Click here to load reader
Upload
stephen-de-mora
View
218
Download
3
Embed Size (px)
Citation preview
www.elsevier.com/locate/marpolbul
Marine Pollution Bulletin 49 (2004) 410–424
Distribution of heavy metals in marine bivalves, fish andcoastal sediments in the Gulf and Gulf of Oman
Stephen de Mora *, Scott W. Fowler, Eric Wyse, Sabine Azemard
Marine Environment Laboratory, International Atomic Energy Agency, 4 Quai Antoine 1er, B.P. 800, MC 98012,
Principality of Monaco, Monaco 98012, Monaco
Abstract
An assessment of marine contamination due to heavy metals was made in the Gulf and Gulf of Oman based on marine biota (fish
and various bivalves) and coastal sediment collected in Bahrain, Oman, Qatar, and the United Arab Emirates (UAE) during 2000–
2001. Sediment metal loadings were generally not remarkable, although hot spots were noted in Bahrain (Cu, Hg, Pb, Zn) and on
the east coast of the UAE (As, Co, Cr, Ni). Concentrations of As and Hg were typically low in sediments and the total Hg levels in
top predator fish commonly consumed in the region were <0.5 lg g�1 and posed no threat to public health. Very high Cd con-centrations (up to 195 lg g�1) in the liver of some fish from southern Oman may result from food-chain bioaccumulation of elevated
Cd levels brought into the productive surface waters by upwelling in the region. Very high As concentrations (up to 156 lg g�1) weremeasured in certain bivalve species from the region. Although not certain, the As is probably derived from natural origins rather
than anthropogenic contamination.
� 2004 Elsevier Ltd. All rights reserved.
Keywords: Trace metals; Oyster; Sediments; Pollution; Cadmium; Arsenic; Gulf
1. Introduction
Pollution studies in the Gulf and Gulf of Oman,
collectively known as the ROPME Sea Area (RSA), are
extremely important. The Gulf comprises a relatively
shallow, semi-enclosed sea with very high evaporation
rates and poor flushing characteristics (Sheppard, 1993).
As a result, contaminant inputs undergo more limiteddilution and slower dispersion than would occur in open
marine systems. The ecosystem is relatively fragile,
experiencing elevated temperatures, salinity and UV
exposure. Many species function close to physiological
limits (Sheppard, 1993), and thus, added stress imposed
by pollutants is likely to have severe consequences.
Maintaining good marine environmental quality is cru-
cial for several socio-economic reasons. The seafood,notably fish and shrimp, is of value for both local con-
sumption and export revenue. Moreover, the region
relies heavily upon the sea water itself as a source of
fresh water through desalination (Price et al., 1993).
* Corresponding author. Tel.: +377-97-97-72-72; fax: +377-97-97-
72-76.
E-mail address: [email protected] (S. de Mora).
0025-326X/$ - see front matter � 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.marpolbul.2004.02.029
The RSA has experienced several impacts in recent
years that have contributed to pollution burdens in the
region. The waterways are heavily utilised, especially
with respect to oil tanker traffic, with the consequential
discharges related to shipping activities. There are some
key industrial developments, especially in Bahrain, that
act as localised sources of organic and inorganic pollu-
tion. Ongoing industrial development in the region, al-beit geographically variable, continues to cause concern
with respect to marine environmental quality. Unfor-
tunately, the regional database with respect to many
metals is not uniform (Fowler, 2002b). Agriculture,
mostly located in the northern zone, is expanding in the
region, with the threatened increase of emissions of
pesticides and other agrochemicals, including metal-
based formulations. However, the current database foragrochemical residues in the Gulf is rather limited
(Fowler, 2002a), and even more so with respect to the
Gulf of Oman.
Superimposed on trends related to changing land
uses, there has been the environmental impact of three
wars in the past two decades. Considering metals in the
marine environment, some initial consequences were
described relatively soon after the 1991 Gulf War. Clam
Fig. 1. Location of all sampling sites for sediments (O), fish (X), and
bivalves (+) in Bahrain, Qatar, UAE, and Oman.
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 411
samples collected near Kuwait contained higher levels of
several metals (Cd, Cu, Ni, Pb, and V) in 1991 compared
to 1985 (Kureishy, 1993). Concentrations of oil-related
metals, Ni and V, exhibited slightly elevated concen-trations along the oil-impacted coastline of Saudi Ara-
bia relative to other locations in the Gulf in 1991
(Fowler et al., 1993). The effects did not extend as far as
Qatar, where there was no observable increase in the
concentrations of Hg, Cd, Pb, Cu, Co, and Ni in benthic
and semi-pelagic marine organisms (Sadiq and McCain,
1993). A post war assessment of several potential con-
taminants, including metals, was conducted along thecoast of United Arab Emirates (Banat et al., 1998).
Moreover, the potential long-term effects have contin-
ued to be explored. Various tissues of the blue crab,
Portunus pelagicus, collected in Kuwait were analyzed to
assess the bioaccumulation of several metals associated
with petroleum input a decade after the 1991 Gulf War
oil spillage (Al-Mohanna and Subrahmanyam, 2001).
The concentrations of trace metals in seawater andparticulate matter were determined during 1993 and
1994 in order to assess the environmental consequence
of the massive oil spill off the Kuwait Coast during the
Iraqi invasion (Bu-Olayan et al., 1998). The interpreta-
tion of successive war-induced impacts relies on good
environmental data based on reliable techniques dem-
onstrating good quality control.
Under the ROPME-IAEA contaminant screeningprojects, surveys of heavy metals and organic contami-
nants have taken place in the Gulf and Gulf of Oman
since the early 1980s (Burns et al., 1982; Fowler, 1988;
Fowler et al., 1984). Such pre-war studies have proved
invaluable for the identification of pollution hot spots
and assessing the consequences of the 1991 Gulf War
(Fowler et al., 1993). This paper firstly evaluates marine
pollution of metals in the coastal zone of the easternGulf and Gulf of Oman based on sediment quality.
Sediment samples were collected from several coastal
locations in Bahrain, Oman, Qatar, and the UAE during
2000–2001. A wide range of elements was determined
for pollution assessment and to facilitate interpretation
of the origins of potential contaminants. Secondly, the
paper examines the quality of local seafood with respect
to metal contamination. The focus was on two fishspecies of commercial importance, namely the orange
spotted grouper (Epinephelus coioides, known locally as
hamoor) and the spangled emperor (Lethrinus nebulosus,
known locally as sha’ri, shaeri or sheiry), together with
various bivalves, notably oysters. Overall, the results for
sediments and biota contribute to the regional database
for the RSA, most notably for Oman given the paucity
of such information. Concurrent studies of organotincompounds have been presented elsewhere (de Mora
et al., 2003) and similar assessments are under prepa-
ration for petroleum hydrocarbons and organochlori-
nated compounds.
2. Methods
2.1. Sample collection
Marine samples were collected in the Gulf and Gulf
of Oman during 2000–2001. In general, all sampling
procedures were carried out according to internationally
recognized guidelines (UNEP, 1991). All sampling
locations in Bahrain, Oman, Qatar, and the United
Arab Emirates are shown in Fig. 1. Exact coordinates
and dates for sediment sampling are shown in Table 1.
Similarly, locations for the collection of fish and bivalvesare given in Table 2. Surface sediments were collected
directly into pre-cleaned Teflon containers. To obtain a
suitable mass of material for analysis, soft parts from
1 to 18 individual bivalves were dissected, then drained
of excess liquid and stored in plastic bottles. For fish,
100–300 g of dorsal muscle from a single individual was
dissected for the sample. Fish liver tissue was also re-
moved and prepared for analysis in some cases. Allsamples were frozen ()18 �C) for return to the labora-tory in Monaco.
2.2. Sample treatment
All sediment samples were freeze-dried and sievedthrough a 1 mm clean plastic sieve to remove shell
fragments. In some cases where sample size was small,
the sieved sediments were ground in an agate mortar.
