The Monitoring and Risk Assessment of Aliphatic and Aromatic Hydrocarbons in Sediments of the Red Sea, Egypt

Egyptian Journal of Aquatic Research (2014) xxx, xxx–xxx

HOSTED BY National Institute of Oceanography and Fisheries Egyptian Journal of Aquatic Research

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FULL LENGTH ARTICLE The monitoring and risk assessment of aliphatic and aromatic hydrocarbons in sediments of the Red Sea, Egypt

Dalia M.S. Aly Salem, Fadia Abou-Elmagd M. Morsy, Ahmed El Nemr *, Amany El-Sikaily, Azza Khaled

Environmental Division, National Institute of Oceanography and Fisheries, Kayet Bey, El-Anfoushy, Alexandria, Egypt

Received 11 September 2014; revised 12 November 2014; accepted 12 November 2014

KEYWORDS Abstract Polycyclic aromatic hydrocarbons (PAHs) and aliphatic hydrocarbon were analyzed in Aqaba Gulf; sediments collected from the Suez Gulf, Aqaba Gulf and the Red Sea proper stations Egypt. A geo- Suez Gulf; logical study demonstrated that the sediments in the studied area have a nature from very fine sand BaP equivalent; to very coarse sand, mainly biogenic fragments, and carbonate aggregates. Total aliphatic hydro- Toxic equivalency factor; carbon concentrations (C14–C32) ranged from 33.97 to 553.48 ng/g with a mean value of PAH’s; 174.8 ± 167.06. The highest and lowest alkane concentrations are recorded at El-Tour and Ras Aliphatic hydrocarbon Mohamed, respectively. Accordingly, the variation in n-alkanes content may refer to the anthropogenic sources (sewage, industrial discharges, and shipping activities) and natural inputs (submerged/ floating macrophytes and emergent terrestrial plants and microbial activity). Meanwhile, RPAH concentrations were in the range of 0.74–456.91 ng/g, with the mean value of 32.94 ng/g. The highest concentration of total PAHs is recorded in sediments collected from El-Quseir (456.91 ng/g), followed by that in Sharm El Mayaa (100.05 ng/g) and Suez 10 (97.19 ng/g); while lower concentrations are detected in Sheraton (0.74 ng/g), Ras Mohamed and Na’ama Bay (0.74, 6.86 and 11.1 ng/g, respectively). In this context, ratio of low molecular weight of PAHs (2- and 3-rings) to high (4- to 6-rings) has been used to differentiate between the pyrogenic and petrogenic sources of PAHs in the studied samples. In all studied stations, RLPAHs/RHPAHs ratios were <1, revealing their pyrogenic sources. The concentration levels of PAHs in the current study were compared to the effect range low (ERL) and the effect range medium (ERM) values; the average concentration of level of PAHs for all investigated stations was below the ERL except El-Quseir station which recorded PAHs higher than the ERL but still lower than the ERM. This finding indicated that PAHs in surface sediments of the studied area have no adverse biological effects except at El-Quseir which may cause mild adverse biological effects but not acute effects. To assess the potential health risk of PAHs; the BaP equivalent (BaPE) is used. High levels of BaPE values were found

* Corresponding author. Tel.: +20 1007801845. E-mail addresses: [email protected], ahmed.m. [email protected] (A. El Nemr). Peer review under responsibility of National Institute of Oceanography and Fisheries. http://dx.doi.org/10.1016/j.ejar.2014.11.003 1687-4285 ª 2014 Hosting by Elsevier B.V. on behalf of National Institute of Oceanography and Fisheries. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

at El-Quseir only, indicating that PAHs in this site showed relatively high toxicity among all sites. Toxic equivalency factors (TEFs) of seven carcinogenic PAHs (BaA, BbF, BkF, BaP, Chr, DBA and InP), were used to quantitatively assess the potential toxicological signiﬁcance to human health.

In this study, the toxic equivalent (TEQcarc) values of sediment samples varied from not detected 1 1 (ND) to 72.27 ng TEQ g , with the mean value of 2.94 ng TEQ g . The higher total TEQcarc values were found at El-Quseir Station 72.27 ng TEQ g1. ª 2014 Hosting by Elsevier B.V. on behalf of National Institute of Oceanography and Fisheries. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

Introduction Sinai Peninsula (east) and the Africa proper (west) of Egypt. The bay is subjected to different sources of pollution. The first The polycyclic aromatic hydrocarbons (PAHs) have been and dangerous one is the oil effluents that discharge from the listed as persistent organic pollutants (POPs) (Hu et al., industrial complex south of Suez, which includes the oil 2007; Chung et al., 2007; Christensen and Arora, 2007; refineries of El-Nasr and Suez Petroleum Companies (El Tsang et al., 2011). PAHs can exert adverse effects on the envi- Nemr, 2005, 2011, 2012). The second pollution source is the ronment and human health even far away from their origin sewage of Suez City, which discharges into the bay (Nassar (Petra et al., 2010). Many studies reported that PAHs were and Hamed, 2003). The Gulf of Aqaba is the second arm of widespread and can be accumulated in various environmental the triple junction system (Limits of Oceans and Seas, 2010). systems (Liu et al., 2007). PAHs tend to be adsorbed tightly to The environmental problems in the region of the Gulf of sediments in aquatic system (Mouton et al., 2009; Li et al., Aqaba are primarily induced by associated activities of tour- 2009; Xu et al., 2014). Petroleum hydrocarbon pollution has ism and maritime traffic. Human impacts on the environment been an increasing concern in the last 40 years due to its wide can be summarized into seven broad categories, as follows: usage as an energy source in most industrial and developing wastewater management practices, solid waste management countries. Petroleum hydrocarbons generated from human practices, ship-based activities, ferry traffic, tourism, cruise- activities and industrial processes are widespread and cause boating, and marine aquaculture (REMIP, 2008). This study serious environmental problems due to their persistence, toxic, is a continuation of the previous work to further investigate mutagenic, bioaccumulation and carcinogenic properties the possible PAH sources and their trends in the Red Sea. (Sakari et al., 2008). Aliphatic and aromatic hydrocarbons The objectives of the current study were to: (1) measure the inter to the environment through leaks, spills or accidents, concentrations of PAHs in surface sediment of Suez Gulf, industrial releases, or as by-products from commercial or Aqaba Gulf and the Red Sea to investigate the sources of domestic uses (Ou et al., 2004). Aliphatic hydrocarbons consist PAHs pollution, (2) evaluate the relationship between PAH of straight and saturated carbon chain starting from C6–C40 compositions and particle size fractions, and (3) assess the containing odd and even carbon numbers indicating anthropo- potential human health risk. genic and natural hydrocarbon sources (El Sikaily et al., 2002, 2003; El Nemr and El-Said, 2012; El Nemr et al., 2004, 2007, Materials and methods 2012, 2013). PAHs are compounds containing two or three aromatic Sediment sampling rings with a linear, cluster and angular arrangement. These compounds are divided into two categories based on molecular weight; first, high-molecular weight (HMW) compounds con- Surface sediment samples were collected from sixteen different taining 4–6 combined rings, like indeno (1, 2, 3-c, d) pyrene; locations along the Suez Gulf, Aqaba Gulf and the Egyptian second, low-molecular weight (LMW) compounds containing Red Sea coast during 2011 (Fig. 1). Surface sediments were two or three combined benzene rings, like naphthalene, collected with Van Veen grab from the upper 5 cm. After col- anthracene and fluorene (Tolosa et al., 2005; Abdollahi lection, samples were putted in pre-cleaned wide-mouth glass et al., 2013). bottles, stored at 20 C until analysis. The samples were ana- Aliphatic and aromatic hydrocarbons cause significant lyzed according UNEP techniques (UNEP/IOC/IAEA, 1991, environmental problems due to their carcinogenicity and 1992). The samples were air dried at room temperature, then mutagenicity (Christensen and Bzdusek, 2005; Meyer et al., kept in a clean stopped polyethylene bottle to be ready for 2011). PAHs tend to be sorbed to sediments (Manariotis grain size, total organic carbon (%TOC), and total organic et al., 2011), which may release back into the water column matter. The water content for sample was estimated by drying by any chemical change in the aquatic system (Sofowote exact weight of each sediment sample in the oven at 105 Ctoa et al., 2008; Zhang et al., 2012). constant weight. The Northern Red Sea is an important sea area both for fishing and for its unique and often spectacular marine envi- Grain size analysis ronment (Morgan, 2004).The sources and causes of water pollution in the Red Sea can be categorized into: sewage, The grain size analysis was determined according to Folk persistent organic solids, heavy metals, oils (hydrocarbons), (1974). The samples were air dried, then split to ensure that nutrients, sediment mobilization, and litter. The Gulf of Suez representative portions of the samples will be examined. About occupies the northwestern arm of the Red Sea between the 50 g of each representative sample was washed thoroughly by

