ORI GI NAL ARTI CLE

Assessment of organic pollutants in coastal sediments, UAE

Esam A. Abdel Gawad Mohamed Al Azab
M. M. Lotfy
Received: 12 March 2007 / Accepted: 18 June 2007
Springer-Verlag 2007
Abstract Twenty-ve stations were selected along the
UAE coastal region to delineate the distribution and to
determine the source of total petroleum hydrocarbon
(TPH), total organic carbon (TOC), total Kjeldhal nitrogen
(TKN), polycyclic aromatic hydrocarbons (PAHs) and
polychlorinated biphenyls (PCBs). The concentrations of
TPH ranged between 46 and 223 mg/kg and the level of
TOC was in the range from 0.044 to 17.8 wt%, while
TPAHs occupied the range of 5102.2 lg/kg. On the other
hand, TPCBs showed values between 60 and 205 lg/kg
and TKN ranged from 104 to 1,073 mg/kg. The present
study shows that the distribution of organic compounds in
UAE sediments were within safe limits comparing with
previous studies. The present study revealed that TOC can
be used as an indicator of oil pollution in heavily oiled
sediments. The highest values of TOC, TPH, TPAHs and
TPCBs related to the stations covered in ne sand due to
adsorption properties and the large surface areas of the
grains. The evaporation of low-boiling point compounds
from surface layers leads to the enrichment of sediments
with a thick residual. Al Sharjah-1 exhibited the highest
values of TPH and TOC at Ras Al-Khaima-5, Umm Al-
Quwen-1 and Dubai-1, while the highest values of TPAHs
were at KhorFakkan-9, the highest value of TPCBs was at
Ajman-2, and the highest values of TKN were at Khor-
Fakkan-1, KhorFakkan-6 and Dubai-1.
Keywords Pollution Organic TOC PAHs
PCBS Hydrocarbons TKN UAE
Introduction
The rapid development in the past 15 years in the Arabian
Gulf region generally and in UAE specially has thrown a
heavy burden on coastal zones and reects an adverse
impact on coastal habitats. The petroleum industry, which
is mostly concentrated on the coastal region, raises the
level of oil and other organic compounds in marine sedi-
ments. In the past few years, the Dubai coastal zone was
subjected to several developments, which have affected the
water and sediment quality. According to Mocke et al.
(2002), 20% of the study area is industrial, 16.5% private
usage, 14% public usage and 15.5% Sanctuary (Jebel Ali).
A periodic monitoring of petroleum hydrocarbon level in
Gulf coastal countries is useful in estimating any change in
water and sediment quality.
Contamination by petroleum hydrocarbon is a serious
problem throughout the world. An increase in petroleum
hydrocarbons in the marine environments causes a negative
impact not only on the aquatic life but also may be extend
to affect human heath through interference in the food web
and through contamination of seawater. A large percentage
(>3050%) of spilled hydrocarbons enriched in heavier
more recalcitrant compounds deposited in bottom sedi-
ments, beaches and soils which then act as long-term res-
ervoirs and secondary sources (Colombo et al. 2005)
Furthermore, one of their major economic impacts is the
reducing the recreational utility of coastal waters. Oil in the
sea, whether from spills or chronic sources, is perceived as
a major environmental problem. Occasional major oil spills
receive considerable public attention because of the obvi-
M. Al Azab
Department of Chemistry, Faculty of Science,
UAE University, P.O. Box 17551, Al-Ain, UAE
E. A. Abdel Gawad M. M. Lotfy (&)
Department of Geology, Faculty of Science,
UAE University, P.O. Box 17551, Al-Ain, UAE
e-mail: mostafa.lotfy@uaeu.ac.ae
1 3
Environ Geol
DOI 10.1007/s00254-007-0880-x
ous attendant environmental damage such as oil-coated
shorelines, and dead or moribund wildlife, including, in
particular, oiled seabirds and marine mammals (NAP
2003).
Materials and methods
Sample collection
The stainless Van Veen grab sampler was used to obtain
the sediments samples. Twenty-ve of bottoms offshore
sediment within the depths of 1520 m was gathered
(Fig. 1). Each fully mixed sample was air dried under a
hood at room temperature and sieved to pass a 35-mesh
sieve. The samples were kept frozen at 18C for the future
analyses, the collection were started from Kalba, Fujairah,
Khor Fakkan, Ras Al-Khaimah, Umm Al-Quwen, Ajman,
Sharjah and of Dubai coastal region (Table 1). These
samples were frozen in airtight plastic bags; all necessary
precautions were taken to avoid any contamination or the
loss of volatilize compounds.
Analytical methods
The sediments samples were dried in oven under mild
temperature to remove the moisture before sieving. The
textural class was determined through grain-size analysis
by using standard set of sieves and mechanical shaker. The
dry weight percentage of the size fractions retained on each
sieve was calculated. For the muddy samples, which con-
tains more than 20% mud, pipette analysis is the most
common method used for determining the grain-size dis-
tribution of sediments >4u.
