JKAU: Mar. Sci., Vol. 19, pp: 15-28 (2008 A.D. / 1429 A.H.)
Total Petroleum Hydrocarbon Carcinogens in Commercial
Fish in the Red Sea and Gulf of Aden - Yemen
Nabil A.A. Al-Shwafi
Department of Earth and Environmental Science,
Faculty of Science, Sana’a University, Yemen
Abstract. This paper presents the concentrations of petroleum
hydrocarbons in seventeen important commercial fish species, i.e.,
Crenidens Crenidens, Scomberomorus Commerson, Rastrelliger
Kanagurta, Thunnus Albacares, Carchaias palasrras, Himantura
Uarnak, Caranx Sem, Scomberoides Commersonianus, Chanos
chanos, Lutjanus Sanguineus, Rachycentron Canadus, Euthynnus
Affinis, Epinephelus Areolatus, Panutirus Homarun, Sepia Pharnais,
Sphyraena Jello, Penaeus Semisulcatus from the Red Sea and Gulf of
Aden of Yemen.
The concentrations of petroleum hydrocarbons, showed no
significant variations between fish species, i.e. Crenidens Crenidens:
(mean: 0.9µg.g–1), Scomberomorus Commerson: (mean: 0.9µg.g–1),
Rastrelliger Kanagurta: (mean: 1.7µg.g–1), Thunnus Albacares:
(mean: 0.6µg.g–1), Carchaias palasrras: (mean: 1.1µg.g–1), Himantura
Uarnak: (mean: 0.8µg.g–1), Caranx Sem: (mean: 0.7µg.g–1),
Scomberoides Commersonianus: (mean: 0.7µg.g–1), Chanos chanos:
(mean: 1.1µg.g–1), Lutjanus Sanguineus: (mean: 1.1µg.g–1),
Rachycentron Canadus: (mean: 0.8µg.g–1), Euthynnus Affinis: (mean:
1.3µg.g–1), Epinephelus Areolatus: (mean: 1.1µg.g–1), Panutirus
Homarun: (mean: 1.1µg.g–1), Sepia Pharnais: (mean: 1.2µg.g–1),
Sphyraena Jello: (mean: 0.7µg.g–1),and Penaeus Semisulcatus: (mean:
0.2µg.g–1). The study of relationships between petroleum
hydrocarbons and weights or lengths indicated that these fish species
do not concentrate these compounds in their tissues, a direct
comparison between the concentrations measured in fish from other
areas revealed no serious oil contamination in the investigated area
and no risk from the consumption of fish.
15
16
N.A.A. Al-Shwafi
Introduction
The accidental discharge of hazardous materials such as petroleum and
chemical solvents to the aquatic environment has become the focus of
increasing regulatory and public concern because of the adverse impacts
of such materials on human health and the environment (Ritschard et al.,
1981; National Oceanic and Atmospheric Administration (NOAA), 1982;
PTI Environmental Associates, 1989; and Bourodimos and Carvoumis,
1990).
Petroleum concentrations as low as 0.1 ppm have been shown to be
acutely toxic to marine larvae (USEPA, 1986), and small quantities of
crude oil mixed with sea-water have been shown to affect the feeding
behavior of fish and shellfish (Atema and Stein, 1974; and Connell and
Miller, 1980). These and other toxic effects are dependent on many
factors, including the chemical composition, partitioning properties,
bioavailability, bio-accumulation and the toxicity of the chemical mixture
and its constituents (Connell and Miller, 1980, 1981).
The aliphatic and polycyclic aromatic hydrocarbon fractions of
dissolved petroleum are readily absorbed by most aquatic organisms
because of their high lipid solubility and are bioconcentrated in fish and
shellfish (Variance & Malins, 1977; and Vandermeulen et al., 1985).
Currently 100 million tons of oil transit the Red Sea annually
(PERSGA, 1995). The Red Sea is navigationally complex from its
narrow mouth at Bab el Mendab along its entire reef lined length. Its
narrow width greatly increases, the likelihood of collisions between
vessels. There are marine pollution accidents reported by Saudi Arabia
during 1993. In 1989 the Indian Tanker Kanchenjunga spilled 25.000
barrels after colliding with a reef in front of Jeddah coast (MEPA 1990).
It is important to make the distinction between chronic and
catastrophic oil pollution. Chronic refers to long- term but constant low
level seepage of oil into the marine environment from shipping,
deballasting, etc., and may not be immediately apparent. Catastrophic
events refer specifically to accidental oil spills, which may contaminate
either open oceans or coastal shores (Al-Shwafi, 2008).
