STUDY ON THE DISTRIBUTION OF TOXIC HEAVY

METALS IN THE FISHES, SEDIMENTS & WATERS

OF ARABIAN GULF ALONG THE EASTERN
COAST OF SAUDI ARABIA 1
Saad Al-Sulami, Ahmed M. Al-Hassan, Mohammad Daili and N. M. Kither Mohd.
Research & Development Center
Saline Water Conversion Corporation
P.O.Box 8328, Al-Jubail -31951, Saudi Arabia
Tel: + 966-3-343 0012, Fax: + 966-3-343 1615
Email: [email protected]

Nabil A. Fita, Mustafa M. Ibrahim and Mohammed A. Hassan

Fisheries Res. Center, Al-Qatif

SUMMARY
The Research and Development Center (RDC), SWCC, at Al-Jubail city in
collaboration with the Fisheries Research Center (FRC) at Al-Qatif city, carried
out this study. The study was initiated in the wake of environmental awareness
of the possible impact of the wastes associated with the rapid modernization
and industrial growth of the region in polluting the marine environment. Concern
about pollution in the Arabian Gulf environment, was partly because the Gulf
seawater represents the main feed source for several giant desalination plants
in the region. In addition to this, the Gulf seawater represents an indispensable
source of relatively less costly seafood. FRC undertook the tasks of samples
collection, preservation and transportation to RDC at Al-Jubail, whereas RDC
undertook all the remaining part of the study. Samples included seawater, SW,
from top and bottom depths, fish, shrimp, and sediment samples as well. Sets
of these samples were collected from Manifa and Tarut regions, respectively,
north and south of the Gulf. An initial objective of the project was to monitor
levels of toxic heavy metals, which might have been enriched in seawater due
to pollution. Yet, the major aim targeted by the project, was that of monitoring
levels of these toxic metals in different tissues (muscles and gills) of selected
edible fish and shrimp species; which might have been excessively bio-
concentrating these elements in their tissues. Fish species of the types
Nermipterus tolu, known locally as (Bassi), Gerres argyres (Badah) and
Lethrinus nebulosus (Shieri), in addition to shrimp species, Penaeus
1
Issued as Technical Report No. APP 3803/ 96011, October 2002.

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semsiculcatus, were collected from both regions of the Gulf stream.
Consideration was restricted solely to these four species because they were
the ones that recurred repeatedly as common species in almost all seasonal
collections. Sample collections of water and fish species were made on the
months of April, July, October, and January; to cover the four seasons of the
year. Since sediments represent the final depository sink of heavy metal
pollutants, and provide a good indicator, as well as a record of pollutants
accumulation history in the marine environment, their Levels were also
monitored. The investigation revealed that both of the studied regions were, at
all times, clean and devoid of any serious toxic metal pollution. In general, no
elaborate seasonal variation patterns, common to test species in the two study
sites, could be accounted for with respect to concentration levels of almost all
elements. However, modest exceptions to this generalization may be noted in
case of Fe & Co. For Fe, levels of 20.4 & 31.4 ppm, were recorded,
respectively, in shrimps of Manifa & Tarut, summer collection (April 02). These
levels apear modest in comparison to SASO’s maximum limits of 20, 50 & 250
ppm, for some other toxic metals, such as Cu, Zn & Sn, respectively. However,
most metals, showed only modest concentration factors (CF’s), of ~1000, in
different types of tissues. CF’s were estimated relative to mean values of
surface & bottom SW concentrations. Corresponding estimates of CF’s of Fe
were relatively higher in muscles and gills, ranging, respectively, between
~5000 to ~10000 and ~8000 to ~50000. However, Co showed a high
concentration factor (>100000) in an isolated case of a Badah species(47 ppm)
of Tarut, July 00. Otherwise, Co CF’s values were comparable to that of Fe,
though Fe values were more consistent. Nevertheless, none of the enriched
levels of the twelve heavy metals noted in the edible tissues investigated could
be rated as to pose a pollution hazard or threat. V, on the other hand, also,
showed relatively higher concentrations in the gills of a couple of January
species of Manifa. Because a correspondingly high concentration of Ni
occurred in the gills of the same species collected at the same time and same
place, the two concentration levels were presumed to originate from a common
source. Such a common source could, most likely, be a transient, small-scale,
oil-discharging source. With this presumption, and also because of the solitary
and inconsistent nature of the incidence, the elevated levels of these two

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metals can hardly be attributed to a true bio-concentration or to a seasonal
variation phenomena. Concentration levels of toxic heavy metals such as Cd,
Hg, As, Pb, Cu, and Zn in edible tissues of fish and shrimp species, for which
SASO had recommended maximum allowable limits, were found to lie well
within the set limits. Metal stratification was noted only for Ni and Cu, which
revealed some tendency to enrich in surface and bottom seawater layers,
respectively. The cleanliness of the marine environment of the studied regions
was also reflected in the concentration levels of metals in sediments.
Exchangeable levels of the more toxic metals (mercury, arsenic, cadmium and
lead) in the sediments were either undetectable or present at extremely low
levels. Total metal Levels, in general, were comparable to their analogues
reported for sediments of relatively unpolluted sea floor.

1. INTRODUCTION

Seawater is of great importance for the kingdom of Saudi Arabia, since it constitutes
the unlimited source for potable water production through desalination processes. This
importance is also promoted by the fact that naturally occurring surface water resources
in the Kingdom are meager and limited only to few seasonal valleys (wadis) that run
mostly in the fall season. The situation is further complicated by the fact that rainfall in
some of these regions occasionally drops to fairly low levels. In contrast to this, there
stand the fact that the Kingdom possesses huge volumes of ground waters stocked in
deep underground aquifers of Al-Ruba’al-Khali desert. Fortunately, this enormous
amount of water contained in these aquifers is believed to be fit for human consumption
and other domestic purposes. However, cost-effective accessibility to these
underground waters, and their consequent availability for public use, will probably take
quite a while to achieve. Even then, these ground waters are expected to supplement,
rather than replace, desalinated water. This anticipation is easily justifiable in the light
of the fast, world-leading, exponential growth of population observed in the Kingdom;
in addition to the strategic nature of water as a commodity, which implies
diversification of its sources. Furthermore, the Gulf (as well as the Red sea) acquires an
added importance as a reservoir of vastly abundant and relatively cheap seafood. This
seafood is considered as an important alternative source of livestock proteinaceous
food, particularly in the envisioned scarcity of natural ranges and pastures which could

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have supported various types of livestock indigenous to the Kingdom. All these reasons
make it of dire importance to watch out for preserving and protecting the Gulf
environment against potential pollution threats. Since toxic heavy metals represent a
major category of industrial and other anthropogenic pollutants as a consequence of
urbanization [1], this study was initiated to unravel their distribution in various
components of the coastal marine environment of the Arabian Gulf at the eastern border
of the kingdom of Saudi Arabia. The shores of Arabian Gulf had witnessed phenomenal
development activities during the past few decades in the wake of massive oil
explorations. Several industrial centers have cropped up in this region and the threat
from pollution has been stated to be more real than ever before [2]. With such warning
statements in mind, FRC of the Ministry of agriculture and water, requested support
from SWCC, RDC in order to run a diagnostic collaborative study of heavy metal
pollution status in the region. The present report depicts the outcome of that study,
which essentially dissipated those worries of toxic heavy metal pollution in the region.
However it must be pointed out that results diagnose the present pollution status quo. It
does not imply that the situation will continue as it is, without continuing to take strict
measures of pollution monitoring and control programs.

