The distribution and sources of polycyclic aromatic hydrocarbons in

Environ Monit Assess (2007) 124:343–359 DOI 10.1007/s10661-006-9231-8

ORIGINAL ARTICLE

The distribution and sources of polycyclic aromatic hydrocarbons in surface sediments along the Egyptian Mediterranean coast Ahmed El Nemr · Tarek O. Said · Azza Khaled · Amany El-Sikaily · Aly M.A. Abd-Allah

Received: 25 October 2005 / Accepted: 28 February 2006 / Published online: 21 October 2006 C Springer Science + Business Media B.V. 2007

Abstract Coastal marine sediment samples were collected from 31 sampling stations along the Egyptian Mediterranean Sea coast. All sediment samples were analyzed to determine aliphatic and polycyclic aromatic hydrocarbons (PAHs) as well as total organic carbon (TOC) contents and grain size analysis. Total concentrations of 16 EPA-PAHs in the sediments were varied from 88 to 6338 ng g−1 with an average value of 154 ng g−1 (dry weight). However, the concentrations of total aliphatic were varied from 1.3 to 69.9 ng g−1 with an average value of 15.6 ng g−1 (dry weight). The highest contents of PAHs were found in the Eastern harbor (6338 ng g−1 ), Manzala (5206 ng g−1 ) and El-Jamil East (4895 ng g−1 ) locations. Good correlations observed between a certain numbers of PAH concentrations allowed to identify its origin. The average total organic carbon (TOC) percent was varied from 0.91 to 4.54%. Higher concentra tion of total pyrolytic hydrocarbons ( COMB) than total fossil hydrocarbons ( PHE) declared that atmospheric fall-out is the significant source of PAHs to marine sediments of the Egyptian Mediterranean coast. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (phenanthrene/anthracene vs fluoranthene/pyrene; A. E. Nemr ( ) · T. O. Said · A. Khaled · A. El-Sikaily · A. M. A. Abd-Allah Environmental Division, National Institute of Oceanography and Fisheries, Kayet Bay, Alexandria, Egypt e-mail: [email protected]

COMB/ EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in most locations. Interferences of rather petrogenic and pyrolytic PAH contaminations were noticed in the harbors due to petroleum products deliveries and fuel combustion emissions from the ships staying alongside the quays. Keywords Surface sediment · PAHs · Mediterranean · Egypt · Pollution monitoring · Hydrocarbons · PCA

1 Introduction Mediterranean Sea appears to suffer from high anthropogenic pressure due to inputs from; industrial, sewage effluents, storm water drains, shipping activities, spillage, rivers, atmospheric-fallout, coastal activities and natural oil seeps (UNEP, 1984). The annual inputs of petroleum hydrocarbons are about 750 × 103 tons, among which the land-based industrial inputs amount are about 221 × 103 tons per year (Burns and Saliot, 1986). Thus, the distribution of hydrocarbons in the environment can vary greatly from one area to another. Clark (1997) stated that polycyclic aromatic hydrocarbons (PAHs) and aliphatic contamination in sediments originate mainly from the following sources: (a) accidental spills; (b) partial combustion of fuels (pyrolytic combustion of fossil fuels such as in vehicles, Springer

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heating and power plants, industrial processes and/or open burning); (c) forest and grass fires (d) biosynthesis by marine or terrigenous organisms (land plants, animals, bacteria, macroalgae and microalgae, bacterial and chemical degradation of naturally occurring lipids produced hydrocarbons such as phytanes, hopenes and sterenes); (e) early diagenetic transformation of nonhydrocarbon natural products to hydrocarbons. Hydrocarbon composition can be significantly changed due to selective dissolution, chemical reactions, evaporation, photo-oxidation and biodegradation. Simple aromatics and short chain alkanes are rapidly lost, but higher molecules such as hopanes and steranes are little affected and can be particularly useful in source investigations (Volkman et al., 1992). PAHs are one of the more significant classes of organic chemicals that in the recent years have given rise to a growing concern regarding harmful effects to man and other living organisms. PAHs generally possess high chemical stability and hydrophobic properties, which result in enhanced accumulation and a high capacity for distribution in the environment. A number of PAH compounds are considered as hazardous environmental chemicals (NRC, 1983, 1985). Eljarrat et al. (2001) measured that the toxicity equivalent (TEQ) values of PAHs were several times higher than the TEQ of polychlorinated biphenyls (PCBs) and polychlorinated dioxins/furans (PCDD/Fs), in the sediment from the Catalonian coast, Western Mediterranean. PAHs have been described as mutagenic, carcinogenic and teratogenic (Zedeck, 1980; Varanasi, 1989) and included in the US EPA and the EU priority pollutants list. Hydrophobic contaminants such as PAHs tend rapidly to be adsorbed on particles (Neff, 1979; Landrum and Robbins, 1990). The solubility of aromatic compounds decreases as the octanol-water partition coefficient (Kow ) increases. PAHs solubility decrease with increasing molecular weight (Porte and Albaigés, 1993; Djomo et al., 1996). Thus, low molecular weight PAHs are preferentially dissolved while, the heavier molecular weight compounds are preferentially absorbed onto or associated with particles. Consequently, the uptake of a contaminant is governed by its bioavailability, and organisms are often enriched in the lower molecular weight PAHs relative to the sediment (Porte and Albaigés, 1993; Djomo et al., 1996; Baumard et al., 1998). Because of their low solubility and hydrophobic nature, PAHs tend to be greatly enriched in the inorSpringer

Environ Monit Assess (2007) 124:343–359

ganic and organic air particles that, under the action of atmospheric agents, may be transported in all the ecosystems. Thus, freshwater and marine sediments often contain concentrations of PAHs of higher magnitudes than those in the overlying water. The deposition of suspended particulates transported by rivers may therefore have an increasing effect in the accumulation of PAHs. Once deposited in sediments, PAHs are less subjected to photochemical or biological oxidation, especially if the sediment is anoxic. Thus, sedimentary PAHs tend to be persistent and may accumulate to high concentrations (Witt, 1995). The partitioning of the PAHs between water and sediment is controlled by the sediment characteristics. Therefore, the accumulation of PAHs is not only determined by the mass flux to the seabed, but also by the sediment characteristics. The coastal ecosystem is an important resource throughout the Mediterranean for commercial as well as recreational purposes. In addition, the contamination of the sediment may pose a high toxic threat to the aquatic fauna, which tend to bioaccumulate the organic pollutants (Baumard et al., 1998). The analysis of sedimented PAHs can serve as a useful index of the rates of PAHs input to the aquatic environment. Sediment samples have a substantial integrating effect on temporal patterns of PAHs input and offer good geographical resolution, especially when current patterns, sediment origin, and settling rates are known. Numerous research studies assessed the PAHs inputs in the Northwestern and Central Mediterranean (Tolosa et al., 1996; Lipiatou et al., 1997; Bouloubassi et al., 1997; Benlahcen et al., 1997). Conversely, in the Eastern Mediterranean few data have been published on the presence of PAHs in coastal sediments close to point sources (municipal and river discharges, etc.) (Gogou et al., 2000). In addition, hydrocarbon budgets are available for the Western part of Mediterranean Sea (Lipiatou et al., 1997; Dachs et al., 1999), but there is a tremendous lack of information regarding the Southern Mediterranean (El Sikaily et al., 2002; El Nemr and Abd-Allah, 2003). Although PAHs have been determined previously in marine sediments from a few locations along the Egyptian Mediterranean Sea coast, this is the first systematic study to be undertaken along 500 km of the Egyptian Mediterranean Sea coast. Two relevant criteria are used fairly to discriminate between the various natural and anthropogenic hydrocarbon inputs and to evaluate the extent of hydrocarbon pollution in the area and its link


