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Environ Geol

DOI 10.1007/s00254-007-0880-x

ORIGINAL ARTICLE

Assessment of organic pollutants in coastal sediments, UAE


Esam A. Abdel Gawad Æ Mohamed Al Azab Æ
M. M. Lotfy

Received: 12 March 2007 / Accepted: 18 June 2007


 Springer-Verlag 2007

Abstract Twenty-five stations were selected along the Keywords Pollution  Organic  TOC  PAHs 
UAE coastal region to delineate the distribution and to PCBS  Hydrocarbons  TKN  UAE
determine the source of total petroleum hydrocarbon
(TPH), total organic carbon (TOC), total Kjeldhal nitrogen
(TKN), polycyclic aromatic hydrocarbons (PAHs) and Introduction
polychlorinated biphenyls (PCBs). The concentrations of
TPH ranged between 46 and 223 mg/kg and the level of The rapid development in the past 15 years in the Arabian
TOC was in the range from 0.044 to 17.8 wt%, while Gulf region generally and in UAE specially has thrown a
TPAHs occupied the range of 5–102.2 lg/kg. On the other heavy burden on coastal zones and reflects an adverse
hand, TPCBs showed values between 60 and 205 lg/kg impact on coastal habitats. The petroleum industry, which
and TKN ranged from 104 to 1,073 mg/kg. The present is mostly concentrated on the coastal region, raises the
study shows that the distribution of organic compounds in level of oil and other organic compounds in marine sedi-
UAE sediments were within safe limits comparing with ments. In the past few years, the Dubai coastal zone was
previous studies. The present study revealed that TOC can subjected to several developments, which have affected the
be used as an indicator of oil pollution in heavily oiled water and sediment quality. According to Mocke et al.
sediments. The highest values of TOC, TPH, TPAHs and (2002), 20% of the study area is industrial, 16.5% private
TPCBs related to the stations covered in fine sand due to usage, 14% public usage and 15.5% Sanctuary (Jebel Ali).
adsorption properties and the large surface areas of the A periodic monitoring of petroleum hydrocarbon level in
grains. The evaporation of low-boiling point compounds Gulf coastal countries is useful in estimating any change in
from surface layers leads to the enrichment of sediments water and sediment quality.
with a thick residual. Al Sharjah-1 exhibited the highest Contamination by petroleum hydrocarbon is a serious
values of TPH and TOC at Ras Al-Khaima-5, Umm Al- problem throughout the world. An increase in petroleum
Quwen-1 and Dubai-1, while the highest values of TPAHs hydrocarbons in the marine environments causes a negative
were at KhorFakkan-9, the highest value of TPCBs was at impact not only on the aquatic life but also may be extend
Ajman-2, and the highest values of TKN were at Khor- to affect human heath through interference in the food web
Fakkan-1, KhorFakkan-6 and Dubai-1. and through contamination of seawater. A large percentage
(>30–50%) of spilled hydrocarbons enriched in heavier
more recalcitrant compounds deposited in bottom sedi-
ments, beaches and soils which then act as long-term res-
M. Al Azab
Department of Chemistry, Faculty of Science, ervoirs and secondary sources (Colombo et al. 2005)
UAE University, P.O. Box 17551, Al-Ain, UAE Furthermore, one of their major economic impacts is the
reducing the recreational utility of coastal waters. Oil in the
E. A. Abdel Gawad  M. M. Lotfy (&)
sea, whether from spills or chronic sources, is perceived as
Department of Geology, Faculty of Science,
UAE University, P.O. Box 17551, Al-Ain, UAE a major environmental problem. Occasional major oil spills
e-mail: mostafa.lotfy@uaeu.ac.ae receive considerable public attention because of the obvi-