The sieved and/or powdered sediments were then
Table 1
Location of sediment samples from Qatar, UAE, Bahrain, and Oman
Country Station Site no. Date Location
Qatar Umm Said 1 28/3/00 24�56.3980N, 51�37.7090EDukhan 2 29/3/00 25�21.0690N, 50�45.7180EDoha 3 29/3/00 25�20.2570N, 51�34.4560ERas Laffan 4 30/3/00 25�47.0000N, 51�35.7750ERas Al Nouf 5 30/3/00 25�37.4270N, 51�32.8890E
UAE Jebel Ali 6 1/4/00 25�06.9910N, 55�09.1150EAbu Dhabi 7 1/4/00 24�27.9570N, 54�18.2940EAl Marfa 8 2/4/00 24�06.2000N, 53�29.2070EAlRuweis (Al Dhannah) 9 2/4/00 24�09.8420N, 52�38.8870EAkkah Head, ‘‘Three Rocks’’ north of Bidya 10 4/4/00 25�28.9770N, 56�21.9400EAkkah Beach, South of ‘‘Three Rocks’’ 11 4/4/00 25�28.7210N, 56�21.7700E
Bahrain Askar 12 23/11/00 26�03.1020N, 50�37.9590EOff BAPCO Refinery 13 23/11/00 26�06.1380N, 50�37.7730EJasra 14 25/11/00 26�11.0980N, 50�26.5230ENorth of Meridien Hotel 15 25/11/00 26�16.0560N, 50�31.4230E
Oman Mina Al Fahal (PDO Beach) 16 27/7/01 23�37.9780N, 58�30.6930ERas Al Yei (Masirah east coast) 18 28/7/01 20�31.3480N, 58�57.0740EHilf (Masirah west coast) 19 29/7/01 20�38.1030N, 58�51.8130EMughsayl (beach) 20 30/7/01 16�52.9560N, 53�47.6050ERaysut Port Area (east beach) 21 31/7/01 16�59.00N, 54�01.00EAl Sawadi 23 01/8/01 23�47.2600N, 57�47.6330E
Table 2
Location for the collection of biota
Country Site Site no. Coordinates Species Species
Fish
Bahrain Badaiya 24 26�120N, 50�240E Epinephelus coioides Orange spotted grouper
Bahrain Fasht Al Adham 25 26�030N, 50�430E Epinephelus coioides Orange spotted grouper
Oman Quriyat 26 23�200N, 59�060E Epinephelus coioides Orange spotted grouper
Qatar Al Khawr 27 25�400N, 51�380E Epinephelus coioides Orange spotted grouper
Qatar Doha 3 25�20.2570N, 51�34.4560E Epinephelus coioides Orange spotted grouper
Qatar Umm Said 1 24�56.3980N, 51�37.7090E Epinephelus coioides Orange spotted grouper
UAE Al Marfa 8 24�06.2000N, 53�29.2070E Epinephelus coioides Orange spotted grouper
UAE Dhannah 28 24�120N, 52�390E Epinephelus coioides Orange spotted grouper
Oman Raysut Port Area 21 16�59.00N, 54�01.00E Lethrinus nebulosus Spangled emperor
Oman Sagar 29 16�320N, 53�430E Lethrinus nebulosus Spangled emperor
Qatar Al Dakhira 30 25�450N, 51�400E Lethrinus nebulosus Spangled emperor
Bivalves
Qatar Ras Al Nouf 5 25�37.4270N, 51�32.8890E Circentia callipyga Venus clams
Bahrain North of Meridien Hotel 15 26�16.0560N, 50�31.4230E Pinctada radiata Pearl Oysters
Bahrain Off BAPCO refinery 13 26�06.1380N, 50�37.7730E Pinctada radiata Pearl Oysters
UAE Abu Dhabi 7 24�27.9570N, 54�18.2940E Pinctada radiata Pearl Oysters
UAE Akkah Head 10 25�28.9770N, 56�21.9400E Pinctada radiata Pearl Oysters
UAE Jebel Ali 6 25�06.9910N, 55�09.1150E Pinctada radiata Pearl Oysters
UAE Jebel Ali 6 25�06.9910N, 55�09.1150E Pinna muricata Pen Shells
Oman Al Sawadi 23 23�47.2600N, 57�47.6330E Saccostrea cucullata Rock Oysters
Oman Hilf 19 20�38.1030N, 58�51.8130E Saccostrea cucullata Rock Oysters
Oman Mirbat 22 16�58.500N, 54�41.500E Saccostrea cucullata Rock Oysters
Oman Ras Al Hamra 17 23�38.3630N, 58�29.4950E Saccostrea cucullata Rock Oysters
Oman Ras Al Yei 18 20�31.3480N, 58�57.0740E Saccostrea cucullata Rock Oysters
UAE Akkah Beach 11 25�28.7210N, 56�21.7700E Saccostrea cucullata Rock Oysters
UAE Abu Dhabi 31 24�29.9170N, 54�21.6680E Spondylus sp. Rock Scallops
412 S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424
transferred to clean zip-lock bags and shaken to obtain a
fine homogeneous powder. Between 150 and 300 mg of
dried sediment material were weighed for digestion.
Samples were digested in acid-cleaned Teflon microwave
vessels with 5 ml of ultrapure nitric acid and 2 ml
ultrapure concentrated hydrofluoric acid. A Milestone
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 413
MLS 1200 Mega system was used for samples from
Qatar and UAE and a CEM MARS5 system was em-
ployed for samples from Bahrain and Oman. Each
digestion batch included at least one reagent blank and arepresentative standard reference material, e.g., MESS-2
or BCSS1 (NRCC, Marine sediment), and generally a
sample replicate to check homogeneity and process
efficacy. Samples were digested typically for 30–40 min
at 200 �C. After allowing at least 1 h for cooling, thevessels were opened and 0.9 g boric acid was added to
dissolve the fluoride precipitates. The vessels were then
resealed and put back in the microwave digestion systemfor an additional 20–30 min. Following cooling for at
least 1 h, the digested sample was transferred to a
graduated plastic test tube with an additional 0.5 ml HF
and brought up to volume (either 15 or 50 ml) with
Milli-Q water.
Biota samples were freeze-dried and then ground on
an agate mortar to obtain a fine homogeneous powder.
Separate sub-samples were oven dried (105 �C for 24 h)to determine residual water content. Between 150 and
300 mg of dried sample material were weighed and then
digested in acid-cleaned Teflon microwave vessels with
5 ml of ultrapure nitric acid. Each digestion batch in-
cluded at least one reagent blank and a representative
standard reference material, e.g., DORM-2 or DOLT-2
(NRCC, Dogfish muscle and liver, respectively) and
usually a sample replicate as a check for homogeneityand process efficacy. Microwave digestion typical took
30–40 min at a target digestion temperature of 200 �C.After allowing at least 1 h for cooling, the digested
sample was quantitatively transferred to a graduated
plastic test tube and brought up to volume (either 15 or
50 ml) with Milli-Q water.
Samples were analysed for metals other than Hg
using a Finnigan Element magnetic sector inductivelycoupled plasma mass spectrometer (ICP-MS) with a
microconcentric nebulizer (MCN) and a standard dou-
ble-pass condensing spray chamber for sample intro-
duction. Sample digestates were typically diluted 20· foranalysis with 2% nitric acid. Larger dilutions up to
10,000· were necessary for certain analytes observed atrelatively high concentrations in sediment digestates
(e.g., Fe and Al). An internal standard (1–10 lg l�1 Be,In, and Th) was also added to the diluted samples to
correct for matrix effects and instrument drift. Results
were quantified via an external calibration curve gener-
ated from the responses obtained from multiple dilu-
tions of a multi-element calibration standard that was
prepared from single-element standards (Alfa Aesar).
Analytical quality control included analysis of a 2%
ultrapure nitric acid blank and a drinking water refer-ence material (TMDW1, acquired from High Purity),
together with the procedural blank, a reference material
of similar matrix, and a sample duplicate from the
microwave digestion.
2.3. Analysis of mercury
In the case of Qatar and UAE sediments, approxi-
mately 1 g of sample was digested in a closed Teflon vialwith 4 ml of nitric acid (Merck Suprapur) for 3 h on a
hot plate at 90 �C. Following the addition of 1 ml 10%w/v K2Cr2O7 solution as a preservative, the samples were
diluted to 50 ml with Milli-Q water. For sediment from
Bahrain and Oman, the same aliquots prepared for ICP-
MS analysis were used for the determination of Hg. In
addition, a preservative solution (200 ll of 10%w/vK2Cr2O7) was added to a 10 ml aliquot of the digestatewithin 24 h of preparation. The digested samples were
analysed by cold vapour atomic fluorescence spectro-
metry (CV-AFS) using SnCl2 reduction with a flow
injection vapour generator (VGA-77). Replicate blanks
and the reference material MESS-2 (NRCC, marine
sediment) were analysed for quality control purposes.
Precision of the measurements, determined on replicate
digestions of MESS-2 ranged between 1.2% and 12%.For the analysis of biota, �0.5 g of sample was di-
gested in a closed Teflon vial with 4 ml of nitric acid
(Merck Suprapur) and 2 ml of sulphuric acid (Merck
Suprapur) for 3 h on a hot plate at 90 �C. Following theaddition of 1 ml 10%w/v K2Cr2O7 solution as a pre-
servative, the samples were diluted to 50 ml with Milli-Q
water. Samples from Qatar, UAE, and Bahrain were
analysed by cold vapour atomic absorption spectro-metry (CV-AAS) using SnCl2 reduction on a Varian
SpectrAA-220FS with a flow injection vapour generator
(VGA-77). The concentration of Hg in some samples
was confirmed by CV-AFS due to the very low Hg
content. Replicate blanks and the reference materials
IAEA142 (mussel homogenate), SRM-2976 (NIST,
mussel), and DOLT-2 (NRCC, fish liver) were used for
quality control purposes. Precision of the measurementsbased on replicate digestions was between 0.5% and
3.8% (mean 1.3%). In the case of the samples from
Oman, Hg was analysed only by ICP-MS.