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Fig. 1 Map of the area studied showing the location of the sampling points in the Egyptian Mediterranean Sea coast.

to combustion processes and/or releasing of unburned fossil fuels.

2 Materials and methods 2.1 Sample preparation A total of 31 surface sediment samples were collected in November 1999 at sites shown in Fig. 1 and Table 1. The locations were selected taking into consideration the expected polluted area due to industrial and human activities (Table 2). Sediments were collected utilizing a stainless-steel grab. Six grabs were taken from each location from which the top 3 cm were scooped into pre-cleaned wide-mouth glass bottles, frozen and transported to the laboratory and stored at −20 ◦ C until analysis. The boat was moved up to 4–6 m between grabs so that the samples would be representative of the area from which they were taken. The samples were analyzed for aliphatic and aromatic hydrocarbons following well established techniques (UNEP/IOC/IAEA, 1991 and 1992). The samples were analyzed for aliphatic and PAHs, grain size distribution and total organic carbon (TOC). About 3–4 g of each sample was taken and weighed in an aluminum dish. The sample was oven-dried at 105 ◦ C to a constant weight to obtain percentage water content for each sample. 2.2 Grain size analysis Grain size analysis was carried out using the conventional method (Folk, 1954; Galehouse, 1971). Raw

samples were treated with 30% (v/v) hydrogen peroxide solution to destroy the organic matter content, and about 100 g of washed sediment was dried at 105 ◦ C and subsequently placed in the topmost sieve and the entire column of sieves was shaken on a mechanical shaker (Betriebsanleitung vibration testing sieve mechanical machine Thyr 2) for 20 min. The sieve meshes give the glass intervals 2, 1, 0, 0.5, 0.2, 0.125, and 0.063 mm.

2.3 Extraction of PAHs Before chemical treatment, individual samples were removed from the refrigerator and allowed to thaw at room temperature for about 5 h. Each sample was then thoroughly mixed and 30 g of the sediment was mixed with 90 g of anhydrous sodium sulfate. Duplicates were taken from each sediment sample. The sediment sample was then sonicated in an ultrasonic bath with 2 × 100 mL hexane for 30 min each, followed by third extraction with 100 mL dichloromethane. The three extracts were then combined and desulphurised through activated copper powder and then concentrated to a few milliliters in a rotary evaporator at low temperature (∼35 ◦ C), followed by concentration with nitrogen gas stream down to a volume 1 mL. Clean-up and fractionation was performed by passing the concentrated extract through a silica/aluminum oxide column. The chromatography column was prepared by slurry packing 20 mL (10 g) of silica, followed by 10 mL (10 g) of aluminum oxide and finally 1 g of anhydrous sodium sulfate. The extract (1 mL) was sequentially eluted from the column with 25 mL of hexane for the saturated aliphatic fraction (F1). Then 60 mL of Springer

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Environ Monit Assess (2007) 124:343–359 Table 1 Location (latitude and longitude), depth, percentage of sand, silt, and clay for the studied area Site No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31

Site name Sidi-Kerir El-Nobareya El-Mex Western Harbor NIOF Eastern Harbor Shatby Sidi Gaber Gleem Saray Sidi Bisher El-Montazah Mamouraa Abu-Qir Abu-Qir Abu-Qir (EPS) El-Maadia Rosetta Rosetta El-Borg Ras El-Bar Damietta Manzala El- Jamil (West) Manzala El- Jamil (East) Port Said Port Said Romana Bardaweel Bardaweel

Position ◦

◦

31 03 58 N-29 40 36 E 31◦ 04 55 N-29◦ 42 13 E 31◦ 09 00 N-29◦ 47 30 E 31◦ 10 02 N-29◦ 50 40 E 31◦ 12 40 N-29◦ 52 09 E 31◦ 12 34 N-29◦ 52 27 E 31◦ 12 43 N-29◦ 53 36 E 31◦ 13 22 N-29◦ 55 46 E 31◦ 14 39 N-29◦ 57 24 E 31◦ 14 59 N-29◦ 57 40 E 31◦ 15 13 N-29◦ 58 05 E 31◦ 17 13 N-30◦ 01 01 E 31◦ 17 49 N-30◦ 01 13 E 31◦ 18 17 N-30◦ 07 12 E 31◦ 19 10 N-30◦ 03 16 E 31◦ 16 57 N-30◦ 08 27 E 31◦ 16 34 N-30◦ 10 02 E 31◦ 27 54 N-30◦ 2135 E 31◦ 28 40 N-30◦ 22 07 E 31◦ 35 06 N-30◦ 58 52 E 31◦ 31 03 N-31◦ 49 45 E 31◦ 25 03 N-32◦ 00 31 E 31◦ 02 33 N-32◦ 08 54 E 31◦ 18 15 N-32◦ 12 00 E 31◦ 19 31 N-32◦ 12 33 E 31◦ 18 11 N-32◦ 16 21 E 31◦ 17 50 N-32◦ 19 34 E 31◦ 17 37 N-32◦ 18 16 E 31◦ 03 22 N-32◦ 38 01 E 31◦ 12 53 N-33◦ 16 35 E 31◦ 07 34 N-33◦ 29 21 E

Depth (m)

Sand %

Silt %

Clay %

6 5 5 6 6 6 5 5 6 5 5 5 6 4 4 4 4 5 5 10 10 7.5 7.5 7 7 7.5 6.5 7.5 10 5 10

100 100 100 100 100 100 100 100 100 100 100 100 100 100 75.50 78.14 74.05 65.45 68.12 63.85 59.16 69.10 60.99 72.03 67.55 77.26 85.18 81.85 77.12 66.19 68.81

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.15 10.86 9.16 15.55 11.88 12.03 15.44 12.35 15.05 12.88 21.24 10.75 10.32 7.90 14.58 14.71 11.20

0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 15.35 11.00 16.80 19.00 20.00 24.12 25.40 18.55 23.98 15.09 10.99 12.13 4.50 10.26 8.30 19.10 19.99

EPS: Electric Power Station

Table 2 Sources of marine pollution and other impacts and the main sites of pollution in the Mediterranean Sea Sources of Pollution and others impacts

Main sites of pollution and/or other impacts

Industrial wastewater and domestic sewage from residential areas and tourist resort areas. Much of the wastewater is discharged into the coastal lakes which are connected to the sea. The Maryut receive the sewage from Cairo via El-Baqar canal. Nile water and agricultural drains contaminated with hazardous industrial waste, domestic sewage, organic matter, fertilizers and pesticides.