It would seems that the major type of oil pollution in the Red Sea
and the Gulf of Aden belongs to the former type “chronic”. Both the Red
Sea and the Gulf of Aden are classified as “Special Areas” under the
Total Petroleum Hydrocarbon Carcinogens in Commercial Fish…
17
international MARPOL convention 73-78. This means that operational
discharges from shipping are restricted. Nevertheless evidence suggests
that oil pollution from this source has a far greater effect on the marine
environment than accidental spills. An example of a chronic oil pollution
source on the Yemeni coast is the authorized discharge of ballast water
effluent of the SAFER supertanker storage at Ras Isa. Similar problems
occur in the Gulf of Aden with vessels deballasting at Aden refinery.
However, the problem of passing vessels deballlasting in the Gulf of
Aden or the Red Sea appears to be the greater cause of oil pollution in the
Yemen waters. There are two power stations supplied by underwater
pipeline, Ras Kathenib and Al-Mocha. Both receive heavy fuel oil via
pipelines. The public Electricity Corporation reported that frequent
accidents occur to the pipeline and loading hoses when tankers are
subjected to strong winds.
Description of the Region
The Red Sea is a long, narrow body of water, separating north-east
Africa from Arabian Peninsula. It is nearly 2000 km of navigable waters
at the south with the Indian Ocean via Bab el-Mandeb. The average
width of the Red Sea is 280 km, while, the width is only 28 km at the
strait of Bab El-Mandeb. The maximum depth is 2246 m with an average
of 700 m. The mean surface temperature increases southward, maximum
surface water temperature is observed from June to September and attain
30 to 32°C in the south (Abdallah, 1996). The shallow coastal water may
reach a temperature of 38°C. The average salinity is about 35‰, but it is
higher in shallow coastal areas as a result of evaporation (Al-Shwafi et
al., 2005).
The tides are semi-diurnal and spring tide varies from 0.6 m in the
north to 0.9 m in the south. The sea level is strongly influenced by the
rate of evaporation and the balance between the inflow and outflow of
the water from and to the Gulf of Aden. Surface water transport in
summer is directed south by the prevailing northerly winds for about 4
months, at a velocity of 12-50 cm sec–1, while in winter the flow is
reversed, pushing water into the Red Sea from the Gulf of Aden, the net
value of the latter movement is greater than summer outflow (Al-Shwafi,
2003).
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N.A.A. Al-Shwafi
The Red Sea is unique amongst deep bodies of water for having an
extremely stable warm temperature throughout its deeper water. Below
about 250-300 m, the water maintains a constant temperature of about
21.5°C.which extends down to the sea floor in all areas except where
heated brine pools exist (Edwards and Head, 1987).
The Gulf of Aden is a highly productive fishery area due to the
upwelling processes. The high primary productivity, due in part, to the
upwelled nutrients, supports a food web, which ultimately sustains the
fish community. The seasonality of the monsoon winds drive the
upwelling and, in turn, cause a seasonal periodicity throughout the food
web (Abubaker et al., 2007).
Aim of the Present Investigation
The aim of the study was to perform a baseline study on the state of
pollution in the muscle tissues of the common fish species, which were
surviving in the Red Sea of Yemen and Gulf of Aden. The objectives of
the present study were to:
1. Determine levels, petroleum hydrocarbons in the flesh of the
seventeen fish species collected from the Red Sea of Yemen and the Gulf
of Aden, and attempt to identify the most important source/s of
contamination to the region.
2. Shed some light on the sub-lethal effects of the most prominent
contaminants upon the marine resources in the area, as well as its
possible implications with human health consumers.
3. Collect and review relevant existing data and arrange the results
that are obtained during the study in a manner thus to serve as a baseline
data for further follow- up study in the region.
Materials and Methods
Seventeen fish species “Crenidens Crenidens, Scomberomorus
Commerson, Rastrelliger Kanagurta, Thunnus Albacares Carchaias
palasrras, Himantura Uarnak, Caranx Sem, Scomberoides
Commersonianus, Chanos chanos, Lutjanus Sanguineus, Rachycentron
Canadus, Euthynnus Affinis, Epinephelus Areolatus, Panutirus Homarun,
Sepia Pharnais, Sphyraena Jello, Penaeus Semisulcatus” were collected
from the local fishermen of Aden and Hodiedah cities during summer
Total Petroleum Hydrocarbon Carcinogens in Commercial Fish…
19
1998. All morphometric sample measurements were reported (Table 1
and 2). The samples were taken from the fish flesh for the determination
of petroleum hydrocarbon concentrations.