3. Results and discussion
3.1. Sediments
Concentrations, expressed on a dry weight basis, for a
wide range of elements in the coastal sediments from the
RSA are presented in Table 3. Only two locations stand
out in terms of their elevated levels of trace elements in
sediments: off the BAPCO (Bahrain Petroleum Com-
pany) refinery in Bahrain and at Akkah Beach on the
east coast of UAE (Fig. 2). As outlined below, elevatedlevels at the BAPCO site signals localised anthropogenic
inputs, whereas the Akkah Beach location may reflect
the metal-rich mineralogy of the region. Concentrations
of trace elements at locations other than these hot spots
Table 3
Trace element concentrations (lg g�1 dry weight) in near shore sediments from Qatar, UAE, Bahrain, and Oman
Location No. Al V Cr Mn Fe Co Ni Cu Zn As Ag Cd Sb Hg Pb
Qatar
Umm Said 1 5870 24.7 31.9 84.9 4790 1.96 17.1 8.17 – 5.2 0.30 0.09 0.17 0.0114 3.00
Dukhan 2 18000 20.1 34.0 127 4160 1.73 12.2 3.03 – 6.3 0.39 0.07 0.12 0.0034 3.88
Doha 3 9120 32.1 40.8 88.0 5680 2.20 20.8 8.02 – 5.0 0.30 0.08 0.22 0.0167 3.16
Ras Laffan 4 484 2.7 11.5 13.2 305 0.10 0.74 1.22 – 1.0 0.47 0.03 0.01 0.0007 0.43
Ras Al Nouf 5 2410 9.0 17.2 37.6 1480 0.61 5.31 1.41 – 3.9 0.42 0.08 0.07 0.0015 1.63
UAE
Jebel Ali 6 8530 10.4 31.7 96.6 2740 1.16 8.3 1.92 – 1.9 0.33 0.05 0.09 0.0022 2.10
Abu Dhabi 7 2570 4.6 17.6 32.9 874 0.34 2.0 1.99 – 1.3 0.58 0.02 0.04 0.001 0.78
Al Marfa 8 21000 23.1 37.6 225 5820 2.61 15.5 3.58 – 2.7 0.14 0.11 0.21 0.0015 2.93
Al Ruweis 9 26000 35.5 171 358 8940 2.40 8.6 2.62 – 2.2 0.20 0.11 0.29 0.0013 5.88
Akkah Head 10 534 4.5 83.5 60.3 4020 6.13 139 0.64 – 0.7 0.47 0.05 0.04 0.0006 0.69
Akkah Beach 11 2680 18.2 303 360 29600 45.2 1010 3.31 – 9.6 0.23 0.09 0.22 0.0009 1.30
Bahrain
Askar 12 1595 5.94 11.8 22.6 1091 0.307 3.79 3.12 8.92 3.16 0.014 0.046 0.055 0.0107 13.2
BAPCO refinery 13 8954 28.4 41.8 84.3 6475 2.43 23.2 48.3 52.2 4.96 0.161 0.182 0.123 0.2202 99.0
Jasra 14 6155 11.3 14.2 42.2 1945 0.683 6.63 2.74 18.4 6.88 0.012 0.061 0.129 0.0032 2.49
North of Meri-
dien Hotel
15 601 3.47 3.36 26.9 471 0.172 2.46 2.38 6.12 5.00 <0.01 0.040 0.046 0.0025 0.673
Oman
Mina Al Fahal 16 3850 18.6 119 133 5540 2.91 43.4 2.03 6.48 5.01 0.010 0.16 0.162 <0.0001 1.59
Ras Al Yei 18 18300 44.1 133 209 10700 6.92 77.8 6.66 11.4 1.72 0.006 0.14 0.086 <0.0001 0.449
Hilf 19 14800 34.9 39.9 265 11600 5.75 48.8 4.91 8.12 2.25 0.017 0.15 0.12 0.0112 1.82
Mughsayl 20 632 4.70 6.46 27.8 334 0.125 1.84 0.602 1.61 0.740 0.009 0.21 0.025 <0.0001 0.253
Raysut Port
Area
21 2100 5.02 31.2 29.1 905 0.276 2.49 0.827 1.57 1.09 0.002 0.20 0.025 0.0019 0.729
Al Sawadi 23 2750 12.8 96.2 70.4 3500 2.45 50.9 1.60 4.92 4.22 0.002 0.10 0.124 0.0002 1.82
414
S.deMora
etal./Marin
ePollu
tionBulletin
49(2004)410–424
Fig. 2. Concentrations of selected heavy metals in sediments of the ROPME Sea Area. Data are arranged in order along the coast from western
Bahrain to southern Oman. Concentrations on a dry weight basis are given in lg g�1 for all metals, except Hg, which are presented as ng g�1.
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 415
were for the most part substantially lower, and fell
within the ranges reported previously for these elements
in the RSA (Fowler et al., 1993).
Akkah Beach in the Gulf of Oman represents anoteworthy hot spot for several metals (Fig. 2), and also
hydrocarbon contaminants (IAEA, unpublished data).
The extremely elevated Ni concentration, 1010 lg g�1, isby far the highest level of Ni reported for RSA sedi-
ments (Fowler, 2002b; ROPME, 1999). Other maximum
concentrations measured at this site included 303 lg g�1
Cr and 45 lg g�1 Co. Whereas most sediments in thisstudy exhibited Fe:Al concentration ratios <1, the sed-iments at Akkah Beach and Akkah Head were unusual
in having very high ratios, namely 11.0 and 7.5,
respectively. Regarding this particular eastern region of
UAE, very high concentrations of Cr (506 lg g�1), Ni(187 lg g�1), and Co (36 lg g�1) were found in sedimentsfrom Bidya approximately 4 km south of Akkah Beach
in June 1994 (IAEA, unpublished data).
There is no major industrial activity or high popula-tion centre near Akkah Beach, which is a fairly remote
area. It is unlikely that these high levels were related to
the March 1994 oil spill off Bidya (Shriadah, 1998), as
the corresponding concentration of V, a metal some-
times used as a marker for oil, was not particularly
elevated compared to the level present in other sedi-
ments from the region (Fowler, 2002b). Moreover, the
V:Ni ratio was relatively low owing to the extremely
high Ni content. Thus, it is difficult to ascribe anthro-
pogenic causes to the apparent metal enrichment. These
sediments were especially rich in Ni and Cr, but alsocontained high levels of Fe, Mn, and As. The geology of
Oman and eastern UAE is rich in ophiolites and me-
talliferrous sediments of marine origin. The Oman
ophiolites contain chromite and various nickel sulfide
minerals (Leblanc and Ceuleneer, 1991; Lorand and
Ceuleneer, 1989). Thus, the high metal concentrations
are most likely due to the local mineralogy, and are
natural, rather than pollution.In the case of the sediments collected off the BAPCO
refinery complex in Bahrain, maximum levels were
measured for several metals: 99 lg g�1 Pb, 48.3 lg g�1
Cu, 52.2 lg g�1 Zn, and 0.220 lg g�1 Hg (Fig. 2). Thecontamination likely emanates from the industrial and
refinery complex around the aluminium plant situated
just shoreward of the sampling site. Relatively high
concentrations of certain metals were also observednearby at Askar, supporting the hypothesis of a point
source of contamination at the BAPCO site for Cu, Hg,
Pb, and Cd, the effects of which diminish with distance
from the source. This spatial decrease is most notable
for Pb and Hg (Table 3). Very high metal concentrations
in sediments from near this site have been reported since
the early 1980s; for example, in 1983–1984 Hg levels in
Fig. 3. Map showing the concentrations (in lg g�1 dry) of Cd (a) andAg (b) in sediments from the ROPME Sea Area. The mid-point of the
concentration bar represents the sampling location.
416 S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424
sediments off Askar ranged from 0.106 to 0.286 lg g�1
(Fowler, 1988). Considering that the Hg content in the
present survey was only 0.0107 lg g�1 (Table 3), theorder of magnitude decrease over 17 years may reflect anactual reduction in Hg inputs in this area during that
time.
With respect to Oman, maximum concentrations for
most of the trace elements were found in sediments from
Masirah Island, particularly those from Ras Al Yei on
the east coast. As the population density is very low and
there are no major industrial activities on the island, the
trace metal concentrations in coastal sediments are mostlikely natural and reflect the local mineralogy. Thus, the
relatively elevated concentrations of V, Co, and Ni are
probably related to the high Fe and Mn content in these
sediments, given that Masirah Island largely comprises
an ophiolite with associated hydrothermal activity
(Abbotts, 1979). The only notable acceptation was Cd,
which exhibited somewhat higher concentrations in
sediments from the Raysut Port area and Mughsayl inthe south. Cadmium concentrations at pristine sites
in the Gulf of Oman were high compared to locations in
the Gulf, and were comparable to the polluted site off
the BAPCO refinery in Bahrain (Fig. 3a). Although
there are few data from Oman for comparison, the levels
of Cu, Pb, and V were similar to previously reported
concentrations (Fowler, 1988; Fowler et al., 1993). The
trend in enhanced Cd levels towards the south wasconsistent with data from earlier surveys that indicated
elevated sediment Cd concentrations around Salalah
compared to other areas in Oman (Fowler et al., 1993).
In contrast to the trend for Cd in sediments, Ag
exhibited very low concentrations in Oman (Fig. 3b).