1.1 Background

Because of the fact that Gulf seawater is a vital primary source of feed water for
desalination plants, in addition to its importance as a reservoir of seafood, there was
always a great concern regarding protection of its hygienic and aesthetic properties
against potential threats of various types of pollutants. In this respect, there was a
common interest, shared by both the Research and Development Center and the
Fisheries Research Center, in preservation of the coastal seawater of the Arabian Gulf
against sundry sources of potential pollutants in the vicinity. Consequently, the present
project was undertaken jointly by the two research centers, with the objective of
monitoring toxic metal levels in representative samples of the three main components
of the marine Gulf environment; namely, the aqueous phase (surface and bottom
seawater), biota (fish and shrimp tissues) and sediments (surface sediments only).

FRC co-investigators team selected 3 sampling locations at the start of the project, but
difficulties regarding this became evident later and sampling of water, sediments, fish

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and prawn were restricted to only 2 stations, one north and the other south of the Saudi
coast of the Arabian Gulf. These two stations : (1) Manifa (adjacent to an oil field) and
(2) Tarut Bay (Adjacent to an agricultural drainage area and originates from Ras
Tannoura) were proposed (Figure 1). Seawater samples were decided to be collected
from surface and bottom levels from both locations. Samples of fish, sediments and
water were to be collected from the same locations throughout the period of study in
accordance with the adopted schedule. Sample collection, preservation and
transportation to the SWCC R&D Center, were tasks undertaken by Al-Qatif Fisheries
Research Center (FRC) personnel, in accordance with agreed upon sampling strategy
and methods. A maximum of six representative pelagic and demersal fish species, of
comparable length and weight, were presumed to be collected. However, because of
difficulties in reproducible seasonal sampling, the maximum number of species was
reduced to four. FRC team following preliminary field survey determined predominant
fish species in the region.

1.2 Environment of the Sampling Sites

1.2.1 Manifa Region
This region falls in the northern part of the Saudi Arabian coast, close to Kuwait shores.
It is considered as one of the most important fishing areas in the coast, and as such, it is
furnished with several sites with fish catch facilities. The region, with its muddy seabed
and nutrients-rich over- lying water, represents a natural spawning and nursing zone for
shrimp and fish species. In reproductive seasons, massive numbers of juvenile shrimps
can be seen gathering in shallow coastal areas. The benthic floors of these areas, which
are mostly covered with extensive sea grass belts, represent a flourishing habitat for
these juvenile shrimp species. Thus the region is considered most important because of
its high productivity of shrimp and fish species. Lately, however, the region being close
to Kuwait shores suffered from reception of large quantities of oil as a result of the gulf
war.

1.2.2 Tarut Bay

Tarut Bay extends from Ras Tannoura southwards to Al-Khobar area. It is considered
one of the coastal regions that are of vital importance in the Saudi side of the Gulf. It
comprises extended regions for spawning and breeding of shrimp and fish. It is also
distinguished by the dominance of dense forests of Avecinia species (Avecinia marina).

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The dense mangrove stand of the mono-specific Avecinia species serves as an ideal
nursery, providing both food and shelter to juvenile fish and shrimp species. The
bottom of the bay is characterized by being muddy and fertile in nature with dense
population of Helmenthis and Annalids, which serve as plentiful food resources for fish
species. The seawater of the bay is also characterized by a high primary productivity
with a big diversity in both phytoplanktonic and zooplanktonic species.

1.3 Literature Review

The industrial growth that has been achieved within the last few decades in the
Kingdom of Saudi Arabia was, in general, rapid, diverse and enormous. The eastern
coast of the Kingdom has, in particular, received the lion’s share of this unparalleled
industrial boom. Also, as part of the country, the eastern district was also subject to the
exponential population increase seen in the Kingdom at large. Furthermore, most of the
industrial firms, and the population residence as well, were mostly concentrated on the
coastal areas of the Gulf. These miraculous developmental achievements were
accompanied, as it is usually the case, by some distressing environmental concerns.
One such concern is certainly related to the increased vulnerability of the proximal
marine environment of the Gulf to anthropogenic pollution problems. Among the most
alarming types of potential pollutants, generated as a direct outcome of industrial (and
domestic) waste disposal, are toxic and heavy metal pollutants. Anthropogenic sources
could be characterized as point sources and no n-point (diffuse) sources and also put on
a spatial scale e.g. local, regional or global. The results obtained in this study reflect
mostly a local, cumulative pollutant buildup, from both non-point and remote point
sources of heavy metal pollution. Metals are widely used in the technosphere and the
pool of metals in the urban areas can be large [1]. Increased metal pollution
concentrations in the environment as an effect of urbanization have also been shown in
many studies (e. g. [1-6]). It is because of concern regarding such increased risks of
heavy metal enrichment in the environment, from neighboring anthropogenic sources,
that this study was planned to monitor metal concentration levels in different
components of the coastal marine environment of the Arabian Gulf on the Saudi
Arabian side.

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Such industrial pollutants can reach the aquatic environment in different forms and
phases and via different routes. It can be transmitted in the gaseous phase as aerosol, or
in the liquid phase as dissolved or suspended solids in effluent wastes and surface
runoffs. Atmospheric fallout is another important route in transporting metal-containing
solid pollutants, in form of suspended particulate matter, emitted from point or non-
point sources, to the marine environment. Toxic metals can reach the marine
environment through any of these routes depending on the form and structure in which
the metal exists. When a toxic metal contaminant reaches the aquatic environment, it
may dissolve in the aqueous phase and remain as such in the water column. It may
otherwise become adsorbed on some suspended solids of organic or inorganic nature.
Whether the metal ends up dissolving in the water column or adsorbed on some
particulate matter, it may, further, become ingested, assimilated or excreted by marine
micro- or macro- flora or fauna including various filter feeders; or it may eventually
settle down into the benthic environment.

Phyto- and zooplanktons are micro-organisms at the first and second lower trophic
levels which are capable of extracting, and bio-concentrating, heavy metals inside their
cellular tissues. Fish, as a consequence of being predators on these and other micro-
organisms, accumulate higher levels of these metals than their preys. Eventually, man
at the apex of the food chain pyramid, being a seafood consumer, is susceptible to the
potential harm of toxic metals pollution resulting from metal enrichment in edible
marine species, at the higher trophic levels (bio-magnification). Metals are found to
accumulate to variable levels in different organs of the same individual species. The
accumulation also depends upon age, size, and developmental stage in the life cycles of
individual species [7]. Sites of metal accumulation, storage and impact also vary
widely among different organs of a marine organism. [8]. The degree of
bioaccumulation of metals varies widely from one organism to another, from one metal
to another, and from one set of ambient conditions to another. The ambient conditions
include abiotic physical factors such as temperature, solar energy, and depth of the
water column, in addition to the general hydrographic characteristics of the region.
Similarly, chemical conditions of the ambient seawater also play variable roles in
determining the degree of bioaccumulation. These include pH, salinity, concentrations
of organic and inorganic complexing ligands and chelators, relative concentrations and
forms of other co-existing metals. It had also been shown that bioaccumulation vary

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significantly with organism age and size [9]. Therefore, for a meaningful comparison of
the ability of individual fishes of the same or different species, to bio-concentrate a
given metal, they must be of comparable age. Studies carried out on the relationship
between age, weight and length of individual fishes, including museum specimens and
freshly caught fish, demonstrated the dependency of heavy metal enrichment on the
weight and length or size of fish [7,10,11]. This is a very fortunate relationship since
length or weight can be measured much more easily and conveniently than age.