All solvents were redistilled in an all-glass distillation apparatus
equipped with a 150 cm vacuum-jacketed fractionation column filled
with 3 mm diameter glass helices. Blanks of 1000- fold concentrates
were determined by gas chromatography with flame ionization detection.
The gas chromatograph was a Hewlet Packard HP5980-GC with split/
splitless injector furnished with a 25m × 0.3 mm fused silica capillary
with a chemically bonded gum phase SE54. Water used for cleaning the
adsorption resin and sample work-up was purified with a Millipore milliQ system. Sodium chloride and sodium sulfate were Kiln fired at 450°C
overnight and cooled in a greasless desiccator. Silica gel used for column
chromatography was solvent extracted with n-hexane in a glass cartridge
inserted into an extraction apparatus, as described by Ehrhardt (1987).
After extraction, the Silica gel was first dried in the same cartridge by
passing ultra pure nitrogen through it and was then activated by heating
the cartridge in an electric tube oven to 200°C for 6 h with the stream of
nitrogen reduced to a few ml per minute
The extraction method is that of Wade et al., (1988). A total of 10 g
of wet tissues was Soxhlet- extracted with methylene chloride and
concentrated in Kuderna-Danish tubes. The extracts were fractionated by
alumina silica gel column (80-100 mesh) chromatography. The extracts
were sequentially eluted from the column with 50 ml of pentane
(aliphatic fraction) and 200 of 1:1 pentane- dichloromethane (aromatic
fraction) and concentrated for instrumental analysis.
Aliphatic hydrocarbons (n-C13-n-C34), pristane, and phytane were
analyzed by gas chromatography (HP-5980) in the splitless mode with
flame ionization detection (FID). A 30m × 0.32 mm i.d. fused- silica
column with DB-5 bonded phase (J&W Scientific, Inc.) provided
component separations. The FID was calibrated at five concentrations,
and deuterated n-alkanes were used as surrogates and internal standards.
Aromatic hydrocarbons were quantified by gas chromatography with
mass spectrometric detection (HP-5890-GC and HP-5970-MSD). The
samples were injected in the splitless mode onto a 30m × 0.25 mm (0.32
µm film thickness) DB-5 fused silica capillary column (J & W Scientific
Inc.) at an initial temperature of 60°C and temperature programmed at
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N.A.A. Al-Shwafi
12°C/min to 300°C and held at the final temperature for 6 min. The mass
spectral data were acquired, and the molecular ions for each of the PAH
analyte were used for quantification. The GC/MS was calibrated by the
injection of standards at five concentrations. Analyte identification was
based on the retention time of the quantitation ion for each analyte and a
series of confirmation ion. Deurated aromatic compounds were used for
surrogate and internal standards.
Results and Discussion
In order to establish the concentrations of petroleum hydrocarbons in
marine species and to learn whether these concentration can constitute a
hazard to consumers seventeen important commercial fishes, i.e.,
Crenidens
Crenidens,
Scomberomorus
Commerson,Rastrelliger
Kanagurta, Thunnus Albacares, Carchaias palasrras, Himantura
Uarnak, Caranx Sem, Scomberoides Commersonianus, Chanos chanos,
Lutjanus Sanguineus, Rachycentron Canadus, Euthynnus Affinis,
Epinephelus Areolatus, Panutirus Homarun, Sepia Pharnais, Sphyraena
Jello, Penaeus Semisulcatus which represent an important food for the
Yemeni population were investigated. Total body weight, length together
with concentrations of petroleum hydrocarbons are summarized in Tables