Alexandria Damietta Rosetta

Oil pollution from ships and oil terminals.

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The outlet from Lake Maryut The outlet of the Rosetta branch of the Nile The outlet of the Damietta branch of the Nile The outlet from Lake Burullus The outlets from Lake Manzala and Port Said Port Said Port Damietta Summed pipeline


hexane and dichloromethane (80:20) for the unsaturated and aromatic hydrocarbons fraction (F2). F1 and F2 were concentrated by using gentle stream of nitrogen for instrumental analysis. 2.4 Analytical quality controls To control the analytical reliability and assure recovery efficiency and accuracy of the results, 6 analyses were conducted on PAH compound reference materials, HS-5 (sediments) provided by NRC-IMB of Canada and SRM-2974 (Freeze-dried mussels tissue) (Mytilus edulis) provided by NIST of U.S.A as well as sediment samples of known PAH levels spiked with a mixture consisting of 2 μg each of PAHs were analyzed as above to validate the analytical method used in this study. Detection Limits (DL) are provided in Table 3. The lowest DL was 0.02 μg ml−1 for lower molecular mass compounds while indeno[1,2,3-cd]pyrene has the heist at 0.1 μg ml−1 . The recovery efficiency ranged from 92 to 111% for HS-5, 88 to 96% for SRM-2974 and 93 to 105% for the spiked samples. The mean recovery for PAHs were as followed: Naph 90.1%, Acthy 92.3%, Ace 105.2%, F1 102.4%, Phe 99.2%, Ant 101.6%, Flu 95.4%, Pyr 92.5%, BaA 89.7%, Chr 107.1%, BaP 94.6%, BbF 90.5%, DBA 101.8%, BghiP 93.7% and InP 97.5%. Concentrations reported in this study were not corrected for recovery rates. 2.5 Chemical Anhydrous sodium sulfate were extracted with hexane in a Soxhlet apparatus for 8 h and then with methanol or dichloromethane for another 8 h, precombustion in a muffle furnace at approximately 400 ◦ C overnight and cooled in a greaseless desiccator. Silica gel and aluminum oxide used for column chromatography were solvent extracted with n-hexane in a glass cartridge inserted into an extraction apparatus, as described by Ehrhardt (1987). After extraction, they were first dried in the same cartridge with a nitrogen stream, activated by heating the cartridge in an electric tube oven to 200 ◦ C for 6 h, and then stored in umber bottle. All solvents were pesticides grade purchased from Merck. 2.6 Instrumental analyses Blanks of 1000 fold concentration (1000 ml of solvent used was concentrated to 1 ml) were analyzed by

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Gas Hewlett Packard HP-5890 series II equipped with split/splitless injector and a fused silica capillary HP-1 (30 m, 0.32 mm, 0.17 μm) 100% dimethylpolysiloxane. The temperature was programmed from 60–300 ◦ C with rate of 5◦ C min−1 and was then maintained at 290 ◦ C for 25 min. The injector and detector temperatures were set at 280 and 300 ◦ C, respectively. Nitrogen was used as the carrier gas at a flow of 1.3 mL min−1 . 2 μL volume of each sample was injected in the splitless mode and the purge time was 1 min. The response factor of individual PAH compounds to the internal standard was measured and calculated at least three times at the beginning, in the middle, and at the end for each batch of GC injections (15 samples). The unresolved complex mixture (UCM) was obtained according to published method (Tolosa et al., 1996, 2004). Identification and quantification of 16 PAH compounds were based on matching their retention time with a mixture of PAH standards. Some samples were randomly chosen and analyzed by GCMS (Hewlett-Packard 5889B MS ‘Engine’) with selected ion monitoring (SIM) mode for confirmation. HP-1 column was used and programmed as above, with helium as carrier gas. The mass spectrometer scanned 50–350 Daltons per second; electron energy was 70 eV. The 16 PAH compounds were naphthalene (Naph, m/z 128), acenaphthylene (Acth, m/z 152), acenaphthene (Ace, m/z 154), fluorene (Fl, m/z 166), phenanthrene (Phe, m/z 178), anthracene (Ant, m/z 178), fluoranthene (Flu, m/z 202), pyrene (Pyr, m/z 202), benzo[a]anthracene (BaA, m/z 228), chrysene (Chr, m/z 228), benzo[b]fluoranthene (BbF, m/z 252), benzo[k]fluoranthene (BkF, m/z 252), benzo[a]pyrene (BaP, m/z 252), benzo[ghi]perylene (BghiP, m/z 278), indeno[1,2,3-cd]pyrene (InP, m/z 278), and dibenzo[a,h]anthracene (DBA, m/z 278). 2.7 Principal component analysis Principal component analysis (PCA) was used to distinguish between the samples to assess different sources of PAHs and how they are being deposited in the Suez Gulf. Possible sources include automotive exhaust, used crankcase oil, wood combustion, coal-fired power plants, coal tar, creosote and petroleum oil spills. The PCA was used to elucidate linear combinations of PAHs that may be useful to distinguish between these sources as has been demonstrated by other researches (Simpson et al., 1998; Dickhut et al., 2000). Data Springer

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0.04 0.01 0.01 0.01 0.02 0.01 0.03 0.03 0.04 0.04 0.05 0.05 0.05 0.06 0.08 0.10

Naph Acthy Ace Fl Phe Ant Flu Pyr BaA Chr BaP BbF BkF DBA BghiP InP PAHs PAHCARC CARC UCM-ALP C12 –C40 Pristane Phytane ALP

88.6 37.6 N.D. N.D. N.D. N.D. 85.4 58.6 94.7 90.9 135.8 27.8 171.3 212.7 N.D. 152.8 1156 624 54 0.06 15.39 0.04 0.38 16.86

1

N.D. N.D. N.D. N.D. 60.6 24.5 40.2 40.3 76.7 123.2 N.D. 32.3 92.7 N.D. 73.1 N.D. 563 109 19 0.03 0.93 0.72 0.75 1.34

2 592.2 N.D. 25.1 63.1 21.0 27.9 63.5 57.9 113.7 195.1 1606.6 1114.1 190.5 17.8 116.9 120.9 4326 2973 69 0.04 1.37 N.D. N.D. 7.17

