Marine Pollution Bulletin 75 (2013) 174–181

Contents lists available at ScienceDirect

Marine Pollution Bulletin

journal homepage: www.elsevier .com/locate /marpolbul

Spatial variations in polycyclic aromatic hydrocarbons concentrationsat surface sediments from the Cyprus (Eastern Mediterranean):Relation to ecological risk assessment

0025-326X/$ - see front matter � 2013 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.marpolbul.2013.07.042

⇑ Corresponding author. Tel.: +90 232 278 55 65; fax: +90 232 278 50 82.E-mail address: enis.darilmaz@deu.edu.tr (E. Darılmaz).

Enis Darılmaz ⇑, Aynur Kontas�, Esin Uluturhan, _Idil Akçalı, Oya AltayDokuz Eylul University, Institute of Marine Sciences and Technology, Inciralti, 35340 Izmir, Turkey

a r t i c l e i n f o

Keywords:Polycyclic aromatic hydrocarbonsPyroliticPetrogenicSediment quality guidelinesCyprusMediterranean

a b s t r a c t

The objective of the present study was to evaluate the distribution, sources, origins, and environmentalrisk assessment of polycyclic aromatic hydrocarbons (16 US EPA priority pollutants) pollution in 23 sur-face sediments from Cyprus coast. The mean total polycyclic aromatic hydrocarbons (PAHs) concentra-tions in the sediments from Gemi Konagi, Girne and Gazi Magusa areas were found 47, 52 and 50 ng/g,respectively. Molecular ratios and principle component analysis indicated that PAH pollution originatedmainly from fossil sources, with higher pyrolytic contributions. The 2–3 ring PAHs were dominant inCyprus sediments. Concentrations of PAHs observed in this study were compared with available soilquality guidelines and the concentrations were lower than the guideline values. The guideline values sug-gested that the Cyprus sediments were likely to be not contaminated by toxic PAH compounds.

� 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Polycyclic aromatic hydrocarbons (PAHs) are well known asenvironmental pollutants. They are dangerous even at low concen-trations and included in the priority pollutant list of the EuropeanUnion and US Environmental Protection Agency (EPA) due to theirmutagenic and carcinogenic properties (US EPA, 1993; Nieva-Canoet al., 2001). PAHs are generated by incomplete combustion of or-ganic materials arising in part from natural combustion such asforest fires, volcanic eruptions and from anthropogenic sourcessuch as industrial production, transportation and waste incinera-tion (Baek et al., 1991; Lorber et al., 1994; Yang et al., 1998 Grovaet al., 2002). Petroleum production, import and export of petro-leum products also contribute significantly to the extent of PAHcontamination especially in the marine samples (Baek et al.,1991; Lorber et al., 1994; Nwachukwu, 2000; Nwachukwu et al.,2001).

Several PAHs are known to be potential human carcinogens;these include benz[a]anthracene, chrysene, benzo[b]flouranthene,benzo[k]flouranthene, benzo[a]pyrene and benzo[ghi]perylene(IARC, 1983; Anyakora et al., 2005). They are mutagenic and carcin-ogenic environmental contaminants that are widely present in theair, water, sediments and aquatic systems (Menzie et al., 1992;Shaw and Connell, 1994; Yu, 2002; Nadal et al., 2004). As a result,

16 un-substituted PAHs are included by US Environmental Protec-tion Agency (EPA) priority pollutant list for monitoring. Because ofthat many studies have recently been conducted to evaluate insediments (Readman et al., 2002; King et al., 2004; Durjava et al.,2007; Maskaoui and Hu, 2009; Barakat et al., 2011; Bajt, 2012;Commendatore et al., 2012; El Nemr et al., 2013). PAHs distributein aquatic systems by their physicochemical properties includingsolubility, vapor pressure and lipophilicity (Zhou et al., 1998). Be-cause of their hydrophobic and persistent nature, PAHs enteringthe marine environment preferentially adsorb onto particulatesand accumulate in bottom sediments (Chiou et al., 1998). The mainsources of PAHs in the Mediterranean are emissions from combus-tion, oil, traffic, sewage sludge incineration, sewage sludge, sewagesludge dumping, timber operations, oil spills, sewage runoff, oilspills in shipping and refineries (UNEP, 2002).

Some studies have been carried out on the pollution of the Cy-prus (Elderfield et al., 1972; Pyatt, 1999; Yükselen and Alpaslan,2001; Yükselen, 2002; Fatta et al., 2004, 2007; Johansson et al.,2005). However; there has been little data about PAH contamina-tions in sediment at this area (Kucuksezgin et al., 2013). The aimof this study is to investigate the distribution of PAHs indicatedas priority pollutants by US EPA in the sediments, to describe thespatial distribution of PAHs, to determine the source of PAH pollu-tion (pyrolitic or petrogenic) and to evaluate the ecological risksfrom PAH contamination from Cyprus. It is expected that the re-sults of this study shall be available and useful data as a referencefor future studies.

E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181 175

2. Materials and methods

2.1. Study area

The island of Cyprus lies in the north-eastern corner of the Med-iterranean Sea and occupies an area of 9251 km2. Maritime trans-portation, tourism, treated or untreated domestic and industrialwastewater discharges, oil spills, agricultural wastes reaching thesea by rivers and also mining activities are the main reasons of pol-lution from Cyprus. Sediment samples were taken from Gemi Kon-agi, Girne and Gazi Magusa areas (Fig. 1). The depths, salinities andtemperatures of stations were also given at Table 1.