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Environ Geol

ous attendant environmental damage such as oil-coated Table 1 Location for the collection of sediments
shorelines, and dead or moribund wildlife, including, in Stations Location Stations Location
particular, oiled seabirds and marine mammals (NAP
2003). 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
Materials and methods KH 4 Coastal-KhorFakkan Ras5 Coastal-Ras Al-Khaimah
KH 5 Coastal-Kalba Qu1 Coastal-Umm-Al-Quwain
Sample collection KH 6 Coastal-Kalba Qu2 Coastal-Umm-Al-Quwain
KH 7 Coastal-Kalba Qu3 Coastal-Umm-Al-Quwain
The stainless Van Veen grab sampler was used to obtain KH 8 Coastal-Kalba Aj1 Coastal-Ajman
the sediments samples. Twenty-five of bottoms offshore KH 9 Coastal-Fujairah Aj2 Coastal-Ajman
sediment within the depths of 15–20 m was gathered KH 10 Coastal-Fujairah Sh1 Coastal-Sharjah
(Fig. 1). Each fully mixed sample was air dried under a KH 11 Coastal-Fujairah Sh2 Coastal-Sharjah
hood at room temperature and sieved to pass a 35-mesh KH 12 Coastal-Fujairah Du1 Coastal-Dubai
sieve. The samples were kept frozen at –18C for the future Du2 Coastal-Dubai
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 The concentration of total petroleum hydrocarbon
samples were frozen in airtight plastic bags; all necessary (TPH) was measured in accordance as it is explained by
precautions were taken to avoid any contamination or the ROPME (2000). From the homogenized, field-moist sedi-
loss of volatilize compounds. ment 20 g were extracted in a Soxhlet by using hexane
solvent. TPH was determined by measuring the absorbance
Analytical methods of fluorescence using a Nicolet Infrared Spectrophotome-
ter. The percentage weight of total organic carbon (TOC)
The sediments samples were dried in oven under mild was carried out by following the Walkey-Black (1947)
temperature to remove the moisture before sieving. The method based on the oxidation of organic matter with
textural class was determined through grain-size analysis concentrated Sulfuric acid and titration to the end point
by using standard set of sieves and mechanical shaker. The with ferrous ammonium sulfate.
dry weight percentage of the size fractions retained on each Total Kjeldhal nitrogen (TKN) was determined
sieve was calculated. For the muddy samples, which con- according to Kjeldahl method (EPA 1993) using block
tains more than 20% mud, pipette analysis is the most digestion and steam distillation. This method requires the
common method used for determining the grain-size dis- digestion of the solid sample to solution using strong acid
tribution of sediments >4u. at high temperatures. The digestion tube was placed in the
distillation unit and the distillate was titrated with stan-
dardized HCl acid. The quantification of polycyclic aro-
55 o 56 0
matic hydrocarbons (PAHs) were brought out through high
performance liquid chromatography (HPLC) with a fluo-
rescence detector, the sample was dried with anhydrous
Arabian Gulf 26o sodium sulfate and extracted in a Soxhlet extraction using
Ras Al-khaimah
Ras4
mixture of hexane: acetone (50:50) for 2 h boiling and
Ras1 rinsing. The extract was injected into HPLC column. Fi-
Gulf of Oman nally, the determination of polychlorinated biphenyl (PCB)
Umm Al-quwen
QU2 QU3 was carried out using gas chromatography with an electron
QU1
Khor Fakkan capture detector (GC-ECD). The sample was extracted in a
Ajman AJ1 Kh4
AJ2
Sh1 Kh1
Soxhlet extraction using solvent (1:1 hexane: acetone) for
Sharjah
Sh2 Fujairah 2 h, the residual of the solvent after evaporation was col-
Kh12
Dubai United Arab Emirates 25 o lected and injected into GC-ECD column to recognize PCB
DU1 Kalba
Kh5
compounds (EPA 1999). N-alkanes and isoprenoids
DU2 Locations
20
hydrocarbons were determined by gas chromatography
0 40 60 Km

Oman
Cities with a flame ionization detector (GC-FID) with the fol-
lowing specification and condition, Varine, Saturn 3800
Fig. 1 Location map of the studied sites in UAE GC system, equipped with flam ionization, detector FID,

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Environ Geol

GC column: CP-Sil 8, 30 m · 0.32 mm ID, df = 1, Carrier Table 2 Concentrations of TPH, TOC and TKN in UAE sediments
Gas: He 1.5 ml/min, Temperature program of the oven Sample ID TPH (mg/kg) TOC wt% TKN (mg/kg)
100–160C at 15C/min for 2 min, followed by 160–300C
at 5C/min for 30 min. The detection limits of our ana- Kh1 86 0.162 305
lytical compounds have been done as reference material Kh2 134 0.088 104
analysis by Al-Darwish et al. (2005) and Al katheeri Kh3 163 0.089 132
(2004). Kh4 199 0.088 116
Kh5 157 0.191 nd
Kh6 119 0.28 286
Results and discussion Kh7 156 0.119 104
Kh8 140 0.044 nd
Sediments distribution Kh9 101 0.088 nd
Kh10 141 0.103 nd
The objectives of determining the grain-size distribution of Kh11 126 0.191 nd
sediments in this study is to correlate the level of con- Kh12 93 0.058 nd
taminants to grain size, and to determine the texture of the Ras1 128 11.25 nd
sediments, i.e., the percentage of fine particles in the sed- Ras2 74 3.832 nd
iment. The coarse sandy sediments are mainly restricted to Ras3 91 8.787 108
the southern regions of the Gulf, and the fine clay silt Ras5 97 17.05 nd
sediments are mainly concentrated in the northern regions Qu1 82 17.8 1,073
(Al-Ghadban et al. 1996). The textural classes in the Gulf Qu2 54 8.219 nd
of Oman area fall into four main groups: fine sand, medium Qu3 134 12.33 nd
sand, coarse sand, and pebble (Fig. 2a). The textural clas- Aj1 125 11.88 nd
ses in the Arabian Gulf area also fall in five other groups: Aj2 152 3.46 nd
fine sand, medium sand, coarse sand, very coarse sand and Sh1 223 5.548 nd
granule (Fig. 2b). Most of the study area (36%) is medium Sh2 64 3.985 nd
sand, while the fine size deposits represent (24%), coarse
Du1 76 17.05 239
sand represent (16%), very coarse sand (12%), pebble (4%)
Du2 46 14.59 nd
and granule (8%).
Average ± SD 118.44 ± 43.668 5.49128 ± 6.440 98.68 ± 223.979