Silver is often considered a good tracer for sewage dis-
charges (Papakostidis et al., 1975; Ravizza and Bothner,
1996). Thus, the maximum concentration, 0.58 lg g�1,observed at Abu Dhabi likely indicates an anthropo-
genic input. Apart from Abu Dhabi and Akkah Head,
the Ag content of sediments in Qatar was higher than
elsewhere in the RSA.
Considering Hg in more detail, the concentrations in
sediments were quite low, ranging from <0.001 to 0.0167
lg g�1, apart from the one hot spot at the BAPCO site
(0.220 lg g�1). For comparison within the region, Hglevels were seen to vary between 0.19 and 2.34 lg g�1
in coastal sediments from Doha, Qatar (Al-Madfa
et al., 1994) and the Hg content in surface sediments
throughout the Gulf was found to range from 0.032 to
0.27 lg g�1 (Kureishy and Ahmed, 1994), and from
0.042 to 0.375 lg g�1 (Al-Majed and Rajab, 1998).
Furthermore, the levels in near-shore sediments were
reported to vary from <0.02 to 0.613 lg g�1, with thehighest Hg concentrations found in Kuwait and the
United Arab Emirates (Fowler, 2002b). The low Hg
content reported here agrees favourably with some
baseline measurements that have been reported for other
regions (Fowler, 1990). Hg levels were found to be quite
low (<0.09 lg g�1) through most of the Caspian Sea
(de Mora et al., 2004). Estimated from subsurface con-
centrations in sediments, baseline Hg levels in San
Francisco Bay were observed to be 0.06 ± 0.01 lg g�1
(Hornberger et al., 1999) and 0.059 ± 0.013 lg g�1 in theYatsushiro Sea (Tomiyasu et al., 2000). Thus, Hg con-
centrations in coastal sediments of the Gulf and Gulf ofOman are generally quite low by international stan-
dards.
Although the hot spot near the BAPCO refinery did
exceed the sediment quality guideline value of 0.15
lg g�1 (Long et al., 1995), much higher concentrationshave been reported at polluted sites world-wide. In
Azerbaijan, the sediments in Baku Bay and adjacent
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 417
areas to the south were contaminated, with Hg con-
centrations up to 0.45 lg g�1 (de Mora et al., 2004). TheGulf of Trieste is exceedingly polluted due to historic
cinnabar mining in the catchment region, with total Hgranging from 0.064 to 30.38 lg g�1 and averaging 5.04lg g�1 (Covelli et al., 2001). Surface sediments from the
Yatsushiro Sea off Japan had maximum Hg concentra-
tions in the range of 0.086–3.46 lg g1 with the highestvalues found in Minamata Bay near the Minamata
River, the sources of the pollution (Tomiyasu et al.,
2000).
Arsenic is another element that has previously at-tracted much attention in the RSA, but often with re-
spect to biota rather than sediments. Concentrations in
coastal sediments found here vary from 0.7 to 9.6 lg g�1.Only the highest value, found at Akkah Beach in the
Gulf of Oman, exceeded the sediment quality guideline
value for As, 8.2 lg g�1 (Long et al., 1995). There arefew data from the RSA for comparison; however, our
results are much lower than those (7.13–35.2 lg g�1)previously reported for the region (Fowler et al., 1993).
Uncontaminated coastal sediments normally have con-
centrations in the range 5–15 lg g�1 (Neff, 1997). SimilarAs contents were reported in the North Caspian Sea,
commonly <5 lg g�1, (de Mora et al., 2004; Winkelset al., 1998) and off California, having a range of 1.6–
13.8 lg g�1 and a mean concentration of 5.1 lg g�1
(Schiff and Weisberg, 1999). More elevated concentra-tions, �20 lg g�1, were observed in surface sediments
from the South Caspian Sea (de Mora et al., 2004) and
the Gulf of Finland (Vallius and Lehto, 1998). Ex-
tremely As-contaminated sediments in the North Sea off
the English coast have concentrations reaching 137
lg g�1 (Whalley et al., 1999). Clearly, the As levels re-ported here are quite low by global standards, and
generally not of environmental concern.
3.2. Fish
Two economically important species in the RSA were
investigated, namely the orange spotted grouper (Epi-
nephelus coioides, hamoor) and the spangled emperor
(Lethrinus nebulosus, sheiry). Although both species are
demersal carnivores, hamoor feed preferentially on fishand crustaceans whereas sheiry tend to eat echinoderms,
worms molluscs and crustaceans (Carpenter et al.,
1997). Data for a suite of trace elements in fish muscle
and liver are set out in Table 4, in all cases expressed on
a dry weight basis.
Mercury concentrations in the muscle and liver of
grouper varied in the ranges 0.50–2.35 and 0.287–4.65
lg g�1, respectively. Mercury is known to bioaccumulatein fish, and thus relatively high concentrations can be
attained in top predators, such as hamoor. Furthermore,
the total Hg concentrations generally increase with age,
and thus size, of the fish. The Hg content in both the
liver and the muscle depended upon the size (wet weight)
of the fish (Fig. 4). This has been shown previously only
for Hg in grouper muscle as a function of fish length (Al-
Majed and Preston, 2000b; Kureishy, 1993; Sadiq et al.,2002). The highest concentration of Hg (2.35 lg g�1 dryor 0.49 lg g�1 wet) in muscle was measured in a 4.7 kggrouper from Al Marfa in UAE, and only just ap-
proached 0.5 lg g�1 wet, a level considered by many
countries to be the upper acceptable limit for consum-
able fish, including for instance Saudi Arabia (Sadiq
et al., 2002). Despite the difficulties in comparison,
particularly due to the size of fish, the Hg levels ingrouper fell within the range reported in other recent
surveys within the RSA (Al-Majed and Preston, 2000a;
Al-Majed and Rajab, 1998; Sadiq et al., 2002). Some
earlier observations (Fowler, 1988) were lower, namely
0.17–0.40 lg g�1, but based on 5 fish averaging <2 kg.For the spangled emperor, mercury concentrations in
the muscle and liver varied in the ranges 0.34–0.52 and
0.33–1.02 lg g�1, respectively. The Hg content in musclefrom the spangled emperor was comparable to previous
measurements, 0.29–0.33 in Bahrain and UAE (Fowler
et al., 1993), but somewhat lower than has been ob-
served in Kuwait, 0.76–0.88 lg g�1 (Al-Hashami andAl-Zorba, 1991), and Saudi Arabia, 0.65–1.35 lg g�1
(Fowler et al., 1993).
The As concentrations in the muscle of grouper and
spangled emperor ranged 0.83–14.4 and 2.5–10 lg g�1,respectively. There was no size dependence of the As
content in either the liver nor the muscle in grouper, in
agreement with previous general observations in the
marine environment (Phillips, 1990). The highest con-
centration of As in grouper muscle was found in the
smallest fish, which was from Fasht Al Adham, Bahrain.
For comparison, pervious measurements of As in mus-
cle of grouper have been reported in the ranges <0.25–0.49 lg g�1 wet (Attar et al., 1992) and 0.7–53 lg g�1 dry(Fowler et al., 1993). Regarding spangled emperor, the
maximum As level in both muscle and liver samples was
from a fish caught in Al Dakhira, Qatar. The As content
in muscle of spangled emperor has previously been re-
ported in the ranges 1.03–3.58 lg g�1 wet (Attar et al.,1992) and 1.3–27 lg g�1 dry (Fowler et al., 1993). Al-though dependent upon the species considered, the fewother data that have been reported for the RSA have
suggested that the As levels in RSA fish are amongst the
highest reported in the literature (Attar et al., 1992;
Fowler et al., 1993; Madany et al., 1996). In contrast,
the As concentrations in RSA fish reported here are
generally lower than those previously observed, and also
seem to be relatively low by global standards (see Attar
et al., 1992; Francesconi and Edmonds, 1993). This isclearly a topic of regional interest that merits further
investigation.