Total phosphorus (TP), inorganic phosphorus (IP), and organic phosphorus (OP)

30° Suez 01 Suez 05 The TP content was determined according to Aspila et al. (1976), where 0.2–0.5 g of the sample is transferred into an Suez 10 Sinai uncovered crucible and ignited in a muffle furnace at 550 C Nuweibaa 29° for 2 h and left to cool, then transferred to 100-ml measuring flasks with the help of about 50 ml of 1 N HCl. Then, the flask Dahab Saudi was shaken for 14–18 h on an electric horizontal shaker. After El Tour Arabia 28° the extraction, aliquots of the ignited solutions were trans- Ne'ama bay ferred into a 15 ml test tube and centrifuged at 2000 rpm for Ras Mohamed Ras Sharm El-Mayaa about 5 min; then, clarified extracts were finally diluted and Hurghada analyzed for TP using the modified single solution method Sheraton 27° described by Murphy and Riley (1962). The IP was determined using the same method for TP omitting ignition. The OP was Safaga estimated by subtracting the value of IP from that of TP for

El-Quseir the same sample. 26° Red Sea PAH analysis

Marsa Alam Chemicals 25° Egypt Aluminum oxide and Silica gel were sonicated in n-hexane according to methods of Ehrhardt (1987). After ﬁltration, they were dried by nitrogen stream, activated by heating, then par- 24° tially deactivated by 5% water and stored in closed bottles. All solvents used were pesticide grade obtained from BDH or Merck. Sodium sulfate anhydrous was Soxhlet extracted with

Bir Shalatin n-hexane for 8 h followed by dichloromethane or methanol 23° Shalatin for another 8 h, pre combustion overnight in a furnace at El-Rahba 400 C, and cooled in greaseless desiccators. 32° 33° 34° 35° 36° Procedure Figure 1 Sampling locations along the Egyptian Red Sea coast. Thirty grams of dried sediment was taken and subjected to extraction by sonication twice in 100 ml n-hexane for 30 min, water and dried at 50 C then kept in clean stopper jars ready then sonicated in 100 ml CH2Cl2. The collected extracts were for mechanical analysis. Samples containing more than 90% of concentrated by rotary evaporator at low temperature the fractions coarser than 4 phi (0.063 mm) were subjected to (40 C), then concentrated to 1 ml by nitrogen stream. dry sieving, while those containing more than 10% of finer Cleanup of samples and fractionation were done by elusion fraction (>4 phi) were subjected to pipette analysis. through a silica/aluminum oxide column (prepared by packing 10 g of silica, 10 g of Al2O3, and 1 g of sodium sulfate anhy- n Total carbonates, total organic carbonates, and total organic drous). The extract was eluted with 30 ml of -hexane for the alkanes (F1). Then, the PAHs fraction (F2) was eluted with matters 70 ml of 9:1 ratio of hexane/dichloromethane. F1 and F2 were concentrated under vacuum to 5 and then to 1 ml by using a Total carbonates were estimated as described by Molnia gentle stream of nitrogen and subjected to the gas chromatog- (1974). About 500 mg of dry sample was weighted in a clean raphy mass spectrometry (GC–MS) analysis (UNEP, 1995). dry beaker to which 25 ml 3 N hydrochloric acid was added and heated to 50–60 C, left to react; after complete reaction, GC analyses filtered through glass filter paper, washed several times with distilled water, then dried in an oven at 40 C and reweighed the filter paper until constant weight. The difference in weight 1000-fold concentration (1000 ml of n-hexane used was con- is the weight of carbonate and the residue is the non-carbonate centrated to 1 ml) was used as blanks and analyzed by the Agi- fraction (silicate). The %TOC was determined according to the lent Technologies 7890A GC system with a 7693 Autosampler, method described by Walkely and Black (1934). This method split/splitless injector, and a fused silica capillary HP-5 (30 m, utilizes exothermic heating and oxidation with potassium 0.32 mm, 0.17 lm) 100% dimethylpolysiloxane equipped with dichromate and concentrated H SO of powdered sediment 5975C inert MSD with triple-Axis Detector and FID Detector 2 4 in the same time split 1:1 for each detector. Programmed the sample and titration of the excess dichromate with ferrous 1 ammonium sulfate solution. Total organic matter was calcu- temperature from 60 to 300 C using a rate of 5 C min lated by the following equation: and maintained at 290 C for 25 min. The GC injector and the detector (FID) were set at 280 and 300 C, respectively. TOC% ¼ 1:8 TOM% Helium was applied as the carrier gas using flow of 1 ml min1.