The concentration of total petroleum hydrocarbon
(TPH) was measured in accordance as it is explained by
ROPME (2000). From the homogenized, eld-moist sedi-
ment 20 g were extracted in a Soxhlet by using hexane
solvent. TPH was determined by measuring the absorbance
of uorescence using a Nicolet Infrared Spectrophotome-
ter. The percentage weight of total organic carbon (TOC)
was carried out by following the Walkey-Black (1947)
method based on the oxidation of organic matter with
concentrated Sulfuric acid and titration to the end point
with ferrous ammonium sulfate.
Total Kjeldhal nitrogen (TKN) was determined
according to Kjeldahl method (EPA 1993) using block
digestion and steam distillation. This method requires the
digestion of the solid sample to solution using strong acid
at high temperatures. The digestion tube was placed in the
distillation unit and the distillate was titrated with stan-
dardized HCl acid. The quantication of polycyclic aro-
matic hydrocarbons (PAHs) were brought out through high
performance liquid chromatography (HPLC) with a uo-
rescence detector, the sample was dried with anhydrous
sodium sulfate and extracted in a Soxhlet extraction using
mixture of hexane: acetone (50:50) for 2 h boiling and
rinsing. The extract was injected into HPLC column. Fi-
nally, the determination of polychlorinated biphenyl (PCB)
was carried out using gas chromatography with an electron
capture detector (GC-ECD). The sample was extracted in a
Soxhlet extraction using solvent (1:1 hexane: acetone) for
2 h, the residual of the solvent after evaporation was col-
lected and injected into GC-ECD column to recognize PCB
compounds (EPA 1999). N-alkanes and isoprenoids
hydrocarbons were determined by gas chromatography
with a ame ionization detector (GC-FID) with the fol-
lowing specication and condition, Varine, Saturn 3800
GC system, equipped with am ionization, detector FID,
0 20 40 60 Km
United Arab Emirates
Oman
Kalba
Fujairah
Khor Fakkan
Gulf of Oman
Arabian Gulf
Ras Al-khaimah
Umm Al-quwen
Ajman
Sharjah
Dubai
Locations
Cities
Kh5
Kh12
Kh1
Kh4
Ras1
Ras4
QU1
QU2
QU3
AJ1
AJ2
Sh1
Sh2
DU1
DU2
25
o
26
o
56
0
55
o
Fig. 1 Location map of the studied sites in UAE
Table 1 Location for the collection of sediments
Stations Location Stations Location
KH1 Coastal-KhorFakkan Ras1 Coastal-Ras Al-Khaimah
KH 2 Coastal-KhorFakkan Ras2 Coastal-Ras Al-Khaimah
KH 3 Coastal-KhorFakkan Ras3 Coastal-Ras Al-Khaimah
KH 4 Coastal-KhorFakkan Ras5 Coastal-Ras Al-Khaimah
KH 5 Coastal-Kalba Qu1 Coastal-Umm-Al-Quwain
KH 6 Coastal-Kalba Qu2 Coastal-Umm-Al-Quwain
KH 7 Coastal-Kalba Qu3 Coastal-Umm-Al-Quwain
KH 8 Coastal-Kalba Aj1 Coastal-Ajman
KH 9 Coastal-Fujairah Aj2 Coastal-Ajman
KH 10 Coastal-Fujairah Sh1 Coastal-Sharjah
KH 11 Coastal-Fujairah Sh2 Coastal-Sharjah
KH 12 Coastal-Fujairah Du1 Coastal-Dubai
Du2 Coastal-Dubai
Environ Geol
1 3
GC column: CP-Sil 8, 30 m 0.32 mm ID, df = 1, Carrier
Gas: He 1.5 ml/min, Temperature program of the oven
100160C at 15C/min for 2 min, followed by 160300C
at 5C/min for 30 min. The detection limits of our ana-
lytical compounds have been done as reference material
analysis by Al-Darwish et al. (2005) and Al katheeri
(2004).
Results and discussion
Sediments distribution
The objectives of determining the grain-size distribution of
sediments in this study is to correlate the level of con-
taminants to grain size, and to determine the texture of the
sediments, i.e., the percentage of ne particles in the sed-
iment. The coarse sandy sediments are mainly restricted to
the southern regions of the Gulf, and the ne clay silt
sediments are mainly concentrated in the northern regions
(Al-Ghadban et al. 1996). The textural classes in the Gulf
of Oman area fall into four main groups: ne sand, medium
sand, coarse sand, and pebble (Fig. 2a). The textural clas-
ses in the Arabian Gulf area also fall in ve other groups:
ne sand, medium sand, coarse sand, very coarse sand and
granule (Fig. 2b). Most of the study area (36%) is medium
sand, while the ne size deposits represent (24%), coarse
sand represent (16%), very coarse sand (12%), pebble (4%)
and granule (8%).