The most unusual findings here relate to Cd mea-
surements. Cd concentrations in muscle for both species
Table 4
Trace element concentrations (lg g�1 dry weight) in fish from Qatar, UAE, Bahrain, and Oman
Location Species Weight
(kg)
Tissue V Cr Mn Fe Co Ni Cu Zn As Se Ag Cd Sb Hg Pb U
Qatar
Al Khawr O.S.G.a 1.7 Muscle 0.03 0.03 0.19 21.7 <0.005 0.03 0.56 8.2 3.1 2.20 0.003 0.013 <0.001 1.04 0.113 0.007
Liver 0.25 <0.01 3.63 801 0.324 <0.01 38.4 143 3.0 6.23 0.300 0.787 <0.001 0.930 0.103 0.012
Umm Said O.S.G. 2.2 Muscle 0.03 <0.01 0.29 2.4 <0.005 0.09 0.49 5.8 2.4 2.82 0.002 0.001 <0.001 0.970 0.551 0.005
Liver 0.17 0.01 2.40 1070 0.402 0.05 80.6 356 2.8 8.54 0.298 0.109 <0.001 1.13 0.108 0.008
Doha O.S.G. 1.7 Muscle 0.04 0.05 0.35 3.3 0.013 0.09 0.54 67.3 2.2 2.09 0.005 0.003 <0.001 0.987 0.209 0.006
Liver 0.26 <0.01 3.87 1210 0.517 0.08 90.9 317 2.4 7.29 0.437 0.417 <0.001 1.28 0.074 0.010
Al Dakhira S.E.b 1.7 Muscle 0.03 <0.01 0.18 4.0 <0.005 0.03 0.59 6.5 10.0 4.68 0.005 0.005 <0.001 0.343 0.108 0.009
Liver 0.31 0.08 4.20 1570 0.583 <0.01 33.7 228 22.4 – 0.196 1.46 <0.001 0.333 0.276 0.046
UAE
Al Marfa O.S.G. 4.7 Muscle <0.01 <0.01 0.063 25.1 0.014 <0.01 0.37 13.5 4.1 2.35 <0.001 <0.001 <0.001 2.35 0.025 0.035
Liver 0.29 0.03 3.21 478 0.164 0.05 36.2 184 2.6 7.09 0.281 0.594 <0.001 4.65 0.085 0.011
Al Marfa S.E. 1.7 Muscle 0.04 <0.01 0.12 203 <0.005 <0.01 0.71 1.82 5.0 2.71 0.002 0.001 <0.001 0.452 0.119 0.007
Liver 1.00 0.05 5.19 1350 0.163 0.08 39.0 2400 19.2 12.2 0.675 7.19 <0.001 0.587 0.385 0.023
Dhannah S.E. 1.7 Muscle <0.01 0.03 0.06 23.3 0.012 <0.01 0.88 11.5 2.5 3.14 <0.001 <0.001 <0.001 0.509 <0.01 0.027
Liver 1.04 0.02 4.09 1900 0.228 <0.01 9.25 1160 9.2 22.6 0.248 9.9 4 <0.001 1.02 0.308 0.069
Dhannah O.S.G. 2.8 Muscle <0.01 0.05 0.14 24.3 0.012 <0.01 19.5 23.3 1.9 2.37 <0.001 <0.001 <0.001 1.62 – 0.033
Liver 0.40 <0.01 5.05 481 0.185 0.07 18.6 380 1.5 5.46 0.277 0.108 <0.001 2.30 0.092 0.009
Bahrain
Badaiya O.S.G. 1.6 Muscle <0.01 0.013 0.297 3.10 <0.01 <0.01 0.235 15.9 1.23 3.27 0.002 0.001 <0.001 0.740 0.028 <0.001
Liver 0.238 0.019 3.88 1024 0.395 0.063 170 379 2.15 6.01 0.186 0.499 <0.001 1.31 <0.001 0.003
Badaiya O.S.G. 1.15 Muscle <0.01 0.020 0.256 13.9 <0.01 <0.01 0.294 17.9 1.38 2.73 <0.001 <0.001 <0.001 0.820 0.005 <0.001
Liver 2.67 0.028 5.31 2866 0.423 0.085 159 295 2.62 5.80 0.747 0.369 0.002 2.10 0.012 0.011
Fasht Al
Adham
O.S.G. 1.26 Muscle <0.01 0.075 0.677 9.09 <0.01 0.05 0.593 27.1 4.66 2.18 <0.001 0.002 <0.001 0.705 0.020 <0.001
Liver 0.201 0.047 3.28 2150 0.410 0.061 276 421 2.23 5.67 1.29 2.14 0.002 0.725 0.017 0.002
Fasht Al
Adham
O.S.G. 1.03 Muscle <0.01 0.024 0.406 3.88 <0.01 <0.01 0.389 25.8 14.4 2.37 <0.001 0.001 <0.001 0.669 0.028 <0.001
Liver 0.030 0.023 2.81 822 0.162 0.039 75.5 183 2.81 4.23 0.253 1.05 <0.001 0.287 0.001 0.001
Oman
Quriyat O.S.G. 1 1.8 Muscle <0.05 0.072 0.204 8.46 <0.05 <0.05 0.513 13.4 0.834 2.21 <0.005 <0.005 <0.005 0.517 0.025 <0.005
Liver 0.771 0.062 3.63 1499 0.377 0.100 104 1714 2.61 17.5 0.248 11.4 <0.005 1.3 0.107 0.022
Quriyat O.S.G. 2 1.8 Muscle <0.05 0.054 0.182 10.6 <0.05 <0.05 0.511 12.8 1.35 2.16 <0.005 0.005 <0.005 0.498 0.011 <0.005
Liver 0.422 0.060 1.85 520 0.224 <0.05 164 1335 2.84 8.27 0.516 11.2 <0.005 0.985 0.076 0.009
Raysut
Port Area
S.E. Muscle <0.05 <0.05 0.114 5.20 <0.05 <0.05 0.519 11.1 2.07 1.24 <0.005 0.011 0.012 0.522 0.014 <0.005
Liver 1.09 <0.05 4.12 1207 0.256 <0.05 98.8 1627 11.6 5.22 0.339 109 <0.005 0.398 0.175 0.008
Sagar S.E. Muscle <0.05 0.077 0.087 8.13 <0.05 0.111 0.58 10.47 2.88 1.30 <0.005 0.014 <0.005 0.435 0.011 <0.005
Liver 1.937 <0.05 4.788 1302 0.253 <0.05 38.6 1484 11.9 8.05 0.222 195 <0.005 0.480 0.426 0.005
– Not analysed.aOrange spotted grouper.b Spangled emperor.
418
S.deMora
etal./Marin
ePollu
tionBulletin
49(2004)410–424
Fig. 4. The concentration (in lg g�1 dry) of Hg in both liver and muscle of orange spotted grouper (hamoor or Epinephelus coioides) as a function ofthe wet weight of the fish. The lines show the linear regression for the two sets of data.
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 419
were quite low, <0.014 lg g�1, and less than previousmeasurements of up to 0.23 lg g�1 that have been ob-served in the RSA (Fowler et al., 1993). The concen-
trations are typical of levels that have been found in
various fish species from pristine areas (Hellou et al.,
1996; Rom�eo et al., 1999; Zauke et al., 1999). However,the Cd content in liver, especially for spangled emperor,
was much higher than observed in the muscle. For
example, Cd levels in the liver of spangled emperor from
Dhannah (9.94 lg g�1) and Al Marfa (7.19 lg g�1) wererelatively high, but of particular note were the extremely
high concentrations (109 and 195 lg g�1) in fish liver
from southern Oman. These levels were an order of
magnitude higher than those in the same species from
UAE (Table 4). To our knowledge, such high Cd
concentrations in fish liver have not been reported pre-
viously. Many species of fish exhibit higher Cd con-
centrations in liver relative to muscle, but levels havegenerally been reported to be <10 lg g�1 (Hellou et al.,1996; Zauke et al., 1999). Relatively high content of Cd
in liver, found to vary from 4.67 to 51.0 lg g�1, wasobserved in five species of fish caught off the Maurita-
nian coast (Rom�eo et al., 1999).The source of this Cd enrichment in fish from
southern Oman is conjectural. Anthropogenic contam-
ination cannot be ruled out, but is unlikely given theopen water conditions, together with the limited popu-
lation and industry in the region. The apparent
enhancement is more likely due to food chain transfer of
high levels of Cd brought into the surface waters
through the strong upwelling of nutrient-rich waters
that was occurring during the sampling period. This
mechanism also has been suggested to account for the137Cs levels noted in seaweeds along the southern coastof Oman (Jupp and Goddard, 2001). Cadmium, which
has been shown to maintain a one to one relationship
with phosphorus in upwelled waters (Bruland, 1983),could be readily bioaccumulated in the lower portion of
the food chain and passed along and eventually bio-
concentrated to high levels in the liver of top predator
fish, much as is Hg. Indeed, such a pathway has been
implied to explain the elevated Cd in liver from fish in
Mauritania (Rom�eo et al., 1999). It is interesting to notethat the limited data for Cd in liver of commercial deep-
sea fish were not particularly elevated (Mormede andDavies, 2001).
