to Pyrene; Phe/Anth: ratio of Phenanthrene to Anthracene; these ratiosindicate pyrolytic sources of PAHs when (Phe/Anth) < 10 and (Fluo/Pyr) >1 and it indicate petrogenicsources when Phe/Anth) > 10 and (Fluo/Pyr) <1.

produces PAHs with a 4–5 or 6-ring structure and minimal alkylated products (Bıcegoet al., 2006). The concentration ratios used in this study to distinguish between petrogenicPAHs and pyrolytic PAHs were Phe/Anth, Fluo/Pyr, Anth/Anth+Phe and Fluo/Fluo+Pyr.Those ratios were chosen for their significance in the determination of PAH sources (Socloet al., 2000; Gschwend and Hites, 1981).

A (Phe/Anth) ratio under 10 and a (Fluo/Pyr) ratio over 1 are generally characteristic ofpyrolytic sources. Based on these ratios, Phe/Anth had a mean of 1.77 and 1.12, respectively,in Layer-I and Layer-II. Fluo/Pyr had a mean of 7.24 and 0.36, respectively, in Layer-I andLayer-II. Plot of Phe/Anth versus Fluo/Pyr is shown in Figure 3. Results demonstratethat the SMTB2-C1, SMTB4-C1, SMTB3-C2 and SMTB4-C2 sites present a pyrolyticcontamination source, whereas the SMTB1-C1, SMTB3-C1, SMTB1-C2 and SMTB2-C2sites were characterized by both pyrolytic and petrogenic contaminations.

When (Anth/Anth + Phe) ratio is < 0.1, it indicates a petrogenic source and when it is> 0.1, it indicates a combustion source. Nevertheless a (Fluo/Fluo + Pyr) ratio < 0.5 is ingeneral associated with petrogenic sources (gasoline, diesel, fuel oil, crude oil combustionsand emission from vehicles), whereas when this ratio is > 0.5, it indicates pyrolytic sources(kerosene, grass, coal and wood combustion samples) (Mille et al., 2007).

In the present study, the An/(An + Phe) had a mean of 0.4 and 0.51. The Flu/(Flu+ Pyr) had a mean of 0.23 and 0.25, respectively, in Layer-I and Layer-II. Those valuessuggest the predominance of combustion source in the sediment. In addition, the ratio ofFlu/(Flu + Pyr) between 0.40 and 0.50 was considered as more characteristic of liquidfossil fuel (vehicle and crude oil) combustion, whereas a ratio above 0.50 is characteristicof grass, wood or coal combustion (Yunker et al., 2002). All values of Flu/(Flu + Pyr)were ≤ 0.5. Plot of (Anth/Anth + Phe) versus Flu/(Flu + Pyr) are shown in Figure 4. Theplot shows petrogenic PAH contamination in the SMTB1-C1 site, which is located close tothe STIR effluent. The data indicate also that the SMTB3-C1, SMTB1-C2 and SMTB2-C2

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Distribution and Sources of PAHs 303

0.0

0.1

0.2

0.3

0.4

0.5

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Petrogenicorigin

Pyrolyticorigin

Mixed origin

Anth/Anth+Phe

Fluo/Fluo+Pyr

SMTB1-C1

SMTB4-C1

SMTB3-C2SMTB4-C2

SMTB2-C1 SMTB2-C2

SMTB3-C1

SMTB1-C2

Figure 4. Plot of Fluo/(Fluo + Pyr) versus (Anth/Anth + Phe). � indicates sediment from differentsampling sites. Anth/Anth+Phe: ratio of Anthracene to the sum of Anthracene and Phenanthren:(Anth/Anth + Phe) < 0.1 indicates petrogenic source while when this ratio is > 0.1 it indicatescombustion source. Fluo/Fluo+Pyr:ratio of Fluorene to the sum of Fluorene and Pyrene; (Fluo/Fluo+ Pyr) ratio < 0.5 indicates petrogenic sources, whereas when this ratio is > 0.5, it indicates pyrolyticsources.

sites appear to be contaminated by pyrolytic PAHs. The SMTB2-C1, SMTB4-C1, SMTB3-C2 and SMTB4-C2 sites indicate a mixture of pyrolytic and petrogenic sources. Ourresults show that the site considered to be distant from the refinery has also mixed PAHpetrogenic and pyrolytic origins. This observation confirms that the refinery’s PAH pollutionhas affected distant areas or that other sources might be implicated (industrial activities,combustion, and oil transportation) in the hydrocarbon pollution of superficial sedimentfrom the Jarzouna coast. It is clear from our findings that chemical fingerprinting representsa powerful “tool” for hydrocarbon source identification and differentiation. However, inmany cases, particularly for complex hydrocarbon mixtures or extensively weathered anddegraded oil residues, there is no single fingerprinting technique that can meet the objectivesof forensic investigation and quantitatively allocate hydrocarbons to their respective sources.Combined and integrated multiple “tools” are often necessary under such situations.

