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بحث رقم 56
بحث رقم 56
To cite this article: Omayma E. Ahmed, Ahmed M. Eldesoky & Mohamed M. El Nady (2019): Oil
hydrocarbon fingerprints of the different marine organisms in some Egyptian Gulf of Suez waters,
Petroleum Science and Technology
ABSTRACT KEYWORDS
Oil hydrocarbon fingerprints derived from polycyclic aromatic and aliphatic Egypt; n-alkanes; CPI; ACL;
hydrocarbon were analyzed in marine organisms of various aquatic species TAR; PAHs; Suez Gulf
muscles collected from 10 different sites along Suez Gulf, Egypt. All sam-
ples were analyzed for n-alkanes (C15–C37) and polycyclic aromatic hydro-
carbons (EPA list of PAHs). n-Alkanes in ten aquatic species were found to
be in the range of 11.391–96.747 ng/g wet weight with a mean value of
60.755 ng/g wet weights. Different indices were calculated for the n-alka-
nes to assess their sources as carbon preference index (CPI), average chain
length (ACL), terrigenous/aquatic ratio (TAR), natural n-alkane ratio (NAR)
and proxy ratio (Paq). Most of the various species of n-alkanes were discov-
ered to be from natural sources. Polycyclic aromatic hydrocarbons (PAHs)
varied between 81.499 and 5895.608 ng/g wet weight with an average of
2521.126 ng/g wet weight. The contents of ƩPAHs were the highest in the
tissues. The carcinogenic risks for humans from residual ƩPAHs in the vari-
ous fish tissues higher than105.
1. Introduction
The Gulf of Suez (Figure 1) extends for about 250 km southeast from the Suez port in the north
to Shadwan Island in the south with a maximum depth of about 250 m at its mouth. The width
of the Suez Gulf fluctuates between 20 and 40 km, and its depth throughout its axis is fairly con-
stant with a mean of 45 m, the Suez Bay in the northern part of the Gulf of Suez as a eutrophic
region characterized by anticlockwise water circulation. The Suez Bay ecosystem is suffering of
adverse effects of sewage discharge as well as industrial wastes from various activities based near
the Suez Gulf (Omayma et al. 2019).
Polycyclic aromatic hydrocarbons (PAHs) and n-alkanes are marine environment chronic
constituents and their concentrations have considerably increased due to anthropogenic activ-
ities. This caused undesirable effects, especially in coastal areas adjacent to highly populated
urban zones. N-Alkanes consist of saturated and straight carbon chains of C15–C36 which con-
tain even and odd carbon numbers that indicate anthropogenic and natural sources of hydro-
carbon. PAHs are organic compounds that result from the partial combustion of organic
matter pyrolytic, and oil and its derivative petrogenic sources. They are widely dispersed in
the marine environment, particularly in harbors, dockyards, marinas, estuaries and other shal-
low coastal areas with anthropogenic inputs (El Nemr et al. 2013). The evaluation and
CONTACT Mohamed M. El Nady mohamedelnady217@gmail.com Egyptian Petroleum Research Institute, Nasr city, P.O.
11727, Cairo, Egypt.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
ß 2019 Taylor & Francis Group, LLC
2 O. E. AHMED ET AL.
Figure 1. Map of study area showing Aquatic Species collection locations Suez Gulf, Egypt.
comparison levels of PAHs and their temporal changes in a marine coastal region are very
important from an environmental point of view (Omayma et al. 2019). Mussels have been
widely used for the monitoring of toxic pollutant levels in coastal environment (Saad et al.
2015). The aim of the present work is to investigate the precedence of n-alkanes and PAHs in
the collected the various species of Suez Gulf, Egypt and also, to determine the most polluted
Regions, diagnose the sources of these pollutants and calculate the cancer risk assessment of
these compounds to draw a complete picture of the pollution in these regions and then try to
find the best way for treatment.
Table 1. Concentration of n-alkanes (ng/g wet weight) and calculated distribution indices in the collected Aquatic species
muscles along the Suez Gulf.
