Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf...

15
Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf of Oman Imma Tolosa, Stephen J. de Mora * , Scott W. Fowler, Jean-Pierre Villeneuve, Jean Bartocci, Chantal Cattini Marine Environment Laboratory, International Atomic Energy Agency, 4 Quai Antoine 1 er , MC 98000, Principality of Monaco, Monaco Abstract The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biota and coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels of total petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low compared to world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCO oil refinery in Bahrain, having concentrations of 779 lgg 1 total petroleum hydrocarbon equivalents and 6.6 lgg 1 P PAHs, can they be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalves around Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicated that the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCO refinery that contained substantial concentrations of carcinogenic PAH combustion products. Ó 2005 Elsevier Ltd. All rights reserved. Keywords: Biota; Sediments; Pollution; Petroleum hydrocarbons; PAHs 1. Introduction The Gulf, also known as the Arabian Gulf or Persian Gulf, represents a highly stressful environment due to a combination of both prevailing natural conditions and development pressures along its coastline. The Gulf re- gion has approximately two-thirds of the worldÕs proven oil reserves and the eight riparian states (Iran, Iraq, Kuwait, Bahrain, Qatar, Saudi Arabia, UAE and Oman) currently account for approximately one-fourth of the worldÕs oil production (Khan, 2002). Problems associ- ated with oil pollution and non-living resources appear to be of greater significance in the Gulf compared with other regions (Munawar et al., 2002). This region has undergone considerable development, and consequently urbanization, industrialization, port areas and refineries have become major sources of pollution to the marine environment. Also, a combination of tanker traffic and either accidental or intentional spills have prevailed. The spill that took place during the 1991 Gulf War is only one of three major events (Fayad et al., 1996). A significant number of studies in the Gulf has looked at petroleum hydrocarbons, mainly with respect to deter- mining concentration, composition and degradation just after the 1991 oil spill (Al-Lihaibi and Al-Omran, 1996; Al-Lihaibi and Ghazi, 1997; Banat et al., 1998; Fowler et al., 1993; Massoud et al., 1998; Massoud et al., 1996; Readman et al., 1996; Readman et al., 1992; Saeed et al., 1996). These investigations provided evidence that firstly, the oil spill was restricted to the Saudi Arabian coastline within 400 km from the point of spillage and 0025-326X/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.marpolbul.2005.06.029 * Corresponding author. Tel.: +377 97 97 72 72; fax: +377 97 97 72 76. E-mail address: [email protected] (S.J. de Mora). www.elsevier.com/locate/marpolbul Marine Pollution Bulletin 50 (2005) 1619–1633

Transcript of Aliphatic and aromatic hydrocarbons in marine biota and coastal sediments from the Gulf and the Gulf...

www.elsevier.com/locate/marpolbul

Marine Pollution Bulletin 50 (2005) 1619–1633

Aliphatic and aromatic hydrocarbons in marine biotaand coastal sediments from the Gulf and the Gulf of Oman

Imma Tolosa, Stephen J. de Mora *, Scott W. Fowler, Jean-Pierre Villeneuve,Jean Bartocci, Chantal Cattini

Marine Environment Laboratory, International Atomic Energy Agency, 4 Quai Antoine 1er, MC 98000, Principality of Monaco, Monaco

Abstract

The composition and spatial distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) were investigated in biotaand coastal sediments from four countries surrounding the Gulf (Bahrain, Qatar, United Arab Emirates and Oman). The levels oftotal petroleum hydrocarbons (TPH), aliphatic unresolved mixture and PAHs in sediments and biota were relatively low comparedto world-wide locations reported to be chronically contaminated by oil. Only in the case of the sediments collected near the BAPCOoil refinery in Bahrain, having concentrations of 779 lg g�1 total petroleum hydrocarbon equivalents and 6.6 lg g�1 PPAHs, canthey be categorized as chronically contaminated. Some evidence of oil contamination was also apparent in sediments and bivalvesaround Akkah Head and Abu Dhabi in the UAE, and near Mirbat in Oman. Contaminant patterns in sediments and biota indicatedthat the PAHs were mainly from fossil sources, with the exception of the high PAH concentrations in sediments near the BAPCOrefinery that contained substantial concentrations of carcinogenic PAH combustion products.� 2005 Elsevier Ltd. All rights reserved.

Keywords: Biota; Sediments; Pollution; Petroleum hydrocarbons; PAHs

1. Introduction

The Gulf, also known as the Arabian Gulf or PersianGulf, represents a highly stressful environment due to acombination of both prevailing natural conditions anddevelopment pressures along its coastline. The Gulf re-gion has approximately two-thirds of the world�s provenoil reserves and the eight riparian states (Iran, Iraq,Kuwait, Bahrain, Qatar, Saudi Arabia, UAE and Oman)currently account for approximately one-fourth of theworld�s oil production (Khan, 2002). Problems associ-ated with oil pollution and non-living resources appearto be of greater significance in the Gulf compared with

0025-326X/$ - see front matter � 2005 Elsevier Ltd. All rights reserved.doi:10.1016/j.marpolbul.2005.06.029

* Corresponding author. Tel.: +377 97 97 72 72; fax: +377 97 97 7276.

E-mail address: [email protected] (S.J. de Mora).

other regions (Munawar et al., 2002). This region hasundergone considerable development, and consequentlyurbanization, industrialization, port areas and refinerieshave become major sources of pollution to the marineenvironment. Also, a combination of tanker traffic andeither accidental or intentional spills have prevailed.The spill that took place during the 1991 Gulf War isonly one of three major events (Fayad et al., 1996). Asignificant number of studies in the Gulf has looked atpetroleum hydrocarbons, mainly with respect to deter-mining concentration, composition and degradation justafter the 1991 oil spill (Al-Lihaibi and Al-Omran, 1996;Al-Lihaibi and Ghazi, 1997; Banat et al., 1998; Fowleret al., 1993; Massoud et al., 1998; Massoud et al.,1996; Readman et al., 1996; Readman et al., 1992; Saeedet al., 1996). These investigations provided evidence thatfirstly, the oil spill was restricted to the Saudi Arabiancoastline within 400 km from the point of spillage and

1620 I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633

secondly, the contamination had degraded within somefew months due to weathering processes.

In 1994, two tankers collided spilling 16,000 tonnes ofIranian crude oil into the Gulf of Oman. Despite dam-age caused to the marine environment, studies demon-strated a significant decrease in contamination levels,almost returning to normal conditions within eightmonths of the accident (Shriadah, 1998; Shriadah,2000). The recovery was likely accelerated as a resultof the physical characteristics of the region and self-purification processes. Enhanced degradation of thepetroleum products was inferred due to the existenceof microorganisms acclimated to oil pollution, and tothe high ambient temperatures in the Gulf causing anincrease in evaporation and photo-oxidation rates.

The regional monitoring and surveillance programmeorganized by ROPME has generated reliable, long-termdata for the Gulf. The aim of this survey undertaken in2000–2001 was to screen for trace inorganic (de Moraet al., 2003, 2004) and organic contaminants (de Moraet al., 2005) in key coastal areas from the Gulf and theGulf of Oman, and to compare the results with earliersurveys in the same areas. The present work evaluatesmarine contamination of petroleum hydrocarbons inthe coastal zones of UAE, Qatar, Bahrain and Omanbased on the quality of sediment and some local seafoodspecies. Sediments are one of the many environmentalcompartments in which oil pollution accumulates.Therefore, sediments can hold and release pollutantscausing detrimental effects to biota long after the initialinput of pollution has ceased. These contaminants mightbe released slowly and be bioaccumulated in organismsthat dwell in and around the sediment. Seafood re-sources are of vital importance to the Gulf States andto date only limited efforts have been made to evaluateseafood quality. Therefore, information on seafood con-tamination is sparse. For the most part, studies havefocussed on potential petroleum hydrocarboncontamination of the fisheries following the massive oilspill during the 1991 Gulf War (Al-Majed et al., 1998;Al-Yakoob et al., 1993; Fayad et al., 1996; Fowleret al., 1993; Krahn et al., 1993; Saeed et al., 1995; SenGupta et al., 1993). More recent data on concentrationslevels of petroleum hydrocarbons in biota is needed toassess their contamination risk for human consumption.Overall, the results presented here for sediments andbiota contribute to the regional database for the Gulfand the Gulf of Oman.