of terrigenous fine grain size sediments. The change of mean Table 1 Results for reference material. grain size may reflect different erosions and accretions, as well PAH name Required Found Recovery % as the influence of shell fragments (El Nemr et al., 2013). Naphthalene 27 29.1 107.8 Meanwhile, the major reservoir of organic-carbon in the global Phenanthrene 35 38.6 110.3 carbon cycle is the sedimentary organic matter (OM), which Anthracene 9.8 10.2 104.1 composed of material derived from different plankton species Fluoranthene 84 85.9 102.3 which comprise the ecology of the primary producers and con- Pyrene 77 79.2 102.9 sumers in overlying water surface. It has been estimated that Benzo(a)anthracene 53 51.1 96.4 only 1% of the produced OM might be transferred into the Chrysene 35 36.8 105.1 deep biosphere due to the degradation by aerobic and anaero- Benzo(b)fluoranthene 46 44.4 96.5 Benzo(k)fluoranthene 46 47.1 102.4 bic remineralization processes (Hedges and Keil, 1995; Benzo(a)pyrene 48 51.4 107.1 Middelburg and Meysman, 2007). The composition and Dibenzo(a,h)anthracene; 38 38.5 101.3 amount of OM preserved in marine sediments varies greatly Benzo(ghi)perylene among regions and depositional environment (Zonneveld Sum of C14–C34 8100 8155 100.7 et al., 2010a,b). In this study, total organic matter of studied areas ranges between 0.10% at El-Tour and 1.31% at Sheraton (Table 3). All studied locations (except Suez 01 and Sheraton) have low TOM (Table 3), which is an indication to the prevail- Two-microliter of each sample was injected using splitless ing of some hydrodynamic factors that provoked winnowing mode followed by 1 min purge time. The individual PAH any material less dense than shells. Also, the low value attri- response factor was measured to the internal standard and cal- bute to the position of the sampling from the terrestrial dis- culated at the beginning, in the middle, and at the end for each charge, which is regarded as the main contributor of the batch of injections in GC (ten samples). Identification and organic detritus, may indicate the dominance of oxidizing con- quantification of 16 PAHs were based on matching their reten- ditions, which may be due to permanent sediment reworking tion time with the standards of PAH for the FID. The SIM and a low sedimentation rate (El Nemr et al., 2013). On the mass spectrometer used electron energy 70 eV. The 16 PAHs same manner, the sediments in Ne’ama Bay, Quseir and Marsa Molecular weight were reported elsewhere (El Nemr et al., Alam are mainly silicates (Table 3). It seems that two factors 2007). may produced the richness in the carbonate content: first the eroded carbonate-rich coastal materials and second the mixing Analytical quality controls of sediments with shell fragments of lamellibranchs, gastro- pods, and other calcareous debris. The high carbonate content To control the accuracy of the results, the IAEA-408 reference records at the rest of the studied stations (Table 3) may be material (sediment) provided by the International Atomic resulted from wave directions, displaces, and concentrates Energy Agency Marine Environmental Studies Laboratory 4 sand comprising whole shells and fragments. The determined Quai Antoine 1er BP. No. 800, MC98 012 MONACO Cedex total carbonate content ranges from 24.58% at Marsa Alam was processed at the same time as the sediment samples. The to 98.93% at Shalatin El-Rahaba. The sources of carbonates lowest detection limit (0.02 lgml1) was reported for the in marine sediments are residual from weathering of limestone lower molecular mass compounds, while the highest rock, terrestrial and biogenic from skeletal parts (El Nemr (0.1 lgml1) was for indeno [1, 2, 3-cd] pyrene. The PAHs et al., 2013). Also, the results of total inorganic and organic in the samples were obtained by a combination of the retention phosphorus contents are listed in Table 3. The total phospho- time match and the mass spectra match against that of the rus varied from a minimum of 195.12 lg/g at Suez 05 to a max- PAH standards. The external standardization method was imum of 2634.97 lg/g at Safaga. The inorganic phosphorus used for the quantitation. The recovery efficiency ranged from constitute is the dominant form, while the organic phosphorus 96.4% to 110.3 % (Table 1). comprises 31% of the total estimated phosphorus; where, Phosphorus (P) is one of essential nutrients for life on earth, Results and discussion and is presented in soils, sediments, waters, and organisms.

Grain size provides important data on the sediment prove- Alkane distribution and characterization nance, depositional conditions and transport history (Folk and Ward, 1957; Friedman, 1979; Bui et al., 1990; Blott and The aliphatic hydrocarbon concentrations and other related pye, 2001). Table 2 represents the spatial pattern of grain size, parameters are shown in Table 4. Total aliphatic hydrocarbon mean, sorting, skewness, and kurtosis. The sediments in the concentrations (C14–C32) ranged from 33.97 to 553.48 ng/g studied areas have a nature from very fine sand to very coarse with a mean value of 174.8 ± 167.06. The highest and lowest sand, mainly biogenic fragments, and carbonate aggregates. alkane concentrations are recorded at El-Tour and Ras The texture varies from very coarse sand at El-Tour, Sharm Mohamed, respectively. Low molecular weight (LMW) and El-Mayaa and Na’ama Bay to coarse sand at Marsa Alam high molecular weight (HMW) normal alkane which are used to Medium Sand at Suez 01 and Dahab to fine sand at Suez as a source identifier are shown in Table 5. The ratios of low to 05, Noweibaa, Ras Mohamed, NIOF-Hurghada, Sheraton- high (LMW/HMW) range from 0.18 to 6.11 at El-Quseir and Hurghada, Shalatin El-Rahaba and Bir Shalatin and very Bir Shalatin, respectively. Low LMW/HMW ratio at El-Quseir fine sand at Suez 10, Safaga and El-Quseir (Table 2). The could be attributed to higher plant, sedimentary bacteria and occurrence of fine sediments may be due to the dominance marine animals inputs; whereas the slightly higher LMW/

Table 2 Characterization of the coastal surface sediments of the Egyptian Red Sea during 2011. Station Water content Mean (Ø) Sorting (Ø) Skewness Kurtosis Suez Gulf Suez 01 2.0941 1.96 2.12 0.19 0.58 Medium sand Very poorly sorted Coarse skewed Very platykurtic Suez 05 2.0066 2.49 0.46 0.06 1.21 Fine sand Well sorted Near symmetrical Leptokurtic Suez 10 1.2933 3.11 0.92 0.49 1.58 Very fine sand Moderately sorted Coarse skewed Very leptokurtic El-Tour 1.7499 0.63 1.52 0.65 1.35 Very coarse sand Poorly sorted Strongly fine skewed Leptokurtic Aqaba Gulf Noweibaa 3.989 2.09 1.5 0.41 1.36 Fine sand Poorly sorted Strongly coarse skewed Leptokurtic Dahab 3.9079 1.7 1.01 0.15 0.73 Medium sand Poorly sorted Coarse skewed Platykurtic Sharm El-Mayaa 3.0186 0.45 1 0.83 0.68 Very coarse sand Moderately sorted Strongly fine skewed Platykurtic Ras Mohamed 4.0134 2.71 0.76 0.02 1.16 Fine sand Moderately sorted Near symmetrical Leptokurtic Na’ama Bay 2.922 0.04 0.79 0.26 0.88 Very coarse sand Moderately sorted Coarse skewed Platykurtic Red sea proper NIOF-Hurghada 1.1532 2.22 1.27 0.24 0.87 Fine sand Poorly sorted Coarse skewed Platykurtic Sheraton-Hurghada 0.9228 2.22 1.7 0.16 0.88 Fine Sand Poorly sorted Coarse skewed Platykurtic Safaga 1.0783 3.08 0.82 0.41 1.17 Very fine sand Moderately sorted Coarse skewed Leptokurtic El-Quseir 0.9556 3.11 1.1 0.42 1.69 Very fine sand Poorly sorted Coarse skewed Very leptokurtic Marsa Alam 1.3278 0.26 0.93 0.43 0.68 Coarse Sand Moderately sorted Fine skewed Platykurtic Shalatin El-Rahaba 1.6764 2.71 0.84 0.04 1.37 Fine sand Moderately sorted Near symmetrical Leptokurtic Bir Shalatin 1.7453 2.31 1.77 0.44 0.76 Fine sand Poorly sorted Coarse skewed Platykurtic

Table 3 Description of the coastal surface Sediment of the Egyptian Red Sea 2011.