3 36.6 137.5 N.D. N.D. 135.2 N.D. 195.0 N.D. N.D. 201.0 108.3 279.2 96.3 337.4 297.0 175.0 1999 900 45 0.13 8.68 0.10 N.D. 9.08

4 9.8 N.D. N.D. N.D. 82.8 N.D. 512.8 560.6 N.D. 33.7 26.5 14.0 47.1 83.1 15.6 24.4 1410 148 10 0.01 7.35 0.06 0.03 7.54

5 N.D. N.D. 92.2 29.7 1547.3 N.D. 1820.3 1372.6 1099.5 81.1 N.D. 29.3 116.8 64.0 N.D. 85.6 6338.4 1278 20 0.07 4.76 0.04 0.18 4.85

6 N.D. N.D. 13.6 34.3 182.3 N.D. 62.6 35.8 90.8 92.5 29.1 59.2 33.5 68.8 48.5 77.1 828 325 39 0.08 11.84 0.11 N.D. 13.55

7 5.2 37.7 N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. N.D. 26.0 N.D. N.D. 18.9 N.D. 88 26 30 0.06 6.43 0.83 3.18 11.03

8 N.D. 82.4 N.D. N.D. N.D. 53.2 66.8 N.D. N.D. 57.7 30.8 71.8 69.6 130.9 148.4 51.5 763 285 37 0.08 11.28 0.35 0.76 12.63

9 295.3 N.D. N.D. 40.4 92.3 76.6 66.1 200.9 386.4 404.1 1000.6 173.8 440.7 63.7 240.8 151.7 3633 1776 49 0.01 8.70 0.16 0.49 11.79

10 N.D. N.D. N.D. N.D. 26.7 127.2 61.8 N.D. N.D. 148.3 93.2 108.5 64.2 N.D. N.D. 18.7 649 220 34 0.08 1.44 0.63 2.06 2.09

11 N.D. 65.1 N.D. N.D. 83.9 N.D. 179.1 N.D. N.D. 206.5 183.1 371.3 193.7 342.8 84.1 159.9 1869 1057 57 0.08 2.97 0.50 1.47 3.85

12 N.D. N.D. N.D. N.D. N.D. N.D. 24.5 N.D. N.D. 26.9 N.D. 30.2 64.5 53.7 89.2 16.5 305 100 33 0.06 5.08 0.05 0.17 7.75

13 N.D. 39.6 N.D. N.D. 148.9 N.D. 246.1 43.7 N.D. 139.4 25.7 229.5 215.4 354.1 205.3 169.9 1818 779 43 0.09 10.04 0.45 N.D. 12.90

14 12.1 188.0 35.7 122.8 162.5 10.9 98.5 N.D. 38.6 55.7 22.9 41.5 29.0 55.0 555.8 30.1 1484 188 13 0.02 6.08 N.D. N.D. 6.53

15

513.8 N.D. N.D. N.D. N.D. N.D. 30.8 51.0 N.D. 45.1 142.6 132.6 164.1 59.5 110.0 64.0 1313 399 30 0.01 4.48 N.D. N.D. 5.36

16

LD = detection limit (μg ml−1 ); N.D. = non-detectable; UCM: unresolved complex mixture; ALP: aliphatics; PAHCARC : BaA + BbF + BaP + DBA + InP (IARC probable and possible human carcinogens); CARC: % PAHCARC / PAHs

DL

PAH

Table 3 Concentration (ng g−1 dry wt) of hydrocarbons in Sediment collected from Mediterranean Sea

348 Environ Monit Assess (2007) 124:343–359


analysis including (PCA) was done on the correlation matrix using SPSS-10.

3 Results and discussion 3.1 Aliphatic hydrocarbons Tables 3 and 4 give the total concentrations of the aliphatic hydrocarbons and n-alkanes ranging from C12 to C40 , as well as the isoprenoid hydrocarbon individual concentrations, diagnostic criteria useful for the identification of natural or anthropogenic origins and granulometric parameters for the sediments. The concentrations below their limits of detection were given a value of zero for the calculation. In the present study, the total aliphatic hydrocarbon concentrations varied from 1.37 to 69.87 ng g−1 (dry weight). Higher concentrations occurred at sites 24, 30 and 31. Lower concentrations were found for samples from sites 2, 6, 11, 12, 16, 19 and 21. The total n-alkanes concentrations ranged from 0.93 to 51.77 ng g−1 (dry weight). This was less than the recorded level for clean urban sites in Scotland, UK; with an average value of 3000 ng g−1 wet weight and ranged from 400–7100 ng g−1 (Mackie et al., 1980). In addition, the recorded level for Black Sea ranged from 1200 to 240000 ng g−1 of sediment (Readman et al., 2002). The unresolved complex mixture (UCM) is the compounds presented in the total aliphatic hydrocarbons as complex of molecules that cannot be resolved by capillary GC columns. The UCM comprises a mixture of alicyclic compounds (Tolosa et al., 2004) and has a well-known linkage to degraded or weathered petroleum residues (Readman et al., 1987). However, some UCM distributions, mainly in the lower molecular weight range, can also be attributed to bacterial degradation of natural organic matter such as algal detritus (Venkatesan and Kaplan, 1982). The total nalkanes found in the studied samples represented the major amount of the total aliphatic hydrocarbons found while the UCM represented minor amount of the total hydrocarbons (Tables 3 and 4). All the studied sediment samples were representing a low UCM of alkanes (0.01–0.13 ng g−1 dry wt.) suggesting that most of the aliphatic contaminants were recently discharged into the marine environment. The isoprenoid hydrocarbons, pristane (Pr) (2,6,10,14-tetramethylpentadecane) and phytane (Ph)

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(2,6,10,14-tetramethylhexadecane), are products of geologic alteration of phytol and other isoprenoidyl natural products, and are not primary constituents of most terrestrial biota (Didyk et al., 1978; Peters and Moldowan, 1993). Pristane and phytane are presented in most petroleum oils in a ratio of pristine/phytane (Pr/Ph) lower than 1, so the detection of these two components is often used as good indicators of petroleum contamination. However, a high concentration of pristane alone can be derived from zooplankton (Blumer et al., 1963). In uncontaminated sediments, the ratio Pr/Ph is higher than 1, typically between 3 and 5 (Steinhauer and Boehm, 1992). Most samples had Pr/Ph ratios lower than 1 (Table 5) indicating mainly a petrogenic hydrocarbon inputs to the Mediterranean Sea coast. Highest ratio of Pr/Ph was recorded at station 29 reflecting biogenic origins. In addition, it is noted in the most samples that the pristane dominates n-C17 indicating contributions derived from petroleum origin (Table 5).

