Development in Analytical Chemistry Volume 1, 2014 www.seipub.org/dac
Detection of Anthropogenic Aliphatic and PAHs Fractions in the Near‐shore Waters Along Alexandria Coasts, Egypt Tarek O. Said*1,2, Laila A. Mohamed1, Mohamed A. Okbah1, Islam M. Othman1 Marine Chemistry, National Institute of Oceanography and Fisheries, Alexandria, Egypt.
1
Chemistry Department, Faculty of Science, King Khalid University, KSA.
2 *
tareksaideg@yahoo.co.uk; lila_salam@yahoo.com; m_okbah@yahoo.com; islam_shalaby_2007@yahoo.com
Received 21 September 2014; Accepted 24 December 2014; Published 29 December 2014 © 2014 Science and Engineering Publishing Company Abstract The determination of the residual fractions of 19 aliphatic fractions and 16 PAHs fractions were determined in the near‐shore surface water of Alexandria coast, Egypt. The total average concentrations of aliphatic hydrocarbons fractions (from C10 to C32), varied from a minimum of 670.27 ngL‐1 recorded at Abu Qir to a maximum of 4514 ngL‐1 recorded at El‐Shatby station with a total average of 2435 ngL‐1 during 2013‐2014. The average PAHs values ranged from 1223 to 11183 ng/l with an average value of 4326 ng/l during 2013‐2014. The ∑CARC was the highest during August 2013 with an average of 50.29 ngL‐1. Total hydrocarbon concentrations (THC= ∑ALIP+∑PAHs) were ranged from 1894‐15698 ngL‐1 with an average of 6763 ngL‐1. Keywords Surface Water; PAH; Alexandria; Egypt; GC‐MS
Introduction Scientific interest in the quality of marine ecosystems is quite recent and has especially increased in the past 15 years in relation to application of the European Union (EU)ʹs Water Framework Directive (WFD), (European Commission 2000). In coastal areas where various human activities take place, effects have already become obvious, having social, economic and environmental impacts. However, the quality of marine waters is directly related to the presence and storage of a large number of xenobiotics (Nikolaou et al. 2009). Of all marine pollutants, hydrocarbons have received the greatest attention due primarily to the highly lethal effects of most hydrocarbons on marine organisms, especially aromatics class. Hydrocarbons as potential environmental contaminants are an
assemblage of substances coming from various sources including biogenic, petrogenic and pyrolytic (WHO 1979; Yunker et al. 1993; Page et al. 1996; UNEP 1996; Hostettler et al. 1999; Wilet and Edward 2000; Wu et al. 2001; Gao and Chen 2008).The occurrence of polycyclic aromatic hydrocarbons (PAHs) in the marine environment has attracted the attention of the scientific community, as these compounds are frequently detected in seawater and sediments at increasing levels and have adverse health effects on marine organisms and humans. Several PAHs are potential human carcinogens and are included in the priority list of the European Union’s Water Framework Directive (2000/60/EC). Sixteen PAHs, identified by the US Environmental Protection Agency (EPA) as priority pollutants (Keith and Telliard 1979;Venkatesan et al. 1982; Manoli et al. 2000; Nieva et al. 2001; Zhanga et al. 2004; Tang et al. 2005; Said and Hamed 2006b; Guo et al. 2007), are a class of organic pollutants which have an important impact on marine ecosystems because they include the largest known class of chemical carcinogens and mutagens (Neff 1979; WHO/UNEP 1990; Witt 1995; Tolosa et al. 2004; Cardellicchio et al. 2007; Binelli et al. 2008). Although the study of pollutants in the Egyptian Mediterranean Sea have been investigated by numerous workers (Said et al. 1994; Barakat 2004; Shreadah et al. 2006; El Deeb et al. 2007; Emara et al. 2008; Emara and Shreadah 2009). Along the Mediterranean coast of Alexandria city, there are many areas with high activities of shipping and pleasure boating activities, incorporating numerous Harbours and marinas (Berrojalbiz et al. 2011). The