Location TOC% TOM% TCO3 % TSIO3 %TP(lg/g) IP (lg/g) OP (lg/g) Suez Gulf Suez 01 0.66 1.18 86.88 13.12 215.48 158.11 57.37 Suez 05 0.26 0.47 89.52 10.48 195.12 154.46 40.66 Suez 10 0.14 0.24 96.45 3.55 652.87 446.11 206.76 El-Tour 0.06 0.1 80.35 19.65 501.91 252.61 249.3 Aqaba Gulf Noweibaa 0.19 0.35 78.59 21.41 452.27 279.02 173.25 Dahab 0.14 0.24 82.08 17.92 606.73 381.03 225.7 Sharm El-Mayaa 0.24 0.43 71.29 28.71 344.11 230.83 113.28 Ras Mohamed 0.17 0.31 83.68 16.32 339.31 213.69 125.62 Ne’ama Bay 0.49 0.89 30.81 69.19 409.24 161.46 247.78 Red Sea proper Hurghada 0.42 0.76 84.16 15.83 735.69 360.15 375.54 Sheraton 0.73 1.31 73.86 26.14 694.23 627.84 66.39 Safaga 0.31 0.56 55.6 44.4 2634.97 2143.25 491.72 Quseir 0.2 0.37 43.88 56.12 1444.12 1202.26 241.86 Marsa Alam 0.23 0.42 24.58 75.42 1085.1 747.97 337.13 Shalatin El-Rahaba 0.37 0.66 98.93 1.07 554.97 344.07 210.9 Bir Shalatin 0.35 0.63 80.27 19.73 971.41 427.79 543.62

Table 4 Total aliphatic hydrocarbon (ng g1 ) and related parameters in sediment collected from the Red Sea. P Location C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 C28 C29 C30 C31 C32 Total ðÞC14–C32 Suez Gulf Suez 01 25.45 236.49 4.6 9.08 3.16 21.69 94.52 12.78 4.34 7.67 10.6 23.87 12.01 ND 12.47 10.58 10.75 6.72 23 529.78 Suez 05 9.21 4.28 9.31 13.17 7.54 8.1 5.41 19.73 ND 13.09 11.9 12.86 9.95 ND 12.89 8.65 7.07 7.3 2.2 162.67 http://dx.doi.org/10.1016/j.ejar.2014.11.003 Suez (10) 14.02 3.07 1.13 7.81 6.04 14.52 26.86 21.76 ND 15.81 19.59 34.19 55.86 ND 71.99 1.97 1.94 2.46 10.73 309.76 El-Tour 15.9 8.79 8.19 73.44 52.47 80.62 40.97 51.91 2.36 41.8 3.7 55.84 34.03 3.7 34.81 3.2 1.09 4.19 36.46 553.48 Aqaba Gulf Nuweiba 6.75 1.13 0.97 17.12 0.96 5.92 4.86 1.12 ND ND 1.85 1.8 1.36 ND 2.46 1.16 2.85 ND ND 50.29 Dahab 9.41 2.05 9.99 12.28 1.96 49.86 14.69 ND ND 0.98 5.14 4.13 8.72 ND 17.93 32.65 32.53 21.87 8.12 232.32 Sharm El Mayaa 13.93 1.51 18.18 4.26 6.01 13.09 ND 8.48 ND 3.63 1.29 1.74 ND ND ND ND ND ND ND 72.12 Ras Mohamed 2.61 3.15 ND 2.18 ND 11.64 14.39 ND ND ND ND ND ND ND ND ND ND ND ND 33.97 Na’ama Bay 10.89 2.43 16.08 8.11 13.52 14.07 22.9 11.61 ND 9.94 9.39 7.63 5.5 ND 4.56 2.88 3.93 0.37 ND 143.81 Red Sea Hurghada NIOF 8.77 2.44 9.13 1.84 0 20.57 12.16 15.91 ND ND ND ND ND ND ND 6.64 ND ND ND 77.46 Sheraton 22.85 7.47 6.91 4.67 5.53 22.97 32.32 3.17 ND 11.65 9.22 9.48 8.43 ND 9.27 6.94 6.41 4.57 15.08 186.93 Safaga 72.79 0.93 4.43 7.01 20.51 12.41 64.22 27.55 ND 19.05 22.11 25.19 32.82 ND 37.9 32.8 54.49 23.61 7.78 465.61 El-Quseir 4.66 0.72 3.63 5.67 7.62 9.43 0.82 8.89 55.91 4.78 5.15 1.99 5.45 2.18 4.38 4.01 1.53 76.62 10.69 214.12 Marsa Alam 10.16 1.05 12.72 28.47 22.75 11.84 30.39 45.61 ND 34.03 32.65 28.09 26.86 ND 25.25 19.38 16.53 10.29 2.76 358.8 Bir Shalatin 26.5 7.19 5.73 5.78 3.73 15.7 55.88 1.03 ND 1.66 3.82 4.08 3.66 ND 4.62 0.86 ND ND ND 140.24 El-Rahaba Shalatin 9.35 2.89 29.06 9.36 2.62 19.41 23.22 12.46 ND 4.4 10.58 7.64 11.21 ND 8.17 3.88 6.08 1.49 ND 161.81 Mean 16.45 17.85 8.75 13.14 9.65 20.74 27.73 15.13 3.91 10.53 9.19 13.66 13.49 0.37 15.42 8.48 9.08 9.97 7.30 230.82 SD 16.57 58.36 7.50 17.36 13.26 18.88 25.74 15.50 13.92 12.30 9.00 15.73 15.82 1.04 19.20 10.65 14.74 19.27 10.33 167.06 Max 72.79 236.49 29.06 73.44 52.47 80.62 94.52 51.91 55.91 41.8 32.65 55.84 55.86 3.7 71.99 32.8 54.49 76.62 36.46 553.48 Min 2.61 0.72 ND 1.84 ND 5.92 ND ND ND ND ND ND ND ND ND ND ND ND ND 33.97 ...AySlme al. et Salem Aly D.M.S. fteRdSea, Red the of Monitoring and risk assessment of aliphatic and aromatic hydrocarbons 7