2. Methods

2.1. Sample collection

Marine samples were collected in the ROPME SeaArea (RSA), which covers the entire Gulf and the Gulf

of Oman. In general, all sampling procedures were car-ried out according to internationally recognized guide-lines (UNEP, 1991). The locations in Bahrain, Oman,Qatar and the United Arab Emirates for the collectionof sediments and biota are shown in Fig. 1. Samplingdates and locations for the collection of sediments aregiven in Table 1. The sediments were stored frozen at�18 �C in aluminium cartons prior to analyses. Table2 provides information regarding the type of biologicalspecimens and from where they were obtained.

For bivalves, the soft parts from 1 to 18 individualswere dissected and drained of excess liquid. For fish,100–300 g of dorsal muscle from a single individualwas dissected for the sample. Fish liver tissue was alsoremoved and prepared for analysis in some cases. Ana-lyses of fish reported here, including the two samplesfrom Quriyat, relate to individual fish rather than repli-cate determinations. All biota samples were stored inglass bottles before freezing at �18 �C until subse-quently analysed.

2.2. Pre-treatment of sediments

Following freeze-drying, samples were sieved throughvibrating stacked stainless steel sieves with mesh sizesfrom 250 lm to 1000 lm. Sediments were then homoge-nized prior to extraction. In some cases, an aliquot foreach sample was taken in order to perform TOC andgrain size analyses. Various internal standards wereadded to the sediments for quantifying the overall recov-ery of the analytical procedures: n-C19-d40 and n-C24-d50for the aliphatic hydrocarbon fraction; naphthalene-d8,anthracene-d10, pyrene-d10 and perylene-d12 for the aro-matic hydrocarbon fraction.

Samples were Soxhlet extracted for 8 h into 250 ml ofhexane:methylene chloride (1:1, v/v). A sulphur removalprocedure was performed using activated elemental cop-per in order to avoid sulphur interferences when usinggas chromatography. The Extractable Organic Matter(EOM) was determined by evaporating a measuredsmall volume of this extract on the pan of an electrobal-ance. The final extracts were then separated into two ali-quots: 1/3 for hydrocarbons, and 2/3 for chlorinatedhydrocarbon analyses.

For the hydrocarbon measurements, the extract waspassed through a silica/alumina column in which the sil-ica and alumina were activated first at 200 �C for 4 hand partially deactivated with 5% water. The chroma-tography column was prepared by slurry packing10 ml of silica, then 10 ml of alumina and finally 1 g so-dium sulphate was added to the surface to avoid distur-bance of the top layer when pouring the solvent. Elutionwas performed using 20 ml of hexane to yield the firstfraction (containing the aliphatic hydrocarbons), then30 ml of hexane:methylene chloride (90:10) and followedby 20 ml of hexane:methylene chloride (50:50). These

Fig. 1. Location of all sampling sites for sediments (s) and biota (·).

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1621

two eluents containing the aromatic hydrocarbons(PAH) were combined for analysis.

Appropriate blanks were analysed with each set ofsamples, together with sediment reference material(IAEA-383 for Qatar and UAE sediments and IAEA408 for sediments from Bahrain and Oman). Bothsediments have certified concentrations of chlorinatedcompounds and hydrocarbons (Carvalho et al., 1999;Villeneuve et al., 2000). The concentration values ofthe target compounds always fell within the 95% confi-dence interval of the assigned reference value for con-centrations of selected hydrocarbons. The precision ofthe measurements obtained through replicates of the ref-erence materials was better than 10% for all targetcompounds.

2.3. Pre-treatment of biota

Sub-samples of the biota (fish or shellfish) were trans-ferred to pre-cleaned glass jars and freeze-dried for 4–5

days. The sample was then re-weighed to determinethe dry/wet ratio and ground using a porcelain mortar.Extractable Organic Matter (EOM) was determined asdescribed previously for the sediments. For hydrocar-bon analyses, various internal standards (n-C18:1, n-C32

and n-C24-d50 for the aliphatic hydrocarbon fraction;9,10 dihydroanthracene for the aromatic hydrocarbonfraction) were added to the freeze-dried sample forquantifying the overall recovery of the analyticalprocedures.

Samples were Soxhlet extracted for 8 h with 250 ml ofmethanol. The extracts were then saponified by adding20 ml of 0.7 M KOH and 30 ml of water (both pre-extracted) and refluxing for 2 h. The resulting mixturewas transferred into a separatory funnel and extracted3 times with hexane (once with 90 ml, twice with50 ml). Then the extracts were combined, filteredthrough glass wool and dried with anhydrous sodiumsulfate. The extracts were concentrated by rotary evap-oration down to 15 ml, and then further concentrated

Table 2Biota sampling sites in Qatar, UAE, Bahrain and Oman

Country Site Site no. Coordinates Species Common name

Bahrain Badaiya 24 26�12 0N, 50�24 0E Epinephelus coioides Orange spotted grouperBahrain Fasht Al Adham 25 26�03 0N, 50�43 0E Epinephelus coioides Orange spotted grouperOman Quriyat 26 23�20 0N, 59�06 0E Epinephelus coioides Orange spotted grouperQatar Al Khawr 27 25�40 0N, 51�38 0E Epinephelus coioides Orange spotted grouperQatar Doha 3 25�20.2570N, 51�34.4560E Epinephelus coioides Orange spotted grouperQatar Umm Said 1 24�56.3980N, 51�37.7090E Epinephelus coioides Orange spotted grouperUAE Al Marfa 8 24�06.2000N, 53�29.2070E Epinephelus coioides Orange spotted grouperUAE Dhannah 28 24�12 0N, 52�39 0E Epinephelus coioides Orange spotted grouperOman Raysut Port Area 21 16�59.0 0N, 54�01.0 0E Lethrinus nebulosus Spangled emperorOman Sagar 29 16�32 0N, 53�43 0E Lethrinus nebulosus Spangled emperorQatar Al Dakhira 30 25�45 0N, 51�40 0E Lethrinus nebulosus Spangled emperorUAE Al Marfa 8 24�06.2000N, 53�29.2070E Lethrinus nebulosus Spangled emperorUAE Dhannah 28 24�12 0N, 52�39 0E Lethrinus nebulosus Spangled emperor

Qatar Ras Al Nouf 5 25�37.4270N, 51�32.8890E Circentia callipyga Venus clamsBahrain North of Meridien Hotel 15 26�16.0560N, 50�31.4230E Pinctada radiata Pearl OystersBahrain BAPCO refinery 13 26�06.1380N, 50�37.7730E Pinctada radiata Pearl OystersUAE Akkah Head 10 25�28.9770N, 56�21.9400E Pinctada radiata Pearl OystersUAE Jebel Ali 6 25�06.9910N, 55�09.1150E Pinctada radiata Pearl OystersUAE Abu Dhabi 7 24�27.9570N, 54�18.2940E Pinctada radiata Pearl OystersUAE Abu Dhabi 31 24�29.9170N, 54�21.6680E Spondylus sp. Rock ScallopsUAE Jebel Ali 6 25�06.9910N, 55�09.1150E Pinna muricata Pen ShellsUAE Akkah Beach 11 25�28.7210N, 56�21.7700E Saccostrea cucullata Rock OystersOman Al Sawadi 23 23�47.2600N, 57�47.6330E Saccostrea cucullata Rock OystersOman Hilf 19 20�38.1030N, 58�51.8130E Saccostrea cucullata Rock OystersOman Mirbat 22 16�58.500N, 54�41.500E Saccostrea cucullata Rock OystersOman Ras Al Hamra 17 23�38.3630N, 58�29.4950E Saccostrea cucullata Rock OystersOman Ras Al Yei 18 20�31.3480N, 58�57.0740E Saccostrea cucullata Rock Oysters