Content of TPH, TOC and TKN nd not detected

Chronic releases from natural and anthropogenic sources worth to noting that Sharjah-1and KhorFakkan-4 showed
(e.g., natural seeps and run-off from land-based sources) high levels of TPH (223 mg/kg and 199 mg/kg, respec-
are responsible for majority of petroleum hydrocarbon in- tively), whereas other locations showed only slight and
put (NAP 2003). Typically, petroleum hydrocarbon con- moderate levels of TPH. These locations showed very high
centrations are a few mg/kg in unpolluted coastal areas and concentrations of TPH compared with the obtained values
from 50 to more than 1,000 mg/kg in polluted areas (Clark from the Gulf region after the 1991 Gulf War. For example,
and Macleod 1977). The values of TPH in UAE sediments Massoud et al. (1996) found TPH in heavily polluted areas
show drastic fluctuations, varying from 46 to 223 mg/kg, affected by the Kuwait oil slick ranged from 266 to
with an average of 118.44 ± 43.67 (see Table 2). It is 1,448 mg/kg. Hayes et al. (1993) reported that the con-

Fig. 2 Textural classes of A Mean size B Mean size


sediments (a) gulf of Oman and
(b) Arabian Gulf in UAE
Fine sand

Medium sand
Fine sand
Medium sand Coarse sand
Coarse sand
Pebble Very coarse
sand
Granule

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Environ Geol

centrations of TPH in sediments at the most severely im- tration of TPH at Dubai-1and Dubai-2 is mostly attributed
pacted locations along the Saudi Arabian coast one year to the presence of dry docks, which might received
after the Gulf War oil spill were 10,000 mg/kg. The high petroleum input from damaged tankers, water depilating
level of TPH at Sharjah-1 and KhorFakkan-4 as well as and tanker maintenance, whereas the source of oil input at
Ajman-2 (Fig. 3a) could be attributed to its location close the other stations referred to is most likely from private
to Sharjah Port, which is used for oil exporting. In addition, usage of coastal zone. On the other hand, the high level of
other resources could be navigation routes, tanker transport TPH at the Arabian Gulf coastal could also be as a result of
and coastal production, which is other sources of oil pol- the movement of surface waters with high oil contents form
lution in the region (Golob and Brus 1984). The distribu- the Gulf of Oman through the Strait of Hormuz (Shriadah
tion map (Fig. 3b) of TPH demonstrates unusual levels of 1998).
THP at Sharjah-1, Khorfakkan-4 and Ajman-2, which may The input of organic matter to coastal systems is, in-
have occurred as a temporal event during or shortly before deed, the triggering mechanism leading to the ecological
the period of samples collection. The moderate concen- consequences of concern (Dell’Anno et al. 2002). TOC
value indicates the sum of organic carbon and represents a
measure for all organic substances in sediments. These
TPH mg/kg substances are from (1) natural sources, such as humic
acids, mineral oils, solvents, pesticides, and polyaromatic
A 250
hydrocarbons or (2) chlorinated organic compounds. The
values of TOC ranged from 0.044 to 17.8 wt% with an
Concentration mg/kg

200
average of 5.49 ± 6.44. Hartmann et al. (1971) pointed out
150 that the sediments of the Arabian Gulf generally contain
between 0.5 and 1.0 wt%, or at the most 2.0%. Literathy
100
et al. (1992) reached the previous finding on the natural
50 background levels of TOC (0.5–0.8 wt%) in the bottom
sediments of Kuwait marine environment. Table 3 illus-
0
trates the concentrations of TOC along UAE coast, which
Ras 1
Ras 2
Ras 3
Ras 5