Although toxicity effect of pollutants to living marine organisms was recognized as

early as the early decades of the 20th century, it received little attention in the past. This
effect, together with other marine pollution effects, such as reduction of aquatic
amenities and possible hampering of customary marine activities, were considered of
secondary importance. Lately, however, there was a growing concern regarding toxic
contaminants in general, and toxic heavy metals in seawater, in particular. This
awareness occurred in the wake of the tragic events of Minamata and Itai- itai of Hg
and Cd poisoning cases, which erupted respectively in Japan around the middle of the
20th century. Ever since, the disease caused by poisoning human beings with seafood
contaminated with mercury, was named Minamata after Japanese Bay where it was first
recognized. The other, itai- itai was the name given to the disease caused by poisoning
humans with seafood contaminated with cadmium. In Minamata Bay the mercury had
come from industrial discharges into the bay. Eating fish that had accumulated mercury
in Minimata village, between the years 1953 and 1960, poisoned hundreds of
individuals. Soon after this tragedy the othe r Itai- itai tragedy erupted, also in Japan,
when eating fish contaminated with cadmium metal this time, poisoned a lot more
humans. The disease was named after a characteristic screams, known as itai scream,
which was a cry common to all poisoned casualties. These Japanese tragic incidents
flared a vivid awareness of the problem of bioaccumulation of metals by marine
organisms and spurred research on the fate and impact of metals on the marine
environment.

Metals can produce deleterious effects on tissues of marine organisms themselves. At

high concentrations they can lead to death of the organism. This level of toxicity is
known as lethal toxicity. At relatively lower concentrations, organisms may suffer

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from various kinds of adverse effects but still survive. Histological changes may occur
in the digestive tubular tracks, gills or epithelial tissues. Symptoms due to interference
with the organisms neurological system may also be observed. Such symptoms may be
a reflection of changes in enzymal or hormonal activities resulting in that the organism
become weak and ecologically vulnerable to death. Lesions, changes in respiration,
growth or reproduction rates, or susceptibility to parasitic pathogens and diseases may
all occur, though may be difficult to detect. These kinds of effects are referred to as
sub- lethal effects (or sub-lethal toxicity). Also, lethal or sub- lethal toxicity may be
referred to as chronic toxicity if it occurred by accumulation of low- level contaminants
over an extended period of time. All metals appear to be susceptible to bioaccumulation
to a greater or lesser extent. However, the form, which the metal assumes, and its
oxidation state will largely determine the amount and the corresponding toxicity of the
metal. Also, whether the metal is present in an ionized form of an oxidized or reduced
state, complexed with an organic substance, or adsorbed on an organic or inorganic
particulate, is a factor determining its uptake by, and toxicity towards, the organisms.

On the basis of the 48- h LC50 lethal toxicity levels of metals towards fish species, the
pollution hazard of the more prominent metals in seawater were ranked as follows:

Hg++ > Cd++ > Cu++ > Ag+ > Ni++ > Pb++ > As3+ > Cr3+ > Sn2+ >
Zn2+

However, if the larval stage is examined, the relative toxicities of the various metals
change:

Hg++ > Ag+ > Cu++ > Zn2+ > Ni++ > Pb++ > Cd++ > As3+ > Cr3+ >
Sn2+

Mercury in both cases is the most toxic, but cadmium is not as toxic to larvae as it is to
mature fish [11]. Zinc is much more toxic to larvae than to adult fish. Lloyd reported
that in 20 mg/L Zn, a cytological breakdown of the gill epithelium of trout occurred in
about 2.5 hours [12]. Weir and Hine [13] reported the lowest levels effecting
physiological impairment and the corresponding 50% fraction of these, equivalent to
lethal concentrations, LC 50 ’s , for several elements including As, Hg and Pb. The
48
calculated LC50 doses for As, Pb and Hg, were, respectively 32.0, 110.0, and 0.82

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mg/L. The 48 hr test were carried out sequentially in 2 steps, that is, a 24-hr 1st
exposure and test, then a 2nd 24-hr exposure and retest [14].

Lethal toxicity of metals to the marine environment is performed using standard

bioassay tests. In these tests marine organisms are placed in seawater containing known
concentrations of the metal for a certain period of time, usually, 48 or 96 hours. The
number of individual organisms, which survive at each metal concentration, is
determined and from these data the LC 50 , or the concentration which is lethal to 50 per
cent of the test organism ensemble, is calculated. The time used for the test is usually
denoted as a superscript immediately before the le tter L. For example, the statement:
96
LC50 symbolizes a concentration that is lethal to 50 % of an organism test group
within 96 hours.

2. OBJECTIVES

Enormous wastewater discharge from industries is liable to contaminate the

neighboring Arabian Gulf water with variable amounts of toxic constituents. These
discharges over a period of time may increase the level of toxic materials above the
natural baseline levels. Monitoring concentration levels of toxic heavy metals as
pollution indicators in various components of the marine environment represents the
principal objectives of the present study. These objectives will be achieved through the
following:

(i) Determination of concentration levels of dissolved heavy metals (As, Cd, Co, Cr,
Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) in the Arabian Gulf seawater, in carefully
selected sites north and south of the eastern Gulf coast of Saudi Arabia.
(ii) Determination of heavy metals levels in muscles and gills of representative,
commercially important fish and shrimp species from above sites.
(iii) Determination of heavy metals content in sediments of the above selected study
sites.
(iv) Determination of distribution pattern of metallic constituents of the above-
mentioned marine environmental components of the study areas on seasonal in as
well as regional basis.
3. EXPERIMENTAL

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3.1 Sampling and Sampling Area

Samples of fish, water and sediments were obtained from two sites in the northern part
of the Gulf coast of Saudi Arabia, near Manifa and Tarut towns (Fig. 1). The former is
adjacent to an oil field while the latter is adjacent to an agricultural drainage area. Fish
species of the types Nermipterus tolu, known locally as (Bassi), Gerres argyres
(Badah) and Lethrinus nebulosus (Shieri), in addition to shrimp species, Penaeus
semisulcatus (Figs. 2-5), were collected on seasonal basis from both regions of the Gulf
stream. The shrimp species is a mono-specific species indigenous to both regions.
Collections were made during the months of July, October 2000, January 2001 and
April 2002. The latter collection was substituted for batch of samples due on April 2001
but was not available. FRC co-investigating staff collected, preserved and transported
the species to R & D Center. The samples were preserved by freezing, packed in an ice-
box and car- transported to R &D Center for analysis. To ensure comparable weight
and age fish samples were collected in the length range of 13 ± 2 cm.

Water samples, collected by FRC technical staff, from surface and bottom seawater
layers, in acid cleaned polythene containers, packed and transported in ice-box to R &
D Center for analysis. Surface samples were collected from a depth not exceeding 1
meter, whereas bottom samples were collected from variable depths ranging from 21 to
25 meters in manifa and 16 to 25 meters at Tarut. Table 1 is a record, submitted by
FRC, for the different bottom sampling depths along with sampling temperatures and
pH values of the seawater.

Sediments were sampled from seabed surface using a homemade, Van Veen type, grab
sampling device supplied by the R & D Center. The samples were packed in plastic
bags, preserved and sent to the Center.

3.2 Sample Preparation

Several methods of ashing were attempted for fish samples. The method finally adopted
used an acidified dilute aqueous solution of 0.25 % hydrogen peroxide and 0.125 M in
nitric acid. The solutions containing the biological samples were refluxed for several
hours at relatively low temperatures.