Content of TPH, TOC and TKN
Chronic releases from natural and anthropogenic sources
(e.g., natural seeps and run-off from land-based sources)
are responsible for majority of petroleum hydrocarbon in-
put (NAP 2003). Typically, petroleum hydrocarbon con-
centrations are a few mg/kg in unpolluted coastal areas and
from 50 to more than 1,000 mg/kg in polluted areas (Clark
and Macleod 1977). The values of TPH in UAE sediments
show drastic uctuations, varying from 46 to 223 mg/kg,
with an average of 118.44 43.67 (see Table 2). It is
worth to noting that Sharjah-1and KhorFakkan-4 showed
high levels of TPH (223 mg/kg and 199 mg/kg, respec-
tively), whereas other locations showed only slight and
moderate levels of TPH. These locations showed very high
concentrations of TPH compared with the obtained values
from the Gulf region after the 1991 Gulf War. For example,
Massoud et al. (1996) found TPH in heavily polluted areas
affected by the Kuwait oil slick ranged from 266 to
1,448 mg/kg. Hayes et al. (1993) reported that the con-
Mean size
Fine sand
Medium sand
Coarse sand
Very coarse
sand
Granule
Mean size
Fine sand
Medium sand
Coarse sand
Pebble
A
B
Fig. 2 Textural classes of
sediments (a) gulf of Oman and
(b) Arabian Gulf in UAE
Table 2 Concentrations of TPH, TOC and TKN in UAE sediments
Sample ID TPH (mg/kg) TOC wt% TKN (mg/kg)
Kh1 86 0.162 305
Kh2 134 0.088 104
Kh3 163 0.089 132
Kh4 199 0.088 116
Kh5 157 0.191 nd
Kh6 119 0.28 286
Kh7 156 0.119 104
Kh8 140 0.044 nd
Kh9 101 0.088 nd
Kh10 141 0.103 nd
Kh11 126 0.191 nd
Kh12 93 0.058 nd
Ras1 128 11.25 nd
Ras2 74 3.832 nd
Ras3 91 8.787 108
Ras5 97 17.05 nd
Qu1 82 17.8 1,073
Qu2 54 8.219 nd
Qu3 134 12.33 nd
Aj1 125 11.88 nd
Aj2 152 3.46 nd
Sh1 223 5.548 nd
Sh2 64 3.985 nd
Du1 76 17.05 239
Du2 46 14.59 nd
Average SD 118.44 43.668 5.49128 6.440 98.68 223.979
nd not detected
Environ Geol
1 3
centrations of TPH in sediments at the most severely im-
pacted locations along the Saudi Arabian coast one year
after the Gulf War oil spill were 10,000 mg/kg. The high
level of TPH at Sharjah-1 and KhorFakkan-4 as well as
Ajman-2 (Fig. 3a) could be attributed to its location close
to Sharjah Port, which is used for oil exporting. In addition,
other resources could be navigation routes, tanker transport
and coastal production, which is other sources of oil pol-
lution in the region (Golob and Brus 1984). The distribu-
tion map (Fig. 3b) of TPH demonstrates unusual levels of
THP at Sharjah-1, Khorfakkan-4 and Ajman-2, which may
have occurred as a temporal event during or shortly before
the period of samples collection. The moderate concen-
tration of TPH at Dubai-1and Dubai-2 is mostly attributed
to the presence of dry docks, which might received
petroleum input from damaged tankers, water depilating
and tanker maintenance, whereas the source of oil input at
the other stations referred to is most likely from private
usage of coastal zone. On the other hand, the high level of
TPH at the Arabian Gulf coastal could also be as a result of
the movement of surface waters with high oil contents form
the Gulf of Oman through the Strait of Hormuz (Shriadah
1998).