Du1
Du2
Q u1
Q u2
Q u3
Kh1
Kh2
Kh3
Kh4
Kh5
Kh6
Kh7
Kh8
Kh9
Kh10
Kh11
Kh12
Sh1
Sh2

Ag1
Ag2

have been reported by several researchers from 1992 to


Stations 2003. TOC in UAE sediments (Fig. 3b) shows high levels
TOC wt%
for the western region sediments compared with the eastern
western partregion sediments. The real distribution of TOC
B 20
(Fig. 4b) exhibits that the western part shows higher levels
18
16 of TOC compared with other eastern part which shows
14
lower levels of TOC in UAE sediments. Table 3 displays
Toc wt %

12
10 discordance in the distribution of petroleum hydrocarbons
8 and the percentage of organic matter in sediments. This
6

4
finding is confirmed by significant negative correlation
2 (r = –0.423) between TPH and TOC, which shows dis-
0
agreement with earlier findings of Shriadah (1998), who
Ras 1
Ras 2
Ras 3
Ras 5

Du1
Du2
Q u1
Q u2
Q u3
Kh1
Kh2
Kh3
Kh4
Kh5
Kh6
Kh7
Kh8
Kh9
Kh10
Kh11
Kh12
Sh1
Sh2

Aj1
Aj2

found that of organic carbon in the sediments, the greatest


Stations
was the adsorption of petroleum hydrocarbons. Therefore,
TKN (mgN/Kg) it may be suggested that the percentage of TOC could be
C 1200
used as an indicator of petroleum pollution in the area; this
Concentration mg/kg

1000
conclusion is in agreement with the earlier observations of
800 Emara (1998). Ammonification refers to the way some
600 organisms fix nitrogen to either NH+4 or organic nitrogen
400
(nitrogen fixation); nitrification refers to organisms that
nitrify NH+4 to NO3. Both nitrification and ammonification
200
convert gaseous nitrogen into bioavailable chemical forms
0
(Wilson et al. 1993). TKN stands for total Kjeldahl nitro-
Ras 1
Ras 2
Ras 3
Ras 5

Du1
Du2
Q u1
Q u2
Q u3
Kh1
Kh2
Kh3
Kh4
Kh5
Kh6
Kh7
Kh8
Kh9
Kh10
Kh11
Kh12
Sh1
Sh2

Aj2
Aj1

gen, which is the sum of ammonia (NH3) and organic


Stations
nitrogen.
Fig. 3 Distribution of TPH (a), TOC (b) and TKN (c) in UAE According to measurement of TKN in UAE sediments,
sediments the values showed very wide variation, ranging from 0 to

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Environ Geol

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 0.14–2.65 1.02 ± 1.15
Abu-Hilal and Khordagui (1992) The Arabian Gulf and Gulf of Oman. Annual report Sharjah 0.44–1.36 0.78 ± 0.35
Abu-Hilal and Khordagui (1992) The Arabian Gulf and Gulf of Oman. Annual report Ajman 0.24–1.42 0.7 ± 0.5
Shriadah (1998) Indian Journal of Marine Sciences Ras Al-Khaimah, 0.12–0.89 0.34 ± 0.29
Shriadah (1998) Indian Journal of Marine Sciences Umm Al-Quwain 0.15–0.38 0.27 ± 0.22
Shriadah (1998) Indian Journal of Marine Sciences Sharjah 0.49–1.2 0.57 ± 0.43
Shriadah (1998) Indian Journal of Marine Sciences Abu Dhabi 0.45–0.77 0.61 ± 0.4
El-Sammak (1998) Regional conference on the marine environment Dubai Creek 0.0052–0.445 0.153
of the Gulf
Al-Qubaisi (2001) Master science Thesis UAEU Dubai 0.06–0.27 0.1 ± 0.08
Deshgooni (2002) Master science Thesis UAEU Dubai Creek 0.3–5.8 2.7 ± 1.6
Al Katheeri (2004) Master science Thesis UAEU Abu Dhabi 0.14–14.96 4.77 ± 3.70
Tolosa et al. (2005) Marine Pollution Bulletin Gulf of Oman 0.1–1.53 0.443 ± 0.5452
Al-Darwish et al. (2005) Environmental Geology Dubai offshore 0.16–5.9 0.86 ± 1.44
Present study Environmental Geology UAE 0.088–17.8 5.49128 ± 6.440