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Exchangeable metals were leached from sediments through equilibration with an
aqueous solution of 1 M HCl. The total metal content was determined in sediments
after complete digestion with nitric, perchloric and hydrofluoric acids. Metals in water
samples were extracted and analyzed in accordance with the standard method of
analysis [15].

3.3 Chemical Analysis

Analysis of metals in water and biological materials was carried out by atomic
absorption spectroscopy using a GBC model Avanta Σ, (GBC Scientific Equipment
Pty. ltd.) as well as an earlier Varian AA spectrometer model GTA 5890. Later
collection of fish and prawn samples were analyzed using a Perkin Elmer Analyst 800.
Also digestion of the latter samples was carried out simultaneously on a CEM
microwave oven along with above- mentioned peroxide procedure. The two methods
when tested for selected representative samples, gave comparable analytical results
against the same standards used as reference material.

Sediment samples were mostly analyzed using an inductively coupled plasma emission
spectrometer (Hitachi ICPES), while some were analyzed with AAS.

The fatty material encountered in the fish digestate was extracted in two successive
small aliquots of methyl isobutyl ketone (MIBK) fortified with cyclohexane in the ratio
of 3:1. The combined extracts were further analyzed in a GC/MS model HP (Hewlet
Packard Inc.) supported with a library consisting of 3 databases from Wiley, NIST and
HPPEST.

4. RESULTS AND DISCUSSION

4.1 Ashing of Biological Material

Ashing of biological materials, both dry and wet, can be achieved in several ways [15-
20]. Dry ashing procedures are, on one hand, always shrouded with the fear of losing
some of the analytes, partially or even totally at times. On the other hand, most of the
procedures used for wet ashing are lengthy, laborious, and also susceptible to analyte
losses and/or contamination. This is usually because these procedures use harsh

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oxidation conditions with highly concentrated strong mineral acids, boiling or
evaporating repeatedly to dryness, before finally redissolving the residue in an aqueous
solution [16,17]. However, in spite of all these tedious steps, frequently the digestion
turns out to be incomplete and wax- like lumps or oily droplets separate out in a distinct
phase as the digestates cool down to room temperature. Such cases are encountered, for
example, in wet ashing certain types of fish tissues, specially gills. The digestion
usually fails to break down the fatty components of these tissues. This is particularly
true, for instance, when using the digestion procedure described by Varian group [17].

As mentioned before, the wet ashing procedure adopted in this work used dilute
hydrogen peroxide acidified with dilute nitric acid for digestion of fish and shrimp
tissues at a relatively low refluxing temperature. However, as it was the case with
Varian procedure, the clear, warm, peroxide solution of the mineralized tissues, on
cooling, also resulted in the same fatty material of gills separating out in an immiscible
oily phase, which solidifies on chilling. Although the two procedures ended up to the
same result, yet the peroxide procedure is more convenient in that it is a neat and clean
procedure requiring minimal steps and with no need for repeated evaporation to
dryness. Moreover, the dilute aqueous peroxide solution containing the analytes is best
suited for AAS analysis and can be aspirated directly into the instrument. This modified
procedure of wet ashing, using dilute acidified peroxide, was developed in our
laboratories during the course of this study.

The problem of the fatty material can be surmounted in either of two ways. One way is
by filtration and the other by solvent extraction. As has been described in the
experimental section, both techniques were used and compared in this study. The
objective was to analyze this fraction of fatty material to see how much, if at all, it
contains of each of the analyte metals. The result of the analyses revealed that none of
the analytes were present at any detectable level in the fatty material, whether solvent
extracted or filtered off and then dissolved. This result was not surprising in the light of
the repulsive nature of opposing polarities of the fatty material and the heavy metal ions
under consideration. However, some fatty materials do contain polar functional groups,
which, under favorable conditions, are capable of binding metals resulting in metal
complexes or metal chelates. For this reason, it appeared relevant to investigate the
nature of this fatty substance in order to rationalize with the complete absence of metals

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in it. Since the substance appeared to have a fairly low melting point, it can be
anticipated that its boiling point and vapor pressure can be well suited for gas
chromatographic (GC) analysis. Thus, a sample of the fatty material, obtained from gill
digestion was analyzed using a gas chromatograph equipped with a mass spectrometric
detector, GC/MS. The results of the analysis revealed that the fatty material is
composed mostly of long chain carboxylic acids (fatty acids). Hexadecanoic (palmitic),
octadecanoic (stearic) and heptadecanoic (margaric) acids represented the major fatty
acid constituents of the substance. Further details of the GC/MS analysis of the fatty
material are given in Table 2. The mass spectrogram is shown in Figure 6.
Identification of the unknown gill fat components was based on the MS library. There
are three search libraries associated with the MS model HP used for this identification:
Wiley, NIST 98 and HPPEST databases. The identification made for the above-
mentioned compounds was given with very high matching quality reaching as high as
99%. It may be noted that the minimum match quality specified for Wiley is 70%
whereas that of NIST is 60%.

These carboxylic acids could have scavenged some of the trace metals present in the
fish dige state, yet this did not happen obviously because of the low acidic pH of the
medium. It is probably worthwhile to point out that these above- mentioned aliphatic
carboxylic acids are derivatives of parent aliphatic alkanes of C16 , C18 & C17 . Such
aliphatic compounds although ubiquitous in biological material they are also found
among petroleum hydrocarbons, though in the latter case, unlike the present case, odd
numbered chain prevail over even numbered. Thus, it is quite unlikely that these
aliphatic carboxylic acids had their origin as oil contaminants in the surrounding marine
environment that became infiltrated and adsorbed inside the gill tissue, until finally
terminally oxidized during the peroxide digestion. This unlikelihood is supported by the
comple te absence of any traces of polyaromatic hydrocarbons (PAH), which are
common oil contaminants in the marine environment, and are not synthesized by biotic
species. . However, a drawback is that conc. HNO3 (69%, Sp.Gr. 1.42) had to be used
according to ma nufacturer recommendations for fish tissue digestion.

Other methods of ashing include wet ashing in a microwave oven. Earlier and recent
attempts of such technique have been reported [16,19, 20]. Several samples of fish
tissues were wet ashed in a CEM typ e of microwave oven, which arrived lately in our

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laboratory. The ashing was complete and superb. Crystal clear digestate solutions were
obtained without any fatty materials.

4.2 Moisture Content in Fish Gill and Muscle Tissues

The moisture content of fish and shrimp species was evaluated in order to enable
comparison of analytical results of metals concentrations reported on both dry and wet
basis. The moisture content was generally appreciably lower in gills compared to
muscular tissues of all three types of edible fish –Bassi, Badah and Shiery (Table 3).
Within the three species, Badah species has the lowest moisture content with a mean
value of ~ 60%, Shiery species has the highest moisture content with a mean value of ~
70%, whereas Bassy, lying in between, had a mean value of ~ 66% (Fig. 7). The
moisture content in muscle tissues of the three species followed roughly the same order
as for gills, except that Shiery and Badah showed slightly higher average values of 78%
compared to that of Bassy (77 %). The value of water content in shrimp averaged 78 to
79%. These results are in fair agreement with results published by Zhou et. al, showing
lower moisture content in gills compared to muscle tissues of a Tilabia species [21].

The fact that gills generally possess appreciably lower moisture content than other
muscular tissue is consistent with the fact that during wet digestion with acidified
hydrogen peroxide, gills produced sizably more fatty material than did plain muscles.
This is apparently in keeping with a more lyophilic (more hydrophobic) nature of gill
tissue as compared to muscle tissue.