3.3. Bivalves
Several composite samples of oysters were obtained
in the Gulf and Gulf of Oman, comprising five samples
of pearl oysters (Pinctada radiata) and six samples of
rock oysters (Saccostrea cucullata). Composite samplesof rock scallops (Spondylus sp.), Venus clams (Circentia
callipyga), and pen shells (Pinna muricata) were ob-
tained from single sites. The concentrations, expressed
on a dry weight basis, of trace elements in different
bivalves are shown in Table 5. The pen shells from Jebel
Ali, UAE, had relatively high concentrations of Co (12.9
lg g�1) and Ni (35.8 lg g�1). They also had an excep-tionally high Mn content (1110 lg g�1). No comparabledata from the RSA are available for this species. Rock
scallops have been analysed in past surveys in UAE and
Bahrain. The specimens collected at Abu Dhabi con-
tained considerably lower concentrations of V, Pb, Ag,
Co, Cr, and Ni than in scallops analysed in earlier years
(Fowler et al., 1993). Only Zn levels (1150 lg g�1) werehigher in the sample from Abu Dhabi (Table 5). Apart
from As, metal concentrations in the one clam samplefrom Ras Al Nouf, Qatar, are comparable to or lower
Table 5
Trace element concentrations (lg g�1 dry weight) in bivalves from Qatar, UAE, Bahrain, and Oman
Location Species V Cr Mn Fe Co Ni Cu Zn As Se Ag Cd Sb Hg Pb U
Qatar
Ras Al Nouf Clams 0.76 0.97 17.7 517 4.45 23.9 8.35 69.1 156 7.15 3.03 1.17 0.027 0.315 1.45 0.390
UAE
Jebel Ali Pen Shells 2.05 3.41 1110 501 12.9 35.8 19.4 1830 153 12.8 1.92 10.7 0.007 0.207 1.23 0.498
Pearl Oysters 0.95 0.34 12.9 180 0.181 0.54 4.61 1430 37.7 5.45 0.430 9.97 <0.001 0.0371 0.389 0.149
Abu Dhabi Rock Scallops 0.43 <0.01 5.36 131 0.117 0.07 7.65 1150 40.0 5.71 0.017 6.78 <0.001 <0.147 0.098 0.010
Pearl Oysters 3.23 2.36 8.40 320 1.86 7.02 17.3 159 30.6 5.71 0.540 2.73 0.013 0.0987 2.29 0.381
Akkah Head Pearl Oysters 0.44 0.29 25.0 106 0.313 0.93 5.10 306 21.0 3.92 0.235 7.82 <0.001 0.0087 0.147 0.119
Akkah Beach Rock Oysters 0.28 0.49 12.0 89.9 0.227 1.12 63.8 425 16.2 2.69 1.17 6.15 <0.001 0.0280 0.250 0.094
Bahrain
Off BAPCO refinery Pearl Oysters 7.30 0.794 4.31 271 0.150 0.884 4.46 4290 24.9 4.89 0.011 3.68 0.019 0.112 3.92 0.218
North of Meridien
Hotel
Pearl Oysters 4.48 0.672 6.16 214 0.168 0.709 3.13 1825 45.7 5.10 0.047 3.79 0.011 0.035 0.396 0.169
Oman
Al Sawadi Rock Oysters 0.272 0.929 7.11 164 0.640 1.46 130 745 11.1 2.42 1.76 19.9 <0.005 0.147 0.673 0.174
Ras Al Hamra Rock Oysters 0.40 0.88 2.77 142 0.310 1.07 210 1614 15.3 2.46 3.23 9.83 <0.005 0.153 0.550 0.199
Ras Al Yei Rock Oysters 1.05 3.76 6.50 406 0.360 3.14 121 391 17.2 1.87 2.11 21.9 <0.005 0.050 0.384 0.288
Hilf Rock Oysters 0.44 1.05 4.46 137 0.325 1.39 276 1596 14.9 2.07 2.33 10.6 <0.007 0.153 0.447 0.246
Mirbat Rock Oysters 0.730 0.494 3.44 150 0.184 0.796 60.9 1074 14.8 2.17 2.59 8.99 <0.005 0.079 0.501 0.143
420
S.deMora
etal./Marin
ePollu
tionBulletin
49(2004)410–424
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 421
than previous limited measurements of clams, Meretrix
meretrix and Tapes sulcarius, from Saudi Arabia
(Fowler et al., 1993).
All pearl oysters were collected in the Gulf, except forthe sample from Akkah Head. Very high concentrations
of Zn (4290 lg g�1), V (7.3 lg g�1), and Pb (3.92 lg g�1)were found in pearl oysters near the BAPCO site in
Bahrain. Local contamination of the sediments with
respect to both Pb and Zn was previously discussed. The
pearl oysters from Abu Dhabi contained relatively high
concentrations of Cr, Fe, Co, Ni, Cu, and Ag (Table 5).
Whereas the Ag content in sediments from Abu Dhabiwas the maximum observed in this study (Table 3), the
concentrations of the other elements in these sediments
were not especially noteworthy. Similarly, the maximum
Cd concentration in the sample from Jebel Ali, UAE,
was not reflected in the local sediments. The pearl oyster
sample from Akkah Head, the only one collected in the
Gulf of Oman, actually contained the lowest levels
measured for several elements, namely V, Cr, Fe, As,Hg, and Pb. Table 6 compares concentrations of Cd,
Cu, Ni, Pb, and Zn in pearl oysters from various loca-
tions in the RSA. In general, the metal contents agree
well with previous studies, but the high Zn level found
near the BAPCO refinery was exceptional.
All rock oysters were collected in the Gulf of Oman.
Although relatively few studies of rock oysters in the
RSA are available for comparison (Table 6), the contentof several metals are comparable to previous observa-
tions. Moreover, the concentrations of most elements
were comparable to those in the pearl oysters. Whereas
markedly lower As was found in the rock oysters, Cd,
Cu, and Ag were notably more enriched in the rock
Table 6
Metal concentrations (lg g�1 dry weight) in pearl oysters (Pinctada radiata) a
Location Species Cd Cu Ni
Bahrain Pinctada radiata 0.25–3.8 0.4–3.4 0.2–8.
Bahrain Pinctada radiata 3.3–17.9 1.8–6.9 0.44–1
Bahrain Pinctada radiata 3.3–3.8 3.9–6.9
Bahrain Pinctada radiata 3.68–3.79 3.13–4.46 0.709–
Kuwait, 1990 Pinctada radiata 0.82–0.94 0.79–0
Kuwait, 1992 Pinctada radiata 7.70± 2.8 3.67± 0.9 4.33±
Kuwait, 1994 Pinctada radiata 160–174 1.42–1
UAE Pinctada radiata 2.6–20.8 1.9–23.6 1.64
UAE Pinctada radiata 2.6–34.2 3.0–9.7
UAEa Pinctada radiata 2.73–9.97 4.61–17.3 0.54–7
Oman Saccostrea cucullata 2.8–34.8 20–235 0.41–1
Oman Saccostrea cucullata 6.2–19.3 46–265
Oman Saccostrea cucullata 8.99–21.9 60.9–276 0.80–3
UAEb Saccostrea cucullata 6.15 63.8 1.12
a From the Gulf coast.b From the Gulf of Oman.
oysters. As noted above for pearl oysters from Akkah
Head, it is of particular interest that concentrations in
the rock oysters from Akkah Beach were not enhanced
in the same trace metals (notably As, Co, Cr, and Ni)that were greatly elevated in the local sediments. This
observation suggests that the metals associated with the
local sediments are not readily bioavailable to the local
filter-feeding bivalves. The rock oysters from Ras Al Yei
on the seaward side of Masirah Island, Oman, contained
the highest levels of many of the trace elements analysed
(Table 5). In particular, Cd, a nutrient-type element
associated with upwelled waters has always exhibitedhigh concentrations in oysters from this location (16–35
lg g�1), especially during the southwest monsoon season(Fowler et al., 1993). During the monsoon months,
many of these trace metals are possibly enhanced in the
water and the filterable suspended particulates when
upwelling and rough sea conditions are predominant.
Arsenic in bivalves from the RSA deserves particular
consideration, and Table 7 compares As content inoyster species from various locations. Of the bivalves
examined in this study, clams and pen shells contained
the highest levels of As with 156 and 153 lg g�1,respectively. The highest As concentrations reported
previously for bivalves from the RSA were approxi-
mately 100 lg g�1 in clams collected from Ras Al
Tanajib in Saudi Arabia in 1991 (Fowler et al., 1993)
and 1998 (IAEA, unpublished data). If As data for allthe bivalves sampled in the present and previous surveys
are examined, it is clear that on average clams typically
contain higher As concentrations than the other bivalve
species. For example, the average As concentration for
clams collected in these surveys since 1991 is 67.4 ± 42.6
nd rock oysters (Saccostrea cucullata) from the Gulf and Gulf of Oman
Pb Zn Reference
95 1.25–14.0 159–1532 Al-Sayed et al. (1994)
.24 0.32–3.9 898–1607 Fowler et al. (1993)
1.0–1.1 Fowler (1988)
0.884 0.396–3.92 1825–4290 This study
.92 0.40–0.62 50.6–509 Bu-Olayan and Subrahmanyam
(1997)
3.17 45.4± 19.5 Bou-Olayan et al. (1995)
.62 0.40–0.52 554–561 Bu-Olayan and Subrahmanyam
(1997)
0.14–3.0 1261 Fowler et al. (1993)
0.39–0.9 Fowler (1988)
.02 0.147–2.29 159–1430 This study
.69 0.06–2.2 152–1073 Fowler et al. (1993)
0.27–3.8 Fowler (1988)
.14 0.384–0.673 391–1610 This study
0.250 425 This study
Table 7
Worldwide As concentrations in oysters (lg g�1 dry weight dw or wet weight ww)
Location Species As Reference
Bahrain and UAE Pinctada radiata 4.5–73 dw Fowler et al. (1993)
Oman Saccostrea cucullata 14–23 dw Fowler et al. (1993)
North and South Carolina, USA 9.2a dw Lauenstein et al. (2002)
Maryland, USA Crassostrea virginica 16.3± 2.9 dw Riedel and Valette-Silver (2002)
South Carolina, USA Crassostrea virginica 15.6± 3.8 dw Riedel and Valette-Silver (2002)
Florida, USA Crassostrea virginica 23.6± 5.5 dw Valette-Silver et al. (1999)
Southeast USA Crassostrea virginica 25.4± 10.4 dw Valette-Silver et al. (1999)
Southwest Spain Crassostrea angulata 1.67–3.58 ww Suner et al. (1999)
Bahrain and UAE Pinctada radiata 21.0–45.7 dw This study
Oman and UAE Saccostrea cucullata 11.1–17.2 dw This study
aMedian of 281 mussel (Mytilus edulis) and oyster (Crassostrea virginica) samples.