2.2. Sampling

Surface sediment samples were collected using box core duringa cruise of the R/V K. Piri Reis (Institute of Marine Sciences andTechnology, Dokuz Eylül University) within the framework of theIMST-187 Project in May 2010. All sampling procedures followedaccording to internationally well established guideline (UNEP/IOC/IAEA, 1992). The sediment samples were placed in a pre-cleaned aluminum foil and frozen (�20 �C) until analysis.

2.3. Sample preparation

Sediment samples were freeze-dryed and sieved through astainless steel sieve (250 lm). Sediments were then homogenizedprior to extraction. All solvents and chemicals used were of chro-matographic grade. Na2SO4 was pre-cleaned by Soxhlet extractionwith methanol and hexane and additionally pre-combusted at400 �C for 6 h. SiO2 (Silica gel, 230–400 mesh) and Al2O3 (Alumi-num oxide 90 active neutral, 70–230 mesh) were pre-cleaned bySoxhlet extraction with methanol and hexane for 8 h and thendried at 105 �C. Before use, they were activated at 200 �C for 4 hand partially deactivated with 5% water. Sulfur compounds wereremoved using activated elemental copper in order to avoid poten-tial interferences during gas chromatography. Naphthalene-d8,hexamethyl benzene and cadalene were added to the sedimentsas internal standards.

Fig. 1. Sampling ar

2.4. Quality control and quality assurance

Quality control procedures were applied to this study. Proce-dural blanks were performed at the same time as the analyses.Concentrations of all target compounds were below the detectionlimit in blank samples. Internal standards were added to each sed-iment sample prior to the analyses for recovery determination.Internal standard solutions were obtained from the IAEA-MarineEnvironment Laboratory (MEL), Monaco. Sediment reference mate-rial (IAEA-417) was also analyzed prior to the analysis of samplesto assess the accuracy of the work. All concentration values werewithin the assigned reference value for selected PAHs (95% confi-dence interval). The precision of replicate measurements of the ref-erence material was better than 10% for all target PAHs.

2.5. Statistical analyses

Principal component analysis (PCA) was performed using PRI-MER 5 statistical package. Multivariate statistical analyses havebeen largely used as a tool to assess the environmental data. In thisstudy, PCA was applied to the sediment samples. The data werestandardized to eliminate scaling before PCA processing. Prior toanalyses, values below the detection limit were replaced with zerothen standardized.

2.6. Extraction and cleanup

Using the microwave assisted extraction system (MARS), 10–15 g of freeze-dried sediment samples were placed in a glass tubewith 40 ml of mixture hexane/dichloromethane (50:50), and inter-nal standards were added to the samples. Sulfur was removed byactivated copper and extracts were then transferred into a silica-alumina column for cleanup and elution of PAHs. Extracts wereconcentrated on a rotary evaporator about to 15 ml and then aN2 stream to about 1 ml. Samples were analyzed using an Agilent6850 series Gas Chromatograph (GC) coupled to an Agilent 5975cMass Spectrometer (MS) an electron impact ionization source (EI)in the selected ion monitoring (SIM) mode and a 30 m � 0.25 lm(i.d.) DB-5MS column. The temperature was programmed from50 �C (1 min) to 200 �C at 25 �C min�1, from 200 �C to 316 �C(20 min) at 8 �C min�1. The mass spectrometer scanned

eas of Cyprus.

Table 1Coordinates and physical properties of (surface and bottom) sampling stations in Cyprus.

Station no Latitude Longitude Depth (m) Salinitity (psu) Temperature (�C)

Gemi Konagi1 35�10’57.600N 32�44’55.800E 50 39.13–39.15 20.0–18.12 35�10’24.000N 32�46’02.400E 51 39.13–39.16 20.2–17.93 35�11’42.600N 32�44’23.400E 96 39.13–39.22 20.0–17.24 35�10’57.600N 32�46’09.000E 99 39.15–39.20 20.2–17.05 35�11’13.200N 32�45’01.200E 111 39.13–39.21 20.0–17.06 35�11’37.800N 32�44’55.800E 240 39.22–39.14 19.7–15.97 35�22010.200N 32�53039.600E 50 39.21–39.16 19.6–17.58 35�22015.000N 32�52030.000E 101 39.21–39.21 19.7–16.99 35�23010.200N 32�50053.400E 203 39.18–39.17 19.6–16.1

Girne10 35�23017.400N 33�02048.600E 96 39.20–39.23 20.1–17.311 35�23042.000N 33�02049.200E 231 39.09–39.10 20.3–15.612 35�25050.400N 33�51003.600E 52 39.20–39.22 20.2–18.513 35�25060.000N 33�51006.000E 101 39.21–39.22 20.1–17.314 35�26012.600N 33�50056.400E 201 39.20–39.19 19.9–16.3

Gazi Magusa15 35�37017.400N 34�31024.000E 52 39.21–39.20 20.2–18.216 35�36042.600N 34�31018.600E 107 39.22–39.24 20.4–17.017 35�36022.200N 34�31008.400E 200 39.22–39.13 20.3–15.818 35�24046.200N 34�10044.400E 64 39.22–39.21 20.0–18.219 35�18057.000N 34�02020.400E 55 39.27–39.22 20.5–18.220 35�18020.400N 33�58045.600E 24 39.27–39.23 20.4–19.221 35�18000.000N 33�58051.000E 50 39.26–39.21 20.4–17.922 35�17027.000N 33�59037.800E 101 39.26–39.23 20.2–17.323 35�17013.800N 34�00001.200E 203 39.26–39.13 20.2–15.8

176 E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181

45–450 Da per second; electron energy was 70 eV. The 16PAH compounds were naphthalene (m/z 128), acenaphthylene(m/z 152), acenaphthene (m/z 154), fluorene (m/z 166), phenan-threne (m/z 178), anthracene (m/z 178), fluoranthene (m/z 202),pyrene (m/z 202), benzo[a]anthracene (m/z 228), chrysene(m/z 228), benzo[b]fluoranthene (m/z 252), benzo[k]fluoranthene(m/z 252), benzo[a]pyrene (m/z 252), indeno[1,2,3-cd]pyrene(m/z 276), dibenzo[a,h]anthracene (m/z 278) and benzo[ghi]pery-lene (m/z 276).