The input of organic matter to coastal systems is, in-
deed, the triggering mechanism leading to the ecological
consequences of concern (DellAnno et al. 2002). TOC
value indicates the sum of organic carbon and represents a
measure for all organic substances in sediments. These
substances are from (1) natural sources, such as humic
acids, mineral oils, solvents, pesticides, and polyaromatic
hydrocarbons or (2) chlorinated organic compounds. The
values of TOC ranged from 0.044 to 17.8 wt% with an
average of 5.49 6.44. Hartmann et al. (1971) pointed out
that the sediments of the Arabian Gulf generally contain
between 0.5 and 1.0 wt%, or at the most 2.0%. Literathy
et al. (1992) reached the previous nding on the natural
background levels of TOC (0.50.8 wt%) in the bottom
sediments of Kuwait marine environment. Table 3 illus-
trates the concentrations of TOC along UAE coast, which
have been reported by several researchers from 1992 to
2003. TOC in UAE sediments (Fig. 3b) shows high levels
for the western region sediments compared with the eastern
western partregion sediments. The real distribution of TOC
(Fig. 4b) exhibits that the western part shows higher levels
of TOC compared with other eastern part which shows
lower levels of TOC in UAE sediments. Table 3 displays
discordance in the distribution of petroleum hydrocarbons
and the percentage of organic matter in sediments. This
nding is conrmed by signicant negative correlation
(r = 0.423) between TPH and TOC, which shows dis-
agreement with earlier ndings of Shriadah (1998), who
found that of organic carbon in the sediments, the greatest
was the adsorption of petroleum hydrocarbons. Therefore,
it may be suggested that the percentage of TOC could be
used as an indicator of petroleum pollution in the area; this
conclusion is in agreement with the earlier observations of
Emara (1998). Ammonication refers to the way some
organisms x nitrogen to either NH
4
+
or organic nitrogen
(nitrogen xation); nitrication refers to organisms that
nitrify NH
4
+
to NO
3
. Both nitrication and ammonication
convert gaseous nitrogen into bioavailable chemical forms
(Wilson et al. 1993). TKN stands for total Kjeldahl nitro-
gen, which is the sum of ammonia (NH
3
) and organic
nitrogen.
According to measurement of TKN in UAE sediments,
the values showed very wide variation, ranging from 0 to
TPH mg/kg
0
50
100
150
200
250
1
h
K
2
h
K
3
h
K
4
h
K
5
h
K
6
h
K
7
h
K
8
h
K
9
h
K
0
1
h
K
1
1
h
K
2
1
h
K
1
h
S
2
h
S
1
s
a
R
2
s
a
R
3
s
a
R
5
s
a
R
1
g
A
2
g
A
1
u
D
2
u
D
1
u
Q
2
u
Q
3
u
Q
Stations
A
TOC wt%
0
2
4
6
8
10
12
14
16
18
20
1
h
K
2
h
K
3
h
K
4
h
K
5
h
K
6
h
K
7
h
K
8
h
K
9
h
K
0
1
h
K
1
1
h
K
2
1
h
K
h
S
12
h
S
1
s
a
R
2
s
a
R
3
s
a
R
5
s
a
R
1
u
D
2
u
D
1
u
Q
2
u
Q
3
u
Q
Stations
T
o
c

w
t

%
C
o
n
c
e
n
t
r
a
t
i
o
n

m
g
/
k
g
C
o
n
c
e
n
t
r
a
t
i
o
n

m
g
/
k
g
B
TKN (mgN/Kg)
0
200
400
600
800
1000
1200
1
h
K
2
h
K
3
h
K
4
h
K
5
h
K
6
h
K
7
h
K
8
h
K
9
h
K
0
1
h
K
1
1
h
K
2
1
h
K
1
h
S
2
h
S
1
s
a
R
2
s
a
R
3
s
a
R
5
s
a
R
A
j
2
A
j
1
A
j1
A
j2
1
u
D
2
u
D
1
u
Q
2
u
Q
3
u
Q
Stations
C
Fig. 3 Distribution of TPH (a), TOC (b) and TKN (c) in UAE
sediments
Environ Geol
1 3
1,073 mg/kg, with an overall average of 98.68 223.98
(Table 2) at KhorFakkan-1, KhorFakkan-6 and Dubai-1.
The level of TKN suggested by Alloway (1993) in coastal
sediments is 300 mg/kg. The high concentrations of TKN
are probably originated from run-off of fertilizers, livestock
and human wastes and municipal sewage-treatment facili-
ties. This indicates coastal discharges or may be attributed
to high levels of TPH (223 mg/kg), which increases the
mortality rate among the aquatic organisms such as phy-
toplankton and zooplankton that in turn enhances the
bacterial decomposition activity, which increases the rate
of nitrite. The signicant negative correlation (r = 0.175)
between TKN and TPH did not conrm the bacterial
decomposition. According to the measurements of TKN in
UAE sediments, the values showed wide variations within
the range of 01,073 mg/kg (Fig. 3c). Figure 4c illustrates
the distribution trend of TKN in UAE sediments the high
level of TKN (305 mg/kg) KhorFakan-1, which has mod-
erately value of TPH (86 mg/kg), majority attributed to
highly terrestrial input (El-Sabrouti et al. 1990).