Table 5 Concentrations of n-alkanes (ng/g) and calculated distribution indexes in surface sediments of the Red Sea 6 LMW LHC Location LMW (R C20) HMW (R P C21) % LMW % HMW HMW CPI NAR TAR Paq CP1 CP2 SHC ACL n-alkanes/C16 Suez Gulf Suez 01 394.99 134.79 74.56 25.44 2.93 0.44 0.34 0.06 0.65 0.90 0.69 0.27 27.01 115.17 Suez 05 57.02 105.64 35.05 64.94 0.54 0.40 0.17 0.62 0.62 0.92 0.81 0.95 27.72 17.47 Suez (10) 73.45 236.30 23.71 76.28 0.31 0.02 0.35 0.17 0.92 0.96 0.85 2.09 25.59 274.12 El-Tour 280.38 273.09 50.66 49.34 1.03 0.13 0.22 0.07 0.93 0.92 0.77 0.53 25.68 67.58 Aqaba Gulf Nuweiba 37.71 12.60 74.99 25.05 2.99 0.25 0.14 0.05 0.61 0.98 0.84 0.30 26.57 51.85 Dahab 100.24 132.07 43.15 56.85 0.76 0.85 0.11 0.85 0.09 0.92 0.90 1.31 29.46 23.26 Sharm El Mayaa 56.98 15.14 79.01 20.99 3.76 NC 0.91 ND 1.00 0.68 0.57 0.05 25.00 3.97 Ras Mohamed 33.97 ND 100.00 ND NC NC 0.11 ND NC 1.00 NC 0.00 NC NC Na’ama Bay 88.00 55.81 61.19 38.81 1.58 0.31 0.00 0.13 0.84 0.88 0.73 0.34 26.26 8.94 Red Sea Hurghada NIOF 54.91 22.55 70.89 29.11 2.44 NC 0.56 0.27 0.00 0.86 1.00 0.09 29.00 8.48 Sheraton 102.72 84.22 54.95 45.05 1.22 0.42 0.16 0.33 0.65 0.86 0.65 0.66 27.63 27.05 Safaga 182.30 283.30 39.15 60.84 0.64 0.40 0.22 2.77 0.44 0.97 0.87 1.13 28.34 105.10 El-Quseir 32.55 181.58 15.20 84.80 0.18 0.79 0.12 5.23 0.08 0.93 0.86 1.15 30.66 58.99 Marsa Alam 117.38 241.45 32.71 67.29 0.49 0.41 0.05 0.72 0.68 0.96 0.78 0.99 27.41 28.21 Bir Shalatin 120.51 19.73 85.93 14.07 6.11 0.13 0.49 0.03 0.87 0.95 0.78 0.14 25.70 24.47 El-Rahaba Shalatin 95.91 65.91 59.27 40.73 1.46 0.23 0.09 0.17 0.69 0.81 0.78 0.45 26.88 5.57 Mean 114.31 116.51 56.28 43.73 1.76 0.37 0.02 0.72 0.60 0.90 0.79 0.65 27.26 54.68 SD 97.70 99.11 23.79 23.79 1.63 0.24 0.35 1.38 0.32 0.08 0.11 0.58 1.59 69.95 Max 394.99 283.30 100.00 84.80 6.11 0.85 0.91 5.23 1.00 1.00 1.00 2.08 30.66 274.12 Min 32.55 ND 15.20 ND 0.18 0.02 0.49 ND ND 0.68 0.11 0.05 1.59 3.97

HMW ratio at Sharm El Mayaa (3.76), Nuweiba (2.99) and greater contribution from vascular plants (Rieley et al., 1991; Suez 01 (2.93) could be attributed to fresh oil inputs (Sakari Hedges and Prahl, 1993); CPI values close to unity are thought et al., 2008). Accordingly, the variation in n-alkanes content to indicate greater input from petroleum, recycled organic may refer to the anthropogenic sources (sewage, industrial dis- matter, and/or microorganisms (Kennicutt et al., 1987). In charges, and shipping activities) and natural inputs (sub- the present study, CPI values for all stations show no signifi- merged/floating macrophytes and emergent terrestrial plants cant differences between stations. The CPI range was 0.02– and microbial activity; (Oyo-Ita et al., 2010; El Nemr et al., 0.85 (Table 5) which reflects that all sediment samples are 2013). probably contaminated with petrogenic hydrocarbons based The LHC/SHC ratios were calculated to determine the on CPI values <3 indicating oiled sediments (Jeng, 2006). dominant higher plant and/or macrophyte-derived and phyto- The n-alkanes/n-C16 ratio is usually high (>50) in biogenic plankton-derived OM in the sediments, and had values ranging samples and is lower (<15) in petrogenic samples (Colombo from ND to 2.09 (Table 5). The ratios obtained for most sta- et al., 1989). Calculations of the value of n-alkanes/n-C16 tions with high values (0.14–2.09) are dominated by macro- (Table 5) indicated a mixture of sources including biogenic phyte waxes and/or higher plant, whereas samples from and petrogenic. The ratio of terrigenous to aquatic (TAR) n- stations Ras Mohamed and Sharm El Mayaa with low values alkanes defined as (0.00 and 0.05) are dominant by phytoplankton-derived OM TAR ¼ðC27 þ C29 þ C31Þ=ðC15 þ C17 þ C19Þ (Commendatore et al., 2000; El Nemr et al., 2013). Sample from station Hurghada NIOF has an intermediate value Was used previously (Jeng and Huh, 2006) for possible (0.09) suggesting a mixture of both input sources with no changes investigation in the terrigenous/aquatic mixture of particular dominant trend (Oyo-Ita et al., 2010). The anthro- hydrocarbons. As shown in Table 5, the TAR values were pogenic source may be petroleum, but it can also be recycled ranging from 0.00 at Sharm El Mayaa and Ras Mohamed organic matter of different origins, such as sewage, soil organic sediments to 5.23 at El-Quseir sediments, indicating that sed- matter washed by rains, and effluents from treatment plants. iments from Sharm El Mayaa and Ras Mohamed were quite Biogenic sources may be, for example, algae, plankton, different from El-Quseir sediments with respect to hydrocar- marine animals, terrestrial vascular plants, and bacteria bons. The high TAR value for El-Quseir sediments may be (Commendatore et al., 2000). One other ratio that can be used attributed to n-alkanes with short-chain which being more for source identification of aliphatic hydrocarbon pollution is prone to degradation than longer-chain ones (Jeng and Carbon Preference Index (CPI) which was defined as a ratio Huh, 2006). Average carbon chain length (ACL) is very use- of odd to even carbon. Odd number carbon is normally attrib- ful for the identification of environmental changes for a par- uted to natural sources, whereas even number carbon is attrib- ticulate ecosystem. A constant value for ACL indicates that uted to anthropogenic sources. Due to the CPIs of terrestrial little environmental changes are occurring in the system (El higher plant waxes (Jeng, 2006) yielding high values, usually Nemr et al., 2013). The NAR is defined as follows (Mille 5–10, higher CPI values found in sediment or soil show et al., 2007):

R The Paq ranged from 0.0 to 1.0 (Table 5) and according to Ficken et al. (2000), values of Paq between 0.01 and 0.23 are due to terrestrial plant waxes; whereas values of PAHs

R Paq between 0.48 and 0.94 are due to submerged/ﬂoating species of macrophytes. Generally, our results showed the contribution of both higher plant/macrophyte waxes derived and phytoplankton-derived OC (El Nemr et al., 2013).

Polycyclic aromatic hydrocarbons

The concentrations of individual PAH and total PAH (RPAHs) in surface sediments from different studied stations are presented in Table 6. RPAHs concentrations in sediments vary signiﬁcantly among the studied stations. RPAH concentrations were in the range of 0.74–456.91 ng/g, with the mean value of 32.94 ng/g. The highest concentration of total PAHs is recorded in sediments collected from El-Quseir (456.91 ng/ g), followed by that in Sharm El Mayaa (100.05 ng/g) and Suez 10 (97.19 ng/g), while lower concentrations are detected in Sheraton (a), Ras Mohamed and Na’ama bay (0.74, 6.86 and 11.1, respectively). The variability in PAH content along the studied sediments may be related to the different sources of discharged waters, proximity to human activities, and fuel combustion emissions. Additionally, some published studies detailing PAHs levels in sediments from other areas such as rivers or seas are listed in Table 7. Indicating the concentrations of PAHs in sediments of the Red Sea proper were relatively less than those in some areas of the world. However, Baumard et al. (1998a) classiﬁed the relative contamination ) in surface sediments collected from the Red Sea.