4.3 Heavy Metal Levels in Fish and Shrimp Tissues Versus Ambient Seawater
Environment

4.3.1 Heavy Metal Levels in Surface and Bottom Seawater

Arsenic, As, and mercury, Hg, were invariably undetectable in all samples of seawater
of both Manifa and Tarut regions of the Arabian Gulf, over the whole study period.
Similarly, Chromium and manganese were seldom detected in these samples. Only sub-
ppb levels of Cr and Mn were encountered in a couple of surface samples for Mn, and a
couple of bottom seawater samples for Cr (Table 4). Cadmium level in the open
seawater is reported to range from 0.01 to 0.05 mg/L, while in coastal waters its levels
range from 0.05 to 1.0 mg/L. Concentrations as high as 10 mg/L have been encountered

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in polluted waters [8]. Cadmium in the regional seawater of Manifa was found at much
lower levels (0.1 to 1.4 µg/L) compared to the above reported coastal ranges. However,
despite these low levels of Cd, it showed a tendency to stratify and become slightly
enriched in the bottom seawater layers. This tendency was observed only during the
cooler months of October and January in Manifa area; whereas, in April and July its
concentration in both layers was quite homogeneous and almost identical. No similar
tendency towards stratification was observed in Tarut region, where Cd concentrations
were comparable in both layers of seawater over all seasons. Paired and multiple
sample Student t tests, at the 95% level of confidence, were used to statistically verify
the significance of stratification differences. A paired Student t test applied to the mean
values of surface and bottom Cd concentration levels, showed statistically significant
differences between the two levels during the cooler months at 95% confidence level.

In contrast to Cd, which showed the lowest detectable concentration in the gulf
seawater of the study areas, Ni recorded the corresponding highest metal concentration
(Fig. 8). Its overall annual ave rage, in surface and bottom layers, over all seasons, and
over the whole study region, was about 11.5 ppb. For this overall average, the
corresponding regional and seasonal mean values ranged from 2.4 –22.0 & 2.4 –14.4 in
Manifa compared to 10.4 –14.9 & 9.4 to 12.9 ppb in Tarut surface and bottom seawater
layers, respectively.

Second only to nickel, vanadium also showed relatively high concentration levels in
both surface and bottom seawater, in both of Manifa and Tarut regions, though no
stratification tendency was observed. Its concentration in surface and bottom layers was
fairly homogeneous in both sites. In Manifa surface and bottom layers, it averaged,
respectively, 5.3 and 5.4 ppb. Similarly, in the corresponding layers of Tarut its
concentration averaged to comparable values of 5.8 and 5.3 ppb, respectively.

On the other hand, Ni, showed a tendency to stratify and become more consistently
enriched in the surface seawater layer of Tarut region. Its mean seasonal values,
averaged over the four seasons, amounted to about 13.3 ppb in the surface seawater of
Tarut, versus 11.3 ppb in the bottom; whereas the corresponding values exhibited in
Manifa amounted to 12.1 ppb in surface and 9.1 ppb in bottom layers. However, such

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stratification tendency was dis tinctly notable in Tarut waters only during the warmer
month of April, otherwise it was not consistent.

Cu exhibited a relatively more pronounced tendency for stratification. Contrasting

nickel, Cu showed a generally consistent tendency to enrich in bottom rather than
surface seawater layers in both of the study sites. In case of Cr, although it was
undetectable in most of the analyzed seawater samples, yet, when detected it was only
at low levels in surface layers of seawater of both Tarut and Manifa sites.

The apparent stratification of Cd in Manifa regional water during the cooler months of
the year (October – January), may be caused by preferential depletion of the metal from
the surface seawater through uptake of the metal, by phytoplankton as well as floating
macrophytes flourishing during these months. Bishop [22] reported a concentration
factor from seawater to such marine organisms, to be commonly of 100 to 1000. For
phytoplankton in relatively clean water, he reported a Cd content of 300 to1000 ng/g
(0.3 – 1 ppm) dry weight, while in polluted areas concentrations up to 220000ng/g (220
ppm) have been observed. Maine et. al. [23], studied several species of floating
macrophytes in Argentina, during the lower temperature period of the year where a
winter daily mean varied between 10 and 15 °C. These authors reported that all studied
species were highly efficient in the Cd uptake from the surrounding water. They noted
Cd % removal ranging from 63 to 74%. If similar phenomena were taking place to a
comparable extent during the cooler months of any of the study sites, then, this may
lead to a similar depletion of Cd from the surrounding surface seawater of that study
site. In fact, the necessity of monitoring the bioaccumulation of certain elements in
species of the marine algal flora of the Arabian Gulf had been suggested. Several
investigators have advocated, or shown that, the use of a wide variety of marine
macroalgae as an indicator of heavy metals gives at least a qualitative picture of heavy
metals contamination in the study area [24]. In this case, phytoplanktonic as well as
macrophytic species indigenous to the region may be screened so as to isolate the
species that are more efficient in removal of e.g. Cd (or say Cr or Cu). If the
phenomenon is confirmed, then it might be worthwhile to investigate the possibility of
using such species not only as pollution indicators, but also as pollution controllers.
They can even be further developed for use as protective measures for specific metals

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pollution, had they been carefully studied and developed so that they may be introduced
to coastal industrial areas that are vulnerable to a specific types of metal pollution.

4.3.2 Metals in Fish Muscles and Gills and Shrimp Tissues

The Saudi Arabian Standards Organization, SASO (1977), had suggested maximum
allowable limits (MALs) for some of the more toxic heavy metals in fish, crustaceans
(shrimp) and mollusks species, as follows:

Cadmium, Cd 0.5 mg/Kg (ppm)

Mercury, Hg 1.0 ditto (ppm)
Lead, Pb 2.0 ditto (ppm)
Arsene, As 1.0 ditto (ppm)
Copper, Cu 20.0 ditto (ppm)
Zinc, Zn 50.0 ditto (ppm)
Stannane (Tin), Sn 250.0 ditto(ppm)

On the other hand, the U. S. Environmental Protection Agency (EPA) and the U. S.
Food and Drug Administration (FDA) workgroup have introduced what they referred to
as the screening values and tolerance levels for 25 contaminants. Of these 25 there were
3 metals, 21 organic and 1 organometallic toxic contaminants. The 3 toxic metals, viz.
As, Hg and Cd, were already included in SASO’s MALs list. However, the U.S. EPA
has described criteria for these contaminants to be used by fish advisories to enable
them to issue appropriate advice on fish consumption limits. Determination of these
consumption limits depend on several factors such the type, age, size and habitat of fish
species; the community structure, fish consumption and preference habits, fishing area
characteristics, in addition to metal anlyte level in fish, its toxicity potency and
estimated health risk levels. General equations are provided for calculating these
values [25]. Furthermore, these values have to be worked out for each of three sectors,
which USEPA and FDA have defined as distinctly different classes of consumers with
respect to their sensitivity to fish contaminants. These consumer sectors are the
subsistence fishers, sport (or recreational) fishers and general public fishers. For
example, for Hg, an FDA action and tolerance level of 1.0 ppm, with corresponding
EPA recommended screening values of 0.4 ppm for recreation fishers and 0.049 ppm
for subsistence fishers were assigned [25].

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In the present study, however, mercury and arsenic, were not detected in any of the
tissues of fish or shrimp species from the two study sites, over the whole study period.

Cadmium when detected occurred at fairly low levels, within SASO limits, in the
muscle tissues of fish. The same can be said regarding concentration levels of Zn, Cu,
and Pb, which all lie below, or well below, the limits (Table 5).