Content of TPAHs and TPCBs
Polycyclic aromatic hydrocarbons are a class of organic
pollutants that are released into the environment in large
quantities, mainly due to human activities. There are two
primary sources of PAHs to the marine environment,
pyrogenic and petrogenic: pyrogenic PAHs are derived
from combustion sources and petrogenic PAHs are derived
from petroleum inputs. In UAE sediments, TPAHs values
uctuated between 5 and 102.5 mg/kg with an average of
30.64 23.59 (Table 4, Fig. 5a). The distribution map of
TPAHs exhibits increasing trends in the western sediments
rather than the eastern ones (Fig. 6a). The maximum value
was reported at KhorFakan 9. The primary source of
anthropogenic PAHs in the environment is thought to be
atmospheric depositions (Witt 1995). TPAHs in UAE
sediments found to be lower than the values recorded along
the Saudi Arabian coast (10300 lg g
1
) 1 year after the
Gulf War (Hayes et al. 1993), in heavily oil contaminated
sediments. However, the level is still high compared with
other regions in the world. This conrms the earlier con-
clusion proposed by Evans et al. (1990) that the highest
amount of PAHs is usually associated with sediments that
have a high TOC. The distribution pattern appeared to be
related to oil pollutant sources, such as discharge from
vessels and port activities (Hong et al. 1995). Polychlori-
nated biphenyls are now widespread in the environment
and can be detected in air, water, soil, sediments and
organisms; the typical environmental concentration is 2
50 lg kg
1
in soil (Killops and Killops 1993). PCBs tend to
adsorb to ne particulates or be bio accumulated into lipids
in aquatic biota (Olsen et al. 1982). According to Fang
et al. 2003 phenanthrene/anthracene (P/A) ratio is equal to
1 for coastal sediment samples within the study area,
except for station KH7 (0.9), which reects pyrogenic
sources of PAHs benzo(a)anthracene/(benzo(a) anthra-
cene + chrysene stations KH4, KH7, KH8, KH9, and
KH10 have values of BaA/(BaA + Chry) 0.4 which re-
ects petrogenic sources, while stations KH1, KH2, KH3,
KH5, KH6, KH11, and KH12 attain the values of BaA/
(BaA + Chry) ranging from 0.5 to 0.75, indicating pyro-
genic sources. According to Guinan (2001) uoranthene/
(uoranthene + pyrene) ratio Flu/(Flu + P) > 1 indicates
pyrogenic sources while values <1 indicate petrogenic
sources of PAHs. Within the study area, the Flu/(Flu + P)
Table 3 Compared total organic carbon contents (TOC wt%) in sediments from the UAE coasts
Reference Journal title Area Range Average SD
Abu-Hilal and Khordagui (1992) The Arabian Gulf and Gulf of Oman. Annual report Dubai 0.142.65 1.02 1.15
Abu-Hilal and Khordagui (1992) The Arabian Gulf and Gulf of Oman. Annual report Sharjah 0.441.36 0.78 0.35
Abu-Hilal and Khordagui (1992) The Arabian Gulf and Gulf of Oman. Annual report Ajman 0.241.42 0.7 0.5
Shriadah (1998) Indian Journal of Marine Sciences Ras Al-Khaimah, 0.120.89 0.34 0.29
Shriadah (1998) Indian Journal of Marine Sciences Umm Al-Quwain 0.150.38 0.27 0.22
Shriadah (1998) Indian Journal of Marine Sciences Sharjah 0.491.2 0.57 0.43
Shriadah (1998) Indian Journal of Marine Sciences Abu Dhabi 0.450.77 0.61 0.4
El-Sammak (1998) Regional conference on the marine environment
of the Gulf
Dubai Creek 0.00520.445 0.153
Al-Qubaisi (2001) Master science Thesis UAEU Dubai 0.060.27 0.1 0.08
Deshgooni (2002) Master science Thesis UAEU Dubai Creek 0.35.8 2.7 1.6
Al Katheeri (2004) Master science Thesis UAEU Abu Dhabi 0.1414.96 4.77 3.70
Tolosa et al. (2005) Marine Pollution Bulletin Gulf of Oman 0.11.53 0.443 0.5452
Al-Darwish et al. (2005) Environmental Geology Dubai offshore 0.165.9 0.86 1.44
Present study Environmental Geology UAE 0.08817.8 5.49128 6.440
Environ Geol
1 3
ratio was ranging from 0 at KH1, KH6 and KH12 to 1 at
KH2, KH3 and KH8 for coastal sediments. The concen-
tration at most stations was less than 1, indicating petro-
genic sources of PAHs.
On the basis of all the above-calculated ratios, it can be
concluded that sources of pollution within the study area
are predominantly of petrogenic origin (oil spill), in addi-
tion to minor contribution from pyrogenic sources (com-
bustion of oil products and shipping activities at nearest
harbor).
TPCBs in UAE sediments values ranged from 60 to
205 lg/kg. The maximum value was reported at Ajman 2,
with an average of 104.6 34.38 (Table 4, Fig. 5b).
Figure 6b represent the distribution map of TPCBS towards
the western region where the maximum value is about three
times higher than the minimum. Ajman-2 represents four
times higher than the typical environmental concentration.
However, both PCBs and PAHs showed the maximum va-
lue at KhorFakan-9 and Ajman-2, respectively, but PCBs
exhibit wider range of distribution in the study area (Fig. 7).