3.2 PAH concentrations Individual and total concentrations, as well as characteristic ratios for the identification of PAH origins are given in Tables 3 and 4. Total PAHs ( PAHs) concentrations in sediments varied significantly among the studied locations. The values ranged from 88 to 6338 ng g−1 dry weight. The highest concentration of total PAHs was recorded in sediments collected from station 6, followed by that in stations 25, 26 and 23. Lower concentrations were detected in samples of stations 2, 8, 11 and 13. In this study, sediment samples collected near the sewage outlet, cities and harbor appeared to have extremely high concentrations of total PAHs. These suggest that PAHs accumulated in Mediterranean Sea sediments came from different sources such as sewage discharge from nearby human activities and fuel combustion emissions. The degree of sediment contamination by PAHs in this study is moderate in comparison with other aquatic systems in other countries (Table 6). Although the number of PAHs analyzed in any given study may differ, the 16 compounds analyzed herein comprise the vast majority of PAHs found in most estuarine or marine sediments. The average concentration of PAHs in the present study is lower than those in some areas of urbanized estuaries in the other countries represented in Table 6. Springer

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17.8 18.5 15.2 N.D. 168.8 83.3 416.7 350.0 266.1 112.6 531.8 298.0 712.7 N.D. 505.8 142.0 3639 1238 34 0.03 15.07 0.29 N.D. 17.526

PAH

Naph Acthy Ace Fl Phe Ant Flu Pyr BaA Chr BaP BbF BkF DBA BghiP InP PAHs PAHCARC CARC UCM-ALP C12 –C40 pristane Phytane ALP

71.1 19.0 16.1 29.6 78.8 34.4 46.8 60.4 154.1 238.1 171.3 296.4 276.6 105.8 236.0 450.8 2285 1178 52 0.09 9.78 N.D. N.D. 10.969

18 557.0 37.8 19.3 N.D. 134.3 110.8 104.2 277.3 392.2 612.2 125.7 267.6 118.7 53.7 365.3 252.7 3429 1092 32 0.02 1.86 N.D. N.D. 2.966

19 396.8 26.8 N.D. N.D. N.D. 62.0 64.3 N.D. N.D. 36.7 190.7 213.2 43.2 39.7 70.3 161.1 1305 605 46 0.01 13.71 0.11 N.D. 18.201

20 1170.4 27.7 29.6 37.4 80.5 136.1 173.4 53.5 72.8 83.3 572.4 578.4 311.8 386.0 447.0 69.1 4229 1679 40 0.02 2.91 0.09 0.11 3.0768

21 139.5 32.9 26.1 29.8 N.D. N.D. 83.5 28.8 40.7 55.5 150.5 273.4 305.1 149.4 252.0 283.0 1850 747 40 0.02 5.77 N.D. N.D. 17.932

22 212.2 285.4 41.1 139.6 141.2 N.D. 496.5 N.D. 444.7 746.6 358.1 291.4 124.5 569.0 124.8 580.5 4556 2244 49 0.01 7.74 N.D. N.D. 9.46

23 N.D. 141.3 N.D. 69.7 217.6 N.D. 160.3 N.D. N.D. 153.5 53.5 222.7 106.9 235.5 52.2 113.5 1527 625 41 0.07 48.55 0.58 0.12 57.32

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Table 4 Concentration (ng g−1 dry wt) of hydrocarbons in Sediment collected from Mediterranean Sea

1048.5 N.D. N.D. N.D. 101.7 64.5 67.9 218.3 544.4 534.6 27.1 701.1 643.8 183.6 488.2 582.4 5206 1494 29 0.02 13.97 0.69 0.62 19.86

25 N.D. N.D. N.D. N.D. 14.2 N.D. N.D. 457.3 744.5 496.7 155.9 682.2 81.8 1020.7 533.6 708.4 4895 3312 68 0.07 8.86 N.D. N.D. 13.97

26 N.D. N.D. N.D. 14.2 30.6 N.D. 48.1 N.D. 69.1 189.3 300.9 461.2 266.1 290.0 37.6 127.1 1834 1248 68 0.08 13.66 0.10 0.10 15.07

27 N.D. 67.1 N.D. 54.5 141.7 223.0 171.6 117.2 9.1 564.9 316.4 324.4 223.9 220.7 136.3 168.1 2739 713 26 0.08 16.01 0.06 N.D. 18.73

28 N.D. 29.5 N.D. N.D. 92.5 N.D. 142.2 12.1 43.0 272.4 187.5 508.5 253.5 546.9 53.1 186.9 2328 1430 61 0.05 17.13 2.55 0.03 18.60

29 N.D. 274.0 462.8 531.5 311.8 N.D. 306.5 354.9 78.4 423.8 157.1 300.2 83.9 189.0 77.1 52.7 3604 777 22 0.01 51.77 12.81 N.D. 69.87

30

152.9 N.D. N.D. 15.4 56.7 N.D. 17.1 36.3 N.D. 29.3 2540.0 1381.0 43.3 N.D. 31.7 33.9 4337 3955 91 0.03 50.59 0.42 N.D. 52.19

31


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Table 5 TOC, Total Hydrocarbons (TH), pyrolytic ( COMB), fossil ( PAH), Phe/Ant, Flu/Pyr, COMB/ PAHs (C/P), n-C17/pristane (Pr), n-C18/phytane (Ph) and pristane/phytane (Pr/Ph) Site No. TOC % TH COMB PHE Phe/Ant Flu/Pry C/P n-C17 /Pr Pr/Ph 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31

1.11 1.29 3.29 1.25 1.23 4.54 1.21 1.29 1.32 2.46 0.91 2.01 1.41 1.97 1.56 1.34 3.19 2.85 3.42 1.88 3.12 2.14 3.48 1.37 3.99 3.87 1.04 1.27 1.89 3.17 3.58

1158 580 4333 2008 1415 6346 842 99 776 3636 660 1877 309 1830 1491 1319 3657 2296 3432 1323 4257 1853 4562 1533 5256 4909 1843 2753 2347 3694 4390

1030 478 3597 1689 1318 4669 598 45 627 3129 495 1720 305 1629 927 800 3336 2036 2570 819 2748 1622 3736 1098 3991 4881 1790 2253 2206 2024 4113

126 85 729 309 93 1669 230 43 136 505 154 149 NA 188 557 514 304 249 859 486 1482 228 820 429 1215 14 45 486 122 1580 225

0.0 2.5 0.8 135.2 0.0 1547.3 182.3 0.0 53.2 1.2 0.2 83.9 0.0 148.9 4.5 0.0 2.0 2.3 1.2 0.0 0.6 0.0 141.2 217.6 1.6 14.2 30.6 0.6 92.5 311.8 56.7

1.5 1.0 1.1 195.0 0.9 1.3 1.7 0.0 66.8 0.3 61.8 179.1 24.5 5.6 98.5 0.6 1.2 0.8 0.4 64.3 3.2 2.9 496.5 160.3 0.3 0.0 48.1 1.5 11.8 0.9 0.5

0.89 0.85 0.83 0.85 0.93 0.74 0.72 0.51 0.82 0.86 0.76 0.92 1.00 0.90 0.62 0.61 0.92 0.89 0.75 0.63 0.65 0.88 0.82 0.72 0.77 1.00 0.98 0.82 0.95 0.56 0.95

0.2 3.1 NA 1.6 3.6 3.9 3.9 0.4 1.0 0.6 0.7 0.2 3.1 0.0 1.6 3.6 3.9 3.9 0.4 1.0 0.6 0.7 0.3 NA 1.3 NA 1.0 5.6 0.1 0.0 0.7

1.0 0.1 NA NA 0.2 2.1 NA 0.3 0.5 0.3 0.3 1.0 0.1 NA NA 0.2 2.1 NA 0.3 0.5 0.3 0.3 5.0 NA 1.1 NA 1.0 NA 74.4 NA NA

NA: not available.