422 S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424
lg g�1 (range 19–156 lg g�1, n ¼ 11). It is noteworthythat this average concentration is six times higher than
the national median (9.2 lg g�1 dry) in bivalves, prin-cipally oysters (Crassostrea virginica) and mussels (My-
tilus edulis), collected during 1986–1997 for the USA
National Status and Trends Mussel Watch project
(Lauenstein et al., 2002). Several related studies (Riedel
and Valette-Silver, 2002; Valette-Silver et al., 1999) have
focused on the southeast coast of the USA owing to therelatively elevated As content (25.4 ± 10.4 lg g�1) inoysters, which averaged more than double the national
average and had maximum values reaching 66 lg g�1.The elevated concentrations of these oysters were
attributed to higher inputs of As to the southeastern
region of the USA from natural phosphate deposits and
soil pesticide residues. In surveys dating from 1991, As
concentrations in pearl oysters and rock oysters fromthe RSA averaged 32.6 ± 17.4 (n ¼ 15, range 4.5–73
lg g�1) and 16.7 ± 4.8 lg g�1 (n ¼ 15, range 11.1–29.7
lg g�1), respectively. As evident in Table 7, the levels arecomparable to those in oysters from the southeastern
coast of USA and should accordingly be considered of
concern. Aside from these data, virtually no other
published information is available on As levels in biv-
alves from the RSA. Given these observations, it wouldbe worthwhile to examine in more detail what factors
might contribute to enhanced As concentrations in
many biota from the RSA.
4. Conclusions
Several heavy metals and trace elements were deter-mined in coastal sediments and marine biota (fish and
bivalves) from Bahrain, Oman, Qatar and the United
Arab Emirates. Sediment in the Gulf of Oman off the
east coast of UAE contained extremely high levels of
some heavy metals, especially Ni. In contrast, metal
levels in oysters from Akkah Head and Akkah Beach
(UAE) were not particularly enhanced. The metals in
the sediments are probably derived from Oman ophio-
lites and are present in mineralogical phases that aregenerally not bioavailable to the local organisms. The
metals in the region are thus interpreted to be natural in
origin, rather than the result of contamination.
The origins of high trace metal levels in rock oysters
from certain locations on Masirah Island, Oman, are
not evident, but may be due to natural geochemical and
oceanographic processes. Likewise, the very high Cd
concentrations in the livers of some fish from southernOman may result from food-chain bioaccumulation of
elevated Cd levels brought into the productive surface
waters by prominent upwelling in the region.
Hg concentrations are generally very low in sediments
and the total Hg levels in top predator fish commonly
consumed in the RSA were found to be below the 0.5
lg g�1 wet threshold safety value set by many countries.Hg content was similar to levels measured in the samespecies during earlier years.
Most interesting, and as yet unexplainable, is the
observation of very high arsenic concentrations in cer-
tain bivalve species from the RSA when compared to
those from other regions in the world. Again, it is not
clear whether this is related to point sources of con-
tamination (unlikely) or to natural biogeochemical
processes in the region (more likely). It is evident that tointerpret sources of possible metal contamination
properly, it is imperative to understand the natural
bioaccumulation potential and natural background
levels of elements like As in the species under study since
content and ratios of heavy metals vary greatly among
the bioindicator species (particularly bivalves) used in
the RSA.
Acknowledgements
This was a collaborative project between the IAEA
and ROPME, financially supported by both organiza-
tions. The IAEA Marine Environment Laboratory
operates under agreement between the International
Atomic Energy Agency and the Government of the
S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424 423
Principality of Monaco. We acknowledge with gratitude
the logistic support received in each country: in Bahrain
from the Ministry of Housing, Municipalities & Envi-
ronment; in Oman from the Ministry of RegionalMunicipalities and Environment; in Qatar from the
Ministry of Municipal Affairs and Agriculture; and in
the UAE from the Federal Environment Agency. We
thank Dr. Nahida Al-Majed from ROPME for assis-
tance organising the field studies and with sample col-
lection in Bahrain and Oman.
References
Abbotts, I.L., 1979. Intrusive processes at ocean ridges: evidence from
the sheeted dyke complex of Masirah, Oman. Tectonophysics 60,
217–233.
Al-Hashami, A.H., Al-Zorba, M.A., 1991. Mercury in some commer-
cial fish from Kuwait: a pilot study. Sci. Total Environ. 106, 71–82.
Al-Madfa, H., Dahab, O.A., Holail, H., 1994. Mercury pollution in
Doha (Qatar) coastal environment. Environ. Toxicol. Chem. 13,
725–735.
Al-Majed, N.B., Preston, M.R., 2000a. An assessment of the total and
methyl mercury content of zooplankton and fish tissue collected
from Kuwait territorial waters. Mar. Pollut. Bull. 40, 298–307.
Al-Majed, N.B., Preston, M.R., 2000b. Factors influencing the total
mercury and methyl mercury in the hair of the fishermen of
Kuwait. Environ. Pollut. 109, 239–250.
Al-Majed, N.B., Rajab, W.A., 1998. Levels of mercury in the marine
environment of the ROPME sea area. In: Otsaki, A., Ab-
dulraheem, M.Y., Reynolds, R.M. (Eds.), Offshore Environment
of the ROPME Sea Area after the War-Related Oil Spills. Terra
Scientific, Tokyo, pp. 124–147.
Al-Mohanna, S.Y., Subrahmanyam, M.N.V., 2001. Flux of heavy
metal accumulation in various organs of the intertidal marine blue
crab, Portunus pelagicus (L.) from the Kuwait coast after the Gulf
War. Environ. Int. 27, 321–326.
Al-Sayed, H.A., Mahasneh, A.M., Al-Saad, J., 1994. Variations of
trace metal concentrations in seawater and pearl oyster Pinctada
radiata from Bahrain (Arabian Gulf). Mar. Pollut. Bull. 28, 370–
374.
Attar, K.M., El-Faer, M.Z., Rawdeh, T.N., Tawabini, B.S., 1992.
Levels of arsenic in fish from the Arabian Gulf. Mar. Pollut. Bull.
24, 94–97.
Banat, I.M., Hassan, E.S., El-Shahawi, M.S., Abu-Hilal, A.H., 1998.
Post-Gulf-War assessment of nutrients, heavy metal ions, hydro-
carbons, and bacterial pollution levels in the United Arab Emirates
coastal waters. Environ. Int. 24, 109–116.
Bou-Olayan, A.-H., Al-Mattar, S., Al-Yakoob, S., Al-Hazeem, S.,
1995. Accumulation of lead, cadmium, copper and nickel by pearl
oyster, Pinctada radiata, from Kuwait marine environment. Mar.
Pollut. Bull. 30, 211–214.
Bruland, K.W., 1983. Trace elements in sea-water. In: Riley, J.P.,
Chester, R. (Eds.), Chemical Oceanography. Academic Press,
London, pp. 157–220.
Bu-Olayan, A.H., Subrahmanyam, M.N.V., 1997. Accumulation of
copper, nickel, lead and zinc by snail, Lunella coronatus and pearl
oyster, Pinctada radiata from the Kuwait coast before and after the
gulf war oil spill. Sci. Total Environ. 197, 161–165.
Bu-Olayan, A.H., Subrahmanyam, M.N.V., Al-Sarawi, M., Thomas,
B.V., 1998. Effects of the Gulf War oil spill in relation to trace
metals in water, particulate matter, and PAHs from the Kuwait
coast. Environ. Int. 24, 789–797.
Burns, K.A., Villeneuve, J.-P., Anderlini, V.C., Fowler, S.W., 1982.
Survey of tar, hydrocarbon and metal pollution in the coastal
waters of Oman. Mar. Pollut. Bull. 13, 240–247.
Carpenter, K.E., Krupp, F., Jones, D.A., Zajong, U., 1997. The living
marine resources of Kuwait, eastern Saudi Arabia, Bahrain, Qatar,
and the United Arab Emirates. FAO Species Identification Field
Guide for Fishery Purposes, FAO, Rome, p. 239.
Covelli, S., Faganeli, J., Horvat, M., Brambati, A., 2001. Mercury
contamination of coastal sediments as the result of long-term
cinnabar mining activity (Gulf of Trieste, northern Adriatic Sea).