Hydrocarbons
Hydrocarbons from both anthropogenic and natural sour-
ces including biogenic sources are very common in the
0 20 40 60 Km
United Arab Emirates
Oman
Kalba
Fujairah
Khor Fakkan
Gulf of Oman
Arabian Gulf
Ras Al-khaimah
Umm Al-quwen
Ajman
Sharjah
Dubai
Locations
Cities
Kh5
Kh12
Kh1
Kh4
Ras1
Ras4
QU1
QU2
QU3
AJ1
AJ2
Sh1
Sh2
DU1
DU2
25
o
26
o
56
0
55
o
A
0 20 40 60 Km
United Arab Emirates
Oman
Kalba
Fujairah
Khor Fakkan
Gulf of Oman
Arabian Gulf
Ras Al-khaimah
Umm Al-quwen
Ajman
Sharjah
Dubai
Locations
Cities
Kh5
Kh12
Kh1
Kh4
Ras1
Ras4
QU1
QU2
QU3
AJ1
AJ2
Sh1
Sh2
DU1
DU2
25
o
26
o
56
0
55
o
B
0 20 40 60 Km
United Arab Emirates
Oman
Kalba
Fujairah
Khor Fakkan
Gulf of Oman
Arabian Gulf
Ras Al-khaimah
Umm Al-quwen
Ajman
Sharjah
Dubai
Locations
Cities
Kh5
Kh12
Kh1
Kh4
Ras1
Ras4
QU1
QU2
QU3
AJ1
AJ2
Sh1
Sh2
DU1
DU2
25
o
26
o
56
0
55
o
C
Fig. 4 Distribution maps of TPH (a), TOC (b) and TKN (c) in UAE
sediments
Table 4 Concentrations of TPAHs and TPCBs in Dubai sediments
Sample ID TPCBs (mg/kg) TPAHS (mg/kg)
Kh1 115 49.9
Kh2 95 27.5
Kh3 140 52.9
Kh4 130 36.4
Kh5 80 62.6
Kh6 140 16.5
Kh7 80 50.9
Kh8 105 40.7
Kh9 75 102.2
Kh10 125 13.5
Kh11 90 11.6
Kh12 75 24.4
Ras2 70 14.2
Ras3 95 17.9
Ras5 110 42.9
Ras1 75 26.4
Qu1 110 10.7
Qu2 90 28.4
Qu3 110 11
Ag1 180 5
Ag2 205 5
Sh1 95 13.8
Sh2 60 22
Du1 90 11
Du2 75 68.7
Average S.D 104.6 34.367 30.644 23.590
Environ Geol
1 3
marine and inland environments. Biogenic hydrocarbons
are generated either by biological processes or in the early
stages of diagnosis in recent marine sediments. Biological
sources include land plants, phytoplankton, animals, bac-
teria, macroalgae and microalgae. Stated that the distinct
characteristics of biogenic hydrocarbons including a much
higher abundance of odd n-alkanes is a wide range be-
tween n-C21 to n-C33 and high CPI and pristane/phytane
values. It has been recognized in the studied coastal
sediments in UAE that the biogenic hydrocarbons have
the following chemical composition characteristics: (1)
n-alkanes show a distribution pattern of odd carbon-
numbered alkanes being much abundant than even
carbon-numbered alkanes in the range of n-C 21 to n-C33,
resulting in unusually high carbon preference index (CPI)
values, which is dened as the sum of the odd carbon-
numbered alkanes to the sum of the even carbon-num-
bered alkanes (oils characteristically have CPI values
around 1.0); (2) A notable absence of the unresolved
complex mixture (UCM) hump in the chromatograms;
(3) pristane is often more abundant than phytane, sug-
gesting a phytoplankton input and resulting in abnormally
high pristane/phytane ratio values in most studied loca-
tions (Fig. 8av). In the study of the hydrocarbon bio-
geochemical setting of coastal sediments in the UAE, we
found that very high pristane/phytane ratios (0.494.48)
TPAHs mg/Kg
0
20
40
60
80
100
120
1
h
k
2
h
k
3
h
k
4
h
k
5
h
k
6
h
k
7
h
k
8
h
k
9
h
k
0
1
h
k
1
1
h
k
2
1
h
k
1
s
a
R
2
s
a
R
3
s
a
R
5
s
a
R
1
h
s
2
h
s
A
j
1
A
j
21
u
D
2
u
D
Stations
g
K
/
g
m
n
o
i
t
a
r
t
n
e
c
n
o
C
A
TPCBs mg/Kg
0
50
100
150
200
250
1
H
K
2
H
K
3
H
K
4
H
K
5
H
K
6
H
K
7
H
K
8
H
K
9
H
K
0
1
H
K
1
1
H
K
2
1
H
K
1
h
S
2
h
S
1
s
a
R
2
s
a
R
3
s
a
R
5
s
a
R
A
j
1
A
j
21
u
D
2
u
D
1
u
Q
2
u
Q
3
u
Q
Stations
g
K
/
g
m
n
o
i
t
a
r
t
n
e
c
n
o
C
B
Fig. 5 Distribution of TPAHs (a) and TPCBs (b)
0 20 40 60 Km
United Arab Emirates
Oman
Kalba
Fujairah
Khor Fakkan
Gulf of Oman
Arabian Gulf
Ras Al-khaimah
Umm Al-quwen
Ajman
Sharjah
Dubai
Locations
Cities
Kh5
Kh12
Kh1
Kh4
Ras1