Table 1Sediment sampling sites in Qatar, UAE, Bahrain and Oman

Country Station Site no. Date Location

Qatar Umm Said 1 28/3/00 24�56.3980N, 51�37.7090EDukhan 2 29/3/00 25�21.0690N, 50�45.7180EDoha 3 29/3/00 25�20.2570N, 51�34.4560ERas Laffan 4 30/3/00 25�47.0000N, 51�35.7750ERas Al Nouf 5 30/3/00 25�37.4270N, 51�32.8890E

UAE Jebel Ali 6 1/4/00 25�06.9910N, 55�09.1150EAbu Dhabi 7 1/4/00 24�27.9570N, 54�18.2940EAl Marfa 8 2/4/00 24�06.2000N, 53�29.2070EAl Ruweis (Al Dhannah) 9 2/4/00 24�09.8420N, 52�38.8870EAkkah Head, ‘‘Three Rocks’’ north of Bidya 10 4/4/00 25�28.9770N, 56�21.9400EAkkah Beach, South of ‘‘Three Rocks’’ 11 4/4/00 25�28.7210N, 56�21.7700E

Bahrain Askar 12 23/11/00 26�03.1020N, 50�37.9590EBAPCO Refinery 13 23/11/00 26�06.1380N, 50�37.7730EJasra 14 25/11/00 26�11.0980N, 50�26.5230ENorth of Meridien Hotel 15 25/11/00 26�16.0560N, 50�31.4230E

Oman Mina Al Fahal (PDO Beach) 16 27/7/01 23�37.9780N, 58�30.6930ERas Al Yei (Masirah east coast) 18 28/7/01 20�31.3480N, 58�57.0740EHilf (Masirah west coast) 19 29/7/01 20�38.1030N, 58�51.8130EMughsayl (beach) 20 30/7/01 16�52.9560N, 53�47.6050ERaysut Port Area (east beach) 21 31/7/01 16�59.00N, 54�01.00EAl Sawadi 23 01/8/01 23�47.2600N, 57�47.6330E

1622 I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633

to about 5 ml under a gentle flow of clean nitrogen. Fi-nally, the extract was cleaned up and fractionated by

passing it through a silica/alumina column as describedfor the sediments.

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1623

Appropriate blanks were analysed with each set ofbiota samples, together with mussel reference material(IAEA-142) for quality assurance/quality control. Theanalytes of interest were within the 95% confidenceinterval of the median reference value (Villeneuveet al., 2004). Precision of measurements, determinedfrom replicate measurements of the reference materialwas better than 10% for all target compounds.

2.4. UVF Protocols

UV fluorescence was used to quantify the total petro-leum hydrocarbon (TPH) content in sediments andbiota. Emission scans and synchronous excitation/emis-sion scans were recorded to evaluate the relative fluores-cence and to characterize the aromatic hydrocarbons.Standard response curves of fluorescence intensityversus concentration were generated for Kuwait crude(ROPME) oil and for the standard aromatic hydrocar-bon, chrysene. Samples were diluted in order to give areading within the linear calibration range of the fluo-rimeter. Conditions of the fluorimeter were adjusted asfollows. For the first procedure, a fixed excitation wave-length of 310 nm was used; the emission wavelength waseither 360 nm for single measurements or scanned from320 nm to 550 nm. In the second procedure that wasused for qualitative characterization, the excitationwavelength was scanned from 237 nm to 527 nm andthe emission wavelength was scanned from 260 nm to550 nm, with a Dk = 23 nm.

2.5. Instrumental analyses of petroleum hydrocarbons

The quantification of individual hydrocarbon com-pounds was carried out using a Carlo Erba 8000 seriesgas chromatograph with a flame ionization detector(FID) and on-column injection. The carrier gas washelium at a flow rate of 1.1 ml min�1. The column usedwas: HP-Ultra 2 (crosslinked 5% Ph Me Silicone; 25m · 0.32 mm i.d. · 0.17 lm) and the temperature pro-gramme was initially 60 �C for 2 min, 60–290 �C at3 �C min�1, and then 290 �C for 25 min. The detectortemperature was set at 300 �C. It should be noted thatthe sum of all aliphatic and all aromatic hydrocarbonsmeasured by gas chromatography provides a measure-ment of the total hydrocarbon concentration.

The polycyclic aromatic hydrocarbons were also ana-lysed in a Hewlett–Packard 5989B MS ‘‘Engine’’ usingselective ion monitoring (SIM) to enhance sensitivity.The quantification was performed using ions 128, 142,152, 154, 156, 166, 178, 184, 192, 198, 202, 216, 228,252, 276, 278. Electron impact (EI) mass spectra wereobtained at 70 eV of ionization energy. Helium as thecarrier gas at 1.5 ml min�1 and a HP-5 MS (cross-linked5% Ph Me Silicone) column (30 m · 0.25 mm i.d. ·0.25 lm film thickness) were used. Temperatures were:

injector 270 �C, transfer line 280 �C, ion source 240 �Cand analyser 100 �C. The oven temperature programmewas 60 �C initially, 60–100 �C at 10 �C min�1, 100–285 �C at 4 �C min�1, and then 285 �C for 20 min.

The sum of all PAH compounds (P

PAHs) includesthe parent and some substituted compounds (naphthalene;1-methylnaphathlene, 2-methylnaphtahelene, 2,6-dimethyl-naphthalene; acenaphthylene; biphenyl, acenaphthene,fluorene, dibenzothiophene; 1-methyldibenzothiophene,4-methyldibenzothiophene; phenanthrene; anthracene;2-methylphenanthrene, 1-methylphenanthrene; fluor-anthene; pyrene; 1-methylpyrene; benzo[a]anthracene;chrysene; triphenylene; benzo[b,j,k]fluoranthenes;benzo[e]pyrene; benzo[a]pyrene; perylene; indeno[1,2,3-cd]pyrene; benzo[ghi]perylene; dibenz[a,h]anthracene).Parent PAHs includes the three to six ring parent poly-cyclic aromatic hydrocarbons (m/z: 178 (phenanthrene/anthracene), 202, (pyrene/fluoranthene); 228 (benzo[a]-anthracene/chrysene); 252 (benzofluoranthenes, benzo[e]-pyrene, benzo[a]pyrene; 276 (indeno[1,2,3-cd]pyrene,benzo[ghi]perylene)).

3. Results and discussion

3.1. Sediments

The total organic carbon (TOC) and concentration ofdifferent classes of hydrocarbons and diagnostic param-eters at each sediment-sampling site are summarized inTable 3. Except for the site at Abu Dhabi, surface sedi-ments collected in the UAE were generally characterizedby a low content of TOC (0.10–0.39%). In contrast, sed-iments from Bahrain exhibited the highest levels ofTOC, with values from 3.25% to 5.08%. Qatar andOman showed intermediate values of TOC ranging from0.56% to 2.21%.

Trends in both total petroleum hydrocarbons andaliphatic hydrocarbons have been used to identify‘‘hot spots’’ in the four countries. In the UAE, onlythe area around Akkah Head and Akkah Beach onthe east coast in the Gulf of Oman showed indicationsof some oil contamination with 73–100 lg g�1 totalpetroleum hydrocarbons as ROPME oil equivalents.These total petroleum concentration levels are higherthan those measured eight months after the 1994 spillnear Akkah Head (11–17 lg g�1 as Iranian crude oil;Shriadah, 1998), but they fell in the range reportedfor near-shore marine sediments of the UAE in 1994,namely 0.4–212 lg g�1 (Abu-Hilal and Khordagui,1994). They are significantly lower that those reportedfrom coastal areas of the ROPME Sea Area that wereaffected by the Gulf War Spill (Fowler et al., 1993;Readman et al., 1996) and similar to those measuredin identical sites from Jebel Ali in 1991 (Fowleret al., 1993).

Table 3Total organic carbon, hydrocarbon concentrations and diagnostic parameters in sediments from the Gulf and the Gulf of Oman

TOC (%) TPH equiv.ROPME oil(lg g�1 dry wt.)