Table 6 Comparison of sediment PAH concentrations (ng g−1 dry wt) measured in this study with those in other countries Sites

No. of samples

mean

range

reference

Egyptian Mediterranean coast Kyeonggi Bay, Korea Casco Bay, USA Washington coast, USA Baltic Sea Western Mediterranean Sea Safax Area, Tunisia Gulf of Naples, Southern Italy Beijing, China

31 24 23 13 15 31 18 15 47

154 120 2900 200 1200 1300 1865 3115 1056

88-6338 9.1-1400 16-21000 29-460 720-1900 180-3200 1121-5217 92-12561 14-4238

This study Kim et al., 1999 Kennicutt et al., 1994 Prahl and carpenter, 1983 Witt, 1995 Lipiatou and Saliot, 1991 Louati et al., 2001 Romano et al., 2004 Ma et al., 2005

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It has been demonstrated that the nature of the sediment influences the distribution and concentration of PAHs. The concentrations of PAHs in sediments were affected by chemical composition of the sediments such as organic matter and clay content (Kim et al., 1999). Sediments with high organic carbon content were charcterised with high values of PAHs (Witt, 1995; Yang, 2000). However, a moderate correlation was found between PAHs and total organic carbon (TOC) concentrations in the present Mediterranean sediments (Table 7). This may be suggesting that both of direct input and type of sediment found locally would determine the distribution and concentrations of PAHs in sediments. Moreover, Simpson et al. (1998) showed that the relationship between total PAHs and organic carbon was only significant for highly contaminated sites where total PAH concentration was greater than 2000 ng g−1 dry weight. In this study, half of the sediment samples had total PAH concentrations more than 2000 ng g−1 where the samples contain higher TOC (Table 5). A positive relationship was existed between total PAHs and %TOC of the sediments (Fig. 2). The importance of sedimentary organic matter on the partitioning of PAHs in sediments has been well documented. Chiou et al. (1998) found that the high partitioning of PAHs to sedimentary organic matter was mainly due to the significant aromatic fraction of the organic matter. They considered the sedimentary organic matter as a natural “heterogeneous polymer” where PAHs interact more favorably with the aromatic regions. Seven locations (St. 3, 6, 21, 23, 25, 26 and 31) had concentrations more than the Effects Range-Low (ERL) value (4022 ng g−1 ) suggested by Long et al. (1995). They reported that the concentrations below

Fig. 2 A plot of total PAHs concentration (ng g−1 dry wt) vs %TOC of the sediments collected from Mediterranean Sea. Springer


the ERL value represent a minimal-effect range, i.e. adverse biological effect would rarely be observed below the ERL. On the other hand, if the concentration was higher than the Effects Range-Median (ERM) value (44792 ng g−1 ), adverse effects on biological systems will frequently occur. The concentrations of individual PAH recorded in the present study ranged from non-detectable levels to 2540 ng g−1 , and were much lower than the ERM values (Fig. 3). The average concentrations of the individual PAH were lower than the ERL except for Dibenzo(a,h)anthracene (Fig. 3). High concentration of Dibenzo(a,h)anthracene (above the ERM value) at most studied locations might need a more detailed study. In addition, similar observations were found relative to the Threshold Effect Level (TEF) and Probable Effect Level (PEL) (CCME, 2001), where Dibenzo(a,h)anthracene has average concentration over the TEL and PEL (Fig. 4). The individual PAH concentrations in this study were also lower than the national sediment quality criteria proposed by the USEPA (1993) for fluoranthene (3000 ng g−1 ), acenaphthylene (2400 ng g−1 ) and phenanthrene (2400 ng g−1 ). Benzo(a)pyrene (BaP), the most potent carcinogenic PAHs, and the sum of six carcinogenic PAHs ( PAHCARC ) (IARC, 1983) were highest at stations number; 3, 23, 26, 30 and 31 with a concentration of 2973, 2244, 3312, 3604 and 4337 ng g−1 , respectively (Tables 3 and 4). BaP was ranged from non-detected at stations 2, 6 and 8 to 2540 ng g−1 at station 31 with a mean of 298 ng g−1 , falling in the concentration range between rural and urban areas (Menzie et al., 1992). 3.3 Origin of PAHs in sediment The aromatic compound distributions differ according to the production sources, and on the chemical composition and temperature combustion of the organic matter (Neff, 1979). One difficulty in identifying PAH origins is the possible coexistence of many contamination sources, and the transformation processes that PAHs can undergo before deposition in the analyzed sediments. Nevertheless, some compounds could exhibit comparable evolution kinetics that could be used to identify the origin of organic matter in the environment (Colombo et al., 1989). The compounds of pyrene, phenanthrene and benzo(b)fluoranthene are components of fossil fuels and a portion of them is associated with their combustion (Kavouras et al., 2001). Benzo(a)pyrene is usually


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Table 7 Correlations study between sand, silt, clay percentage, total organic compound, total hydrocarbons, prolytic ( COMB), and fossil ( PHE) Sand Silt Clay TOC TH COMB PHE Sand Silt Clay TOC TH COMB PHE

−0.953∗∗∗ −0.974∗∗∗ −0.509∗∗ −0.408∗ −0.346 −0.402∗

0.859∗∗∗ 0.487∗∗ 0.421∗ 0.367∗ 0.385∗

0.495∗∗ 0.373∗ 0.318 0.388∗

0.593∗∗∗ 0.585∗∗∗ 0.365∗

0.966∗∗∗ 0.679∗∗∗

0.466∗∗

Correlations are significant at ∗ p < 0.05 (low), ∗∗ p < 0.01 (moderate) and ∗∗∗ p < 0.001 (high).

Fig. 3 Diagram showed the average concentration (ng g−1 dry wt) of PAH in Mediterranean Sea sediments relative to ERL and ERM.

Fig. 4 concentration (ng g−1 dry wt) of average PAHs in sediment samples relative to Threshold Effect Level (TEF) and Probable Effect Level (PEL).