Ras4
QU1
QU2
QU3
AJ1
AJ2
Sh1
Sh2
DU1
DU2
25
o
26
o
56
0
55
o
A
0 20 40 60 Km
United Arab Emirates
Oman
Kalba
Fujairah
Khor Fakkan
Gulf of Oman
Arabian Gulf
Ras Al-khaimah
Umm Al-quwen
Ajman
Sharjah
Dubai
Locations
Cities
Kh5
Kh12
Kh1
Kh4
Ras1
Ras4
QU1
QU2
QU3
AJ1
AJ2
Sh1
Sh2
DU1
DU2
25
o
26
o
56
0
55
o
B
Fig. 6 Distribution map of TPAHs (a) and TPCBs (b) in UAE
sediments
TPAH&TPCBs mg/Kg
0
50
100
150
200
250
1
h
K
2
h
K
3
h
K
4
h
K
5
h
K
6
h
K
7
h
K
8
h
K
9
h
K
0
1
h
K
1
1
h
K
2
1
h
K
2
s
a
R
3
s
a
R
5
s
a
R
1
s
a
R
1
u
Q
2
u
Q
3
u
Q
1
g
A
2
g
A
1
h
S
2
h
S
1
u
D
2
u
D
Station
g
K
/
g
m
n
o
i
t
a
r
t
n
e
c
n
o
C
Fig. 7 Comparison between the distribution of TPAHs and TPCBs in
UAE sediments
Environ Geol
1 3
and CPI values (0.751.33). The CPI has been a useful
parameter for estimating biogenic or anthropogenic con-
tributions since it was rst put forward. The n-alkanes
from higher plants waxes show a pronounced odd carbon
number preference, while fossil fuel and microbial
hydrocarbons exhibit CPI 1. The carbon number ranges
used for calculations are different among different
researchers. In the present study, the CPI for n-alkanes
was calculated as follows: CPI1 (whole range for n-alk-
anes) = R(C13C35)/R(C14C36); CPI2 (petrogenic n-
kh 2
0
1
2
3
4
5
6
Carbone number
kh1
0
1
2
3
4
5
6
7
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
Carbon number
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
kh3
0
2
4
6
8
10
12
14
Carbon number
kh5
0
1
1
2
2
3
3
4
4
5
Carbon number
kh4
0
1
1
2
2
3
3
4
Carbon number
kh6
0
2
4
6
8
10
12
Carbon number
kh7
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
Carbon number
kh8
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Carbon number
Fig. 8 Distribution of n-alkanes in the offshore sediments in UAE
Environ Geol
1 3
alkanes) = R(C13C23)/R(C14C24), and CPI3 (higher
plant wax n-alkanes) = R(C25C35)/R(C26C36) (Zhu
and Wang 2004). Within the study area, the CPI1 of
coastal sediments samples was ranging from 0.89 to 1.35
reecting similar petrogenic sources of pollution rather
than biogenic. The CPI2 for the coastal sediment samples
was ranging from 0 to 0.89. Thus, most CPI2 values were
closed to 1 indicating petrogenic sources rather than
biogenic sources. Finally, CPI3 values ranging from 0.8 to
1.4 for coastal sediments, suggesting higher plants waxes
as the predominant source for the obtained n-alkanes
range of the studied samples.
kh10
0
2
4
6
8
10
12
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
kh9
0
2
4
6
8
10
12
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
kh11
0
1
2
3
4
5
6
7
8
9
10
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
Carbon number
kh12
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
AJ-1
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
AJ-2
0
5
10
15
20
25
30
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
QU-2
0
2
4
6
8
10
12
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
QU-1
0
4
8
12
16
20
24
3
1
C
5
1
C
6
1
C
8
1
C
9
1
C
1
2
C
3
2
C
5
2
C
7
2
C
9
2
C
1
3
C
3
3
C
5
3
C
7
3
C
9
3
C
Carbon number
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
Fig. 8 continued
Environ Geol
1 3
High concentrations of pristane relative to phytane in
most coastal sediments indicate biological hydrocarbon
input from a marine biological source (planktonic or bac-
terial origin).
Factor analysis
The principal component factor analysis, at its simplest,
can be regarded as an ordination technique for reducing
multivariate data into fewer dimensions (Rock 1988).