1 level into four categories or groups: (a) low, 0–100 ng/g; (b) moderate, 100–1000 ng/g; (c) high, 1000–5000 ng/g; and (d) very high, more than 5000 ng/g. According to this classiﬁca- tion scale (Table 8), all the stations studied, except El-Quseir, are slightly contaminated, with a total PAH concentration of 0.74–100.05 ng/g, while El-Quseir is moderately contaminated (456.91 ng/g). Meanwhile, sediment sample concentrations in the Red Sea proper are higher than those reported in Jamaica, but lower than those of more developed countries of the world such as France (The Basque Country), Croatia, India, Brazil and China, even if they are higher than levels reported for Georgia (Table 7)(Chen and Chen, 2011; El Nemr et al., 2013).

Source identiﬁcation of PAHs Concentration of individual PAHs (ng g The main sources of PAHs in aquatic system originate mainly from pyrolytic or petrogenic sources (Zakaria et al., Table 6 PAHs Naph Acthy Ace Fl Phe Ant Flu Pyr BaA Chr BbF BkF BaP BghiP InP Suez Gulf Suez 01Suez 05Suez 10El-TourAqaba Gulf 1.96Nuweiba 0.86Dahab 0.3 9.15Sharm El 0.27 0.04 MayaaRas Mohamed 2.68 2.64 1.63 1.49Na’ama Bay 0.49 0.23 2.15 0.06 0.02 4.45Red 4.64 Sea 0.89 1.68 1.92 0.99 proper 1.04 0.33 0.36Hurghada 0.43 1.69 9.98 0.3 0.71 5.27Sheraton 2.76 0.69 3.25 16.16 0.26 1.9 ND 0.67Safaga ND 1.65 2.23 0.3 ND 1.14 0.36El-Quseir 5.24 4.03 1.4 11.04 8.09 0.72 ND NDMarsa 3.07 1.42 Alam 10.06 0.83 3.04Bir 0.33 0.31 6.14 Shalatin 88.55 0.11 3.18 ND 0.02 0.39 0.5 0.24 0.9El-Rahaba 7.75 0.75 Shalatin 2.32 0.78 ND 2.82 0.01 3.27 8.44 4.06 2.82 1.27 1.04 1.62 3.33 0.55 1.87 0.1 0.31 1.28 18 0.22 12.32 ND 0.63 1.5 0.03 0.63 0.07 0.76 0.94 0.67 1.12 0.87 3.42 0.72 ND2002; 0.11 ND 1.69 ND 2.45 1.57 11.67 1.19 0.24 0.42 ND 0.56 7.25 1.02 ND 0.17 0.04 1.53 ND 2.05 0.13 1.28 0.19 0.91 2.17 0.87 3.22Stout 0.32 4.54 2.74 0.06 0.45 ND 3.94 97.19 29.43 1.63 1.13 7.18 0.84 8.47 6.84 0.13 ND 3.05 ND ND 0.06 0.7 0.34 1.39 ND 28 4.62 0.36et 0.56 0.94 18.99 1.72 45.52 14.29 ND 3.35 0.06 0.32 0.24 1.5al., 0.49 3.76 2.7 36.43 0.77 0.06 0.13 0.74 ND 0.17 9.49 0.13 13.23 0.45 2.922004 100.05 0.02 0.15 0.51 ND 2.85 16.84 0.31 2.49 17.23 46.84 48.56 0.08 ND 0.46 53.57 7.07 21.66 0.74 385.18 2.23). 7.67 ND 1.94 0.06 3.66Pyrolytic 8.73 ND 0.09 8.57 32.82 0.16 49.97 6.86 ND 0.06 4.23 0.47 4.46 1.49 46.23 33.41 2.21 0.89 11.99 11.1 ND 2.28 12.97 0.05 2.05 7.07 3.07 ND 0.31 31.01 4.29 3.43 0.05 0.39 1.67 1.55 ND 3.20 0.97 4.02 61.27PAHs 6.83 3.61 0.36 27.22 0.37 0.3 0.03 1.46 0.26 0.51 1.25 1.27 0.74 11.13 1.03 72 92.82 1.29 6.77which 3.34 ND 456.91 0.18 0.62 61.53 50.7 0.46 442.82 ND 32.47 0.83 3.38 46.38derived 4.86 14.38 40.89 ND 17.2 27.7 1.05 96.92 11.11 2.32 62.16 2.50 from 64.42 ND 0.76 72.27 52.97 54.64 77.26 0.12 1.62 7.57 45.27 3.62 3.91 1.36 0.10 6.00 2.39 2.39 0.93

Table 7 A comparison of PAHs concentrations in surface sediments collected from the Egyptian Red Sea coast with these collected from different estuaries and bays (ng/g dry weight) around the world. Location Range Mean References Egypt(Red Sea) Suez Gulf 18.99–97.19 45.51 This study Aqaba Gulf 6.86–100.05 40.998 This study Red Sea proper 0.74–456.91 93.49 This study Asia Dalian Bay, China 32.70–3558.88 1152.08 Liu et al. (2001) Daya Bay, China 115–1134 481 Zhou and Maskaoui (2003) Deep Bay, China 184.1–581.5 353.8 Qiu et al. (2007) Hsin-ta Harbour, Taiwan 1156–3382 Fang et al. (2003) Jiaozhou Bay, China 16–2164 559.1 Wang et al. (2006) Kyeonggi Bay, Korea 9.1–1400 120 Kim et al. (1999) Liaodong Bay, China 276.26–1606.89 743.03 Men et al. (2009) Masan Bay, Korea 207–2670 680 Yim et al. (2005) Meizhou Bay, China 196.7–299.7 256.1 Lin et al. (2003) Minjiang River Estuary, China 174.96–817.40 437.21 Yuan et al. (2001) Pearl River Estuary, China 323–2372 1587 Mai et al. (2001) Xiamen Harbour, China 247–480 367 Zhou et al. (2000) Yalujiang Estuary, China 68–1500 Wu et al. (2003) Yangtze Estuary, China 84.6–620 259 Hui et al. (2009) Leizhou Bay, China 22.83–17.00 Zhu (2007) Zhanjiang Bay, China 22.65–79.76 Zhu (2007) Leizhou Bay, China 21.72–319.61 103.91 Huang et al. (2012) Zhanjiang Bay, China 41.96–933.90 315.98 Huang et al. (2012) America Boston Harbour, USA 7266–358,092 Wang et al. (2001) Casco Bay, USA 16–20,748 2854 Kennicutt et al. (1999) Chesapeake Bay, USA 0.56–180 52 Foster and Wright (1988) Kitimat Harbour, Canada 310–528,000 66,700 Simpson et al. (1996) Narragansett Bay, USA 569–216,000 21,100 Hartmann et al. (2004) Penobscot Bay, USA 290–8800 2600 Johnson et al. (1985) San Diego Bay, USA 80–20,000 3000 Anderson et al. (1996) San Francisco Bay, USA 2653–27,680 7457 Pereira et al. (1996) Todos os Santos Bay, Brazil 8–4163 714.1 Venturini and Tommasi (2004) Todos Santos Bay, Mexico 7.6–813 96 Macias-Zamora et al. (2002) Europe Aquitaine Bay, France 3.5–853 256 Soclo et al. (2000) Santander Bay, Spanish 20–344,600 49,079.40 Viguri et al. (2002)