31
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present paper is considered as one of the most important records to investigate levels and distributions of aliphatic and PAHs fractions in seawater of the swimming areas of Alexandria, Egypt. Materials and Methods Surface water samples were collected from 10 sampling stations on local motorboat using Niskin bottle (Figure 1). The location of each sampling station was determined using a GPS (Trimble Navigation) to pinpoint sampling locations. Sampling sites were selected taking into consideration the expected polluted areas due to industrial and human activities. Samples were subsequently kept refrigerated at – 4℃ prior to analysis in the laboratory. One liter of seawater was poured into glass separatory funnel, extracted twice with 2 x 40ml of methylene chloride. The extract was stored in dark at low temperature (~5℃). Before analysis, the stored extracts were evaporated to dryness in a rotary evaporator at 30℃ under reduced pressure. The residue was re‐dissolved in 1ml of n‐ hexane before fractionation with column chromatography (Parsons et al. 1985). M e d i t e r r a n e an S e a
FIG. 1 SAMPLING STATIONS OF WATER SAMPLES COLLECTED FROM SWIMMING AREAS OF ALEXANDRIA, EGYPT DURING 2013‐2014; I: ABU QIR, II: EL‐MONTAZAH, III: EL‐ASAFRAH, IV: SIDI BISHR, V: GLEEM, VI: STANLY, VII: SIDI GABER, VIII: EL‐ SHATBY, IX: ABUL‐ABBAS AND X: EASTERN HARBOUR.
The extracted volumes were passed through the silica column prepared by slurry packing 20 mls (10g) of silica (activated at 185℃ overnight and deactivated with 12.5 % water afterwards), followed by 10 ml (10g) of alumina (90 neutral, 70‐230 mesh previously activated at 185℃ overnight and deactivated with 12.5% water afterwards) and finally 1g of anhydrous sodium sulphate. Elution was performed using 40 mls of hexane (aliphatic fractions), then 40 ml of hexane/dichloromethane (90:10) followed by 20 mls of
32
hexane/dichloromethane (50:50) (which combined contain PAHs). Finally, the eluted samples were concentrated under a gentle stream of pure N2 to about 0.2 ml. Activated copper was added for desulfurization. Eighty ml of methylene chloride were poured into a rotary evaporator flask and evaporated to dryness at 30℃. The residue was dissolved in 1 ml of n‐ hexane before fractionation, used as a blank (UNEP/IOC/IAEA 1992). Blanks of 1000 fold concentration were analyzed by GC‐MS; Trace‐Ultra coupled to DSQ‐ II MS (thermo electron SPA) equipped with auto injector. The mass spectrometer was operated in full scan mode (50‐650) Daltons per second. The ionization source was supplied with voltage at 70 eV. Three μl volume of each sample was injected in the split‐less mode. Sixteen EPA‐PAH compounds were naphthalene (Naph, m/z 128), acenaphthylene (Acthy, m/z 152), acenaphthene (Ace, m/z 154), 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 276), indeno(1,2,3‐cd)pyrene (InP, m/z 276), and dibenz(a,h)anthracene (DBA, m/z 278). GC/MS is equipped with splitless injector and a fused silica capillary column; Thermo TR‐35 MS (30m, 0.25mm, 0.25μm) with 35% phenyl polysilphenylene‐ siloxane. Helium was used as carrier gas at 1.5ml min−1. The oven temperature program was 60℃ (1 min) ramped at 8℃/min to 100℃, hold for 1 minute then ramped at 5℃/min to 300℃ maintaining about 20℃. The injection and the transfer line temperature were maintained at 280 and 300℃, respectively. 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 USA 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 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%, 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%.