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emitted from catalyst and noncatalyst automobiles. Benzo(a)anthracene and chrysene are often resulted from combustion of both diesel and natural gas (Rogge et al., 1993). The ratio of sum of major combustion specific com pounds ( COMB, Flu, Pyr, BaA, Chr, BbF, BkF, BaP, InP and BghiP) to the sum of 16 EPA-PAHs ( COMB/ PAHs) were ranged from 0.56 to 1.0 and the COMB concentrations displayed values from 45 to 4881 ng g−1 (Table 5), representing average of 81% of total anthropogenic PAHs. This ratio was 1 at stations 13 and 26, which indicated that the PAHs at these two sites manly come from combustion origin. The higher COMB/ PAHs ratio values further indicated that extensive combustion activities affected the PAHs in sediment samples. The sources of PAHs, where from fuel-combustion (pyrolytic) or from crude oil (petrogenic) contamination, may be identified by ratios of individual PAH compounds based on peculiarities in PAH composition and distribution pattern as a function of the emission source (Gschwend and Hites, 1981; Colombo et al., 1989). Ratio values such as phenanthrene/anthracene (Phe/Ant) and fluoranthrene/pyrene (Flu/Pyr) had been used by previous workers (Sicre et al., 1987; Budzinski et al., 1997; Soclo et al., 2000, El Sikaily et al., 2002; El Nemr and Abd-Allah, 2003). Petroleum often contains more phenanthrene relative to anthracene as phenanthrene that is more a thermodynamically stable tricyclic aromatic isomer than anthracene, so a Phe/Ant ratio is observed to be very high in PAH petrogenic pollution, but low ratio in pyrolytic contamination cases (Gschwend and Hites, 1981; Soclo et al., 2000; Yang, 2000). Crude oil had a Phe/Ant ratio of around 50, and motor vehicle exhaust had a ratio of around four (Yang et al., 1991). Low Phe/Ant ratio values (less than10) indicated the major PAH input was from combustion of fossil fuel (Gschwend and Hites, 1981; Colombo et al., 1989). Budzinski et al. (1997) suggested that sediments with Phe/Ant >10 were mainly contaminated by petrogenic inputs and Phe/Ant 10) were found in 13 locations of the studied 31 locations (Table 5), indicating that they were petrogenic. In other sediments the Phe/Ant ratio values were around 0–4.5 (Table 5), suggesting that they were pyrolytic-derived PAHs. Springer


However, the different Phe/Ant ratio values might be related to weathering such as photo-degradation, chemical degradation or biodegradation and also the sediment composition. On the other hand fluoranthene/pyrene (Flu/Pyr) ratio also indicated the origin of PAHs. Sicre et al. (1987) suggested that a Flu/Pyr ratio of less than 1 was attributed to petrogenic sources and values greater than 1 were obviously related to a pyrolytic origin. Combustion of coal and wood gave Flu/Pyr ratios of 1.4 and 1, respectively, while crude oil and fuel oil had values of 0.6–0.9 (Gschwend and Hites, 1981). In the present study, most sites had Flu/Pyr ratio values more than 1 (Table 5). However, the results obtained from the Phe/Ant and Flu/Pyr ratios (Table 5) indicated a petrogenic origin at sites 5, 10, 16, 19, 30 and 31, a pyrolytic origin at sites 1, 2, 3, 11, 13, 17, 20, 21, 22, and 28, and a mixed pattern of petrogenic and pyrolytic contamination at the other locations. 3.4 Correlation between sediment grain size and hydrocarbon contaminations The correlation coefficients between granulometric parameters (% clay, % silt, % sand) and total hydrocar bons (TH), total organic carbons (TOC), COMB and PHE were represented in Table 7. The Pearson correlation coefficient was significant 97% level for Sand correlated to % silt and % clay as will as total hydro carbons and COMB. In addition, total hydrocarbons, COMB and PHE had low correlation (p < 0.05) with each of % sand, silt and clay. Total hydrocarbon has low negative correlation with sand, while it has a low positive correlation with silt and clay. These results suggest that the sediment grain size was not the determining factor for compound deposition. Water circulation of the studied area controlled the deposited of the natural or anthropogenic compounds shortly after their input into the estuarine environment. 3.5 Principal component analysis (PCA) of PAHs PCA, a multivariate technique whose aim is to reduce the number of variables (measured PAHs content in sediment samples) to a smaller set of orthogonal factors of easier interpretation by displaying the correlations existing among the original variables was applied to the selected data set. Data submitted for the analysis were arranged in matrix, where each column corresponds


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to one PAH component and each row represents soil site. The number of factors extracted from the variables was determined according to Kaiser’s rule. This criterion retains only factors with eigenvalues that exceed one. The first step in the multivariate statistical analysis was application of PCA with the aim to group the individual PAH components by the loading plots for 31 contaminated sites. Since the raw data have provided negative loadings, we applied the varimax rotation for the correlation greater than 0.30. Concentrations of 16 EPA-PAHs as active variables and 31 sites were selected. The majority of the variance (80.60%) of the scaled data was explained by five eigenvectors-principal components. The first principal component (PC1) explained 21.33%. The second (PC2), the third (PC3), the fourth (PC4) and the fifth (PC5) principal component explained 16.98%, 16.42%, 13.86% and 12.01% of the total variances, respectively (Table 8). PC1 had a strong significant correlation with Phe (0.94), Flu (0.93), Pyr (0.95) and BaA (0.81). As displayed in Table 9, these compounds gave strong correlation with the total PAHs concentration (p < 0.01). Thus, PC1 is a quantitative correlation component and corresponds to the total PAHs concentration. The compounds of Phe and Pyr are components of fossil fuels and a portion of them is associated with their combustion. In addition, BaA is often resulted from the comTable 8 Factor loadings (Varimax with kaiser normalized: marked loadings are > 0.7) for five principal components (PCs) for PAH in surface sediments for Mediterranean Sea PAH

PC1

PC2

PC3

PC4

PC5

Naph Acthy Ace Fl Phe Ant Flu Pyr BaA Chr BaP BbF BkF DBA BghIP InP % of variance Cumulative %

−0.05 −0.11 0.23 0.06 0.94 −0.04 0.93 0.95 0.81 0.06 −0.07 −0.09 0.09 −0.03 −0.05 0.06 21.33 21.33

0.07 0.25 −0.08 −0.01 −0.09 −0.19 −0.07 0.01 0.47 0.70 −0.16 0.24 0.19 0.86 0.46 0.92 16.98 38.31

−0.06 0.81 0.91 0.98 0.13 −0.02 0.09 0.03 −0.07 0.36 −0.02 −0.02 −0.15 0.03 −0.02 −0.06 16.42 54.73

0.70 −0.17 −0.05 −0.05 −0.10 0.76 −0.09 0.05 0.17 0.35 0.05 0.13 0.70 −0.18 0.70 0.20 13.86 68.59