Conclusions

This work reveals sediment contamination by PAH residues at the rejection area of theTunisia’s only petroleum refinery in Jarzouna-Bizerte coastal region. It extends our under-standing of the current PAH contamination status in the area and represents the first detailedstudy of the distribution, characterization, and sources of polycyclic aromatic hydrocarbonin this Mediterranean area. PAH concentrations are relatively moderate compared to sedi-mentary concentrations along the Mediterranean coasts but evidently must be reduced bythe remediation of the STIR effluent after its rejection in the area of study. PAHs from mostsites have mixed pyrolytic and petrogenic sources. This study suggests that alleviation ofthe PAH pollution should imply a strict control over the petroleum combustion, trafficexhaust, and industrial discharge. This work was performed to study the contamination of

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

304 I. Zrafi-Nouira et al.

the Jarzouna sediment in terms of quantity and possible sources, confirms the contributionof the STIR refinery in this contamination, and highlights that outer sources, such as atmo-spheric or microbiological factors or human activities may interfere to a limited extent inthe measurements. Their contribution is complex, however, and requires separate carefulstudies. This point will be considered in further investigations.

Acknowledgements

We thank STIR refinery employees of Bizerte for their help in sediment sampling. Weare grateful to Dr. Brahim Lahlou, Emeritus Professor, University of Nice, France, forthe manuscript revision. We also thank Mr. Moncef Rassas, Professor at the Faculty ofMedicine of Monastir, Tunisia, and Mr. Mahmoud Rouabhia, Professor and researcher atthe Faculty of Dentistry of Laval University of Quebec, Canada, for their assistance with thelinguistic corrections and scientific correction of this paper. This study was partly supportedby grants from the Ministry of Higher Education, Scientific Research and Biotechnologyof Tunisia, and the University of Monastir.

References

Baumard, P., Budzinski, H., and Garrigues, P. 1998a. Polycyclic aromatic hydrocarbons in sedimentsand mussels of the western Mediterranean sea. Environ. Toxicol. Chem. 17, 765–776.

Baumard, P., Budzinski, H., Michon, Q., Garrigues, P., Burgeot, T., and Bellocq, J. 1998b. Originand bioavailability of PAHs in the Mediterranean sea from mussel and sediment records. Estuar.Coast. Shelf S. 47, 77–90.

Bıcego, M.C., Taniguchi, S., Yogui, G.T., Montone, R.C., Moreira, , da Silva, D.A., Lourenco,R.A., de Castro Martins, C., Sasaki, S.T., Pellizari, V.H., and Weber, R.R. 2006. Assessmentof contamination by polychlorinated biphenyls and aliphatic and aromatic hydrocarbons insediments of the Santos and Sao Vicente Estuary System, Sao Paulo, Brazil. Mar. Pollut. Bull.52, 1804–1816.

Boffetta, P., Jourenkova, N., and Gustavsson, P. 1997. Cancer risk from occupational and environ-mental exposure to polycyclic aromatic hydrocarbons. Cancer Causes Control. 8, 444–472.

Budzinski, H., Jones, I., Bellocq, J., Pierard, C., and Garrigues, P. 1997. Evaluation of sedimentcontamination by polycyclic aromatic hydrocarbons in the Gironde estuary. Mar. Chem. 58,85–97.

Burns, K.A., and Teal, J.M. 1979. The West Falmouth Oil Spill: Hydrocarbons in the salt marshecosystem. Estuar. Cost. Mar. Sci. 8, 349–360.

Caricchia, A.M., Chiavarini, S., Cremisini, C., Marrini, F., and Morabito, R. 1993. PAHs, PBCs andDDE in the Northern Adriatic Sea. Mar. Pollut. Bull. 26, 581–583.

Cerniglia, C.E. 1992. Biodegradation of polycyclic aromatic hydrocarbons. Biodegradation 3,351–368.

DeLaune, D., Gambrel, R.P., Pardue, J.H., and Patrik Jr., W.H. 1990. Fate of petroleum hydrocarbonsand toxic organics in Louisiana coastal environments. Estuaries. 13, 72–80.

De Luca, G., Furesi, A., Micera, G., Panzanelli, A., Piu, P.C., Pilo, M.I., Spano, N., and Sanna,G. 2005. Nature, distribution and origin of polycyclic aromatic hydrocarbons (PAHs) in thesediments of Olbia harbor (Northern Sardinia, Italy). Mar. Pollut. Bull. 50, 1223–1232.