Although, the level of Cd in the edible fish muscles showed values within SASO’s
recommended maximum limit of 0.5 mg/kg, its level in gills and shrimp tissues, only
slightly exceeded this limit. It reached about 0.8 – 0.85 mg/kg dry weight in a couple of
shrimp samples obtained from Tarut during Jan 01 & April 02 cruises. Although Cd
concentration level also exceeded 0.5 ppm in some gill samples (0.6-1.3), nevertheless,
its average level in gills of studied species remained the second lowest of all levels of
the detectable elements, with Cr being the lowermost (Table 5). This may be an
indication that these pelagic fish species are preferential inhabitants of the near surface
zone of the water column where the surrounding seawater had been shown to be poor in
both Cr and Cd content. Since fish species metabolic and biochemical oxidation
processes require gills to continuously extract the necessary oxygen from the
surrounding seawater, the gills are thus subject to a continuous flow of an almost
chromium- and cadmium- free upper layer of seawater. This leads to continuous
flushing of the gill internal and external tissues and may equally lead to Cr- and Cd-
depleted gills. A further support to this inference is that the elements, whose
concentration levels are relatively high in surface seawater, reflect correspondingly
high concentration levels in gill tissues. Ni and V exemplify cases in point. Among the
studied elements, these are, respectively, the two elements with the highest relative
concentration levels in surface and bottom seawater. Their corresponding concentration
levels in gills are, in general, similarly highest.

Zn concentrations were slightly higher compared to e.g. Cd, Cr, Cu & Pb. It occurred in
both muscles and gills of some fish species. Similar results of Zn concentration in
muscles of several marine fish species, being higher than the above mentioned (and
other) trace elements, were also reported [14, 26]. However, Zn shows more
enrichment in muscles than gills of certain species, such as Badah and Shieri. The
tendency of Zn to bio-concentrate in muscles may be attributed to its particular

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tendency to accumulate in the skin layers of fish species [21]. Since muscle samples
used in the current study were not intentionally skinned, variability in the Zn content of
muscles will be expected to occur in as much as there are skin fractions associated with
the muscular tissues. This appears to partly contribute to observed variability of Zn
content in muscles of the same species.

It is interesting to note that the level of V found in the gills of Badah species, sampled
from Tarut bay, in January, 01, was relatively high. A comparable elevation in V level
was also noted in the gills of Shieri sampled from the same area at the same date.
Incidentally, Ni concentration in the gills of the same species, Badah and Shieri, of the
same place and date, Tarut, Jan 01, were also relatively high, though not as high in the
latter as in the former species. This led to the inference that the elevated levels of V &
Ni must have originated from the same source; which could most likely be a transient,
oil- loaded mass of seawater. Such an oil- loaded seawater mass may have formed due to
some accidental spill by a navigating vessel in the vicinity, or may have originated from
some proximal region of chronic ballast disposal activity [5]. The transient nature of the
source can be spotted from the fact that no persistence or longevity of such metal levels
was noticed in the gills of the species sampled at other vicinal sampling dates.
Furthermore, a similar trend was also noticed in the gills content of V & Ni of Manifa
Bassi and shrimp species about the same time (Jan 01). However, because of the
distance between the two sites, it is rather unlikely that their source of origin is the
same. Although such possibility may not be ruled out completely, coincidence of a
similar causative incidence, sounds more plausible. Regarding Ni alone, a gill sample
of Badah sampled from Tarut in July 2000, was also noted for relatively high content of
the metal (31 ppm). In contrast, V in this sample was appreciably lower this time (4.3
ppm), so that a common origin of contaminants may not be easily inferred. Fortunately,
however, gills seem to possess an outstanding ability to depurate and bring the levels of
these metals way down. In other words, they seem to have no tendency to bio-
concentrate these metals. This is obvious from the extremely low levels of these, and
other elements, encountered in gills sampled at various other dates. Thus, it seems that
these elements only adsorb on the internal tissues when water loaded with them
penetrates the gills for oxygen supply. Afterwards, these adsorbates seem to eventually
flush out. In fact gills possess this unique ability of selectively extracting oxygen from a
medium like seawater containing a myriad of other elements, which are essentially

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rejected. It is not very unlikely that, whatever the mechanism that gill use for achieving
such selectivity might be, it may also aid them in cleansing other intruding elements.
However, SASO did not set limits for these two elements, V & Ni, in fish species,
apparently because they are not known for threatening toxicity. Furthermore, it should
be noted that metal levels encountered in this study, are high only relatively, and not in
their absolute magnitude. Though, if these levels are compared, even in the absolute
sense, to SASO’s allowable levels of elements such as Zn (50 ppm), then it will be
realized how low they are. This is apart from the fact they are elevated solely in gill
tissues, which represent only a small fraction of the total edible body weight, and which
consumer are not normally fond of it.

Most of the other remaining elements appeared to show variable, though generally
modest, tendency, to bio-concentrate whether in gills or muscles of fish or shrimp
tissues (Figs. 9 & 10). Yet, in case of gills in particular, metal concentration levels
showed some association with their levels in the surrounding aqueous environment.
This seems to be the case of elements like Pb, Cu, Cd and possibly Cr, Mn, As and Hg,
whose concentration levels in gills, kept some proportionality to their seawater levels.
In contrast, however, with an element like cobalt, this doesn’t seem to be the case,
particularly with Badah species. With this species, a concentration factor of Co in gills,
exceeding 100000 could be estimated in Tarut region, based on its average
concentration in surface and bottom seawater. However, in Manifa no such high Co
concentration factor was attainable with this or other species. Thus, it appears that Co
have a more pronounced capability, though rather inconsistent, to generally concentrate
in gill tissues of certain species, specially in gills; but to a far lesser extent (<10000) in
muscles of fish or shrimp. The second highest concentration factor was estimated for
Fe, also in the gills of Badah, yet in Manifa. Concentration of Fe in fish tissues appear
more consistent, ranging from ~5000 to ~10000 in fish muscles and from <10000 to
~50000 in gills. Fe also showed relatively elevated concentration levels in the tissues of
shrimp during the month of April 02, in both regions of Manifa and Tarut (20.4 & 31
ppm, respectively) and in Tarut alone during Oct. 01 (26.6 ppm). No CF corresponding
to these levels could be given here because data for seawater is not available for this
month. Yet, to be able to confidently rationalize with such values in terms of seasonal
or regional variations, the study, as was intended, needed to have extended over two
years without sampling problems. However, Aboul-Naga [26], in a study of heavy

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metals concentration of three crustacean species in Alexandria, including Penaeus
semisulcatus of this study, reports highest CF of nickel and a very low CF for FE in all
three shrimp species. These results are in contrast to our results obtained on the same
shrimp species. The same contrast also applies to the values quoted for Cd as being the
lowest in his study, whereas it is low to moderate in our study.

However, Powell & Powell [27] reported that despite significant temporal variations in
elements concentrations in muscles tissues of some west coast fish population (p
<0.05), there was no evidence for bioaccumulation of any of these metals or
biomagnification of any of these metals during the 10 years period even in the soft
organ of fish. Powell & Powell studied for the decade (1977 –1987) trace elements (Cu,
Pb, Zn, Cd, Hg, and AS ) measuring them in muscle tissues and other organs of 8
species of tropical marine fishes common to both the east and west coast of the pacific
island of Bougainville. These results were obtained despite the fact the island was
vulnerable to discharged mine tailings from some copper mining industry in the region
[27].