0.33 −0.18 0.04 0.06 −0.07 −0.11 −0.11 −0.04 0.05 0.03 0.93 0.93 0.12 0.00 −0.04 0.06 12.01 80.60

Fig. 5 Score plot of PC1 vs PC2 illustrating the distribution of individual PAH compounds in contaminated areas.

bustion of both diesel and natural gas (Rogge et al., 1993). Thus it can be seen; PC1 reflected the effects of traffic pyrolysis or combustion on the sum of PAHs. PC2 dominated by Chr (0.70), DBA (0.80) and InP (0.92), PC4 dominated by Ant (0.76), BkF (0.70) and BghiP (0.70) and PC5 dominated by BaP (0.93) and BbF (0.93), which were also associated with traffic emission. PC3 represents Acthy (0.81), Ace (0.91) and Fl (0.98), which are related to 3-ring PAHs (two aromatic rings and one five-membered ring), which were associated with petroleum components. The property of individual PAH components which causes their dominancy in each factor cannot be clearly indicated and their clustering was not observed (Fig. 5). Therefore, it is impossible to predict the distribution patterns of individual PAH components in contaminated areas only from a PC1/PC2 plot. The strong adsorption of PAHs by sediments caused by long-range atmospheric transport processes and regional fallout deposition in combination with their transformation, behavior in sediment-water system and mobility imply the random distribution. 3.6 Correlation between PAH concentrations The PAHs whose concentrations are susceptible of covarying in the environment were identified in this study on the basis of the correlation factor values (Table 9). This statistical approach is based on the fact that each pollution source produces a characteristic PAH pattern; so, the correlations of all the individual PAHs can give an idea whether they all originate from the same source or not. A lack of correlation was noticed between anthracene and other PAHs (r2 = 0.001 to 0.338). Significant correlations were noted between Flu–Phe (r2 = 0.925), Flu–Pyr (r2 = 0.859), Flu–BaA (r2 = 0.636), Springer

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−0.076 0.565∗∗∗

−0.174

−0.083 0.722∗∗∗ 0.947∗∗∗

Fl −0.131 0.066 0.303 0.165

Phe 0.338 −0.164 −0.126 −0.093 −0.099

Ant −0.138 0.09 0.248 0.113 0.925∗∗∗ −0.047

Flu −0.062 −0.141 0.288 0.103 0.823∗∗∗ 0.044 0.859∗∗∗

Pyr 0.154 −0.085 0.092 −0.012 0.671∗∗∗ −0.031 0.636∗∗∗ 0.777∗∗∗

BaA 0.2 0.376∗ 0.203 0.296 −0.003 0.291 −0.007 0.077 0.437∗∗

Chr

Correlations are significant at ∗ p < 0.05 (low), ∗∗ p < 0.01 (moderate) and ∗∗∗ p < 0.001 (high).

Naph Acthy Ace Fl Phe Ant Flu Pyr BaA Chr BbF BkF BaP BghiP InP DBA %TOC

Ace

Acthy

Table 9 Correlation coefficient matrix for soil individual PAHs (n=31)

0.225 −0.161 −0.051 0.008 −0.125 0.043 −0.139 −0.104 −0.057 −0.021

BbF

BaP 0.4∗ −0.226 −0.105 −0.132 −0.032 0.279 0.006 0.067 0.239 0.245 0.099 0.216

BkF 0.39∗ −0.141 −0.021 0.013 −0.168 0.001 −0.208 −0.108 0.064 0.205 0.80∗∗∗ −0.034 0.234 −0.014 0.033 −0.081 −0.179 −0.032 0.005 0.279 0.471∗∗ −0.155 0.226 0.011

BghiP 0.402∗ 0.066 −0.076 −0.045 −0.121 0.253 −0.155 0.025 0.294 0.296 −0.049 0.178 0.492∗∗ 0.283

InP 0.227 0.111 −0.101 −0.054 −0.078 −0.043 −0.05 0.072 0.533∗∗ 0.689∗∗∗ −0.091 0.284 0.338 0.652∗∗∗ 0.476∗∗

DBA 0.421∗ 0.041 0.291 0.213 0.444∗∗ 0.003 0.423∗∗ 0.546∗∗∗ 0.748∗∗∗ 0.441∗∗ 0.367∗ 0.532∗∗ 0.346 0.22 0.412∗ 0.527∗∗

%TOC 0.424∗ 0.071 0.259 0.218 0.488∗∗ 0.13 0.484∗∗ 0.578∗∗∗ 0.754∗∗∗ 0.525∗∗ 0.413∗ 0.574∗∗∗ 0.403∗ 0.313 0.382∗ 0.503∗∗ 0.924∗∗∗

Total PAHs



Fl–Ace (r2 = 0.947), Fl–Acthy (r2 = 0.722), Pyr–Phe (r2 = 0.823), BbF–BkF (r2 = 0.800), %TOC–Pyr (r2 = 0.546), %TOC–BaA (r2 = 0.748), in addition, the total PAHs were significantly correlated with most of the 16 PAHs (Table 9). These indicated that Flu, Acthy, Ace, Pyr, Phe, BaA and Chr might originate from the same sources. Chrysene and benzo(a)anthracene are derived from processes of organic matter combustion at high temperature, with values of Chr/BaA ratio lower than 1 (Soclo et al., 2000). In contrast, low maturation of organic matter during burial in the sedimentary matrix could lead to an inversion of this tendency: Chr/BaA = 1 (Soclo et al., 2000). It has been shown that chrysenic derivatives are more stable than benzanthracenic ones because of the possibility of the latter ones to convert to chrysenic compounds. 4 Conclusion The present work represents the detailed study of the distribution and origin of petroleum hydrocarbons in 31 sediment samples collected from about 500 km along the Egyptian Mediterranean Sea coast. The studied samples were less contaminated by petroleum hydrocarbons. Concentrations of PAHs in Mediterranean Sea sediments are shown to be substantially lower than those from other coastal areas and are generally comparable to levels encountered in the other Mediterranean Sea coast. The most contaminated site (6338 ng g−1 ) was the Eastern Harbor (in Alexandria city). The UCM of the total sedimentary aliphatic hydrocarbons is very small, which indicates contamination by non-weathered petroleum (fresh input). A mixture of pyrolytic and petrogenic PAHs were observed with a slight pyrolytic predominance. Acknowledgements The authors would like to express their sincere gratitude to NIOF, EIMP and DANIDA for financial support. We are indebted to Engineer Ahmed Abu El-Soud (EIMP project Manager), Mr. Al Shabraway Mahmoud and Mrs. Mai E. Ahmed (EIMP reference laboratory). Also our deep appreciation for Mrs. Fadia Abu El-Maged, Mr. Mohamed Emam, and Mr. Ahmed ElGamel for their kind assistance during the experimental work.

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