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Re esults and Discussio on 6000.00 Conc ng/L Conc., ng/L
Tab ble 2 and Figure 2 present thee total averrage con ncentrations of aliphattic hydrocarrbons fractiions (fro om C10 to o C32), witth values varied v from m a miinimum of 670.27 6 ngL‐1 recorded at Abu Qir to t a maaximum of 4514 4 ngL‐1 reecorded at Ell‐Shatby witth a tottal average of 2435 ng gL‐1 during 2013‐2014. The con ncentrations below theiir limits of detection were w giv ven a value o of zero for th he calculatio on. A maxim mum con ncentration of o ALIPH frractions was recorded att El‐ Shatby with 122586 ngL‐1 du uring Decemb ber 2013.
X
IX
VIII
VII
VI
V
IV
III
II
I
Station
FIG G. 2 VARIATION N OF AVERAG GE ALIP CONCENTRATIONS (ng L‐1) IN SURFACE ) WATER SAMP PLES OF ALEXA ANDRIA DURIN NG 2013‐‐2014.
Tab bles 3‐8 and Figure 3 show the totall concentrations of PAHs in water. w The cconcentration ns below th heir lim mits of detecttion were giv ven a value of zero for the calcculation. Th he average P PAHs valuees ranged frrom ‐1 122 23 to 11183 n ngL with an average valu ue of 4326 ng gL‐1 durring 2013‐2014 (Table 8).
Compon nent
DL, μg ml‐11; dry weight
Naph h
0..04
Acthy y
0..01
Ace
0..01
Phe
0..02
Ant
0..01
Flu
0..03
SAMPLES COLLEC CTED FROM ALEX XANDRIA, WATER S
Pyr
0..03
EGYPT DURIN NG JUNE 2013
BaA
0..04
TAB BLE 3. CONCENTRATIONS OF IND DIVIDUAL PAHS (n ngL‐1) RECORDED D IN
Com mpound
Station
Chr
0..04
VI
VII VIII
IX
X
BaP
0..05
Naph N
0.0
35.9 0.0 1.6 0.0 0.0
0.0 0 0.0
0.0
0 0.0
BbF
0..05
Acthy A
0.0
0.0 0.0 165.2 0.0 0.0
0.0 0 0.0
0.0
0 0.0
BkF
0..05
Ace
0.0
0.0 0.0 4594 0.0 0.0
0.0 0 0.0
0.0
0 0.0
DBA
0..06
Fllurene
0.0
5.9 0.0 90.7 0.0 0.0
0.0 0 0.0
0.0
0 0.0
Phe
0.0
6 655.4 0.0 6.3 0.0 0.0
0.0 0 0.0
0.0
0 0.0
Ant
0.0
56.9 0.0 50.9 0.0 0.0
0.0 0 0.0
0.0
0 0.0
Flu
0.0
19.7 0.0 283.8 0.0 0.0
0.0 0 0.0
0.0
0 0.0
BghiP P
0..08
InP
0.0001
I
II
III
IV
V
TABLE 2. CONC CENTRATIONS OF ∑ALIPHATIC H HYDROCARBONS
Pyr
0.0
89.0 0.0 126.0 0.0 0.0
0.0 0 0.0
0.0
0 0.0
FRACTIONS (ngL‐11) RECORDED IN W WATER SAMPLES S COLLECTED FRO OM
BaA
0.0
0.0 0.0 2092 0.0 1337.2 0.0 0 0.0
0.0
4115.0
ALE EXANDRIA, EGYP PT DURING 2013‐2014
2000.00 0.00