TPH equiv.Chrysene(lg g�1 dry wt.)

TPH equiv.GC-FID(lg g�1 dry wt.)

UCM aliphatics(lg g�1 dry wt.)

Pn-C14–C34

(lg g�1 dry wt.)

PHs

(n �1 dry wt.)parent

PPAHs

(lg g�1 dry wt.)UCM/n-alk

UAE

Jebel Ali 0.39 0.84 0.09 5.00 4.50 0.28 .6 1.15 16.1Abu Dhabi 1.53 0.28 0.03 7.30 6.50 0.15 .9 0.43 43.3Al Marfa 0.10 0.41 0.044 3.50 3.40 0.038 .39 0.15 89.5Al Ruweis 0.18 0.51 0.055 0.10 <2.1 0.065 .66 0.11Akkah Head 0.34 100 15.0 12.0 10.0 1.10 .4 4.00 9.1Akkah Beach 0.12 73 9.70 16.4 9.00 0.45 .5 1.80 20.0

Qatar

Umm Said 1.20 45 6.00 84.0 66.0 0.92 65.8 71.7Dukhan 0.96 7.1 1.70 31.9 4.60 1.80 29.0 2.6Doha 0.95 16 2.40 45.0 35.0 1.10 12.3 31.8Ras Laffan 1.14 2.9 0.66 2.20 2.20 0.07 .55 0.13 31.4Ras Al Nouf 1.58 64 8.50 48.0 7.90 3.30 .3 1.99 2.4

Bahrain

Askar 3.39 59 6.40 41.8 34.0 0.67 10 979 50.7BAPCO Refinery 5.08 1600 170 779 670 4.30 66 6140 155.8Jasra 3.25 25 2.70 59.0 15.0 3.90 45.6 3.8North of Meridien Hotel 4.84 3.0 0.32 16.6 4.90 1.00 11.4 4.9

Oman

Al Sawadi 2.12 11 1.30 7.60 3.30 0.24 0.70 13.8Mina al Fahal 2.21 8.6 1.00 4.10 3.80 0.11 .1 1.33 34.5Ras Al Yei 1.23 1.3 0.16 0.05 <1.1 0.049 .5 0.03Hilf 0.56 2.2 0.27 5.10 2.40 0.14 18.2 17.1Raysut Port Area 1.64 1.9 0.22 3.20 3.00 0.059 .7 0.47 50.8Mughsayl Beach 0.58 0.41 0.055 0.01 <1.1 0.013 .6 0.02

1624I.Tolosa

etal./Marin

ePollu

tionBulletin

50(2005)1619–1633

PAg g

100096

92342005

00004813

19723071

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1625

In Qatar, total petroleum hydrocarbons as ROPMEoil equivalents were greatest at Umm Said (45 lg g�1)and Ras Al Nouf (64 lg g�1). In Bahrain, only sedi-ments collected offshore from the BAPCO refinery areashowed signs of substantial oil contamination with con-centrations of 1600 lg g�1 for ROPME oil equivalents.Petroleum levels at the Askar site were similar to thosefound in 1991 (Fowler et al., 1993).

Levels of total petroleum hydrocarbons were gener-ally lower in Omani sediments than in those from theother three countries (Table 3). The maximum concen-tration of total petrol hydrocarbons, 11 lg g�1 dryweight as ROPME oil equivalents at Al Sawadi, wassimilar to those measured in 1991 in some of the sameareas of Oman that were not impacted by oil contamina-tion from the Gulf War (Fowler et al., 1993). On theother hand, the TPH concentrations measured at Minaal Fahal in Oman are one order of magnitude lower thanthose reported in 1990 (Badawy et al., 1993), indicatingthat the sediment analysed in the present study was notimpacted by the oil terminal and refinery plant at thissite.

According to some guidelines for pollution levels inbottom sediments of the Gulf (Massoud et al., 1996),concentration levels <15 lg g�1 as Chrysene equivalentsare considered to be the natural background level in thisregion. This threshold value was only surpassed in thesediment from Akkah Head in UAE and was widelyexceeded by the sediments from BAPCO refinery(170 lg g�1).

The total hydrocarbon concentration, as the sum oftotal aliphatic and total aromatic hydrocarbons mea-sured by gas chromatography, ranged from 0.05 to779 lg g�1. Again, the highest amounts were observedoff the BAPCO refinery in Bahrain and at Umm Said

Akkah Head UAE

0.000.501.001.502.002.503.003.50

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

-1 -1-1

BAPCO RefineryBAHRAIN

0200400600800

10001200140016001800

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

-1

Fig. 2. Distribution of selected PAHs in representative sediment samples fromC1–N, monomethylnaphthalenes, C2–N, 2,6 dimethylnaphthalene; P:1-methylphenanthrene; D: dibenzothiophene; C1–D: 1-methyldibenzothiopC1–Py: 1-methylpyrene; BaA: benzo[a]anthracene; C: chrysene + triphebenzo[e]pyrene; BaP: benzo[a]pyrene; Per: perylene; IP: indeno[1,2,3-cd]pyre

in Qatar. Whereas total hydrocarbon concentrations>500 lg g�1 are generally indicative of significant pol-lution (e.g. BAPCO refinery), values <10 lg g�1 areconsidered to denote unpolluted sediments (Volkmanet al., 1992). The levels of petroleum hydrocarbons re-ported here were relatively low compared to those atworld-wide locations reported to be chronically contam-inated by oil, such as 60–646 lg g�1 in Hong Kong(Hong et al., 1995), 35–2900 lg g�1 in the New YorkBight (Farrington and Tripp, 1977) and 11–6900 lg g�1

along the oil-impacted coastline of Saudi Arabia afterthe Gulf War (Readman et al., 1996). The only samplethat was chronically contaminated was the sediment col-lected near the BAPCO oil refinery in Bahrain. There,the concentration, 779 lg g�1, was similar to those mea-sured in Saudi Arabian sediments contaminated by the1991 spill (Fowler et al., 1993).

The concentrations of the unresolved complex mix-ture (UCM) at most of the sites were typically low(UCM <10 lg g�1) and comparable to coastal environ-ments distant from hydrocarbon inputs, such as in theEastern Mediterranean (Gogou et al., 2000), the coast-line of Ukraine in the Black Sea (Readman et al.,2002) and in deep-basin sediments from the Northwest-ern Mediterranean Sea (Tolosa et al., 1996). This back-ground value of 10 lg g�1 was exceeded only at AkkahHead and Akkah Beach in UAE; Umm Said and Dohain Qatar; and Askar, the BAPCO Refinery, and Jasra inBahrain. Higher values up to 670 lg g�1 were measurednear the industrial and refinery complex of BAPCO inBahrain. An important biodegradation of petroleum-related inputs at this site was confirmed by the high ratioof UCM/n-alkanes (155), since values >10 are indicativeof chronic/degraded petroleum contamination (Sim-oneit, 1982). In contrast, the weathering index of the

Umm SaidQATAR

0

5

10

15

20

25

30

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

HilfOMAN

00.5

11.5

22.5

33.5

44.5

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

UAE, Qatar, Bahrain and Oman. Compound codes: N: naphthalene;phenanthrene; A: anthracene; C1–P: 2-methylphenanthrene andhene and 4-methyldibenzothiophene; Fl: fluoranthene; Py: pyrene;nylene; BFl: benzo[b,j,k]fluoranthenes + benzo[a]fluoranthene; BeP:ne; BP: benzo[ghi]perylene.

Table 4Total lipid content and hydrocarbon concentrations levels in bivalves from the Gulf and the Gulf of Oman

Biota Lipid content(mg g�1 dry wt.)

TPH equiv.ROPME oil(lg g�1 dry wt.)

TPH equiv.Chrysene(lg g�1 dry wt.)

TPH equiv.GC-FID(lg g�1 dry wt.)

UCMaliphatics(lg g�1 dry wt.)

Pn-C 34

(lg g� y wt.)

PPAHs

(ng g�1 dry wt.)parent

PPAHs

(ng g�1 dry wt.)