1,073 mg/kg, with an overall average of 98.68 ± 223.98 rather than the eastern ones (Fig. 6a). The maximum value
(Table 2) at KhorFakkan-1, KhorFakkan-6 and Dubai-1. was reported at KhorFakan 9. The primary source of
The level of TKN suggested by Alloway (1993) in coastal anthropogenic PAHs in the environment is thought to be
sediments is 300 mg/kg. The high concentrations of TKN atmospheric depositions (Witt 1995). TPAHs in UAE
are probably originated from run-off of fertilizers, livestock sediments found to be lower than the values recorded along
and human wastes and municipal sewage-treatment facili- the Saudi Arabian coast (10–300 lg g–1) 1 year after the
ties. This indicates coastal discharges or may be attributed Gulf War (Hayes et al. 1993), in heavily oil contaminated
to high levels of TPH (223 mg/kg), which increases the sediments. However, the level is still high compared with
mortality rate among the aquatic organisms such as phy- other regions in the world. This confirms the earlier con-
toplankton and zooplankton that in turn enhances the clusion proposed by Evans et al. (1990) that the highest
bacterial decomposition activity, which increases the rate amount of PAHs is usually associated with sediments that
of nitrite. The significant negative correlation (r = –0.175) have a high TOC. The distribution pattern appeared to be
between TKN and TPH did not confirm the bacterial related to oil pollutant sources, such as discharge from
decomposition. According to the measurements of TKN in vessels and port activities (Hong et al. 1995). Polychlori-
UAE sediments, the values showed wide variations within nated biphenyls are now widespread in the environment
the range of 0–1,073 mg/kg (Fig. 3c). Figure 4c illustrates and can be detected in air, water, soil, sediments and
the distribution trend of TKN in UAE sediments the high organisms; the typical environmental concentration is 2–
level of TKN (305 mg/kg) KhorFakan-1, which has mod- 50 lg kg–1 in soil (Killops and Killops 1993). PCBs tend to
erately value of TPH (86 mg/kg), majority attributed to adsorb to fine particulates or be bio accumulated into lipids
highly terrestrial input (El-Sabrouti et al. 1990). in aquatic biota (Olsen et al. 1982). According to Fang
et al. 2003 phenanthrene/anthracene (P/A) ratio is equal to
Content of TPAHs and TPCBs 1 for coastal sediment samples within the study area,
except for station KH7 (0.9), which reflects pyrogenic
Polycyclic aromatic hydrocarbons are a class of organic sources of PAHs benzo(a)anthracene/(benzo(a) anthra-
pollutants that are released into the environment in large cene + chrysene stations KH4, KH7, KH8, KH9, and
quantities, mainly due to human activities. There are two KH10 have values of BaA/(BaA + Chry) £ 0.4 which re-
primary sources of PAHs to the marine environment, flects petrogenic sources, while stations KH1, KH2, KH3,
pyrogenic and petrogenic: pyrogenic PAHs are derived KH5, KH6, KH11, and KH12 attain the values of BaA/
from combustion sources and petrogenic PAHs are derived (BaA + Chry) ranging from 0.5 to 0.75, indicating pyro-
from petroleum inputs. In UAE sediments, TPAHs values genic sources. According to Guinan (2001) fluoranthene/
fluctuated between 5 and 102.5 mg/kg with an average of (fluoranthene + pyrene) ratio Flu/(Flu + P) > 1 indicates
30.64 ± 23.59 (Table 4, Fig. 5a). The distribution map of pyrogenic sources while values <1 indicate petrogenic
TPAHs exhibits increasing trends in the western sediments sources of PAHs. Within the study area, the Flu/(Flu + P)

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Environ Geol

A 55 o 56 0 Table 4 Concentrations of TPAHs and TPCBs in Dubai sediments


Sample ID TPCBs (mg/kg) TPAHS (mg/kg)

Arabian Gulf 26o Kh1 115 49.9


Ras4
Ras Al-khaimah Kh2 95 27.5
Ras1
Kh3 140 52.9
Gulf of Oman
Umm Al-quwen Kh4 130 36.4
QU2 QU3
QU1
Kh5 80 62.6
Khor Fakkan
Ajman AJ1 Kh4 Kh6 140 16.5
AJ2
Sharjah Sh1 Kh1 Kh7 80 50.9
Sh2 Fujairah
Kh12
Kh8 105 40.7
United Arab Emirates 25 o
Dubai
DU1 Kalba
Kh9 75 102.2
Kh5
DU2 Locations Kh10 125 13.5
0 20 40 60 Km
Cities
Kh11 90 11.6
Oman Kh12 75 24.4
o 0 Ras2 70 14.2
B 55 56
Ras3 95 17.9