TABLE 1.. DETECTION LIM MITS FOR INDIVIDU UAL PAHS RECORDED U USING GC‐MS
4000.00
Chr
0.0
1 141.9 0.0 112.5 0.0 55.6
0.0 0 0.0
0.0
6 64.0
BbF
0.0
4 479.8 0.0 179.9 0.0 0.0
0.0 0 0.0
0.0
0 0.0
Station
Jun., 2013
Aug g., 20133
Dec., 2013
Mar., 2014
Jun n., 20114
BkF
0.0
20.5 0.0 0.0 0.0 0.0
0.0 0 0.0
0.0
0 0.0
Abu‐Qir
15.1
1837.4
1266.1
18.85
213.9
BaP
0.0
20.5 0.0 16.7 0.0 0.0
0.0 0 0.0
0.0
0 0.0
E El‐Montazah
2918.6
3210.4
6131.5
3648.2
52111.8
InP
0.0
1 108.6 0.0 27.6 0.0 0.0
0.0 0 0.0
0.0
0 0.0
0.0
90.5 0.0 41.6 0.0 0.0
0.0 0 0.0
0.0
0 0.0
0.0
0.0 0.0 10.8 0.0 0.0
10.3 0.0 10.3
0 0.0
El‐Asafrah
140.15
1792.550
3219.50
175.19
2568.28
DBA D
Sidi Bishr
1 1551.22
1706.335
3258.87
1939.03
2770.04
B(ghi)P PAHs P
Gleem
0.00
966.119
9447.71
0.00
2095.00
Stanly
1 1031.11
1134.222
2166.19
1288.88
1841.26
Sidi Gaber
2 2007.90
2208.669
4218.28
2509.88
3585.54
El‐Shatby
0.00
5267.997
12585.8
1938.75
2779.64
A Abul‐Abbas
1 1797.00
2239.223
4246.22
79.86
114.09
Eastern Harbour
1 1827.00
1422.775
5021.76
77.44
AV
1 1128.80
2178.557
MAX
2 2918.58
MIN
0.00
0.0 1724.8 0.0 7799 0.0 1392.8 10.3 0.0 10.3 4779.0
∑C CARC
0.0
6 699.5 0.0 2368 0.0 1337.2 10.3 0.0 10.3 4115.0
CA ARC%
0.0
40.6 0.0 30.4 0.0 96.0 100 0.0 0.0 100.0 86.6 8
∑C COMB
0.0
3 328.1 0.0 573.1 0.0 55.6
0.0 0 0.0
0.0
6 64.0
∑C COMB/ 0.0 ∑P PAHs %
19.0 0.0 7.3 0.0 4.0
0.0 0 0.0
0.0
1 13.4
4268.49
∑F FPAHs
0.0
6 697.3 0.0 4858 0.0 0.0
0.0 0 0.0
0.0
0 0.0
∑F FPAHs/ 0.0 ∑P PAHs %
40.4 0.0 62.3 0.0 0.0
0.0 0 0.0
0.0
0 0.0
5156.18
1167.61
2544.80
5267.997
12585.8
3648.22
5211.75
Ph he/ant
0.0
11.5 0.0 0.1 0.0 0.0
0.0 0 0.0
0.0
0 0.0
966.119
1266.08
0.00
114.09
Flu/py F
0.0
0.2 0.0 2.3 0.0 0.0
0.0 0 0.0
0.0
0 0.0
33
Rattio values su uch as Phe//Ant and Flu/Py had been useed by differrent workerss to identify y the origin n of hyd drocarbons (IARC 19833; Garriguees et al. 19993; Ben nlachen et all. 1997). Petrroleum often n contains more m pheenanthrene relative r to anthracene ass phenanthrene tha at is more a thermody ynamically stable tricy yclic aro omatic isomeer than anthrracene, so a Phe/An ratio o is obsserved to be very high in n PAH petrog genic pollutiion, butt low ratio in n pyrolytic co ontamination n cases.