Appl. Geochem. 16, 541–558.
de Mora, S.J., Fowler, S.W., Cassi, R., Tolosa, I., 2003. Assessment of
organotin contamination in marine sediments and biota from the
Gulf and adjacent region. Mar. Pollut. Bull. 46, 401–409.
de Mora, S.J., Sheikholeslami, M.R., Wyse, E., Azemard, S., Cassi, R.,
2004. An assessment of metal contamination in coastal sediments
of the Caspian Sea. Mar. Pollut. Bull. 48, 61–77.
Fowler, S.W., 1988. Coastal baseline studies of pollutants in Bahrain,
United Arab Emirates and the Sultanate of Oman. In: Proceedings
Symposium on Regional Marine Pollution Monitoring and
Research Programmes, ROPME/GC-4/2, ROPME, Kuwait, pp.
155–180.
Fowler, S.W., 1990. Critical review of selected heavy metal and
chlorinated hydrocarbon concentrations in the marine environ-
ment. Mar. Environ. Res. 29, 1–64.
Fowler, S.W., 2002a. Agrochemicals. In: Khan, N.Y., Munawar, M.,
Price, A.R.G. (Eds.), The Gulf Ecosystem: Health and Sustain-
ability. Bakhuys Publishers, Leiden, pp. 193–217.
Fowler, S.W., 2002b. Non-oil industry. In: Khan, N.Y., Munawar, M.,
Price, A.R.G. (Eds.), The Gulf Ecosystem: Health and Sustain-
ability. Bakhuys Publishers, Leiden, pp. 157–172.
Fowler, S.W., Huynh-Ngoc, L., Fukai, R., 1984. Dissolved and
particulate trace metals in coastal waters of the Gulf and western
Arabian Sea. Deep Sea Res. 31, 719–729.
Fowler, S.W., Readman, J.W., Oregioni, B., Villeneuve, J.-P., McKay,
K., 1993. Petroleum hydrocarbons and trace metals in near shore
Gulf sediments and biota before and after the 1991 war: an
assessment of temporal and spatial trends. Mar. Pollut. Bull. 27,
171–182.
Francesconi, K.A., Edmonds, J.S., 1993. Arsenic in the sea. Oceanogr.
Mar. Biol. Annu. Rev. 31, 111–151.
Hornberger, M.I., Luoma, S.N., van Geen, A., Fuller, C., Anima, R.,
1999. Historical trends of metals in the sediments of San Francisco
Bay, California. Mar. Chem. 64, 39–55.
Hellou, J., Zitko, V., Friel, J., Alkanani, T., 1996. Distribution of
elements in tissues of yellowtail flounder Pleuronectes ferruginea.
Sci. Total Environ. 181, 137–146.
Jupp, B.P., Goddard, C.C., 2001. Seaweeds and seagrasses: their
potential as biomonitors of radionuclides. In: International Con-
ference on Fisheries, Aquaculture and Environment in the NW
Indian Ocean, Sultan Qaboos University, Muscat, pp. 42–54.
Kureishy, T.W., 1993. Concentration of heavy metals in marine
organisms around Qatar before and after the Gulf War oil spill.
Mar. Pollut. Bull. 27, 183–186.
Kureishy, T.W., Ahmed, M.H., 1994. Total mercury distribution in
surface sediments from the Arabian Gulf. Qatar Univ. Sci. J. 14,
390–394.
Lauenstein, G.G., Cantillo, A.Y., O’Connor, T.P., 2002. The status
and trends of trace element and organic contaminants in oysters,
Crassostrea virginica, in the waters of the Carolinas, USA. Sci.
Total Environ. 285, 79–87.
Leblanc, M., Ceuleneer, G., 1991. Chromite crystallization in a
multicellular magma flow: evidence from a chromitite dike in the
Oman ophiolite. Lithos 27, 231–257.
Long, E.R., MacDonald, D.D., Smith, S.L., Calder, F.D., 1995.
Incidence of adverse biological effects within ranges of chemical
424 S. de Mora et al. / Marine Pollution Bulletin 49 (2004) 410–424
concentrations in marine and estuarine sediments. Environ. Man-
age. 19, 81–97.
Lorand, J.P., Ceuleneer, G., 1989. Silicate and base-metal sulfide
inclusions in chromites from the Maqsad area (Oman ophiolite,
Gulf of Oman): a model for entrapment. Lithos 22, 173–190.
Madany, I.M., Wahab, A.A.A., Al-Alawi, Z., 1996. Trace metals
concentrations in marine organisms from the coastal areas of
Bahrain, Arabian Gulf. Water Air Soil Pollut. 91, 233–248.
Mormede, S., Davies, I.M., 2001. Trace elements in deep-water fish
species from the Rockall Trough. Fisheries Res. 51, 197–206.
Neff, J., 1997. Ecotoxicology of arsenic in the marine environment.
Environ. Toxicol. Chem. 16, 917–927.
Papakostidis, G., Grimanis, A.P., Zafiropoulos, D., Griggs, G.B.,
Hopkins, T.S., 1975. Heavy metals in sediments from the Athens
sewage outfall area. Mar. Pollut. Bull. 6, 136–139.
Phillips, D.J.H., 1990. Arsenic in aquatic organisms: a review
emphasising chemical speciation. Aquatic Toxicol. 16, 151–186.
Price, A.R.G., Sheppard, C.R.C., Roberts, C.M., 1993. The Gulf: its
biological setting. Mar. Pollut. Bull. 27, 5–15.
Ravizza, G.E., Bothner, M.H., 1996. Osmium isotopes and silver as
tracers of anthropogenic metals in sediments from Massachusetts
and Cape Cod bays. Geochim. Cosmochim. Acta 60, 2753–2763.
Riedel, G.F., Valette-Silver, N., 2002. Differences in the bioaccumu-
lation of arsenic by oysters from Southeast coastal US and
Chesapeake Bay: environmental versus genetic control. Chemo-
sphere 49, 27–37.
Rom�eo, M., Siau, Y., Sidoumou, Z., Gnassia-Barelli, M., 1999. Heavy
metal distribution in different fish species from the Mauritania
coast. Sci. Total Environ. 232, 169–175.
ROPME, 1999. Regional Report of the State of the Marine Environ-
ment, ROPME/GC-9/002. ROPME, Kuwait, p. 220.
Sadiq, M., McCain, J.C., 1993. Effect of the 1991 Gulf war on metal
bioaccumulation by the clam (Meretrix meretrix). Mar. Pollut.
Bull. 27, 163–170.
Sadiq, M., Saeed, T., Fowler, S.W., 2002. Seafood contamination. In:
Khan, N.Y., Munawar, M., Price, A.R.G. (Eds.), The Gulf
Ecosystem: Health and Sustainability. Bakhuys Publishers, Leiden,
pp. 327–351.
Schiff, K.C., Weisberg, S.B., 1999. Iron as a reference element for
determining trace metal enrichment in Southern California coastal
shelf sediments. Mar. Environ. Res. 48, 161–176.
Sheppard, C.R.C., 1993. Physical environment of the Gulf relevant to
marine pollution: an overview. Mar. Pollut. Bull. 27, 3–8.
Shriadah, M.M.A., 1998. Impacts of an oil spill on the marine
environment of the United Arab Emirates along the Gulf of Oman.
Mar. Pollut. Bull. 36, 876–879.
Suner, M.A., Devesa, V., Munoz, O., Lopez, F., Montoro, R., Arias,
A.M., Blasco, J., 1999. Total and inorganic arsenic in the fauna of
the Guadalquivir estuary: environmental and human health impli-
cations. Sci. Total Environ. 242, 261–270.
Tomiyasu, T., Nagano, A., Yonehara, N., Sakamoto, H., Rifardi, Oki,
K., Akagi, H., 2000. Mercury contamination in the Yatsushiro Sea,
south-western Japan: spatial variations of mercury in sediment. Sci.
Total Environ. 257, 121–132.
UNEP, 1991. Sampling of selected marine organisms and sample
preparation for the analysis of chlorinated hydrocarbons. Refer-
ence Methods for Marine Pollution Studies No. 12, Rev. 2. UNEP,
Nairobi, p. 17.
Valette-Silver, N.J., Riedel, G.F., Crecelius, E.A., Windom, H., Smith,
R.G., Dolvin, S.S., 1999. Elevated arsenic concentrations in
bivalves from the southeast coasts of the USA. Mar. Environ.
Res. 48, 311–333.
Vallius, H., Lehto, O., 1998. The distribution of some heavy metals
and arsenic in recent sediments from the eastern Gulf of Finland.
Appl. Geochem. 13, 369–377.
Whalley, C., Rowlatt, S., Bennett, M., Lovell, D., 1999. Total arsenic
in sediments from the western north sea and the Humber estuary.
Mar. Pollut. Bull. 38, 394–400.
Winkels, H.J., Kroonenberg, S.B., Lychagin, M.Y., Marin, G.,
Rusakov, G.V., Kasimov, N.S., 1998. Geochronology of prior-
ity pollutants in sedimentation zones of the Volga and Danube
delta in comparison with the Rhine delta. Appl. Geochem. 13, 581–
591.
Zauke, G.-P., Savinov, V.M., Ritterhoff, J., Savinova, T., 1999. Heavy
metals in fish from the Barents Sea (summer 1994). Sci. Total
Environ. 227, 161–173.