26
o Ras5 110 42.9
Arabian Gulf
Ras4
Ras1 75 26.4
Ras Al-khaimah
Ras1
Qu1 110 10.7
Gulf of Oman Qu2 90 28.4
Umm Al-quwen
QU2 QU3 Qu3 110 11
QU1
Khor Fakkan Ag1 180 5
Ajman AJ1 Kh4
AJ2 Ag2 205 5
Sh1 Kh1
Sharjah Sh1 95 13.8
Sh2 Fujairah
Kh12
United Arab Emirates 25o Sh2 60 22
Dubai
DU1 Kalba
Kh5 Du1 90 11
DU2 Locations
Du2 75 68.7
0 20 40 60 Km
Cities
Average ± S.D 104.6 ± 34.367 30.644 ± 23.590
Oman

55 o 56 0
C
On the basis of all the above-calculated ratios, it can be
Arabian Gulf 26o concluded that sources of pollution within the study area
Ras4
Ras Al-khaimah are predominantly of petrogenic origin (oil spill), in addi-
Ras1 tion to minor contribution from pyrogenic sources (com-
Gulf of Oman
Umm Al-quwen bustion of oil products and shipping activities at nearest
QU2 QU3
QU1
harbor).
Khor Fakkan
Ajman AJ1 Kh4 TPCBs in UAE sediments values ranged from 60 to
AJ2
Sh1 Kh1 205 lg/kg. The maximum value was reported at Ajman 2,
Sharjah
Sh2 Fujairah with an average of 104.6 ± 34.38 (Table 4, Fig. 5b).
Kh12
United Arab Emirates 25 o Figure 6b represent the distribution map of TPCBS towards
Dubai
DU1 Kh5 Kalba
DU2
the western region where the maximum value is about three
Locations
0 20 40 60 Km times higher than the minimum. Ajman-2 represents four
Cities
Oman times higher than the typical environmental concentration.
However, both PCBs and PAHs showed the maximum va-
Fig. 4 Distribution maps of TPH (a), TOC (b) and TKN (c) in UAE lue at KhorFakan-9 and Ajman-2, respectively, but PCBs
sediments
exhibit wider range of distribution in the study area (Fig. 7).

ratio was ranging from 0 at KH1, KH6 and KH12 to 1 at Hydrocarbons


KH2, KH3 and KH8 for coastal sediments. The concen-
tration at most stations was less than 1, indicating petro- Hydrocarbons from both anthropogenic and natural sour-
genic sources of PAHs. ces including biogenic sources are very common in the

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Environ Geol

TPAHs mg/Kg 55 o 56 0
A 120 A
100
C oncentration mg/Kg

Arabian Gulf 26o


80
Ras4
Ras Al-khaimah
60 Ras1
Gulf of Oman
40 Umm Al-quwen
QU2 QU3
20 QU1
Khor Fakkan
Ajman AJ1 Kh4
AJ2
0
Sh1 Kh1
k h1
k h2
k h3
k h4
k h5
k h6
k h7
k h8
k h9
k h10
k h11
k h12
Ras 1
Ras 2
Ras 3
Ras 5

Du1
Du2
s h1
s h2
Aj1
Aj2
Sharjah
Sh2 Fujairah
Stations Kh12
United Arab Emirates 25 o
Dubai
DU1 Kh5 Kalba
B 250
TPCBs mg/Kg DU2 Locations
0 20 40 60 Km
Cities
C oncentration mg/K g

200 Oman

55 o 56 0
150 B

100
Arabian Gulf 26o

Ras4
50 Ras Al-khaimah
Ras1

0
Gulf of Oman
Umm Al-quwen
KH1
KH2
KH3
KH4
KH5
KH6
KH7
KH8
KH9
KH10
KH11
KH12

Ras 1
Ras 2
Ras 3
Ras 5

Du1
Du2
Q u1
Q u2
Q u3
Sh1
Sh2

Aj1
Aj2

QU2 QU3
QU1
Stations AJ1
Khor Fakkan
Ajman Kh4
AJ2
Fig. 5 Distribution of TPAHs (a) and TPCBs (b) Sh1 Kh1
Sharjah
Sh2 Fujairah
Kh12
United Arab Emirates 25 o
Dubai
DU1 Kh5 Kalba
marine and inland environments. Biogenic hydrocarbons
DU2 Locations
are generated either by biological processes or in the early 0 20 40 60 Km
Cities
stages of diagnosis in recent marine sediments. Biological Oman
sources include land plants, phytoplankton, animals, bac-
teria, macroalgae and microalgae. Stated that the distinct Fig. 6 Distribution map of TPAHs (a) and TPCBs (b) in UAE
sediments
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
250 TPAH&TPCBs mg/Kg
the following chemical composition characteristics: (1)
n-alkanes show a distribution pattern of odd carbon-
200
numbered alkanes being much abundant than even
Concentration mg/Kg