Table 8 Total concentrations of polycyclic aromatic hydrocarbons in sediments from various locations in the world. The pollution levels are assigned as low: 0–100 ng/g; moderate: <100–1000 ng/g; high: <1000–5000 ng/g and very high: >5000 ng/g (Baumard et al., 1998a). Geographical areas-continents Islands-countries RPAH (ng/g dw) Pollution levels References Caraibe Jamaica 0.97–358 Low to moderate Jaﬀe´ et al. (2003) Caraibe Guadeloupe 49–1065.7 Low to high Ramdine et al. (2012) Caraibe Guadeloupe 103–1657 Low to high Bernard et al. (1996) North America USA (Georgia) 1.2–160 Low to moderate Kumar et al. (2008) Arabian peninsula Yemen 2.2–604 Low to moderate Mostafa et al., 2009 Asia India (Bay of Bengal) 121.8–533.7 Moderate Zuloaga et al. (2009) Europe Croatia 32–13700 Low to very high Bihari et al. (2006) South America Brazil 80–42,390 Low to very high Nishigima et al. (2001) Asia China 1041–6186 High to very high Tam et al. (2001) Europe France (Pays Basque) 1000–120,000 High to very high Cortazar et al. (2008) Egypt Red sea 0.74–456.91 Low to moderate The present study

Table 9 Polycyclic aromatic hydrocarbons analyzed with abbreviations and number of aromatic rings. Compounds Abbreviations Number of cycles R % Naphthalene Naph C2 26.88 2.58 Acenaphthylene Acthy C2 11.37 1.09 Acenaphthene Ace C2 27.01 2.59 Fluorene Fl C2 4.29 0.41 Phenanthrene Phe C3 54.42 5.23 Anthracene Ant C3 33.5 3.22 Fluoranthene Flu C3 118.83 11.41 Pyrene Pyr C4 44.53 4.28 Benzo(a)anthracene BaA C4 503.43 48.34 Chrysene Chr C4 7.96 0.76 Benzo(b)ﬂuoranthene BbF C4 65.31 6.27 Benzo(K)ﬂuoranthene BkF C4 60.29 5.79 Benzo(a)pyrene BaP C5 13.34 1.28 Dibenzo[a,h]anthracene DBA C5 38.48 3.69 Indeno[1,2,3-cd]pyrene InP C5 7.09 0.68 Benzo(ghi)perylene BghiP C6 24.77 2.38

Table 10 Percentage of distribution of hydrocarbons in different stations according to number of carbon. Stations %C2 %C3 %C4 %C5 %C6 Suez 01 18.30 25.60 48.79 1.56 5.74 Suez 05 14.86 27.77 52.37 4.32 0.68 Suez 10 13.21 28.59 43.58 2.60 12.01 El-Tour 18.11 27.35 41.29 10.15 3.10 Nuweiba 12.02 21.45 56.75 8.34 1.44 Dahab 2.93 3.92 91.41 1.50 0.24 Sharm El Mayaa 1.83 90.36 6.69 0.77 0.36 Ras Mohamed 32.41 67.59 0.00 0.00 0.00 Na’ama Bay 16.44 18.07 54.38 4.43 6.68 Hurghada NIOF 17.80 30.14 41.30 7.49 3.27 Sheraton (a) 8.11 21.62 47.30 16.22 6.76 Safaga 14.15 3.07 73.55 7.08 2.15 El-Quseir 0.85 2.20 88.90 7.26 0.79 Marsa Alam 6.37 33.23 56.88 2.92 0.59 Bir Shalatin 9.17 10.42 68.52 2.92 8.96 El-Rahaba Shalatin 15.67 22.60 51.42 8.74 1.57

Table 11 Ratios of PAHs in sediments in different stations from the Egyptian Red Sea coast. Stations Ratio LMW/HMW BaA/228 Ant/178 InP/BghiP <1 >1 <0.2 >0.35 <0.1 >0.1 <0.2 >0.5 Suez 01 0.527 0.035 0.002 0.112 Suez 05 0.484 0.027 0.009 0.000 Suez 10 0.670 0.044 0.091 0.110 El-Tour 0.524 0.034 0.004 0.832 Nuweiba 0.380 0.079 0.017 0.662 Dahab 0.070 0.007 0.005 1.125 Sharm El Mayaa 0.038 0.015 0.004 Ras Mohamed 0.687 0.000 0.001 Na’ama Bay 0.398 0.020 0.003 0.000 Hurghada NIOF 0.566 0.015 0.009 Sheraton 0.276 0.001 0.000 0.6000 Safaga 0.203 0.076 0.002 0.942 El-Quseir 0.028 1.689 0.008 Marsa Alam 0.475 0.095 0.026 0.600 Bir Shalatin 0.197 0.038 0.003 0.000 El-Rahaba Shalatin 0.428 0.034 0.004 1.216

2005). The RLPAHs include Naph, Acthy, Ace, Fl, Phe, Ant þ and Ant; the RHPAHs include Flu, Pyr, BaA, Chr, BbF, Ant Phe BkF, BaP, InP, DBA, and BghiP (Tables 7 and 10). In all studied stations, RLPAHs/RHPAHs ratios were less than 1, which indicate that they derived from pyrogenic sources Ant (Tables 9–11; Fig. 2). Phe Phe/Ant ratios have been used to study the petrogenic or pyrogenic sources of PAHs in sediments: (a) Phe/Ant (Soclo LAPH et al., 2000; Magi et al., 2002) or alternatively, Ant/ HAPH (Phe + Ant) ratio (Baumard et al., 1998a,b; Yunker et al., 2002; Li et al., 2006; Qiao et al., 2006); reveal that the sediment is mainly contaminated by petrogenic inputs (Table 12). The Phe is thermodynamically more stable and its preva- HPAH R lence over Ant indicates that the PAHs in sediment were mainly due to petrogenesis activities. The petroleum product usually show a quite high value of Phe/Ant ratio. If the Phe/