Denissenko, M.F., Pao, A., Tang M., and Pfeifer, G.P. 1996. Preferential formation of benzo[a]pyreneadducts at lung cancer mutational hotspots in P53. Science. 274, 430–432.

Elloumi, J., Guermazi, W., Ayadi, H., Bouaın, A., and Aleya, L. 2008. Detection of water and sedi-ments pollution of an arid saltern (Sfax, Tunisia) by coupling the distribution of microorganismswith hydrocarbons. Water Air Soil Poll. 187, 157–171.

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

Distribution and Sources of PAHs 305

El Nemr, A., Said, T.O., Khaled, A., El Sikaily, A., and Abd-Allah, A.M.A. 2007. The distributionand sources of polycyclic aromatic hydrocarbons in surface sediments along the EgyptianMediterranean coast. Environ. Monit. Assess. 124, 343–359.

Fernandes, M.B., Sicre, M.A., Boireau, A., and Tronczynski, J. 1997. Polyaromatic hydrocarbon(PAH) distributions in the Seine River and its estuary. Mar. Pollut. Bull. 34, 857–867.

Freitag, D., Ballhorn, L., Geyer, H., and Korte, F. 1985. Environmental hazard profile of organicchemicals. An experimental method for the assessment of the behaviour of organic chemicals inthe ecosphere by means of simple laboratory tests with 14C labelled chemicals. Chemosphere.14, 1589–1616.

Gogou, A., Bouloubassi, I., and Stephanou, E.G. 2000. Marine organic geochemistry of the EasternMediterranean: 1. Aliphatic and polyaromatic hydrocarbons in Cretan Sea surficial sediments.Mar. Chem. 68, 265–282.

Gschwend, P.M., and Hites, R.A. 1981. Fluxes of polycyclic aromatic hydrocarbons to marineand lacustrine sediments in the northeastern United States. Geochim. Cosmochim. Acta. 45,2359–2367.

Hites, R.A., Laflamme, R.E., and Windsor, J.G. 1980. Polycyclic aromatic hydrocarbons in ma-rine/aquatic sediments: their ubiquity. In: Petroleum in the Marine Environment. Advances inChemistry, 185, pp. 289–312 (Petrakis, L. and Weiss, F.T., eds.), ACS, Washington, DC.

Jordan, R.E., and Payne, J.R. 1980. Fate and Weathering of Petroleum Spills in the Marine Environ-ment, Ann Arbor Science Publishers Inc., Ann Arbor, MI.

Khedir-Ghenim, Z., Zrafi-Nouira, I., Bahri, R., Belayouni, H., Mammami, Md., and Saidane, D. 2009.Recognition and distribution of petroleum hydrocarbons in seawater, sediment and in RuditapesDecussatus from the navigation canal of Tunis (Tunisia). Int. J. Water. 5, 35–50.

Laflamme, R.E., and Hites, R.A. 1978. The global distribution of polycyclic aromatic hydrocarbonsin recent sediments. Geochim. Cosmochim. Acta. 42, 289–3003.

Louati, A., Elleuch, B., Kallel, M., Saliot, A., Dagaut, J., and Oudot, J. 2001. Hydrocarbon contami-nation of coastal sediments from the Sfax area (Tunisia), Mediterranean sea. Mar. Pollut. Bull.42, 444–451.

Lipiatou, E., and Saliot, A. 1991. Hydrocarbon contamination of the Rhone delta and WesternMediterranean. Mar. Pollut. Bull. 22, 297–304.

Mastrangelo, G., Fadda, E., and Marzia, V. 1996. Polycyclic aromatic hydrocarbons and cancer inman. Environ. Health. Perspect. 104, 1166–1170.

Mille, G., Asia, L., Guiliano, M., Malleret, L., and Doumenq, P. 2007. Hydrocarbons in coastalsediments from the Mediterranean Sea (Gulf of Fos area, France). Mar. Pollut. Bull. 54, 566–575.

Page, D.S., Boehm, P.D., Douglas, G.S., and Bence, A.E. 1995. Identification of hydrocarbon sourcesin the benthic sediments of Prince William Sound and the Gulf of Alaska following the ExxonValdez spill. In: Exxon Valdez Oil Spill: Fate and Effects in Alaska Waters, pp. 41–83 (Wells,P.G., Butler, J.N. and Hughes, J.S., eds.), ASTM, Philadelphia, PA.

Papagiannis, I., Kagalou, I., Leonardos, J., Petridis, D., and Kalfakakou, V. 2004. Copper and zinc infour freshwater fish species from Lake Pamvotis (Greece). Environ. Int. 30, 357–362.