The amount of organic matter was determined spectrophoto-metrically in samples following the sulfochromic oxidation meth-od (HACH, 1988). The accuracy of this method is ±0.017% organicmatter.

3. Results and discussion

The concentrations of the studied 16 parent PAHs (naphthalene:Nap; acenaphthylene: Acy; acenaphthene: Ace; fluorene: Flu;phenanthrene: Phe; anthracene: Ant; fluoranthene: Flt; pyrene:Pyr; benz[a]anthracene: BaA; chrysene: Chr; benzo[b]fluoranth-ene: BbF; benzo[k]fluoranthene: BkF; benzo[a]pyrene: BaP;indeno[1,2,3-cd]pyrene: InP; dibenz[a,h]anthracene: DA; benzo[g,h,i]perylene: BPer) and organic matter (OM) in sediment fromCyprus summarized in Table 2.

The organic matter contents changed between 0.96% and 3.39%in Cyprus sediments. The maximum concentration of organic mat-ter was found at station 19 (Gazi Magusa) while the minimum or-ganic matter was detected at station 7 (Gemi Konagi). High organicmatter percentage at station 19 may indicate influence from mar-ine organic production due to aquaculture activities. Organic mat-ter content of sediments in Cyprus were similar to the Sea ofMarmara (0.75–4.36%) (Ergin et al., 1993) and higher than thatare reported from the Aegean Sea (0.60–1.41%) (Voutsinou-Tali-adouri and Satsmadjis, 1982) and the Eastern Mediterranean Sea(0.22–1.71%) (Emelianov and Romankevitch, 1979).

All results were calculated on a dry weight basis. Individual andthe total concentrations of PAHs were given in Table 2. The totalPAHs concentrations in sediments ranged from 4.9 to 76 ng/g

depending on the sampling location. Relatively high total PAH lev-els were found at stations 4, 6, 9 and 23. The minimum total PAHlevel was found at station 7 (Fig. 2). The mean values of total con-centration of PAHs (ng/g) in three sampling areas (Gemi Konagi,Girne and Gazi Magusa) were 47, 52 and 50 respectively.

According to Baumard et al. (1998a), pollution levels of PAHscan be characterized as low, moderate, high, and very highwhen total PAH concentrations are within 0–100, 100–1000,1000–5000, and >5000 ng/g limits, respectively. Based on this clas-sification, PAH concentrations of the sediments from Cyprus can beconsidered to be low.

Among the all analyzed compounds, Naphthalene was the pre-dominant species. Individual PAH concentrations (ng/g) in sedi-ments ranged between 3 and 42 for Nap; 0.41–3.55 for Acy; nd-0.53 for Ace; nd-3.61 for Flu; 0.51–15.3 for Phe; 0.52–12.2 forAnt; 0.25–11.1 for Flt; 0.14–8.39 for Pyr; nd-3.56 for BaA; nd-6.24 for Chr. BbF and BkF were detected only two stations at GemiKonagi area. On the other hand BaP, InP, DA and BPer were not de-tected at sampling stations. The minimum concentrations of Nap,Acy, Flu, Phe, Ant, Flt, Pyr, BaA and Chr were detected at Gemi Kon-agi area (Station 7). The maximum concentrations of Ace and Phewere obtained at Girne area besides the highest Nap, Flu, Ant, Fltand Pyr were found at Gazi Magusa area. It is explained that therelatively high individual PAHs and total PAH concentrations atGirne and Gazi Magusa areas depend on shipping, port and mari-time activities.

PAHs have been analyzed and classed with regard to the num-ber of structural rings: PAHs with two ring (Nap), with three rings(Acy, Ace, Flu, Phe and Ant), with four rings (Flt, Pyr, BaA, and Chr),with five rings (BbF, BkF, BaP, DA) and with six rings (InP and BPer).The composition pattern of PAHs by ring size in the surface sedi-ments were shown in Fig. 2. PAHs with two and three rings weregenerally the most abundant, both contributing 50–90% to thesum, closely followed by the four rings class. In addition, 5 ringsPAHs were found only in Gemi Konagi area (stations 5 and 8).

PAHs are introduced into environmental compartments bothfrom natural (organic matter diagenesis, plant synthesis, forestand prairie fires, volcanoes, etc.) and anthropogenic processes

Table 2PAH (ng/g) and Organic Matter (OM, %) in sediments of Cyprus (nd: not detected).