UAE

Jebel Ali Pearl oysters 39 5.5 0.73 30.8 22 1.2 85.7 38.1Pen shells 28 5.4 0.71 49.1 38 1.2 65.3 62.4

Abu Dhabi Rock scallops 21 8.6 0.98 35.7 23 0.86 63.4 43.3Pearl oysters 41 35 4.20 237 120 1.8 251 115

Akkah Head‘‘Three Rocks’’

Pearl oysters 32 14 1.20 25.6 12 0.81 36.6 18.9

Akkah Beach Rock oysters 57 290 35.0 219 130 5.3 846 211

Qatar

Ras Al Nouf Clams 25 0.86 0.19 39.5 21 1.2 105 52.9

Bahrain

BAPCO Refinery Pearl oysters 28 51 7.10 98.0 62 1.6 105 30.3North ofMeridien Hotel

Pearl oysters 27 5.2 0.86 38.5 18 2.1 58.3 15.6

Oman

Al Sawadi Rock oysters 57 26 3.30 52.0 32 1.9 75.8 37.5Ras Al Hamra Rock oysters 48 13 1.60 39.2 24 1.7 26.0 9.80Ras Al Yei Rock oysters 46 9.6 1.20 23.2 9.1 1.9 17.0 5.89Hilf Rock oysters 49 16 2.00 57.0 40 2.1 38.2 26.1Mirbat Rock oysters 57 99 12.0 130 76 6.3 173 45.9

1626I.Tolosa

etal./Marin

ePollu

tionBulletin

50(2005)1619–1633

14–C1 dr

Abu Dhabi UAE

010203040506070

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

-1

Pearl oysters BAPCO RefineryBAHRAIN

0

5

10

15

20

25

30

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

-1

Pearl oysters

MirbatOMAN

01020304050607080

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

-1

Rock oystersAkkah BeachUAE

0

100

200

300

400

500

NC1-N C2-N P A

C1-P DC1-D Fl Py

C1-Py

BaA C BFlBeP BaP Per IP BP

ng g

-1

Rock oysters

Fig. 3. Distribution of selected PAHs in representative bivalve samples from UAE, Bahrain and Oman. Compound codes as those described inFig. 2.

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1627

most contaminated sites of the UAE, e.g. Akkah Headand Akkah Beach, were relatively low and indicativeof a more recent input of oil. These findings suggesteither that any residual oil contamination originatingfrom the spill in 1994 has been completely bioremedi-ated or that these sediment sites were not substantiallyaffected by this oil spill.

PAH concentrations given in Table 3 generally mir-rored those found for the aliphatic unresolved complexmixture and the total petroleum hydrocarbon concen-tration. Most values were exceptionally low, except forthe sediments near the BAPCO refinery that contained6.6 lg g�1 PPAHs—one of the highest values reportedso far in the RSA. Moreover, these high PAH concen-tration levels exceeded the NOAA sediment qualityguideline value for the effects range low (ERL) of4000 ng g�1 dry weight (Long et al., 1995). However, ifthe highly contaminated sites from Bahrain are ex-cluded, PAH concentration levels were <100 ng g�1,which is typical of locations distant from contaminationinputs (Baumard et al., 1998). Compared to the PAHsmeasured here in sediments from Oman, much higherPAH concentrations (400–790 ng g�1) were reportedin sediment samples collected in 1990 from the Minaal Fahal area, where an oil terminal and refinery plantare located (Badawy et al., 1993).

Representative PAH sedimentary patterns for thefour different countries are shown in Fig. 2. A typicalprofile of petrogenic PAHs, with a predominance ofnaphthalene and alkyl-substituted phenanthrenes anddibenzothiophenes over their respective parent com-pounds, was observed at the most contaminated sitesin UAE. In Qatar, a more physical weathering of thepetrogenic profile was also indicated by the loss of themore volatile PAHs, naphthalene and alkylnaphtalenes.Pyrolitic sources, evident by the dominance of theunsubstituted PAH over their alkylated homologues

and the prevalence of 4–6 ring PAH over the low molec-ular weight 2–3 ring PAHs, were extremely high at thesite offshore from the BAPCO refinery and at Askar inBahrain. Another site with a mixture of combustion-derived and petrogenic PAHs was at Hilf on MasirahIsland in Oman.

The extremely high concentrations of pyrolytic PAHsfound at Askar and BAPCO in Bahrain are certainlysome of the highest concentrations reported to date inthe region. Such findings warrant continued monitoringat these sites. Likewise, a continued watch on the areaaround Akkah Head on the east coast of UAE shouldbe maintained in order to follow any changes in theoil contamination.

3.2. Bivalves

The sampling locations for the bivalves are listed inTable 2 and the hydrocarbon concentrations are sum-marized in Table 4. The concentrations ranged from0.9 to 290 lg g�1 dry weight as ROPME oil equivalents,with the highest concentration measured in rock oystersfrom Akkah Beach in the UAE. Although the sedimentsfrom Akkah Beach did not seem to have been affectedby the 1994 oil spill, the high concentrations of totalPHs in rock oysters from this site (289 lg g�1 dry weightas ROPME oil equivalents, 130 lg g�1 of UCM and845 ng g�1 PAHs) might still represent residual hydro-carbons from the 1994 oil spill that occurred in the Gulfof Oman, or just reflect chronic contamination due tothe heavy taker traffic offshore from this location.

The only other bivalves showing some indication ofoil contamination were pearl oysters from Abu Dhabiin UAE and the BAPCO refinery in Bahrain, and rockoysters from Mirbat in southern Oman (Table 4). TotalPH equivalents, UCM and total PAHs were all some-what elevated in these three oyster samples. Also

Table 5Total lipid content and concentrations of hydrocarbons in muscle fish from the Gulf and the Gulf of Oman

Lipid content(mg g�1 dry wt.)

TPH equiv.ROPME oil(lg g�1 dry wt.)

TPH equiv.Chrysene(lg g�1 dry wt.)

TPH equiv.GC-FID(lg g�1 dry wt.)

UCMaliphatics(lg g�1 dry wt.)

Pn-C14–C34

(lg g�1 dry wt.)

PPAHs

(ng g�1 dry wt.)parentP

PAHs(ng g�1 dry wt.)

UAE

Al Marfa Orange-SpottedGrouper

31 0.57 0.058 2.07 1.40 0.18 15.4 5.36

Al Marfa Spangled Emperor 22 0.53 0.067 3.40 0.77 0.17 20.5 8.31Al Dhannah Spangled Emperor 46 1.90 0.26 16.1 6.90 0.56 29.5 9.98Al Dhannah Orange-Spotted

Grouper72 0.20 0.029 4.90 0.89 0.42 22.9 14.4

Qatar

Al Khawr Orange-SpottedGrouper

19 0.51 0.061 15.9 5.80 0.28 52.4 10.3

Umm Said Orange-SpottedGrouper

16 n.a. n.a. 4.01 2.80 0.12 115 16.7

Doha Orange-SpottedGrouper

16 0.18 0.054 11.9 6.40 0.25 29.6 13.9

Al Dakhira Spangled Emperor 22 0.79 0.12 5.90 3.10 0.11 43.4 13.9

Bahrain

Bidaiya Orange-SpottedGrouper-1.6 kg

55 5.20 0.8 15.2 11.0 0.43 37.7 6.24

Bidaiya Orange-SpottedGrouper-1.15 kg

27 1.60 0.42 12.8 10.0 0.42 26.1 2.83

Fasht Al Adhm Orange-SpottedGrouper-1.26 kg

54 1.90 0.42 11.7 8.90 0.44 18.7 2.43

Fasht Al Adhm Orange-SpottedGrouper-1.03 kg

140 3.30 0.52 15.8 11.0 0.58 13.1 7.62

Oman

Quriyat Orange-SpottedGrouper-#1

98 11.0 1.50 34.0 17.0 1.50 11.8 5.40

Quriyat Orange-SpottedGrouper-#2

53 8.70 1.20 25.0 12.0 0.57 28.7 9.40

Raysut Port Area Spangled Emperor 39 3.80 0.52 10.8 7.70 0.40 6.90 3.90Sagar Spangled Emperor 35 5.30 0.79 13.5 10.0 0.33 5.60 2.30