In general, however, the distribution patterns of most elements in the different

components of the marine environment are mainly governed by the nature and
composition of various chemical entities in the aquatic component of the environment.
The presence, type and load of organic and inorganic species and their prospective
interactions and the thermodynamic parameters controlling them, in addition to their
kinetic properties; all contribute in determining to a very large extent the distribution of
almost all non-inert elements in various components of the marine aquatic systems.

4.3.3 Metals in Sediments

Cd showed relatively low concentration levels (about 40 ppm) in the sediments of both
Tarut and Manifa sites, compared to some other elements (e.g. Cu, V, Mn, & Fe). The
portion of exchangeable Cd was much smaller than total Cd content of the sediment (~
25% of the total Cd) (Table 6). As mentioned elsewhere, this relatively small
exchangeable part of the metal is presumed to be potentially available for marine biota.

Manganese, which was found at fairly low, or undetectable, levels in seawater, fish and
shrimp tissues, was found in plentiful amounts in sediments. Nonetheless, Mn, the

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second most abundant metal in nature after iron, is considered one of the essential trace
metals for human life up to a concentration level of 30 mg/70 kg body weight [28,29].
Mn total content in sediments, was about 89 mg/Kg in Tarut, and as high as 269 mg/Kg
in Manifa. In sediments of both sites, however, the exchangeable fraction amounted to
about 75%, or more of the total Mn content. This indicates that Mn had a higher
mobilization rate relative to other elements, such as cadmium and lead, within the bulk
sediments. It may also signify a higher rate of adsorption of Mn form the aquatic
surroundings onto sediments, and/or settleable particulate matter, leading consequently
to the observed impoverishment of its level of existence in both surface and bottom
seawater layers. Lead is also fairly enriched in the sediments of Tarut and Manifa with
the mobile fraction averaging only about 29-34% of the total Pb content of each site.
Lead in the seawater samples occurred at extremely low levels ranging from ~ 0.2 to ~
4.2 ppb. Its concentration levels in edible fish and shrimp tissues also occurred at fairly
low levels (in accordance with SASO limits). The most highly exchangeable metal in
the sediments of the study regions appears to be Zinc. It exists almost exclusively in the
extractable form (≥ 85% to ~100% in Manifa and Tarut respectively).

Zn in seawater recorded levels ranging from ~ 0.1to ~7 ppb while in fish tissues it
showed somewhat elevated levels (Table 4). However, zinc is one of the most abundant
of the essential elements required by the human body and approximately 100 times as
abundant as copper. Thus, as a metal considered essential for human life the required
concentration level is as high as 3000 mg Zn/70 kg body weight [28].

Copper is another essential element for human beings up to a concentration level of

150-mg/70 kg body weight [11]. Copper in the Gulf seawater of Manifa and Tarut
ranged from ~0.2 to ~ 16 ppb (Table 4). Like zinc, copper level in the biological tissues
of the test species was somewhat elevated but being an essential element up to such
high concentrations (150 mg/70 kg) does not seem to pose any problem (Table 5). Total
copper in sediments is present at levels higher than all other elements (excluding iron)
(Fig. 11). The exchangeable portion of copper constituted more than 80% of total
copper (Table 6). Most of the results on sediment contents of metals obtained in this
study are comparable to those reported by Abaychi and Douaboul [30], who studied
similar fractions of eight elements common to this study, in sediments of the northern

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part of the Arabian Gulf. However, these authors who noticed strong variations in the
concentrations of trace elements among different locations within the different
locations of the studied area, also concluded that the rather low concentrations they
obtained in the Arabian Gulf indicate that it is an unpolluted region [30]

Vanadium was included in this study because it is one of the metals associated with oil.
In fact, V together with Ni are the two major heavy metals occurring at relatively high
levels in the Arabian light crude oil. However, their low concentration levels in the
Gulf seawater, clearly indicates the absence of any significant oil pollution in the study
regions. This is in agreement with low levels of oil residues in Gulf sediments reported
elsewhere [33, 34].

Iron is of course the most abundant element in the earth crust [28]. It is also one of the
essential elements for human life at concentrations as high as 7000 mg Fe/70 kg body
weight. Iron levels in the studied areas of the Arabian Gulf also showed strong
variation with location not only in sediments (table 6), as noted elsewhere in sediments
of the gulf [19] and other regions, but also in seawater [28,35]. In the latter it ranged
from a few tenths of a milligram to a little over a hundred milligrams per a liter of
seawater (Table 4). This probably indicates location variation of variable release rates
of trace elements from sediments to the marine environment [27]. In fish species it
ranged from barely detectable to over 150 mg/kg. In sediments it totaled about 6000
mg/kg in Tarut and about 14000 in mg/kg in Manifa. The exchangeable fraction in the
two sites, amounted respectively to about 3600 and 8800 mg/kg.

5. CONCLUSIONS

(1) Analytical results revealed that very low concentration levels of toxic metals are
encountered in the Gulf seawater both in the northern region of Manifa and the
southern region of Tarut.

(2) No concentration levels that are abnormally high were observed in the tissues of
the test species.

(3) Toxic metal levels analyzed in this study meet the available maximum allowable
limits recommended by SASO for fish and shrimp species.

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(4) In sediments, both the exchangeable metal part (which is potentially bio-
available) and the total toxic metal contents are present either at quite low levels
(mercury, arsenic, cadmium, and nickel) or at levels comparable to those reported
in the relevant literature.

(5) There were no consistently distinct trends of abnormal bio-concentration levels in

edible fish tissues.

(6) Gills, compared to muscles, generally tend to accumulate higher levels of certain
heavy metals relative to their counterparts found in other tissues in the present
study, yet, these relatively high levels were considerably low in the absolute
sense of the values.

(7) Cu showed relatively more tendency for stratification. Enrichment of Cu levels

was noticed intermittently in the bottom seawater layers of both areas in general,
though in Tarut it was somewhat more profound. In contrast to Cu, Ni showed an
intermittent tendency to enrich in the surface, rather than bottom, layers. The rest
of the metals showed no distinct stratification between top and bottom seawater
layers and no distinct seasonal variation.

(8) Despite low concentration levels in both top and bottom layers, Cd, also showed
some stratification tendency but only in Manifa during the Cooler months of
October and January.

(9) Spatially, Manifa appears to be relatively more loaded with the tested metals
contents than Tarut, except for Cu and Zn, which are more enriched in Tarut
sediments.

(10) Manifa seawater column is slightly more enriched in metal content than Tarut.
This is reflected in the fact that, for most detectable metals (except V and Mn),
the sum of the total metal content in Manifa, over all seasons, compared to that of
Tarut, is fairly higher. Yet, the absolute concentrations levels of these elements
for both sites, are quite low.

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(11) No distinct or repeating patterns of seasonal variation in the study sites, for metal
concentration levels in seasonally collected fish or shrimp samples, were
observable.