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Nap 21 26 12 36 24 42 3.0 6.0 33 27 27 14 21 31 17 23 16 14 8.0 26 16 25 42Acy 0.59 0.88 0.61 3.6 0.80 1.2 0.41 2.4 2.5 2.3 1.4 0.50 1.7 0.98 2.9 1.4 0.96 1.8 1.5 2.8 1.1 2.3 3.1Ace nd nd nd nd nd nd nd nd nd 0.28 nd 0.53 nd 0.24 0.19 0.22 0.03 nd nd 0.13 0.15 0.19 0.11Flu 0.16 0.55 1.1 2.9 1.2 1.2 nd 1.1 1.2 2.6 0.30 0.98 1.1 0.49 1.3 1.9 0.20 1.2 1.7 1.9 1.4 3.6 0.95Phe 5.6 11 11 15 11 13 0.51 7.7 10 15 8.7 10 9.9 5.8 6.5 9.4 4.4 8.6 11 12 8.7 15 7.8Ant 0.66 1.2 1.3 2.1 2.1 1.7 0.52 1.0 1.6 1.7 7.4 1.5 1.5 1.2 1.8 3.9 3.4 1.4 1.7 12 1.6 4.2 2.2Flt 2.9 6.2 2.7 4.8 4.0 7.7 0.25 3.9 9.0 5.6 6.3 4.0 3.5 3.8 2.0 3.9 3.3 4.2 11 4.1 3.9 5.2 6.6Pyr 0.50 1.5 1.4 2.0 1.9 1.8 0.14 3.1 6.5 4.0 2.5 2.6 2.8 3.1 1.9 2.6 2.7 3.0 8.4 6.5 2.8 4.6 6.0BaA 0.47 1.5 0.31 0.75 1.1 1.6 nd 1.7 3.6 1.8 2.2 1.1 1.0 1.5 0.63 0.66 0.92 2.8 3.0 0.92 0.84 1.4 2.8Chr 1.7 3.8 0.34 3.0 1.9 6.1 nd 3.0 6.2 3.5 6.1 2.6 2.2 2.5 nd nd 2.1 2.1 3.1 0.30 2.2 nd 4.0BbF nd nd nd nd 1.6 nd nd 2.0 nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndBkF nd nd nd nd 1.3 nd nd 0.66 nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndBaP nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndInP nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndDA nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndBPer nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd nd ndPAHs 34 53 31 70 50 76 4.9 32 74 64 62 38 45 50 34 47 34 39 49 67 39 61 76OM 1.7 1.6 1.2 1.2 1.6 1.2 1.0 1.0 1.2 1.7 1.0 1.8 1.4 1.6 2.0 1.9 1.9 1.6 3.4 2.4 2.3 1.3 2.0

Fig. 2. Spatial distribution of total PAH and the composition of 2-, 3-, 4-, 5-rings in the surficial sediments from Cyprus.

E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181 177

(fossil fuel burning, incomplete combustion of organic matter,petroleum, incineration, etc.). PAH molecular indices, such asPhe/Ant, Flt/Pyr, Flt/(Flt + Pyr), Ant/(Ant + Phe), BaA/(BaA + Chr),have been widely used to identify potential PAH sources in marineenvironment samples; these are largely based on the differences inthermodynamic stability observed in compounds (Readman et al.,1987; Budzinski et al., 1997; Baumard et al., 1998a,b; Gogouet al., 1998; Yunker et al., 2002; Tsapakis et al., 2003; Yan et al.,2009). Phe/Ant ratio >10 suggests for the petrogenic sources andPhe/Ant < 10 for the dominance of pyrolytic sources (Budzinskiet al., 1997). In general, a ratio of Phe/Ant of <10, Flt/Pyr of >1and Flt/(Flt + Pyr) > 0.5 suggests that PAH contamination arisesfrom pyrolytic origins. Based on the PAH isomer pair ratio

calculations compiled by Yunker et al. (2002): Flu/(Flu + Pyr) < 0.4implies petroleum, 0.4–0.5 implies petroleum combustion, and>0.5 implies combustion of coal and biomass; Ant/(Ant + Phe) ratio<0.10 are seen in petroleum input or diagenetic sources, whereasvalues >0.1 are characteristic of combustion processes; and BaA/(Chry + BaA) ratio <0.20 indicates petroleum, 0.20–0.35 petroleumand combustion, and >0.35 combustion.

The ratios of Phe/Ant, Flt/Pyr, Flt/(Flt + Pyr), Ant/(Ant + Phe) forCyprus sediment samples reflected that PAH contamination arisesfrom pyrolytic origins in this study area (Fig. 3). On the other hand,ratios of BaA/(BaA + Chr) suggested that the PAHs had mixedsources, including both petrogenic and pyrolytic sources. The ratiosshowed that PAHs were derived primarily from combustion of

Fig. 3. Relations between some of the ratios of PAH species and indexes used in the estimation of PAH sources for the sediments of Cyprus.

178 E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181

fossil fuels/petroleum (gasoline, crude oil, and coal) and biomass(wood and grasses), with minor amounts of PAHs derived frompetroleum input.

The total index, as the sum of single indices respectively nor-malized for the limit value (low temperature source-high temper-ature source), was proposed by Mannino and Orecchio (2008) andused by other researchers (Orecchio, 2010; Tsymbalyuk et al.,2011; Zhang et al., 2011) to characterize the source of PAHs:

Total index ¼ Fl=ðFlþ PyÞ=0:4þ An=ðAnþ PhÞ=0:1þ B½a�A=ðB½a�Aþ ChrÞ=0:2þ IP=ðIPþ B½g;h; i�PÞ=0:2

Typically, high-temperature processes in case of total indexPAHs > 4 are considered as sources of PAHs, and values <4 indicatemainly low temperature sources (petroleum product). The calcu-lated total index values of PAHs for Cyprus sediments ranged from4.04 to 9.77. These results confirm that all the PAHs identified inthe sediment samples originate from combustion processes.