Factor analysis was applied for selected elements and
compounds. The analysis reveals two factor solutions
(Fig. 9a, b). Organic compounds (TOC, TPH, TKN, and
Tpcbs) are positively loaded on factor 1 and may be termed
the pollution factor. The second factor is represented by
TPAHs. In the computation of correlation between TOC,
TPH, TPAHs, TKN, and TPCBs (Fig. 10a, b, Table 5)
from the regression analysis, TOC correlated signicantly
positive with TKN (r = 0.504) and there was a positive
correlation between TPH and TPCBs (r = 0.366; Fig. 11).
QU3
12
14
0
2
4
6
8
10
Carbon number
DU-1
0
5
10
15
Carbon number
20
SH-1
0
1
2
3
4
5
6
7
8
9
10
SH-2
0
2
4
6
8
10
12
Rase 2
0
2
4
6
8
10
12
14
Rase 1
0
5
10
15
20
25
Carbon number
SH-1
1
Carbon number
SH-2
Carbon number
Rase 2
Carbon number
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
1
3
C
1
5
C
1
6
C
1
8
C
1
9
C
2
1
C
2
3
C
2
5
C
2
7
C
2
9
C
3
1
C
3
3
C
3
5
C
3
7
C
3
9
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
C
o
n
c
e
n
t
r
a
t
i
o
n
Fig. 8 continued
-1.0 -0.5 0.0 0.5 1.0
FACTOR(1)
-1.0
-0.5
0.0
0.5
1.0
F
A
C
T
O
R
(
2
)
TOC
TKN
TPH
PAHS
PCBS
Fig. 9 Factor analysis
Environ Geol
1 3
Figure 11 illustrates that the organic pollutants could be
classied into two main groups: (a) TPH, PCBs, PAHs and
TOC, which represent hydrocarbon pollution and (b) TKN,
which represents the main man-made pollution, which
probably originated from run-off of fertilizers, livestock and
human wastes and municipal sewage-treatment facilities.
Conclusions
The analyses of the coastal sediments in UAE indicate the
following:
1. Association of the high TPH and TOC values with the
lithogenic metals rather than man-made conrms the
biogenic origin for the hydrocarbons.
2. The coastal sediments in UAE can be categorized into
two groups, the biogenic cluster was obvious and no
UCM was observed.
3. It has been recognized that hydrocarbons from natural
sources including biogenic source are very common in
the inland environments.
4. The coastal sediments showed typical biogenic n-al-
kane distribution ranging form C21 to C33 with
abundance of odd-carbon number n-alkanes being
much higher than that of even-carbon number n-alk-
anes.
5. TPH showed a wide distribution in the study area and
that is mainly attributed to the nature of the region and
the production and transport of petroleum.
6. Al Sharjah-1 represents the most contaminated part in
the study area and the major source of contamination is
attributed to anthropogenic sources. The presence of
Al Sharjah Port in the eastern part of the study area
provides a reasonable source of the high level of
contamination.
7. The ne and poorly sorted sand tend to have high
values of organic substance and heavy metals. The
adsorption onto ne-grained sediments is probably due
to the larger surface area.
0 50 100 150 200 250
TPHmg/Kg
0
200
400
600
800
1000
1200
T
K
N
m
g
/
K
g
0 5 10 15 20
TPH mg/Kg
0
50
100
150
200
250
T
O
C
w
t
%
A
0 20 40 60 80 100 120
TPAHs mg/Kg
0
5
10
15
20
T
O
C
w
t
%
C D
0 5 10 15 20
TKN mg/Kg
0
200
400
600
800
1000
1200
T
O
C
w
t
%
B
Fig. 10 Scatter plot showing
the relationship between TKN
and TPH (a), TOC and TPH (b),
TOC and TPAHs, and (c) TOC
and TKN (d)
Table 5 Correlation factor between TPH, TKN, TOC, TPAHs and
Tpcbs in offshore sediments at UAE
Correlation
factor
TPH PCBS TKN PAHS TOC
TPH 1.000
PCBS 0.366 1.000
TKN 0.175 0.101 1.000
PAHS 0.062 0.345 0.160 1.000
TOC 0.139 0.221 0.504 0.225 1.000
0 50 100 150 200 250
TPH
PCBS
TKN
PAHS
TOC
Fig. 11 Cluster analysis of TPH, TOC%, TKN, total PAH and total
PCBs associations in offshore sediments at UAE
Environ Geol
1 3
8. The variation in concentrations from one site to an-
other, the high relative standard deviation of most
studied pollutants and the high levels of these pollu-
tants in the developed areas compared with the rural
suggest anthropogenic sources. Also the distance from
the coastal zone can be considered as a controlling
factor of concentration and distribution of pollutants.
Acknowledgments Authors thank the Central Laboratory Unit
(CLU) and Petroleum Geochemistry Laboratory in the United Arab
Emirates for the analysis of the samples.
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