1628I.Tolosa

etal./Marin

ePollu

tionBulletin

50(2005)1619–1633

Al Dhannah UAE

012345678

NC1-

NC2-

N P AC1-

P DC1-

D FlPy

C1-Py

BaA CBFl

BeP BaP Per IP BP

ng

g-1

Orange-spotted grouper

Al DakhiraQATAR

0

5

10

15

20

25

NC1-

NC2-

N P AC1-

P DC1-

D FlPy

C1-Py

BaA CBFl

BeP BaP Per IP BP

ng

g-1

Spangled Emperor

Raysut Port areaOMAN

0

0.2

0.4

0.6

0.8

1

1.2

1.4

NC1-

NC2-

N P AC1-

P DC1-

D FlPy

C1-Py

BaA CBFl

BeP BaP Per IP BP

ng

g-1

Spangled Emperor

BidaiyaBAHRAIN

02468

10121416

NC1-

NC2-

N P AC1-

P DC1-

D FlPy

C1-Py

BaA CBFl

BeP BaP Per IP BP

ng

g-1

Orange-spotted grouper

Fig. 4. Distribution of selected PAHs in representative fish muscle samples from UAE, Qatar, Bahrain and Oman. Compound codes as thosedescribed in Fig. 2.

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1629

noteworthy was that rock scallops from Abu Dhabiexhibited four-fold lower concentrations than the pearloysters. However, the pearl oysters were sampled nearthe flour storage silos just at the entrance to the portof Abu Dhabi where oil contamination from local portactivities is very probable. Nevertheless, the total PHconcentration of 35 lg g�1 in Abu Dhabi pearl oysterswas of the same order as concentrations (19–30 lg g�1)that have been measured in this species from the samegeneral area around the port of Abu Dhabi since 1983(Fowler, 1988). In contrast, the total PH concentration(99 lg g�1 dry weight) in the rock oysters from the moreremote area around Mirbat was approximately threetimes higher than has been measured previously in thisspecies from the remote areas of southern Oman (Fow-ler, 1988; Fowler et al., 1993), but it did approach thequite high levels (116–141 lg g�1 dry weight) reportedfor rock oysters from Musandam in northern Omanduring the early 1980s (Fowler, 1988). Similar TPH con-centrations (81–118 lg g�1 dry weight) were also re-ported for oysters from the coastal waters near Minaal Fahal in Oman in 1990 (Badawy et al., 1993).

The bivalves from the other sites displayed relativelylow concentrations compared to those reported in theearlier surveys. For example, pearl oysters from JebelAli in the UAE and rock oysters from Ras Al Yei inOman exhibited slightly lower concentrations (5.5–9.6 lg g�1) of total PHs compared to the concentrationsmeasured in 1991 (15–31 lg g�1) (Fowler et al., 1993).The concentration of total PHs in the single sample ofclams from Ras Al Nouf in Qatar (0.86 lg g�1 dryweight) was three orders of magnitude lower than con-centrations (570–2600 lg g�1) reported for similar spe-cies from Saudi Arabia collected after the Gulf War(Fowler et al., 1993).

The concentration of the total parent PAHs inbivalve tissues ranged from 6 to 211 ng g�1 dry weight,

which by global standards corresponds to a pollutionlevel from low to moderate pollution (Baumard et al.,1998). Thus, levels of PAHs from the RSA area can becompared with those in molluscs collected at NationalStatus and Trends (NS&T) sites in Alaska (149–262 ng g�1 dry weight) (Valette-Silver et al., 1999). Rep-resentative PAH patterns (Fig. 3) shows a typical profileof petrogenic PAHs, with a predominance of methylatedphenanthrenes and dibenzothiophenes over the parentcompounds. A fresher oil input at Mirbat and the BAP-CO refinery compared to Akkah Beach and Abu Dhabiis apparent from the higher concentrations of lowermolecular weight PAHs, e.g. naphthalene and theiralkylated compounds. A minor input of combustion-derived PAHs is suggested only by the low concentrationsof high molecular weight PAHs, e.g. benzo(a)anthra-cene, benzofluoranthenes and benzo(a)pyrene.

Interestingly, the PAH sedimentary pattern from theBAPCO refinery (Fig. 2) shows a very different profile tothat of the pearl oysters. The differences could be partlydue to the environmental location of the oysters, likelyliving on rocks far from the sediment rendering themmainly exposed to the oil dissolved in the water column.Furthermore, filter-feeding bivalves generally show apreferential accumulation of the lower molecular weightand more water soluble PAHs (petrogenic compounds)compared to the high-molecular weight combustion-generated PAHs that are occluded onto soot particles,thereby making them less readily available (Thompsonet al., 2000; Torsen et al., 2004).

3.3. Fish

Two fish species of commercial importance, namelythe orange spotted grouper (Epinephelus coioides, knownlocally as hamoor) and the spangled emperor (Lethrinusnebulosus, known locally as sheiry) were investigated.

Table 6Total lipid content and concentrations of hydrocarbons in liver fish from the Gulf and the Gulf of Oman

Lipid content(mg g�1 dry wt.)

TPH equiv.ROPME oil(lg g�1 dry wt.)

TPH equiv.Chrysene(lg g�1 dry wt.)

TPH equiv.GC-FID(lg g�1 dry wt.)

UCMaliphatics(lg g�1 dry wt.)

Pn-C –C34

(lg g dry wt.)

PPAHs

(ng g�1 dry wt.)parentP

PAHs(ng g�1 dry wt.)

UAE

Al Marfa Orange-SpottedGrouper

141 4.70 0.32 56.0 18.0 3.90 79.0 59.6

Al Marfa Spangled Emperor 73.0 6.90 0.67 134 56.0 5.30 67.2 58.8Al Dhannah Spangled Emperor 133 38.0 4.10 975 700 58.0 40.0 17.5Al Dhannah Orange-Spotted

Grouper146 3.40 0.37 87.0 29.0 2.90 62.7 42.5

Qatar

Al Khawr Orange-SpottedGrouper

55.0 2.20 0.21 44.0 23.0 2.30 228 35.7

Umm Said Orange-SpottedGrouper

210 19.0 2.20 185 39.0 5.40 179 74.0

Doha Orange-SpottedGrouper

180 8.60 1.10 73.0 37.0 6.00 113 19.8

Bahrain

Bidaiya Orange-SpottedGrouper

169 7.60 1.10 82.0 32.0 6.50 44.3 7.55

Fasht Al Adhm Orange-SpottedGrouper-1.26 kg

162 4.20 0.56 44.0 18.0 2.80 23.6 13.3

Fasht Al Adhm Orange-SpottedGrouper-1.03 kg

171 4.20 0.53 48.0 18.0 2.70 27.0 17.5

Oman

Quriyat Orange-SpottedGrouper-#1

165 11.0 1.60 142 47.0 12.0 78.3 16.6

Quriyat Orange-SpottedGrouper-#2

155 14.0 1.90 87.0 37.0 5.20 63.3 5.92

Raysut Port Area Spangled Emperor 235 11.0 1.60 177 40.0 23.0 161 81.3Sagar Spangled Emperor 215 8.00 1.30 120 40.0 16.0 65.7 10.3

1630I.Tolosa

etal./Marin

ePollu

tionBulletin

50(2005)1619–1633

14�1

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1631

Total PHs based on ROPME oil equivalents in fishmuscle were unexceptional and ranged from 0.18 to11 lg g�1 dry weight (Table 5). These relatively lowPH concentration levels are less than those, 10–31 lg g�1 dry weight, reported for sheiry muscle fromthe oil-impacted coastline of Saudi Arabia after the GulfWar Oil spill (Fowler et al., 1993), but are comparablewith those from sites in Bahrain (0.8 to 3.8 lg g�1 dryweight) and Oman (from 2.4 to 7.3 lg g�1 dry weight)that were not impacted by the 1991 spill (Fowler et al.,1993). The present values compare with uncontaminatedfish tissue, 0.33–3.7 lg g�1 wet weight, from the northand central Arabian Sea collected in 1991 (Sen Guptaet al., 1993), and are also similar to those reported forfish collected in 1990 from coastal waters near MinaAl Fahal in Oman (Badawy et al., 1993).