Sediment data can be evaluated to identify the potentialhazards on aquatic organisms by using SQGs. In this study, the

Threshold Effect Level (TEL) and Probable Effect Level (PEL) weightof evidence approach was used as SQGs (based on Long et al., 1995;Macdonald et al., 1996, 2000; CCME, 1999) in order to evaluatePAH contamination of Cyprus sediments. TEL represents the con-centration below which adverse effects are expected to occur onlyrarely. PEL represents the concentration above which adverse ef-fects are expected to occur frequently. All of the PAH results, ex-cept Naphthalene, were below the TEL values. Naphthalene levelsat the stations 4, 6 and 23 were within the TEL–PEL values. TheTEL/PEL analyses suggested that the Cyprus sediments were likelyto be not contaminated by toxic PAH compounds.

Compared with other areas in the world, the concentrations ofP

PAHs in sediment samples from the Cyprus (4.9–76 ng/g) wereclose to those found in the Cilician Basin-Mediterranean (Kucuk-sezgin et al., 2013), in the Laranjeiras Bay-Brasil (Martins et al.,2012), in the Daya Bay-South China (Yan et al., 2009), in the IzmirBay-Turkey (Darilmaz and Küçüksezgin, 2007), in the Bay of Kav-ala-Greece (Papadopoulou and Samara, 2002). Values slightly high-er than those found in the Tierra del Fuego-Argentina(Commendatore et al., 2012), in the Gulf of Aden-Yemen (Mostafa

Fig. 4. Principal component analysis (PC1 vs. PC2) loading plots for individual PAH compounds in Cyprus sediments.

E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181 179

et al., 2009), and in the Pearl River Estuary-China (Luo et al., 2006).Values much higher concentrations were encountered in the Med-iterranean coast (Egypt) by Barakat et al. (2011), in the CienfuegosBay-Cuba (Tolosa et al., 2009), in the Mar Piccolo Ionian Sea-Italy(Cardellicchio et al., 2007), in the Gulf of Fos-France (Mille et al.,2007), in the Stagnone coastal lagoon, Marsala-Italy (Culottaet al., 2006) and in the marine coastal lagoon of Ganzirri-Italy(Gianguzza et al., 2006).

A one-way ANOVA was employed to compare the spatial differ-ences in the PAHs concentrations of sediments. The results showedno significant differences for Nap, Acy, Flu, Phe, Ant, Flt, Pyr, BaA,Chr and total PAHs among all sampling areas (p < 0.05). Post hoctest indicated that Ace levels at Girne were different from GemiKonagi. The significant regional differences for %OM levels werefound at Girne, Gemi Konagi and Gazi Magusa.

Pearson correlation coefficients were computed between vari-ables including all individual PAH concentrations and organic mat-ter, measured in the surface sediments of the Cyprus. The results ofthe analyses showed that many PAH compounds turned out to besignificantly correlated (p < 0.05). The highest coefficients werethose for Nap-

PPAHs (r = 0.88); Flu-Phe (r = 0.80); Phe-

PPAHs

(r = 0.70); Flt-Pyr (r = 0.71); Flt-BaA (r = 0.81) Flt-Chr (r = 0.70);Flt-

PPAHs (r = 0.69); Pyr-BaA (r = 0.70); BaA-Chr (r = 0.67). Signif-

icant correlation coefficients were noticed between Flt-Pyr, Flt-BaAand Flt-Chr. These significant correlations indicated that Flt, Pyr,BaA and Chr might be originated from the same source (pyrolitic).In this study, organic matter values were not correlated with indi-vidual PAHs compounds. Simpson et al. (1998) showed that organ-ic matter values were only significantly correlated with individualPAH compounds in case of highly contaminated sites, where totalPAHs were greater than 2000 ng/g; dry weight. In addition, Yang(2000) also showed that sediments with high organic carbon con-tent were characterized with high values of PAHs. The total PAHsconcentrations in Cyprus sediments were lower than 2000 ng/g;dry weight.

The data were standardized to eliminate scaling before princi-pal component analysis (PCA) processing. The relationship be-tween PAHs in sediments and possible sources was also exploredstatistically using PCA. The groupings from the PCA were then eval-uated relative to potential sources materials and geographic loca-tion. PCA resulted in two eigenvalues higher than 1, consideredas the criterion to retain a PC. The first principal component(PC1) accounted for 90.5% of the total variance and the secondfor 6.1%, thus accounting for 96.6% of the total variance. The factorscores for the compounds are shown in Fig. 4. Acy, Ace, Flu, Phe,Ant, Flt, Pyr, BaA and Chr showed the highest factor scores forPC1, which represented the pyrolitic component. The second prin-cipal component (PC2) is probably related to the contribution ofpetrogenic sources. Based on these two components, three

different clusters were obtained. A first group with high PC1 load-ings was mainly related to Acy, Ace, Flu, Ant, Flt, Pyr, BaA and Chrwith a contribution of pyrolitic sources. A second cluster with amixed contribution of pyrolitic and petrogenic components in-cluded with Phe. The third cluster (very low pyrolitic contributionand relatively light and fresh oil) characterized by Nap.

4. Conclusions

In this study, the distribution, contamination and sources ofPAHs in Cyprus sediments were investigated. On the basis of ourinvestigations the following conclusions can be drawn as:

� According to level of pollution, concentrations of the total PAHsin the Cyprus is considered to be low.� The results showed that Naphthalene was the predominant spe-

cies among the analyzed compounds.� The composition pattern of PAHs by ring size in the surface sed-

iments showed that PAHs with two and three rings were gener-ally the most abundant, closely followed by the four rings class.� Some molecular ratios showed that PAHs were derived primar-

ily from combustion of fossil fuels, petroleum and biomass, withminor amounts of PAHs derived from petroleum input.� The TEL/PEL values suggested that the Cyprus sediments were

likely to be not contaminated by toxic PAH compounds.� High score of PCA analysis showed that PAHs were represented

mainly from pyrolitic component.� Compared to other worldwide coastal areas, the total PAHs con-

centrations in the sediment demonstrated the low PAHspollution.