15000.00 10000.00 5000.00
Abul‐Abbas
El‐Shatby
Stanly
Sidi Gaber
Glemm
Sidi Bishr Sidi Bishr
El‐Asafrah
El‐Montazah
Abu‐Qir
0.00
Eastern …
Conc., μg/l
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Station
F FIG. 3 DISTRIBU UTION OF AVE ERAGE CONCE ENTRATIONS O OF PA AHS ngL‐1 RECO ORDED IN WAT TER SAMPLES OF ALEXAND DRIA DURING 2013‐2014. TA ABLE 4. CONCENT TRATIONS OF IND DIVIDUAL PAHS (ngL‐1) RECORDED D IN WATER SAMPLE ES COLLECTED FR ROM ALEXANDRIA A, EGYPT DURING G AUGU UST 2013
Station I II III IV V VI VII VIII IX X Naph 0 40 0 2 7 8 124 0 103 8 Acthy 207 49 0 182 49 100 123 172 170 94 Ace 26 1484 2711 5053 1291 36900 651 257 230 874 Phe 0 721 0 7 12 3 18 42 16 3 Ant 125 63 2299 56 26 42 51 3 23 32 Flu 125 22 62 312 82 412 189 260 110 400 Flurene 0 7 16 100 1 55 83 3 2 61 Pyr 135 98 1699 139 71 224 84 6 27 210 BaA 1368 2831 13388 2301 0 14711 1205 3736 863 984 Chr 38 156 83 124 56 61 194 0 104 78 BbF 2 528 57 198 0 1 4 223 104 1 BkF 0 23 0 0 0 7 130 30 26 7 BaP 14 23 5 18 6 87 16 8 2 68 InP 7 119 7 30 1 3 110 31 986 3 DBA 6 100 49 46 0 60 913 58 261 60 B(ghi)P 162 0 7 12 4 9 11 11 3 9 Total PAHs 2215 6261 22933 8579 1605 62322 3906 4842 3030 2892 ∑PAHCARC 1559 3600 14633 2605 10 16311 2259 4068 2219 1125 CARC% 70 57 64 30 1 26 58 84 73 39 ∑COMB 298 305 3299 674 210 758 680 300 269 756 ∑C COMB/∑PAHs % % 13 5 14 8 13 12 17 6 9 26 ∑FPAHs 358 2356 5000 5300 1385 38433 967 474 542 1011 ∑FP PAHs/∑PAHs % % 16 38 22 62 86 62 25 10 18 35 Phe/ant 0 12 0 0 0 0 0 16 1 0 Flu/py 1 0 0 2 1 2 2 42 4 2 BaA/Chr 36 18 16 19 0 24 6 0 8 13 Compound
A maximum concentration of total PAHs was w meeasured in water w colleccted from Eastern Harb bour du uring June 2014, 2 while lower conceentrations were w dettected in sample of loccations: Abu Qir, El‐Asaafra, Gleeem and El‐‐Shatby durin ng June 20133. In this stu udy, thee order of decreasing PAHs con ncentrations for surrface waterss is illustrateed in Figure 3. The averrage con ncentration of PAHs in the preesent study y is mo oderate in comparison c to those in most areass of urb banized estu uaries in the other countrries represen nted in Table 9.
34
TAB BLE 5. CONCENTRATIONS OF IND DIVIDUAL PAHS (n ngL‐1) RECORDED D IN S COLLECTED FRO OM ALEXANDRIA A, EGYPT DURING G WATER SAMPLES DECEMB BER 2013