Ant ratio is higher than 10 (or Ant/(Phe + Ant) > 0.1), it LPAH typically reveals that the PAH source is from pyrolytic activ- R ities (Baumard et al., 1998a; Qiao et al., 2006). As shown in Table 12, the ratios of Phe/Ant and Ant/(Phe + Ant) in all PAHs studied stations except Suez 01 were <10 and >0.1, respec- COMB P tively (Table 12). This implies that the source of PAH could P be due to combustion activities and the sediment is mainly contaminated by petrogenic inputs (Chen and Chen, 2011). The Flu/Pyr and Flu/(Flu + Pyr) ratios are also useful COMB

indicators for evaluating the attribution of PAH pollution R in sediments (Guinan et al., 2001; Magi et al., 2002; Li et al., 2006). As previously mentioned by Baumard et al. (1998a); if the ratio (Flu/Pyr) > 1, PAHs will be from pyrolytic source but when the ratio is less than 1, its source is from petroleum source. Moreover, if Flu/(Flu + Pyr) > 0.5, the pyrolytic source from the combustion of grass, wood, or coal is estimated (Yunker et al., 2002; Qiao et al., 2006). However, if the ratio of Flu/(Flu + Pyr) is between 0.4 and 0.5, PAHs Isomeric ratio of PAHs in sediment collected from the Red Sea. are mainly from the combustion of petroleum; if the ratio <0.4, petroleum contamination is estimated (Yunker et al., 2002; Qiao et al., 2006). As shown in Table 12, the ratio of Table 12 Flu/Pyr < 1 at Stations Suez 10, Dahab, Safaga, Bir Shalatin, StationSuez 01Suez 05Suez 10El-Tour TH NuweibaDahab 559.21Sharm El Mayaa 181.66Ras Mohamed 406.95 19.08Na’ama Bay 589.91 11.97 172.17 103.86Hurghada NIOF 57.68Sheraton 0.65 23.32 40.83 265.73 95.86Safaga 0.63 36.58 104.68El-Quseir 0.59 154.91 0.64 30.83Marsa 10.17 4.06 Alam 0.96 0.68Bir 15.91 Shalatin 6.19 7.74El-Rahaba 38.98 Shalatin 187.67 0.92 12.54 0.59 19.28 0.58 14.75 3.69 194.28 0.70 537.61 671.03 409.5 12.79 0.54 58.21 154.62 2.19 416.86 23.91 20.9 2.79 0.53 59.28 33.08 9.84 38.82 96.37 3.15 0.73 0.48 11.86 0.67 13.48 0.91 0.52 0.82 0.64 31.22 0.65 0.38 4.06 0.07 0.99 0.04 0.82 17.40 0.62 0.16 7.87 7.92 12.44 0.50 12.16 0.07 0.62 1.71 1.58 9.73 16.32 1.24 0.69 0.11 0.57 2.37 0.40 0.37 0.39 1.36 0.34 444.47 0.58 0.15 0.55 1.38 59.85 1.33 2.18 22.75 34.38 0.74 1.42 1.13 118.07 0.58 0.42 12.02 0.03 0.13 0.31 0.28 0.57 0.20 0.41 0.99 0.99 0.43 0.47 0.91 0.53 NC 5.17 0.20 0.67 1.06 1.00 10.17 4.79 0.95 1.60 5.63 1.83 0.96 0.48 0.16 0.60 1.00 1.00 0.17 1.14 6.19 1.00 0.51 38.98 0.15 0.35 12.54 0.61 0.53 3.69 0.47 10.00 1.00 14.75 0.65 NC 0.02 0.95 1.29 0.52 0.68 0.96 0.91 0.54 0.38 1.00 0.98 0.50 2.19 0.04 0.02 0.40 2.79 0.49 0.56 9.84 0.53 0.14 3.15 0.49 0.43 0.99 1.00 0.07 0.99 0.38 0.90 0.69 0.94 1.00 0.62 12.44 0.41 0.16 1.00 12.16 0.24 16.32 9.73 0.92 0.48 0.03 2.37 0.46 0.30 0.21 0.49 0.47 0.17 0.20 0.60 0.13 0.31 0.41 0.45

Table 13 ERL and ERM guideline values of PAHs in surface sediments (ng/g dw) (Long et al., 1995; Mai et al., 2002; Liu et al., 2009a,b,c). ERL ERM This study Mean Minimum Maximum >ERL

Figure 3 Comparison of ERM, ERL with PAHs concentration in sediment samples. and El-Rahaba Shalatin. Moreover, Dahab, Bir Shalatin and Assessment of PAHs using biological thresholds El-Rahaba Shalatin stations recorded Flu/(Flu + Pyr) ratio between 0.4 and 0.5, indicating that they originated from To study the biological effects of PAHs of Aqaba Gulf, Suez petroleum combustion. However, Flu/(Flu + Pyr) for Suez Gulf and the Red Sea proper; the effects range-low (ERL) 10 and Safaga stations were less than 0.4, revealing the petro- and the effects range-median (ERM), were used in this study leum contamination. The other stations which recorded Flu/ (Long et al., 1995; Kim et al., 1999; Mai et al., 2002; Li Pyr < 1 and Flu/(Flu + Pyr) > 0.5 (Table 12), indicating that et al., 2012). For the three ranges of chemical concentrations, the main PAHs source was biomass combustion. Other ratios adverse biological effects were expected rarely (

Please cite this article in press as: Aly Salem, D.M.S. et al., The monitoring and risk assessment of aliphatic and aromatic hydrocarbons in sediments of the Red Sea, Egypt. Egyptian Journal of Aquatic Research (2014), http://dx.doi.org/10.1016/j.ejar.2014.11.003 Monitoring and risk assessment of aliphatic and aromatic hydrocarbons 13 cause mild adverse biological effects but not acute effects ranged from 33.97 to 553.48 ng/g with a mean value of (Fig. 3). 174.8 ± 167.06. The highest and lowest alkane concentrations are recorded at El-Tour and Ras Mohamed, respectively. High Risk assessment levels of PAHs were reported in El-Quseir station, while low levels of PAHs were reported for all other stations. Ratio Some PAHs have a high concern because of their documented between low molecular weight of PAHs (2- and 3-rings) to high carcinogenicity (Qiao et al., 2006). The BaP equivalent (BaPE) (4- to 6-rings) has been used to differentiate between the pyro- was used to quantitatively assess the PAHs potential health genic and petrogenic sources of PAHs in the studied samples. risk (Liu et al., 2009a,b,c; Wang et al., 2009). The BaPE was Risk assessment of PAHs was performed by the BaPE values obtained using the following equation (Liu et al., 2009a,b,c): method. The results obtained showed that there is no risk in the most studied locations except at El-Quseir station. Results BaPE ¼ BaA 0:06 þ BbF 0:07 þ BKf 0:07 þ Bap obtained led to understand the potential risks and sources of þ DahA 0:06 þ Icdp 0:08 PAHs in the Red Sea coast, and to provide more information for protecting human health and water resources in this region. The carcinogenicity of some PAHs is well documented (Qiao et al., 2006). The BaP equivalent (BaPE) is used to esti- mate the PAHs potential health risk (Liu et al., 2009a,b,c; References Wang et al., 2009) following the above equation. The PAHs risk assessment in sediments has been reported Abdollahi, S., Raoufi, Z., Faghiri, I., Savari, A., Nikpour, Y., (Qiao et al., 2006; Wang et al., 2009); however, there is no Mansouri, A., 2013. Contamination levels and spatial distributions available information on the PAHs quantitative risk assess- of heavy metals and PAHs in surface sediment of Imam Khomeini Port, Persian Gulf, Iran. Mar. Pollut. Bull. 71, 336–345. ment. Zhang et al., 2012, developed a new method to quanti- Anderson, J.W., Newton, F.C., Hardin, J., Tukey, R.H., Richter, tatively PAHs risk assessment by combining the BaPE values K.E., 1996. Chemistry and toxicity of sediments from San Diego with estimated source contributions. The BaPE calculated in Bay, including a biomarker (P450 RGS) response. In: Bengtson, this study is reported in Table 6. 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