carbon-numbered alkanes in the range of n-C 21 to n-C33,


resulting in unusually high carbon preference index (CPI) 150

values, which is defined as the sum of the odd carbon-


numbered alkanes to the sum of the even carbon-num- 100
bered alkanes (oils characteristically have CPI values
around 1.0); (2) A notable absence of the ‘‘unresolved 50
complex mixture (UCM)’’ hump in the chromatograms;
(3) pristane is often more abundant than phytane, sug- 0
gesting a phytoplankton input and resulting in abnormally
Ras 2
Ras 3
Ras 5
Ras 1
Q u1
Q u2
Q u3

Du1
Du2
Kh1
Kh2
Kh3
Kh4
Kh5
Kh6
Kh7
Kh8
Kh9
Kh10
Kh11
Kh12

Sh1
Sh2
Ag1
Ag2

high pristane/phytane ratio values in most studied loca-


Station
tions (Fig. 8a–v). In the study of the hydrocarbon bio-
geochemical setting of coastal sediments in the UAE, we Fig. 7 Comparison between the distribution of TPAHs and TPCBs in
found that very high pristane/phytane ratios (0.49–4.48) UAE sediments

123
Environ Geol

and CPI values (0.75–1.33). The CPI has been a useful hydrocarbons exhibit CPI  1. The carbon number ranges
parameter for estimating biogenic or anthropogenic con- used for calculations are different among different
tributions since it was first put forward. The n-alkanes researchers. In the present study, the CPI for n-alkanes
from higher plants waxes show a pronounced odd carbon was calculated as follows: CPI1 (whole range for n-alk-
number preference, while fossil fuel and microbial anes) = R(C13–C35)/R(C14–C36); CPI2 (petrogenic n-

7
6
6 kh1 5
kh 2
Concentration

Concentration
4
4
3
3

2
2

1
1

0 0

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

Carbon number C39 Carbone number

14 4

3 kh4
12 kh3 Concentration
3
10
Concentration

2
8

2
6

1
4

2 1

0
0

C39
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

Carbon number
Carbon number

5
12
4 kh5
4 10 kh6
Concentration

Concentration

3
8
3

2 6

2
4
1
2
1

0
0
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

Carbon number Carbon number


7.00
1.2
6.00 kh7 1.0 kh8
Concentration

Concentration

5.00
0.8
4.00
0.6
3.00

0.4
2.00

1.00 0.2

0.00 0.0
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

Carbon number Carbon number

Fig. 8 Distribution of n-alkanes in the offshore sediments in UAE

123
Environ Geol

12
12
kh9
10
10
kh10

Concentration

Concentration
8
8

6
6

4 4

2 2

0 0
C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39

C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39
Carbon number Carbon number
10
14.0
9
kh11
8
12.0 kh12
Concentration

Concentration
7 10.0
6
8.0
5
6.0
4

3 4.0
2
2.0
1
0.0
0

C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39
C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39

Carbon number Carbon number


30
0.40
AJ-2
0.35 AJ-1 25
Concentration

Concentration

0.30
20
0.25

0.20 15

0.15
10
0.10
5
0.05

0.00 0
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39
Carbon number Carbon number
24
12

QU-1 QU-2
20
10
Concentration
Concentration

16 8

12 6

8 4

4 2

0 0
C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39

C 13

C 15

C 16

C 18

C 19

C 21

C 23

C 25

C 27

C 29

C 31

C 33

C 35

C 37

C 39

Carbon number Carbon number

Fig. 8 continued

alkanes) = R(C13–C23)/R(C14–C24), and CPI3 (higher was ranging from 0 to 0.89. Thus, most CPI2 values were
plant wax n-alkanes) = R(C25–C35)/R(C26–C36) (Zhu closed to 1 indicating petrogenic sources rather than
and Wang 2004). Within the study area, the CPI1 of biogenic sources. Finally, CPI3 values ranging from 0.8 to
coastal sediments samples was ranging from 0.89 to 1.35 1.4 for coastal sediments, suggesting higher plants waxes
reflecting similar petrogenic sources of pollution rather as the predominant source for the obtained n-alkanes
than biogenic. The CPI2 for the coastal sediment samples range of the studied samples.