Total parent PAH concentrations in the fish muscleranged from 2.3 to 16.7 ng g�1 dry weight weight, withthe highest values measured in Qatar and UAE(Table 5). Much higher levels of total parent PAHs,73–135 ng g�1 dry weight, were measured in the muscleof spangled emperor from oil-impacted areas of Qatarsurveyed one year after the 1991 oil spill (Al-Yakoobet al., 1993) and in orange spotted grouper samplesfrom Kuwaiti fish markets in 1993 (181–267 ng g�1 dryweight) (Saeed et al., 1995). Similar to these studiesand as shown in Fig. 4, the PAH composition in fishmuscle reflected a predominant derivation from oil pol-lution rather than from pyrolitic sources. As the bulk ofPAH burden in these samples was very low and con-sisted of low molecular weight PAHs, the correspondingbenzo[a]pyrene equivalent should also be very low in theedible fish from the RSA coastal zone (Law et al., 2002;Saeed et al., 1995). Although the number of samplesanalyses was perhaps too small to provide definitiveconclusions, the low PAH concentrations here do sug-gest that human consumption of fish should be of verylittle concern for public health.

The concentration range of TPH, expressed inROPME oil equivalents, in fish liver was 2.2–38 lg g�1

dry weight (Table 6). These amounts were slightly great-er than those found in muscle tissue, as expected due tothe higher lipid content in liver tissue. The maximumvalue was measured in spangled emperor liver from AlDhannah in UAE, which also exhibited a high concen-tration of aliphatic unresolved mixture (700 lg g�1 dryweight) indicative of a highly weathered oil source. Sim-ilar oil concentrations (12–33 lg g�1 dry weight) werenoted in hamoor liver from UAE and Oman followingthe 1991 Gulf War, whereas much higher concentrations(160–300 lg g�1 dry weight) were reported for sheiry li-ver from the oil-impacted area of Saudi Arabia (Fowleret al., 1993). In contrast to the relatively high concentra-tions of TPH measured in the sheiry liver from AlDhananh, the orange-spotted grouper from the samelocation did not show substantial oil contamination.

Such findings may be related to the different feedinghabits of these fish. Both species are demersal carni-vores; hamoor feed preferentially on fish and crusta-ceans whereas sheiry tend to eat echinoderms, wormsmolluscs and crustaceans (Carpenter et al., 1997).

Total parent PAH concentrations ranged from 6 to81 ng g�1 dry weight in fish liver, with the highest valuesmeasured in sheiry liver from the Raysut Port Area insouthern Oman, where the relatively greater contribu-tion of high molecular weight parent PAHs (Fig. 4),e.g., benzofluoranthenes indicated some additional in-put of combustion-derived PAHs.

4. Conclusions

Although the Gulf is generally regarded as a heavilypolluted water body with respect to oil, these screeningresults from four countries surveyed in 2000 and 2001indicate that the levels of petroleum and PAHs contam-inants were relatively low in sediments. Also, the levelsof petroleum hydrocarbons in various seafood species(fish and bivalves) were comparable to the concentra-tions observed in relatively unpolluted areas elsewherein the world. Nevertheless, oil pollution continues tobe a problem in some specific areas of the RSA. The lev-els of petroleum and PAHs contaminants were relativelyhigh in sediments offshore from the BAPCO industrialcomplex in Bahrain where chronic pollution occurs.Approximately six years after a severe oil spill occurredin the Gulf of Oman off the east coast of the UAE, rel-atively high petroleum hydrocarbon concentrationswere noted in the oysters around Akkah Head. How-ever, the aliphatic profile in the sediments from this areasuggested they originated from a more recent input ofoil. The precise source of this varied mixture of contam-inants found in the rock oysters and sediments fromAkkah Beach has not yet been identified. Regularmonitoring of the area and more specific analyses arerecommended in order to determine if any dumpingactivities have taken place in this particular area.

Acknowledgement

This was a collaborative project between the IAEAand ROPME, financially supported by both organiza-tions. The Agency is grateful for the support providedto its Marine Environment Laboratory by the Govern-ment of the Principality of Monaco. We acknowledgewith gratitude the logistic support received in each coun-try: in Bahrain from the Ministry of Housing, Munici-palities &Environment; in Oman from the Ministry ofRegional Municipalities and Environment; in Qatarfrom the Ministry of Municipal Affairs and Agriculture;and in the United Arab Emirates from the Federal

1632 I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633

Environment Agency. Finally, we thank Dr. Nahida Al-Majed for assistance with sample collection in Bahrainand Oman.

References

Abu-Hilal, A.H., Khordagui, H.K., 1994. Petroleum hydrocarbons inthe nearshore marine sediments of the United Arab Emirates.Environ. Pollut. 85, 315–319.

Al-Lihaibi, S.S., Al-Omran, L., 1996. Petroleum hydrocarbons inoffshore sediments from the Gulf. Mar. Pollut. Bull. 32, 65–69.

Al-Lihaibi, S.S., Ghazi, S.J., 1997. Hydroca rbon distributions insediments of the open area of the Arabian Gulf following the 1991.Gulf War Oil Spill. Mar. Pollut. Bull. 34, 941–948.

Al-Majed, N.B., Al-Safar, F., Rajab, W.A., Farhan, M.S., Al-Ruqaab,E., 1998. Levels of trace metals and hydrocarbons in fish from theROPME sea area. In: Otsaki, A., Abdulraheem, M.Y., Reynolds,R.M. (Eds.), Offshore Environment of the ROPME Sea Area afterthe War-Related Oil Spills. Terra Scientific. Publ. Co., Tokyo, pp.257–279.

Al-Yakoob, S., Saeed, T., Al-Hashash, H., 1993. Polycyclic aromatichydrocarbons in edible tissues of fish from the Gulf after the 1991oil spill. Mar. Pollut. Bull. 27, 297–301.

Badawy, M.I., Al-Mujainy, I.S., Hernandez, M.D., 1993. Petroleum-derived hydrocarbons in water, sediment and biota from the Minaal Fahal coastal waters. Mar. Pollut. Bull. 26, 457–460.

Banat, I.M., Hassan, E.S., El-Shahawi, M.S., Abu-Hilal, A.H., 1998.Post-Gulf-War assessment of nutrients, heavy metal ions, hydro-carbons, and bacterial pollution levels in the United Arab Emiratescoastal waters. Environ. Int. 24, 109–116.

Baumard, P., Budzinski, H., Garrigues, P., 1998. Polycyclic aromatichydrocarbons in sediments and mussels of the western Mediterra-nean Sea. Environ. Toxicol. Chem. 17, 765–776.

Carpenter, K.E., Krupp, F., Jones, D.A., Zajong, U., 1997. The LivingMarine Resources of Kuwait, Eastern Saudi Arabia, Bahrain,Qatar, and the United Arab Emirates. FAO Species IdentificationField Guide for Fishery Purposes. FAO, Rome, p. 239.

Carvalho, F.P., Villeneuve, J.-P., Cattini, C., 1999. Determination oforganochlorine compounds, petroleum hydrocarbons, and sterolsin a sediment sample, IAEA-383. Results of an intercomparisonexercise. Int. J. Environ. Anal. Chem. 75, 315–329.

de Mora, S.J., Fowler, S.W., Cassi, R., Tolosa, I., 2003. Assessment oforganotin contamination in marine sediments and biota from theGulf and adjacent region. Mar. Pollut. Bull. 46, 401–409.

de Mora, S.J, Fowler, S.W., Tolosa, I., Villeneuve, J.-P., Cattini, C.,2005. Chlorinated hydrocarbons in marine biota and coastalsediments from the Gulf and Gulf of Oman. Mar. Pollut. Bull.50 (8), 42–56.

de Mora, S.J., Fowler, S.W., Wyse, E., Azemard, S., 2004. Distribu-tion of heavy metals in marine bivalves, fish and coastal sedimentsin the Gulf and Gulf of Oman. Mar. Pollut. Bull. 49, 410–424.