n-alkanes parameters n-alkanes Range ƩC15–C37 LHC/SHC CPI n-Alkane/C16 TAR ACL Paq NAR
Sauridaundo squamis nC15-nC31 29.721 0.5188 1.511 178.665 4.756 19.266 0.8540 0.3024
Euthynnus affinis nC17-nC33 73.513 7,091 6.329 N.D 61.126 62.084 0.2132 0.6992
Rhabdosargus haffara nC15-nC35 96.747 26.114 11.886 1123.915 121.095 87.699 0.0031 0.6913
Argyrops Spinifer nC15-nC36 11.391 13.976 36.178 2198.986 38.776 10.620 0.0023 0.7882
Nemipterus Japonicus nC15-nC37 42.253 1.419 22.593 171.376 63.964 43.282 0.4980 0.9326
Oreochromis Niloticus nC15-nC36 92.866 18.735 44.261 4018.424 66.736 87.885 0.0158 0.9204
Trachurus Indicus nC15-nC35 35.941 17.916 16.182 2764.900 41.237 33.539 0.0073 0.8949
Peneus Japonicas nC15-nC36 47.051 18.376 22.879 2905.984 119.125 44.318 0.0130 0.8982
Scomber Japonicus nC15-nC36 93.051 21.355 17.600 787.101 52.360 85.980 0.0003 0.8828
Pomadasys Stridens nC15-nC33 85.020 13.342 5.052 N.D 28.755 71.017 0.1294 0.6616
Range of n-alkanes: Range of normal alkanes; LHC/SHC ratio: Ʃ>C23 / Ʃ<C23, CPI: carbon preference index ¼ Ʃ(C23-C31) odd
þ Ʃ (C25-C33) odd/2Ʃ (C24-C32) even, TAR: terrigenous /aquatic ratio ¼ TAR ¼ C27-C29-C31/ C15-C17-C19, ACL: average carbon
length; Paq: A proxy ratio (Paq) quantifying ¼ C23-C25/ C15-C17-C29-C31, NAR: natural n-alkane ratio¼ Ʃ n-alkanes (C19–32)-2Ʃ
even of n-alkanes (C20–32)/Alkanes Ʃ (C19–32); N. D.: not determined.
Software. The sample volume was 100 ll; the column used was Supelcosil LC-PAHs 15 cm,
4.6 mm ID, 4-lm particles; mobile phase was achieved using a acetonitrile/water ratio of
60:40 and was changed gradually to 100% acetonitrile within 20 min. The flow rate was
1.2 ml/min, and the detector used was a UV type, 254 mm.
Figure 2. Distribution of T. n-alkanes (a), Gas chromatograms (b), and PAH cross plots (c) of collected aquatic species muscles
along the Suez Gulf.
PETROLEUM SCIENCE AND TECHNOLOGY 5
microorganisms. The CPI is also used to indicate the presence of straight-chain geolipids in
organic geochemistry (Kanzari et al. 2014).
Table 2. Total Polycyclic aromatic hydrocarbons (ƩPAHs), pyrolytic (ƩCOMB), %ƩCOMB/ƩPAHs, carcinogenic PAHs, % CARC,
fossil ƩPAH), %FPAH/ƩPAH, Flu/Pyr, phe/Ant, BaA/Chr and ƩF-PAH/ƩCOMB ratio in the collected Aquatic species muscles along
the Suez Gulf.
PAHs
parameters
Aquatic ƩCOMB/ %FPAH/ Flu/ phe/ BaA/ ƩF-PAH/
Species ƩPAHs ƩCOMB ƩPAHs ƩPAHCARC % CARC ƩF-PAH ƩPAH Pyr Ant Chr ƩCOMB
Sauridaundo 5766.322 3120.064 54.103 2013.286 34.915 3636.259 63.060 1.446 1.350 0.2768 1.165
squamis
Euthynnus 3211.599 935.941 29.143 355.134 11.058 2108.191 65.643 4.682 3.406 2.076 2.252
affinis
Rhabdosargus 3917.156 486.003 12.407 217.3 5.547 3343.892 85.365 28.816 5.736 0.0248 6.881
haffara
Argyrops 5895.608 1203.382 20.412 470.80 7.987 4635.729 78.630 41.148 2.600 1.937 3.852
Spinifer
Nemipterus 1411.019 309.825 21.958 259.069 18.360 1057.163 74.922 0.530 0.135 0.8419 3.412
Japonicus
Oreochromis 81.499 66.484 81.576 28.286 34.798 15.015 18.424 N.D N.D N.D 0.2258
Niloticus
Trachurus 2346.330 1126.394 48.007 1023.424 43.618 1219.936 51.993 N.D N.D 1.952 1.083
Indicus
Peneus 541.134 99.912 18.463 531.385 98.153 3.710 0.6856 N.D N.D N.D 0.0371
Japonicas
Scomber 515.910 75.735 14.699 464.376 90.011 21.087 4.087 N.D N.D N.D 0.2784
Japonicus
Pomadasys 1524.686 548.209 35.555 548.209 35.956 76.487 64.045 N.D N.D N.D 1.781
Stridens
contaminated by petroleum hydrocarbons, and species with Phen/Ant< 10 are typical impacted
by combustion residues .The ratio of individual PAH compounds was almost stable in all spe-
cies indicating that the sources of PAH contamination might be the same. The Phe/Ant ratio
(<10) is recorded in all species (Table 2) indicating pyrolytic source. Certain PAH compo-
nents ratios of the same molecular weight are well established as an index to study PAH com-
position and deduce their possible sources. Each source of PAHs may provide a signature or
an individual profile, which can be used in the source identification of the PAHs (Kannan
et al. 2005). PAH concentration ratios of the same molecular weight (Figure 2c) such as Flu/
Flu þ Pyr and Ant/Ant þ Phe were used to study the possible sources of PAHs Ant/Ant þ Phe
ratios were mostly lower than 0.1 showed that the PAHs might be derived from petrogenic
sources. The Flu/Flu þ Pyr ratios were mostly lower than 0.5 showed petrogenic sources in all
aquatic species, except in Rhabdosargus haffar higher than 0.5 showing that the wood, grass
and coal combustion could be the possible sources of PAHs. The combustion of crop residues
might be the possible source of PAHs in seawater and consequently in the aquatic species.