Pavoni, B., Mecozzi, M., Berto, D., Ausili, A., Romano, E., Amici, M., Zharova, N., and Amato, E.2003. Environmental pollutants and organic carbon content in sediments from an area of theMoroccan Mediterranean Coast. Toxicol. Environ. Chem. 84, 53–67.

Prahl, F.G., and Carpenter, R. 1983. Polycyclic aromatic hydrocarbon (PAH)-phase associations inWashington coastal sediment. Geochim. Cosmochim. Ac. 47, 1013–1023.

Soclo, H.H., Garrigues, P.H., and Ewald, M. 2000. Origin of polycyclic aromatic hydrocarbons(PAHs) in coastal marine sediments: Case studies in Cotonou (Benin) and Aquitaine (France)Areas. Mar. Pollut. Mar. Pollut. 40, 387–396.

Tolosa, J.M., Bayona, Y.J., and Albaiges, Gs. 1996. Aliphatic and polycyclic aromatic hydrocabonsand sulfur/oxygen derivatives in northwestern Mediterranean sediments: spatial and temporalvatriability, fluxes and budgets. Environ. Sci. Technol. 30, 2495–2503.

Trabelsi, S., and Driss, M.R. 2005. Polycyclic aromatic hydrocarbons in superficial coastal sedimentsfrom Bizerte Lagoon, Tunisia. Mar. Pollut. Bull. 50, 344–359.

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013

306 I. Zrafi-Nouira et al.

Trapido, M. 1999. Polycyclic aromatic hydrocarbons in Estonian soil: contamination and profiles.Environ. Pollut. 105, 67–74.

Tuvikene, A. 1995. Responses of fish to polycyclic aromatic hydrocarbons (PAHs). Ann. Zool. Fenn.32, 295–307.

Venkatesan, M.I. 1988. Occurrence and possible sources of perylene in marine sediments—a review.Mar. Chemistry. 25, 1–27.

Wang, Z.D., Fingas, M., and Page, D. 1999. Oil spill identification. J. Chromatogr. 843, 369–411.Wang, Z., and Fingas, M.F. 2003. Development of oil hydrocarbon fingerprinting and identification

techniques. Mar. Pollut. Bull. 47, 423–452.WHO (World Health Organisation). 1998. Environmental Health Criteria 202: Polycyclic Aromatic

Hydrocarbons—Selected Non-heterocyclic, World Health Organisation, Geneva.Witt, G. 1995. Polycyclic aromatic hydrocarbons in water and sediment of the Baltic Sea. Mar. Pollut.

Bull. 31, 237–248.Yoshida, M., Hamadi, H., Abdulnasser, I., and Jedidi, N. 2002. Contamination of potentially toxic

elements (PTEs) in Bizerte lagoon bottom sediments, surface sediment and sediment repository.In: Study on Environmental Pollution of Bizerte Lagoon, pp. 13–48 (Ghrabi, A. and Yoshida,M., eds.), INRST-JICA Publishers, Tunisia.

Youngblood, W.W., and Blumer, M. 1975. Polycyclic aromatic hydrocarbons in the environment:homologous series in soils and recent marine sediments. Geochim. Cosmochim. Acta. 39,1303–1314.

Yunker M.B., Macdonald, R.W., Vingarzan, R., Mitchell, R.H., Goyette, D., and Sylvestre, S. 2002.PAHs in the Fraser River basin: a critical appraisal of PAH ratios as indicators of PAH sourceand composition. Org. Geochem. 33, 489–515.

Zaghden, H., Kallel, M., Louati, A., Elleuch, B., Oudot, J., and Saliot, A. 2005. Hydrocarbons insurface sediments from the Sfax coastal zone, (Tunisia) Mediterranean Sea. Mar. Pollut. Bull.50, 1287–1294.

Zaghden H., Kallel, M., Elleuch B, Oudot, J., and Saliot, A. 2007. Sources and distribution ofaliphatic and polyaromatic hydrocarbons in sediments of Sfax, Tunisia, Mediterranean Sea.Mar. Chemistry. 105, 70–89.

Zrafi-Nouira, I., Khedir-Ghenim, Z., Barhri, R., Cheraief, I., Rouabhia, M., and Saidane-Mosbahi, D.2008. Hydrocarbon pollution in the sediment from the Jarzouna-Bizerte coastal area of Tunisia(Mediterranean Sea). Bull. Environ. Contam. Toxicol. 80, 566–572.

Dow

nloa

ded

by [

Mos

kow

Sta

te U

niv

Bib

liote

] at

05:

23 2

0 N

ovem

ber

2013