It is explained that the relatively high PAH concentrations atGirne and Gazi Magusa areas depend on shipping, port and mari-time activities. The results from this study could be particularlyimportant and complementary to avoid the spreading of contami-nants from the Cyprus, with an effective management policy thathave to be taken in the future.

Acknowledgments

This study has been supported by the Turkish Scientific andTechnological Research Council TUBITAK/111Y160, Heavy metaland polycyclic aromatic hydrocarbon pollution in sediments ofthe Cyprus (Eastern Mediterranean). We express our deep grati-tude to the scientists and crew of the R/V Koca Piri Reis duringthe cruises. We wish to thank Dr Baris Akcali and Gokhan Kaboglufor them help in the preparation of the map. We also wish to thankDr. Deniz Unsalan for reading the manuscript and corrections re-lated to English language.

180 E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181

References

Anyakora, C., Ogbeche, A., Palmer, P., Coker, H., 2005. Determination of polynucleararomatic hydrocarbons in marine samples of Siokolo Fishing Settlement. J.Chromatogr. A 1073, 323–330.

Bajt, O., 2012. Aliphatic and polycyclic aromatic hydrocarbons in sediments of theSlovenian coastal area (Gulf of Trieste, Northern Adriatic). Environ. Monit.Assess. 184, 7439–7452.

Baek, S.O., Field, R.A., Goldstone, M.E., Kirk, P.W., Lester, J.N., Perry, R., 1991. Areview of atmospheric polycyclic aromatic hydrocarbons: sources, fate andbehavior. Water Air Soil Pollut. 60, 279–300.

Barakat, A.O., Mostafa, A., Wade, T.L., Sweet, S.T., El Sayed, N.B., 2011. Distributionand characteristics of PAHs in sediments from the Mediterranean coastalenvironment of Egypt. Mar. Pollut. Bull. 62, 1969–1978.

Baumard, P., Budzinski, H., Garrigues, P., 1998a. Polycyclic aromatic hydrocarbonsin sediments and mussels of the western Mediterranean Sea. Environ. Toxicol.Chem. 17, 765–776.

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

Budzinski, H., Jones, I., Bellocq, J., Pierard, C., Garrigues, P., 1997. Evaluation ofsediment contamination by polycyclic aromatic hydrocarbons in the Girondeestuary. Mar. Chem. 58, 85–97.

CCME, Canadian Council of Ministers of the Environment, 1999. Canadian SedimentQuality Guidelines for the Protection of Aquatic Environment, CanadianEnvironmental Quality Guidelines, CCME, Winnipeg, Ontario.

Cardellicchio, N., Buccolieri, A., Giandomenico, S., Lopez, L., Pizzulli, F., Spada, L.,2007. Organic pollutants (PAHs, PCBs) in sediments from the Mar Piccolo inTaranto (Ionian Sea, Southern Italy). Mar. Pollut. Bull. 55, 451–458.

Chiou, C.T., McGroddy, S.E., Kile, D.E., 1998. Partition characteristics of polycyclicaromatic hydrocarbons on soils and sediments. Environ. Sci. Technol. 32, 264–269.

Commendatore, M.G., Nievas, M.L., Amin, O., Esteves, J.L., 2012. Sources anddistribution of aliphatic and polyaromatic hydrocarbons in coastalsedimentsfrom the Ushuaia Bay (Tierra del Fuego, Patagonia, Argentina). Mar. Environ.Res. 74, 20–31.

Culotta, L., De Stefano, C., Gianguzza, A., Mannino, M.R., Orecchio, S., 2006. The PAHcomposition of surface sediments from Stagnone coastal lagoon, Marsala (Italy).Mar. Chem. 99 (1–4), 117–127.

Darilmaz, E., Küçüksezgin, F., 2007. Distribution and origin of hydrocarbons insurficial sediments from the eastern Aegean Sea (Izmir Bay). Baseline/Mar.Pollut. Bull. 54, 1813–1838.

Durjava, M.K., ter Laak, T.L., Hermens, J.L.M., Struijs, J., 2007. Distribution of PAHsand PCBs to dissolved organic matter: high distribution coefficients withconsequences for environmental fate modeling. Chemosphere 67, 990–997.

El Nemr, A., El-Sadaawy, M.M., Khaled, A., Draz, S.O., 2013. Aliphatic and polycyclicaromatic hydrocarbons in the surface sediments of the Mediterranean:assessment and source recognition of petroleum hydrocarbons. Environ.Monit. Assess. 185, 4571–4589.

Elderfield, H., Gass, I.G., Hammond, A., Bear, L.M., 1972. The origin offerromanganese sediments associated with the Troodos Masif of Cyprus.Sedimentology 19, 1–19.

Emelianov, E.M., Romankevitch, E.A., 1979. Geochemistry of Organic Matter in theOcean. Springer, Berlin.

Ergin, M., Bodur, M.N., Ediger, D., Ediger, V., Yilmaz, A., 1993. Organic carbondistribution in the surface sediments of the Sea of Marmara and its control bythe inflows from the adjacent water masses. Mar. Chem. 41, 311–326.

Fatta, D., Marneri, M., Papadopoulos, A., Savvides, C., Mentzis, A., Nikolaides, L.,Loizidou, M., 2004. Industrial polllution and control measures for a foundry inCyprus. J. Clean. Prod. 12, 29–36.