Station I II III IV V VI VII VIII IX X Naph 3 1 0 0 58 0 0 0 45 54 Acthy 14 0 20 4 770 1 2 0 159 162 Ace 140 0 11 0 6 0 151 0 159 159 Phe 10 0 16 58 57 3 2 2 20 20 Ant 14 0 58 0 891 0 12 2 71 85 Flu 1 18 196 58 562 20 279 238 437 512 Flurene 1 7 57 58 335 58 147 140 14 17 Pyr 142 4 336 5576 20 33 835 599 419 401 BaA 140 30 381 58 575 2 141 97 0 0 Chr 15 61 437 8811 575 125 15 1669 1308 1221 1 BbF 419 62 200 196 1409 2 20 576 1451 1325 1 BkF 0 0 0 0 575 0 0 0 0 0 BaP 15 3 62 20 575 11 2 12 7 7 InP 14 0 7 11 2280 6 14 7 2 2 DBA 2 0 33 9 1593 3 16 14 2 3 B(ghi)P 20 1 3 12 655 2 1 13 6 10 Total PAHs 950 186 1816 11869 10935 265 1 1638 3368 4098 3977 3 ∑PAHCARC ∑ 610 95 686 3306 7087 25 193 719 1467 1347 1 CARC% 64 51 38 16 65 10 12 21 36 34 ∑COMB 159 90 1026 11502 2067 236 1 1277 2645 2177 2151 2 ∑CO OMB/∑PAHs % % 17 49 56 80 19 89 78 79 53 54 ∑FPAHs 181 1 104 61 1781 4 168 4 454 480 ∑FP PAHs/∑PAHs % % 19 0 6 3 16 2 10 0 11 12 Phe/ant 1 0 0 0 0 10 0 1 0 0 Flu/py 0 4 1 0 29 1 0 0 1 1 BaA/Chr 10 0 1 0 1 0 9 0 0 0 Compound
Thee calculated Phe/An ratio o of <1 (Tables 4‐8) of m most different sea of water samp ples during d asons indicaated tha at the major PAH inputt was from combustion n of fossil fuel viaa pyrolytic process. In n addition, the calcculated Flu/P Py ratio >1 ssuggested th hat the origin n of PA AH was relaated to a pyrolytic orig gin. This iss in acccordance witth Garrigues et al. (1993) and Benlah hcen et al. a (1997) wh ho stated th hat Flu/Py ra atio less than n 1 sug ggested thatt the major PAH was frrom petrogeenic inp puts, and vaalues greateer than 1 were w related to pyrrolytic origiin. The BaA A/Chr ratio has also been sug ggested to identify i PAH sources, and this raatio ten nded to in ncrease as petrogenicc contributtion deccreased. Thee ratio valu ues for crud de and fuel oil ran nged from 0.24 to 0.4 (M Mazmanidi ett al. 1976; IA ARC
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1983). The BaA/CHR ratio in the present study was 2.54 (Tables 4‐8); suggesting that the main source of PAH contamination in Alexandria near‐shore came from crude or fuel oil. TABLE 6. CONCENTRATIONS OF INDIVIDUAL PAHS (ngL‐1) RECORDED IN WATER SAMPLES COLLECTED FROM ALEXANDRIA, EGYPT DURING MARCH 2014
Compound
Station I
II III IV
V
Naph
4
1 1002 0
82 35 84 21 64
Acthy
20 0 29
6 1099 2
Ace
200 0 15
0
8
0 216 0 227
12
Phe
14 0 23 82
82
4
116
Ant
20 0 82
Flu
2 25 281 82 802 29 399 339 624 1146
Flurene
VI VII VIII IX 3 3
0 1273 0 18
X 117
0 227 1571 3
28
3 102 1818
2 10 82 83 479 82 210 201 20
Pyr
202 6 480 822
28 48 1193 855 598
BaA
201 42 544 82 822 3 201 139 0
684 40 1174
Chr
21 88 624 1159 822 178 22 2384 1868 1174
BbF
598 88 286 281 2013 3 28 822 2072 2875
BkF
0
BaP
22 4 88 28 822 16 3
InP
20 0 10 16 3257 8 20 10
2
4652
2
3
3251
9
1336
DBA B(ghi)P
0