Farrington, J.W., Tripp, B.W., 1977. Hydrocarbons in western NorthAtlantic surface sediments. Geochim. Cosmochim. Acta 41, 1627–1641.

Fayad, N.M., El-Mubarak, A.H., Edora, R.L., 1996. Fate of oilhydrocarbons in fish and shrimp after major oil spills in theArabian Gulf. Bull. Environ. Contam. Toxicol. 56, 475–482.

Fowler, S.W. 1988. Coastal baseline studies of pollutants in Bahrain,United Arab Emirates and the Sultanate of Oman. In: ProceedingsSymposium on Regional Marine Pollution Monitoring andResearch Programmes, ROPME/GC-4/2, ROPME. Kuwait, pp.155–180.

Fowler, S.W., Readman, J.W., Oregioni, B., Villeneuve, J.-P., McKay,K., 1993. Petroleum hydrocarbons and trace metals in near shoreGulf sediments and biota before and after the 1991 war: An

assessment of temporal and spatial trends. Mar. Pollut. Bull. 27,171–182.

Gogou, A., Bouloubassi, I., Stephanou, E.G., 2000. Marine organicgeochemistry of the Eastern Mediterranean: 1. Aliphatic andpolyaromatic hydrocarbons in Cretan Sea surficial sediments. Mar.Chem. 68, 265–282.

Hong, H., Xu, L., Zhang, L., Chen, J.C., Wong, Y.S., Wan, T.S.M.,1995. Special guest paper: Environmental fate and chemistry oforganic pollutants in the sediment of Xiamen and VictoriaHarbours. Mar. Pollut. Bull. 31, 229–236.

Khan, N.Y., 2002. Physical and human geography. In: Khan, N.Y.,Munawar, M., Price, A.R.G. (Eds.), The Gulf Ecosystem: Healthand Sustainability. Bakhuys Publishers, Leiden, pp. 3–21.

Krahn, M.M., Ylitalo, G.M., Buzitis, J., Bolton, J.L., Wigren, C.A.,Chan, S.-L., Varanasi, U., 1993. Analyses for petroleum-relatedcontaminants in marine fish and sediments following the Gulf oilspill. Mar. Pollut. Bull. 27, 285–292.

Law, R.J., Kelly, C.A., Baker, K.L., Jones, J., McIntosh, A.D.,Moffat, C.F., 2002. Toxic equivalency factors for PAH and theirapplicability in shellfish pollution monitoring studies. J. Environ.Monitor. 4, 383–388.

Long, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995.Incidence of adverse biological effects within ranges of chemicalconcentrations in marine and estuarine sediments. Environ. Man-age. 19, 18–97.

Massoud, M.S., Al-Abdali, F., Al-Ghadban, A.N., 1998. The status ofoil pollution in the Arabian Gulf by the end of 1993. Environ. Int.24, 11–22.

Massoud, M.S., Al-Abdali, F., Al-Ghadban, A.N., Al-Sarawi, M.,1996. Bottom sediments of the Arabian Gulf–II. TPH and TOCcontents as indicators of oil pollution and implications for the effectand fate of the Kuwait oil slick. Environ. Pollut. 93, 271–284.

Munawar, M.P., Price, A.R.G., Munawar, I.F., Carou, S., Niblock,H., Lorimer, J., 2002. Aquatic ecosystem health of the ArabianGulf: Status and research needs. In: Khan, N.Y., Munawar, M.,Price, A.R.G. (Eds.), The Gulf Ecosystem: Health and Sustain-ability. Bakhuys Publishers, Leiden, pp. 303–325.

Readman, J.W., Bartocci, J., Tolosa, I., Fowler, S.W., Oregioni, B.,Abdulraheem, M.Y., 1996. Recovery of the coastal marineenvironment in the Gulf following the 1991 war-related oil spills.Mar. Pollut. Bull. 32, 493–498.

Readman, J.W., Fillmann, G., Tolosa, I., Bartocci, J., Villeneuve, J.-P., Catinni, C., Mee, L.D., 2002. Petroleum and PAH contamina-tion of the Black Sea. Mar. Pollut. Bull. 44, 48–62.

Readman, J.W., Fowler, S.W., Villeneuve, J.-P., Cattini, C., Oregioni,B., Lee, L.D., 1992. Oil and combustion-product contamination ofthe Gulf marine environment following the war. Nature 358, 662–664.

Saeed, T., Al-Muzaini, S., Al-Bloushi, A., 1996. Post-Gulf Warassessment of the levels of PAHs in the sediments from ShuaibaIndustrial Area, Kuwait. Water Sci. Technol. 34, 195–201.

Saeed, T., Al-Yakoob, S., Al-Hashash, H., Al-Bahloul, M., 1995.Preliminary exposure assessment for Kuwaiti consumers to poly-cyclic aromatic hydrocarbons in seafood. Environ. Int. 21, 255–263.

Sen Gupta, R., Fondekar, S.P., Alagarsamy, R., 1993. State of oilpollution in the northern Arabian Sea after the 1991 Gulf oil spill.Mar. Pollut. Bull. 27, 85–91.

Shriadah, M.M.A., 1998. Impacts of an oil spill on the marineenvironment of the United Arab Emirates along the Gulf of Oman.Mar. Pollut. Bull. 36, 876–879.

Shriadah, M.M.A., 2000. Levels and distribution of petroleumhydrocarbons in the coastal waters and sediments of the UnitedArab Emirates in the Arabian Gulf and Gulf of Oman. Water AirSoil Pollut. 119, 247–256.

Simoneit, B.R.T., 1982. Some applications of computerized GC-MSto the determination of biogenic and anthropogenic organic

I. Tolosa et al. / Marine Pollution Bulletin 50 (2005) 1619–1633 1633

matter in the environment. Int. J. Environ. Anal. Chem. 12, 177–193.

Thompson, R.E., Voit, E.O., Scott, G.I., 2000. A probabilistic modelfor predicting distributions of PAH ratios between oysters andmarine sediments. Ecol. Model. 135, 231–242.

Tolosa, I., Bayona, J.M., Albaiges, J., 1996. Aliphatic and polycyclicaromatic hydrocarbons and sulfur/oxygen derivatives in north-western mediterranean sediments: Spatial and temporal variability,fluxes, and budgets. Environ. Sci. Technol. 30, 2495–2503.

Torsen, W.A., Cope, W.G., Shea, D., 2004. Bioavailability of PAHs:Effects of soot carbon and PAH source. Environ. Sci. Technol. 38,2029–2037.

UNEP, 1991. Sampling of Selected Marine Organisms and SamplePreparation for the Analysis of Chlorinated Hydrocarbons. Ref-erence Methods for Marine Pollution Studies No. 12, Rev. 2,UNEP, Nairobi, p. 17.

Valette-Silver, N., Hameedi, M., Efurd, D.W., Robertson, A., 1999.Jawed status of the contamination in sediments and biota from thewestern Beaufort Sea (Alaska). Mar. Pollut. Bull. 38, 702–722.

Villeneuve, J.-P., de Mora, S.J., Cattini, C., Carvalho, F.P., 2000.Determination of organochlorinated compounds and petroleumhydrocarbons in sediment sample IAEA-408. Results from aworld-wide intercalibration exercise. J. Environ. Monitor. 2, 524–528.

Villeneuve, J.P., Carvalho, F.P., Horvat, M., Cattini, C., 2004.Worldwide intercomparison on the determination of chlorinatedpesticides, PCBs and petroleum hydrocarbons in a mussel tissuehomogenate, IAEA-142. Int. J. Environ. Stud. 61, 437–452.

Volkman, J.K., Holdsworth, D.G., Neill, G.P., Bavor, J.H.J., 1992.Identification of natural, anthropogenic and petroleum hydrocar-bons in aquatic sediments. Sci. Total Environ. 112, 203–219.