Fatta, D., Canna-Michaelidou, S., Michael, C., Georgiou, E.D., Christodoulidou, M.,Achilleos, A., Vasquez, M., 2007. Organochlorine and organophosphoricinsecticides, herbicides and heavy metals residue in industrial wastewaters inCyprus. J. Hazard. Mater. 145, 169–179.

Gianguzza, A., Mannino, M.R., Olivo, A., Orecchio, S., 2006. Occurrence andconcentration of PAHs in clams and sediments of marine coastal lagoon ofGanzirri (Italy). Extraction and GC–MS analysis distribution and sources.Fresenius Environ. Bull. 15, 1023–1030.

Gogou, A., Apostolaki, M., Stephanou, E.G., 1998. Determination of organicmolecular markers in marine aerosols and sediments: one-step flashchromatography compound class fractionation and capillary gaschromatographic analysis. J. Chromatogr. A 799, 215–231.

Grova, N., Feidt, C., Crepineau, C., Laurent, C., Lafargue, P.E., Hachimi, A., Rychen, G.,2002. Detection of polycyclic aromatic hydrocarbon levels in milk collectednear potential contamination sources. J. Agric. Food Chem. 50, 4640–4642.

HACH, 1988. Procedure water and waste water analysis, Publication 3061.IARC (International Agency for Research on Cancer), 1983. Monographs on

Evaluation of Polynuclear Aromatic Compounds, Part 1, Chemical,Environmental, and Experimental Data.

IMST-187, 2010. Kıyı Balıkçılıgı Yönetimi ve Çevre Entegrasyonu Projesi (inTurkish).

Johansson, L., Xydas, C., Messios, N., Stoltz, E., Greger, M., 2005. Growth and Cuaccumulation by plants grown on Cu containing mine tailings in Cyprus. Appl.Geochem. 22, 101–107.

King, A.J., Readman, J.W., Zhou, J.L., 2004. Dynamic behaviour of polycyclic aromatichydrocarbons in Brighton marina, UK. Mar. Pollut. Bull. 48, 229–239.

Kucuksezgin, F., Pazi, I., Gonul, L.T., Duman, M., 2013. Distribution and sources ofpolycyclic aromatic hydrocarbons in Cilician Basin shelf sediments (NEMediterranean). Baseline/Mar. Pollut. Bull. http://dx.doi.org/10.1016/j.marpolbul.2013.01.026 (in press).

Long, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995. Incidence of adversebiological effects within ranges of chemical concentrations in marine andestuarine sediments. Environ. Manage. 19, 81–97.

Lorber, M., Cleverly, D., Schaum, J., Phillips, L., Schweer, G., Leighton, T., 1994.Development and validation of an air-to-beef food chain model for dioxin-likecompounds. Sci. Total Environ. 156 (1), 39–65.

Luo, X., Chen, S., Mai, B., Yang, Q., Sheng, G., Fu, J., 2006. Polycyclic aromatichydrocarbons in suspended particulate matter and sediments from the PearlRiver Estuary and adjacent coastal areas, China. Environ. Pollut. 139, 9–20.

MacDonald, D.D., Carr, R.S., Cader, F.D., Long, E.R., Ingeroll, C.G., 1996. Developmentand evaluation of sediment quality guidelines for Florida coastal waters.Ecotoxicology 5, 253–278.

MacDonald, D.D., Ingersoll, C.G., Berger, T.A., 2000. Development and evaluation ofconsensus-based sediment quality guidelines for freshwater ecosystems. Arch.Environ. Contam. Toxicol. 39, 20–31.

Mannino, M.R., Orecchio, S., 2008. Polycyclic aromatic hydrocarbons (PAHs) inindoor dust matter of Palermo (Italy) area: Extraction, GC–MS analysis,distribution and sources. Atmos. Environ. 42, 1801–1817.

Martins, C.C., Bícego, M.C., Figueira, R.C.L., Angelli, J.F.L., Combi, T., Gallice, W.C.,Mansur, A.V., Rocha, M.L., Wisnieski, E., Ceschim, L.M.M., Ribeiro, A.P., 2012.Multi-molecular markers and metals as tracers of organic matter inputs andcontamination status from an Environmental Protection Area in the SW Atlantic(Laranjeiras Bay, Brazil). Sci. Total Environ. 417–418, 158–168.

Maskaoui, K., Hu, Z., 2009. Contamination and ecotoxicology risks of polycyclicaromatic hydrocarbons in Shantou coastal waters, China. Bull. Environ. Contam.Toxicol. 82, 172–178.

Menzie, C.A., Potocki, B.B., Santodonato, J., 1992. Exposure to carcinogenic PAHs inthe environment. Environ. Sci. Technol. 26, 1278–1284.

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

Mostafa, A., Wade, T., Sweet, S., Al-Alimi, A., Barakat, A., 2009. Distribution andcharacteristics of polycyclic aromatic hydrocarbons (PAHs) in sediments ofHadhramout coastal area, Gulf of Aden, Yemen. J. Mar. Syst. 78, 1–8.

Nadal, M., Schuhmacher, M., Domingo, J.L., 2004. Levels of PAHs in soil andvegetation samples from Tarragona County, Spain. Environ. Pollut. 132, 1–11.

Nieva-Cano, M.J., Rubio Barroso, S., Santos Delgado, M.J., 2001. Determination ofPAHs in food samples by HPLC with fluorometric detection following sonicationextraction without sample clean-up. Analyst 126, 1326–1331.

Nwachukwu, S.C.U., 2000. Enhanced rehabilitation of tropical aquatic environmentspolluted with crude petroleum using Candida utilis. J. Environ. Biol. 21 (3), 241–250.