0
0
822 0
0
0
4
17 935 3
2
1174
17 10 1174
0 48 13 2276 4 22 20
29 1
0
18
Total PAHs
1357 266 3597 2671 15621 414 2423 4833 5854 22315
∑PAHCARC
871 136 980 437 10124 36 276 1027 2096 14463
CARC%
64 51 27 16
∑COMB
227 129 1466 2146 2953 337 1824 3779 3110 4219
∑COMB/∑PAHs % 17 49 41 80 ∑FPAHs
Flu/py BaA/Chr
9 11 21 36
19 81 75 78 53
65 19
WATER SAMPLES COLLECTED FROM ALEXANDRIA, EGYPT DURING JUNE 2014
Station I II III IV V VI VII VIII IX X Naph 5 1 1179 0 97 41 98 25 76 138 Acthy 24 0 34 7 1293 2 3 0 267 1848 Ace 236 0 18 0 10 0 254 0 267 14 Phe 17 0 27 97 96 5 3 3 33 137 Ant 24 0 97 0 1497 0 21 3 120 2139 Flu 2 30 330 97 944 34 470 399 734 1349 Flurene 2 12 96 97 563 97 247 236 24 805 Pyr 238 7 565 967 33 56 14041006 704 47 BaA 236 50 640 97 967 3 237 164 0 1381 Chr 25 103 734 1363 967 210 26 28042198 1381 BbF 704 103 336 330 2368 3 33 967 2438 3383 BkF 0 1876 0 0 967 0 2896 0 0 1382 BaP 26 5 104 33 967 19 3 20 12 1381 InP 24 0 12 19 3831 9 24 12 3 5474 DBA 3 0 56 16 2678 5 26 24 3 3825 B(ghi)P 34 1 5 20 1100 3 2 21 10 1572 Total PAHs 1596218942323142 18377 487 57475685688726254 ∑PAHCARC 1 0 1 1 12 0 0 1 2 17 CARC% 0 0 0 0 0 0 0 0 0 0 ∑COMB 0 2 2 3 3 0 5 4 4 5 ∑COMB/∑PAHs % 0 0 0 0 0 0 0 0 0 0 ∑FPAHs 0 0 1 0 3 0 0 0 1 4 ∑FPAHs/∑PAHs % 0 0 0 0 0 0 0 0 0 0 Phe/ant 1 0 0 0 0 10 0 1 0 0 Flu/py 10 1 0 1 2 0 0 0 0 2 BaA/Chr 10 0 1 0 1 0 9 0 0 1 Compound
TABLE 8. AVERAGE CONCENTRATIONS OF PAHS RECORDED IN WATER SAMPLES COLLECTED FROM ALEXANDRIA DURING 2013‐2014
259 1 1151 88 2544 41 323 27 648 3634
∑FPAHs/∑PAHs % 19 0 32 Phe/ant
65
TABLE 7. CONCENTRATIONS OF INDIVIDUAL PAHS (ngL‐1) RECORDED IN
3
16 10 13
1
11
16
1
0
0
0
0
10 0
1
0
0
0
4
1
0
29
1
0
0
1
29
10 0
1
0
1
0
9
0
0
1
The IARC (1983) probable and possible human carcinogens ∑PAHCARC was ranged from 3.58 to 3044 with an average value of 1978 ngL‐1 and an average % of 33.38 of total PAHs (Tables 3‐8). On the other hand, low MW < 178 PAH includes Naph, Acthy, Ace and Fl can be derives mainly from fossil sources rather than from microbial activity. In this study, the ∑FPAH (Tables 4‐8) varied from <DL to 5300 ng/l with an average of 685 ng/l, accounting for an average of 14% of the total anthropogenic PAHs. Contributions from combustion/pyrolysis of fossil fuel can be assessed by considering un‐substituted PAH with MW > 178 includes Phe, An, Flu, Py, BaA, Chr, BbF, BkF, BaP, BghiP, DBA and InP. The ∑COMB concentrations displayed values from <DL to 4219 ng/l with an average of 783ngL‐1, representing average 25% of total anthropogenic PAHs (Tables 3‐8).