1 and 2 and Fig. 1 and 2. The concentrations from fish of Red Sea of
Yemen (µg.g–1 wet weight) in Crenidens Crenidens, Scomberomorus
Commerson, Rastrelliger Kanagurta, Thunnus Albacares, Carchaias
palasrras, Himantura Uarnak, Caranx Sem, Scomberoides
Commersonianus, Chanos chanos, Lutjanus Sanguineus, Rachycentron
Canadus, Euthynnus Affinis, Epinephelus Areolatus, Panutirus Homarun,
Sepia Pharnais, Sphyraena Jello, Penaeus Semisulcatus fish species
were in the range: (0.03-6.2, 0.04-4.1, 0.03-5.3, 0.02-2.3, 0.03-5.6, 0.054.6, 0.06-3.9, 0.04-4.7, 0.08-6.0, 0.05-4.1. 0.08-5.7, 0.02-4.5, 0.04-6.8,
0.03-2.3, 0.02-3.2, 0.07-6.8 and 0.01-1.3), respectively. The
concentrations in fish from the Gulf of Aden (µg.g–1 wet weight) in
Crenidens Crenidens, Scomberomorus Commerson, Rastrelliger
Kanagurta, Thunnus Albacares, Carchaias palasrras, Himantura
Uarnak, Caranx Sem, Scomberoides Commersonianus, Chanos chanos,
Lutjanus Sanguineus, Rachycentron Canadus, Euthynnus Affinis,
Epinephelus Areolatus, Panutirus Homarun, Sepia Pharnais, Sphyraena
Jello, Penaeus Semisulcatus fish species were scattered in the range:
(0.04-6.3,. 05-4.3, 0.03-5.2, 0.03-3.5, 0.03-5.7, 0.06-5.6, 0.06-4.0, 0.05-
Total Petroleum Hydrocarbon Carcinogens in Commercial Fish…
21
4.8,0.08-6.2, 0.06-4.4, 0.09-5.9, 0.04-5.5, 0.06-7.7, 0.05-3.3, 0.04-3.9,
0.07-6.9 and 0.02-1.5), respectively and without any significant
differences. These insignificant variations were probably related to lipid
contents of muscle tissues and/or other physiological characters (El-Deeb
and El-Ebiary, 1988; Sharidah, 2000 and Collins et al., 1991). It has been
stated (Gesamp, 1982) that fish tend to concentrate petroleum
hydrocarbons in their tissues when exposed to oil, but they do not retain
it indefinitely. The possible relationships between total petroleum
hydrocarbons and weight or standard lengths of the ten fish species have
been investigated. The results given in Table 3 for correlation
coefficients revealed the absence of any significant relationship that
indicate no ability for these fish to concentrate hydrocarbons in their
muscle tissues. This might agree with the finding of Durrani and Siddiqui
(1990) who could not observe hydrocarbons peaks in tissues of Perna
viridis, Mugil sp., and Acanthopagurus sp. from coastal waters of
Karachi.
Table. 1. The weight and length of fish collected during summer 1998 from Red Sea of
Yemen.
No. of
fish
5
Total
weight (g)
250-500
Total
length (cm)
80-100
ΣPHCs
range
0.03-6.2
ΣPHCs
mean ± SD
0.9 ± 0.3
Crenidens Crenidens
15
500-600
30-50
0.04-4.1
0.8 ± 0.1
Rastrelliger Kanagurta
20
50-65
22-30
0.03-5.3
1.0 ± 0.4
Thunnus Albacares
7
500-700
70-90
0.02-3.3
0.5 ± 0.6
Carchaias palasrras
10
200-500.5
55-62
0.03-5.6
1.0 ± 0.1
Himantura Uarnak
10
255-450
62-70
0.05-4.6
0.7 ± 0.3
Caranx Sem
Scomberoides
Commersonianus
Chanos chanos
10
105.6-320
50-55
0.06-3.9
0.6 ± 0.1
10
562-765
72-75
0.04-4.7
0.7 ± 0.6
10
50.108
35-40
0.08-6.0
1.0 ± 0.3
Lutjanus Sanguineus
10
120-142
34-47
0.05-4.1
1.1 ± 0.6
8
152-256
60-63
0.08-5.7
0.7 ± 0.2
10
320-450
44-50
0.02-4.5
1.3 ± 0.5
Fish species
Scomberomorus Commerson
Rachycentron Canadus
Euthynnus Affinis
Epinephelus Areolatus
10
280-320
35-37
0.04-6.8
1.1 ± 0.6
Panutirus Homarun
10
320-460
40-42
0.03-2.3
0.9 ± 0.2
Sepia Pharnais
15
268-357
33-40
0.02-3.2
1.2 ± 0.8
Sphyraena Jello
10
365-452
43-52
0.07-6.8
0.6± 0.9
Penaeus Semisulcatus
25
95-120
25-30
0.01-1.3
0.1± 0.3
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N.A.A. Al-Shwafi
Table. 2. The weight and length of fish collected during summer 1998 from Gulf of Aden.