Nwachukwu, S.C.U., James, P., Gurney, T.R., 2001. Impacts of crude oil on thegermination and growth of cress seeds (Lepidium sp.) after bioremediation ofagricultural soil polluted with crude petroleum using ‘‘adapted’’ Pseudomonasputida. J. Environ. Biol. 22 (1), 29–36.

Orecchio, S., 2010. Assessment of polycyclic aromatic hydrocarbons (PAHs) in soil ofa Natural Reserve (Isola delle Femmine) (Italy) located in front of a plant for theproduction of cement. J. Hazard. Mater. 173 (1–3), 358–368.

Papadopoulou, D., Samara, C., 2002. Polycyclic aromatic hydrocarboncontamination and lumistox solvent extract toxicity of marine sediments inthe north Aegean sea, Greece. Environ. Toxicol. 17 (6), 556–566.

Pyatt, F.B., 1999. Comparison of foliar and stem bioaccumulation of heavy metals byCorsican pines in the mount of Olympus area of Cyprus. Ecotoxicol. Environ. Saf.42, 57–61.

Readman, J.W., Mantoura, R.F., Rhead, M.M., 1987. A record of polycyclic aromatichydrocarbon (PAH) pollution obtained from accreting sediments of the Tamarestuary, UK: evidence for non-equilibrium behaviour of PAH. Sci. Total Environ.66, 73–94.

Readman, J.W., Fillmann, G., Tolosa, I., Bartocci, J., Villeneuve, J.P., Cattini, C., Mee,D.E., 2002. Petroleum and PAH contamination of the Black sea. Mar. Pollut. Bull.44, 48–62.

Shaw, G.R., Connell, D.W., 1994. Prediction and monitoring of the carcinogenicity ofpoycyclic aromatic compounds (PACs). Rev. Environ. Contam. Toxicol. 135, 1–62.

Simpson, C.D., Mosi, A.A., Cullen, W.R., Reimer, K.J., 1998. Composition anddistribution of polycyclic aromatic hydrocarbon contamina-tion in surficialmarine sediment from kitimat harbor Canada. Sci. Total Environ. 181, 265–278.

Tolosa, I., Mesa-Albernas, M., Alonso-Hernandez, C., 2009. Inputs and sources ofhydrocarbons in sediments from Cienfuegos bay, Cuba. Mar. Pollut. Bull. 58,1624–1634.

Tsapakis, M., Stephanou, E.G., Karakassis, I., 2003. Evaluation of atmospherictransport as a nonpoint source of polycyclic aromatic hydrocarbons in marinesediments of the Eastern Mediterranean. Mar. Chem. 80, 283–298.

Tsymbalyuk, K.K., Den’ga, Y.M., Berlinsky, N.A., Antonovich, V.P., 2011.Determination of 16 priority polycyclic aromatic hydrocarbons in bottomsediments of the Danube estuarine coast by GC/MS. Geo-Eco-Marina 17, 67–72.

UNEP/IOC/IAEA, 1992. Determination of petroleum hydrocarbons in sediments,Reference Methods for Marine Pollution Studies, 20, UNEP, 75pp.

E. Darılmaz et al. / Marine Pollution Bulletin 75 (2013) 174–181 181

UNEP, 2002. Regionally based assessment of persistent toxic substances.Mediterranean regional report. Geneva, Switzerland.

US EPA (US Environmental Protection Agency), 1993. Proposed Sediment QualityCriteria for the Protection of Benthic Organism. PA-882-R-93-012, EPA-882-R-93-013, EPA-882-R-93–014. Springer, Washington.

Voutsinou-Taliadouri, F., Satsmadjis, J., 1982. Concentration of some metals in eastAegean sediments. Rev. Int. Oceanogr. Mediterr. 66–67, 71–76.

Yan, W., Chi, J., Wang, Z., Huang, W., Zhang, G., 2009. Spatial and temporaldistribution of polycyclic aromatic hydrocarbons (PAHs) in sediments fromDaya Bay, South China. Environ. Pollut. 157, 1823–1830.

Yang, H., Tanaka, K., Shinada, M., 1998. On the equilibrium structure of MgC2 andAlC2. J. Mol. Struct. (Theochem) 422 (1–3), 159–165.

Yang, G.P., 2000. Polycyclic aromatic hydrocarbons in the sediments of the SouthChina Sea. Environ. Pollut. 108, 163–171.

Yu, H., 2002. Environmental carcinogenic polycyclic aromatic hydrocarbons:photochemistry and phototoxicity. J. Environ. Sci. Health C 20, 149–183.

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

Yükselen, M.A., Alpaslan, B., 2001. Leaching of metals from soil contaminated bymining activities. J. Hazard. Mater. B87, 289–300.

Yükselen, M.A., 2002. Characterization of heavy metal contaminated soils inNorthern Cyprus. Environ. Geol. 42, 597–603.

Zhang, W.H., Wei, C.H., Feng, C.H., Yu, Z., Ren, M., Yan, B., Peng, P.G., Fu, J.M., 2011.Distribution and health-risk of polycyclic aromatic hydrocarbons in soils at acoking plant. J. Environ. Monit. 13, 3429–3436.

Zhou, J.L., Fileman, T.W., Evans, S., Donkin, P., Llewellyn, C., Readman, J.W.,Mantoura, R.F.C., Rowland, S.J., 1998. Fluoranthene and pyrene in thesuspended particulate matter and surface sediments of the Humber Estuary,UK. Mar. Pollut. Bull. 36, 587–597.