123
Environ Geol

14
20

12 QU3
DU-1
15

Concentration
Concentration 10

8
10
6

4
5

0 0
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39
Carbon number Carbon number
10 12

9
SH-1 SH-2
10
8
Concentration

Concentration
7
8
6

5 6
4
4
3

2
2
1

0 0
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39
Carbon number Carbon number
25
14

20 12 Rase 2
Concentration

Concentration

Rase 1 10
15
8

10 6

4
5
2
0 0
C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39

C13

C15

C16

C18

C19

C21

C23

C25

C27

C29

C31

C33

C35

C37

C39
Carbon number Carbon number

Fig. 8 continued

High concentrations of pristane relative to phytane in 1.0


PCBS
most coastal sediments indicate biological hydrocarbon
input from a marine biological source (planktonic or bac- 0.5 TPH
terial origin).
FACTOR(2)

TKN
TOC
0.0
Factor analysis

The principal component factor analysis, at its simplest, -0.5


PAHS
can be regarded as an ordination technique for reducing
multivariate data into fewer dimensions (Rock 1988). -1.0
-1.0 -0.5 0.0 0.5 1.0
Factor analysis was applied for selected elements and
FACTOR(1)
compounds. The analysis reveals two factor solutions
(Fig. 9a, b). Organic compounds (TOC, TPH, TKN, and Fig. 9 Factor analysis
Tpcbs) are positively loaded on factor 1 and may be termed
the pollution factor. The second factor is represented by from the regression analysis, TOC correlated significantly
TPAHs. In the computation of correlation between TOC, positive with TKN (r = 0.504) and there was a positive
TPH, TPAHs, TKN, and TPCBs (Fig. 10a, b, Table 5) correlation between TPH and TPCBs (r = 0.366; Fig. 11).

123
Environ Geol

Fig. 10 Scatter plot showing A 1200 B 250


the relationship between TKN
1000
and TPH (a), TOC and TPH (b), 200
TOC and TPAHs, and (c) TOC 800

TKN mg/Kg

TOC wt%
and TKN (d) 150
600
100
400

50
200

0 0
0 50 100 150 200 250 0 5 10 15 20
TPHmg/Kg TPH mg/Kg

C 20 D 1200
1000
15
800

TOC wt%

TOC wt%
10 600

400
5
200

0 0
0 20 40 60 80 100 120 0 5 10 15 20
TPAHs mg/Kg TKN mg/Kg

Table 5 Correlation factor between TPH, TKN, TOC, TPAHs and Conclusions
Tpcbs in offshore sediments at UAE
Correlation TPH PCBS TKN PAHS TOC The analyses of the coastal sediments in UAE indicate the
factor following:
TPH 1.000 1. Association of the high TPH and TOC values with the
PCBS 0.366 1.000 lithogenic metals rather than man-made confirms the
TKN –0.175 0.101 1.000 biogenic origin for the hydrocarbons.
PAHS –0.062 –0.345 –0.160 1.000 2. The coastal sediments in UAE can be categorized into
TOC –0.139 0.221 0.504 –0.225 1.000 two groups, the biogenic cluster was obvious and no
UCM was observed.
3. It has been recognized that hydrocarbons from natural
TOC sources including biogenic source are very common in
the inland environments.
PAHS 4. The coastal sediments showed typical biogenic n-al-
kane distribution ranging form C21 to C33 with
PCBS abundance of odd-carbon number n-alkanes being
much higher than that of even-carbon number n-alk-
TPH anes.
5. TPH showed a wide distribution in the study area and
TKN that is mainly attributed to the nature of the region and
the production and transport of petroleum.
0 50 100 150 200 250
6. Al Sharjah-1 represents the most contaminated part in
Fig. 11 Cluster analysis of TPH, TOC%, TKN, total PAH and total the study area and the major source of contamination is
PCBs associations in offshore sediments at UAE attributed to anthropogenic sources. The presence of
Al Sharjah Port in the eastern part of the study area
Figure 11 illustrates that the organic pollutants could be provides a reasonable source of the high level of
classified into two main groups: (a) TPH, PCBs, PAHs and contamination.
TOC, which represent hydrocarbon pollution and (b) TKN, 7. The fine and poorly sorted sand tend to have high
which represents the main man-made pollution, which values of organic substance and heavy metals. The
probably originated from run-off of fertilizers, livestock and adsorption onto fine-grained sediments is probably due
human wastes and municipal sewage-treatment facilities. to the larger surface area.

123
Environ Geol

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Acknowledgments Authors thank the Central Laboratory Unit
of polycyclic aromatic hydrocarbons in the sediments of Hsin-Ta
(CLU) and Petroleum Geochemistry Laboratory in the United Arab
Harbor and adjacent coastal areas, Taiwan. Mar Pollut Bull
Emirates for the analysis of the samples.
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