Fish species
Scomberomorus Commerson
Crenidens Crenidens
Rastrelliger Kanagurta
Thunnus Albacares
Carchaias palasrras
Himantura Uarnak
Caranx Sem
Scomberoides
Commersonianus
Chanos chanos
Lutjanus Sanguineus
Rachycentron Canadus
Euthynnus Affinis
Epinephelus Areolatus
Panutirus Homarun
Sepia Pharnais
Sphyraena Jello
Penaeus Semisulcatus
No. of
fish
5
15
20
7
10
10
10
Total
weight (g)
270-450
620-650
70-80
453-720
500-700
259-470
115-325
Total length
(cm)
80-90
33-54
32-73
60-89
57-65
65-73
53-59
ΣPHCs
range
0.04-6.3
0.05-4.3
0.03-5.2
0.03-3.5
0.03-5.7
0.06-5.6
0.06-4.0
ΣPHCs
mean ± SD
0.9± 0.3
0.9± 0.3
1.1± 0.5
0.6± 0.8
1.2± 0.2
0.9± 0.5
0.7± 0.3
10
653-777
75-77
0.05-4.8
0.7± 0.6
10
10
8
10
10
10
15
10
25
55-112
120-142
170-268
333-470
295-354
332-472
297-380
395-460
100-129
38-44
36-50
66-69
49-53
38-40
43-45
38-45
46-55
35-43
0.08-6.2
0.06-4.4
0.09-5.9
0.04-5.5
0.06-7.7
0.05-3.3
0.04-3.9
0.07-6.9
0.02-1.5
1.2± 0.3
1.1± 0.7
0.9± 0.4
1.3±0.6
1.1±0.7
1.2± 0.4
1.3± 0.8
0.8-± 0.6
0.2-± 0.1
Fig. 1. Mean concentration of petroleum hydrocarbons in fish (ug/g wet weight) from Red
Sea - Yemen.
Total Petroleum Hydrocarbon Carcinogens in Commercial Fish…
23
Fig. 2. Mean concentration of petroleum hydrocarbons in fish (ug/g wet weight) from Gulf
of Aden.
Table 3. Correlation coefficients of relationships between petroleum hydrocarbons in
muscle tissues and both length and weight of the seventeen fish species.
Fish species
Scomberomorus Commerson
CrenidensCrenidens
RastrelligerKanagurta
Thunnus Albacares
Carchaias palasrras
Himantura Uarnak
Caranx Sem
Scomberoides Commersonianus
Chanos chanos
Lutjanus Sanguineus
Rachycentron Canadus
Euthynnus Affinis
Epinephelus Areolatus
Panutirus Homarun
Sepia Pharnais
Sphyraena Jello
Penaeus Semisulcatus
No.
10
30
40
14
20
20
20
20
20
20
16
20
20
20
30
20
50
Correlation coefficients
with length
0.03
0.02
0.10
0.02
0.04
0.05
0.04
0.03
0.08
0.04
0.01
0.09
0.10
0.02
0.04
0.11
0.01
Correlation coefficients
with weight
0.11
0.10
0.12
0.01
0.03
0.13
0.01
0.14
0.12
0.11
0.03
0.15
0.08
0.12
0.03
0.13
0.02
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N.A.A. Al-Shwafi
Except for the concentrations (µg.g–1 wet weight) reported by
Badawy et al. (1993) in Epinepehelus tauvina (2.5 ± 0.3 ) and Lelhrinus
miniatus (0.19 ± 0.02) from the Mina al-Fahal of Oman, and those
reported by El- Deeb and El- Ebiary (1988) in fish tissues of Argyrops
sp. (24.7) and Malio sp. (53.4) from the eastern and southern coast of
Qatar, no other data base is available in the region for comparison.
However, concentrations of hydrocarbons in different fish species from
various marine envirnments are reported. Hydrocarbons concentrations
(µg.g–1 wet weight) in Mullus barbatus from the open Adriatic Sea (0.010.33). Aegean Sea (0.92-3.30), and North East Mediterranean 90.040.25) are reported (Dujimov and Sucevic, 1989; Saydan et al., 1988;
Sunay et al., 1982). High concentrations (µg.g–1 wet weight) are reported
in Mytilus edulis (295), Cardium edule (198), Ensis siliqua (199),
Amigdala degussata (208) and Venus verirtucosa (185) from Italian
central Mediterranean coasts. Moreover, high concentrations are also
found in the flesh of estuarine Callionymus lyra (23.1-216.0) from the
European and North American waters (Burns and Teal, 1973; and
Farrington et al., 1972 & 1973 and Haffer, 1983 & 1985). It is clear that
hydrocarbons found in tissues of the ten fish species studies here are
lower than most of the reported levels from the Gulf region and other
marine ecosystems.
Conclusions and Recommendations
It can be concluded from the present investigation on the light of the
above reasoning author may thus conclude that the impact of human
activities on the marine environment is relatively low. Beach deposits are
the main source of petroleum hydrocarbons in Red Sea of Yemen/Gulf of
Aden environment.
It is recommended that a continuous monitoring programme for the
Red Sea and Gulf of Aden region should be formulated and conducted to
ensure that the concentrations of petroleum hydrocarbons is within the
baseline levels established in the present study.
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27
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