However, Flu/Flu þ Pyr ratios in Argyrops Spinifer, Sauridaundo squamis, Nemipterus Japonicus,
and Rhabdosargus haffar were more than 0.5 showing pyrogenic input of PAHs, where the
rest of samples were below 0.5 showing some petrogenic input of PAHs. Figure 3 shows evi-
dence of more contributions from petroleum combustion of PAHs. Aquatic species contami-
nated with PAHs that present Ant/Ant þ Phe ratio> 0.10 and Fl/Fl þ Pyr ratio> 0.50, show
that combustion products are predominant. It was the same case for BaA/BaA þ Chr ratio
>0.35 that is together associated with Flu/Flu þ Pyr ratio> 0.40. Thus, the PAH isomer ratios
showed that the PAHs in aquatic species of the studied locations were mainly derived from
combustion sources (Kanzari et al. 2014). The distribution of different PAHs rings also indi-
cates different sources of the PAHs from petrogenic and pyrogenic origins. This is because
PAHs from a petrogenic origin predominantly consist of lower molecular weights (two and
three rings), whereas the pyrogenic origin PAHs generally have higher molecular weights, such
as four- and five-ring PAH species (Kannan et al. 2005).
PETROLEUM SCIENCE AND TECHNOLOGY 7
Figure 3. Plot of Ant/Ant þ Phe (a), BaA/BaA þ Chr (b) and IP/IP þ BP (c) against Fl/Fl þ Pyr in the collected aquatic species
muscles along the Suez Gulf.
8 O. E. AHMED ET AL.
Table 3. Risk assessment on potency equivalent concentration lg/g/d wet wt., of PAHs for human consumption of Aquatic
Species along the Suez Gulf, Egypt.
Cancer risk level Cancer risk level Cancer risk level
Aquatic species (lg/g/d wet wt.) (lg/g/d wet wt.) (lg/g/d wet wt.)
Sauridaundo squamis 0.0882552 8.83 E-02 8.83 102
Euthynnus affinis 0.0491544 E-02 4.92 4.92 102
Rhabdosargus haffara 0.0599532 E-02 6.00 6.00 102
Argyrops Spinifer 0.0902338 E-02 9.02 9.02 102
Nemipterus Japonicus 0.021596 E-02 2.16 2.16 102
Oreochromis Niloticus 0.0012472 1.25 E-03 1.25 103
Trachurus Indicus 0.0359112 3.60 E-02 3.59 102
Peneus Japonicas 0.0082821 E-03 8.82 8.28 103
Scomber Japonicus 0.0078961 E-03 7.90 7.9 103
Pomadasys Stridens 0.0233358 2.33 E-02 2.33 102
SV ¼ ½ðRL=SFÞXBW=CR
where SV is the screening value (lg/g) that is used as a threshold value against the residue level
in similar tissue collected from the environment; RL is the maximum acceptable risk level
(dimensionless, using 105); SF is the oral slope factor (lg/g) and the SF value of BaP is 7.3 ((lg/
g/d)1; BW is body weight (kg) and an average of 70 kg is used for the calculations; and CR
refers to the consumption rate (g/d) and is substituted by the USEPA standard value for the aver-
age intake rate of fish, which is 142.2 g/d. When the carcinogenic risk is 105, the calculated SV
threshold is 0.67 ng/g wet wt, the potency equivalent concentration (UNEP 2002), which is far
higher than the wet weight contents of PAHs in various tissues and organs acquired from this
research. Therefore, we can clarify that the carcinogenic risk from these aquatic species found in
the Suez Gulf is significantly more than 105 (Table 3). In addition, BaP equivalent concentra-
tions of PAHs in the fish measured in this research were also more the national standards limit-
ing pollutants, in which BaP equivalent concentrations are suggested more than 5 ng/g for grain
and meat and 10 ng/g for vegetables (Xu, et al. 2007).
4. Conclusions
This study provides valuable information about the distribution, transport and sources of n-alka-
nes and PAHs in the aquatic species obtained from the Suez Gulf. The n-alkanes were mainly
from recycled organic matter and/or marine microorganisms. A total concentration of 16 PAHs
ranged from 11.391 to 96.747 ng/g wet wt. The PAH concentration ranged between 81.499 and
5895.608 ng/g wet wt., can be classified as higher concentration levels. Therefore, now, the adverse
effects and toxicity of PAHs on the exposed bio-organisms in the studied area are of higher con-
cern. The sources of PAHs obtained through the use of diagnostic ratios are from both pyrogenic
and petrogenic sources derived from combustion (through atmospheric input) and also from
fresh petrogenic inputs with a dominance of pyrogenic PAHs. The potency equivalent concentra-
tion of PAHs on a wet weight basis in various tissues was found to be highest than the SV value
from USEPA 0.67 ng/g, wet wt) Therefore, its carcinogenic risk for humans was higher
than 105.
PETROLEUM SCIENCE AND TECHNOLOGY 9
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