Station I II III IV V VI VII VIII IX X AV Max MIN
Jun 0 1725 0 7799 0 1393 10 0 10 479 1142 7799 0
2013 Aug 2215 6261 2293 8579 1605 6232 3906 4842 3030 2892 4185 8579 1605
PAHs, ng/l 2014 Dec Mar Jun 950 1357 1596 186 266 2189 1816 3597 4232 1869 2671 3142 10935 15621 18377 265 414 487 1638 2423 5747 3368 4833 5685 4098 5854 6887 3977 22315 26254 2910 5935 7460 10935 22315 26254 186 266 487
AV
Max
MIN
1224 2215 2125 6261 2387 4232 4812 8579 9308 18377 1758 6232 2745 5747 3746 5685 3976 6887 11183 26254 4326 9047 11183 26254 1224 2215
0 186 0 1869 0 265 10 0 10 479 282 1869 0
The Sum of five carcinogenic PAHs (∑CARC; sum of BaA+BbF+BaP+DBA+InP) recommended by IARC was the highest during August 2013 with an average of 50.29 ngL‐1 (Table 4). The maximum concentration of (∑CARC was 3600 ngl‐1 recorded at El‐Montazah. Total hydrocarbon concentrations (THC= ∑ALIP+ ∑PAHs) were ranged from 1894‐15698 ngl‐1 with an average of 6763 ngL‐1 (Table 10). This value is safe and
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not affecte on marine organisms of the area of investigation. TABLE 9. COMPARISON OF PAHS CONCENTRATIONS (ngL−1) IN WATER RECORDED IN THE PRESENT STUDY WITH OTHER AREAS OF THE SURROUNDINGS
Range Reference (ngL‐1) Nearshore areas of Alexandria 1223 ‐ Present study coasts, Egypt 11183 127.17‐ Abu‐QirBay, Alexandria, Egypt Shreadah et al 2013 456.19 75.10‐ Eastern Harbour, Alexandria, Egypt Shreadah et al 2013 286.02 29.31‐ WesternHarbour, Alexandria, Egypt Shreadah et al 2013 292.72 107.95‐ El‐Max Bay, Alexandria, Egypt Shreadah et al 2013 209.0 Jiulong River Estuary and Western 6960‐ Maskaouia et al. Xiamen Sea, China 26900 2002 Deep Bay, South China 69.4 ‐ 24.7 Qiu et al. 2009 192.5 ‐ Tonghui River of Beijing, China Zhanga et al. 2004 2651 400 ‐ Said and Hamed Red Sea Coast, Egypt 96,450 2006a El Nemr and Abd‐ Alexandria Coast, Egypt 13 ‐ 120 Allah 2003 El Nemr and Abd‐ Alexandria Coast, Egypt 117.5 ‐ 564 Allah 2003 <2 and Brighton Marina, UK FAO 1967 11,400 Jiulong River Estuary and Western 6960 ‐ Maskaoui et al. Xiamen Sea, China 26,900 2002 Aquatic Environment, El‐Menofiya 226.9 ‐ Nasr et al. 2010 Governorate, Egypt 1492.2 24,390 ‐ Creek, Niger Delta region Duke 2008 283,600 Bahía Blanca Estuary, Argentina ND ‐ 4000 Arias et al. 2009 Gerlache Inlet Sea, Antarctica 5.27 ‐ 9.43 Stortini et al. 2009 Deep Bay, South China 69.4 ‐ 24.7 Gao and Chen 2008 Name of Site
TABLE 10. AVERAGE CONCENTRATIONS OF ALIPHATIC AND PAHS FRACTIONS (ngL‐1) RECORDED IN WATER SAMPLES COLLECTED FROM
ALIP 670.27 4224.09 1579.12 2245.10 2501.78 1492.33 2906.06 4514.43 1695.28 2523.49 2435.20 4514.43 670.27
PAHs 1223.54 2125.38 2387.49 4812.04 9307.59 1758.11 2744.91 3745.52 3976.00 11183.38 4326.40 11183.38 1223.54
Total 1893.82 6349.47 3966.61 7057.14 11809.37 3250.44 5650.96 8259.95 5671.29 13706.87 6761.59 15697.81 1893.82
This is in accordance with conclusion derived from Mazmanidi et al. who stated that the THC
36
Conclusions The investigation of water in Alexandria coasts revealed that Aliphatic and PAHs were detected using selected GC‐MS technique. The baseline data can be used for regular ecological monitoring, considering the industrial and agricultural growth around this important ecosystem. Finally the present data calls for continuous and effective environmental measures to protect the water body of the areas of the Egyptian Mediterranean Sea from pollutants. REFERENCES
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