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Table 1. Temporal Environmental Parameters : Temp, Salinity and Depth, of Sea
water at Study Area

Parameter Month Manifa Tarut

Apr 00 21.5 24.8
July 00 33.9 26
Temperature ( 0 C )
Oct 00 28.8 30
Apr 02 24.7 25
Apr 00 40.4 42.6
July 00 41.6 39
Salinity ‰
Oct 00 41.3 42
Apr 02 39.6 42
Apr 00 21 15
July 00 22 18.2
Depth (m)
Oct 00 21 16.2
Apr 02 25 24.7

Table 2. GC/MS Separation and Identification of Chemical Components of Gill Fatty

Material in Fish Species of the Arabian Gulf

Retention
Peak # Compound ID Quality % Library Area %
Time

1 Hexanedecanoic acid (Palmitic acid) 99 Wiley275.L 30.47 60.5

2 Octanedecanoic acid (Stearic acid) 99 Wiley275.L 33.42 24.03

3 9-Octadecanoic acid 99 Wiley275.L 33.06 4.01

4 Tetradecanoic acid (Myristic acid) 99 Wiley275.L 26.93 3.87

5 Heptadecanoic acid (Margaric acid) 99 Wiley275.L 31.83 3.39

6 n-Nonanal (Nonyl aldehyde) 95 Wiley275.L 12.94 2.29

7 Pentadecanoic aaacid 99 Wiley275.L 28.6 1.91

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Table 3. Moisture content(x ±3, n=3) in Fish Muscles(M), Gills(G)and
Shrimp Tissues in Manifa and Tarut Regions of The Arabian
Gulf (%W/W)

%Moisture
Metals
SITE

M G
FISH

BASSI 70 ± 3 60 ± 1

Manifa
BADAH 78 ± 1 66 ± 2

SHIERI 78 ± 1 70 ± 1

Manifa SHRIMP 78 ± 1

Tarut SHRIMP 79 ± 1

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 Table 4. Metals in Arabian Gulf Seawater of Manifa and Tarut Coastal Regions (ppb) (S: Surface, B: Bottom)

Metal V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg
SITE Month S B S B S B S B S B S B S B S B S B S B S B S B
April 4.1 6.6 0.16 0.14 22 10.0 7.2 5.8 0.3 0.4 2.2 1.6 0 0 5.8 5.8 6.4* 12.7* 0 0 0 0 0 0
July 6.7 6.1 0.1 0.1 2.4 2.4 0.1 0.2 0.3 0.3 0.2 0.5 0.7 0 3.2 5.6 0.7 0.9 0 0 0 0 0 0
Manifa
Oct 5.5 3.6 0.1 1.4 10.5 9.8 0.1 0.1 0.5 0.4 3.3 0.4 0 0 6.8 9.5 0.6 0.4 0 0 0 0 0 0
Jan 5.1 5.5 0.1 1.4 13.4 14.4 0.3 0.3 0.3 0.6 0.6 0.7 0 0 2.2 3.6 6.3 2.9 0 0 0 0 0 0
April 6.0 6.8 0.2 0.1 14.9 12.0 2.2 0.2 0.4 0.3 0.7 0.5 0 0 3.4 4.4 1.2 1.6 0 0.4 0 0 0 0
July 4.4 3.2 0.1 0.1 14 9.4 0.4 0.1 0.3 0.4 0.8 4.2 0.4 0 6.8 11.8 3.5 1.2 0 0 0 0 0 0
Tarut
Oct 5.9 6.7 0.2 0.1 14.3 12.9 0 0 0.3 0.3 0.7 0.5 0 0 0 0 0 0 0 0.4 0 0 0 0
Jan 6.7 4.3 0.2 0 10.4 9.4 0.1 0.3 0.4 0.2 0.6 3.6 0 0 0.2 16.0 0.6 0.6 0 0 0 0 0 0
Mean levels average of 3 replicates with % RSD Ranging between (<1.0 – 12.9)
–1
*: [Fe]×10

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 Table 5. Distribution of Heavy Metals in Fish Muscles (m) and Gills(G) and Shrimp Tissues in Manifa and Tarut Regions
Metals * V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg
SITE
FISH Month M G M G M G M G M G M G M G M G M G M G M G M G
JUL 00 X X X X X X X X X X X X X X X X X X X X X X X X
OCT 00 3.0 3.4 0.4 0.2 0.2 0.3 ND 3.0 0.4 ND 0.9 1.2 1.0 ND ND 1.8 2.2 ND ND ND ND
BASSI
JAN 01 0 17.0 0.3 0.4 23.0 17.0 2.5 4.8 1.5 1.4 0 6.0 0 0 0.4 0.7 5.5 31.0 0 23.0 0 0 0 0
APR 02 0.57 0.26 0.1 0.2 0.6 0.9 0.5 0.5 9.0 16.4 1.6 2.2 0.1 0.1 0.6 0.4 0.1 10.4 0.2 1.1 0.04 0.1 0.13 0.01
JUL 00 0.8 0.3 0.5 0.8 2.4 2.5 ND 0.4 0.6 1.4 1.7 0 0 ND ND 0.1 0.1 0 0 0 0
OCT 00 0.7 0.9 0.4 0.4 0.6 0.5 ND 1.2 1.0 0.1 0.8 0.3 0.7 ND ND 0.4 0.9 0 0 0 0
Manifa BADAH
JAN 01 X X X X X X X X X X X X X X X X X X X X X X X X
APR 02 0.4 0.7 0.1 0.2 0.4 0.8 0.5 0.6 0.4 0.3 0.4 2.0 2.2 0.1 0.1 0.4 0.7 10.2 0.2 1.1 0.3 0.1 0 0.1
JUL 00 1.0 1.5 0.4 0.5 1.5 2.1 ND 0.4 0.4 0.9 1.8 0 0 ND ND 0 0.1 0 0 0 0
OCT 00 3.1 3.6 0.2 0.6 1.1 1.7 ND 0.2 0.3 0.3 1.0 0 0 ND ND 0 0.1 0 0 0 0
SHIERI
JAN 01 X X X X X X X X X X X X X X X X X X X X X X X X
APR 02 0.37 0 0 0.1 0.4 0 0.2 0.03 5.6 0 1.4 0.01 0 0 0.6 0.01 3.1 0 0.1 0.02 0.25 0 0.08 .0.04
JUL 00 X X X X X X X X X X X X X X X X X X X X X X X X
OCT 00 X X X X X X X X X X X X X X X X X X X X X X X X
BASSI
JAN 01 X X X X X X X X X X X X X X X X X X X X X X X X
APR 02 0 0 0 0 0.1 0.6 0.5 0.8 0 0.5 0.3 0.7 0.1 0 1.1 2.0 9.0 5.5 0.2 0.4 0.2 0.7 0.1 1.2
JUL 00 3.0 4.3 0.3 1.2 0.1 31.0 13.0 4.3 0.1 47.0 0 5.4 0 0 0.2 0.1 19.0 0 0.2 0.6 0 0 0 0
OCT 00 X X X X X X X X X X X X X X X X X X X X X X X X
Tarut BADAH
JAN 01 0 22.0 0.2 1.1 0.1 23.0 1.1 4.8 0.1 35 0.5 5.0 0 9.0 0.5 0.7 3.9 13 0 7 0 0 0 0
APR 02 x x x x x x x x x x x x x x x x x x x x x x x x
JUL 00 0 8.3 0.25 1.3 0.3 12.0 5.4 2.0 0.3 2.2 0.25 4.7 0 0 0 0.5 11.0 20 0.4 0 0 0 0 0
OCT 00 X X X X X X X X X X X X X X X X X X X X X X X X
SHIERI
JAN 01 0 21.0 0.1 0.4 0.1 6.0 2.6 2.3 0.1 1.5 0.2 1.5 0 0 0 0 15.0 10.0 0 0 0 0 0 0
APR 02 0 0 0.1 0.4 1.0 1.5 1.1 1.4 1.5 2.0 1.6 0.3 0 0 2.6 2.6 8.0 12.0 0.4 0.5 0.9 1.0 0.2 0.05
JUL 00 2.0 0.1 1.6 ND 4.6 0.5 1.1 ND ND 5.2 0 0
OCT 00 2.4 ND 0.8 ND 2.1 0.1 0.2 ND ND 2.3 0 0
Manifa SHRIMP
JAN 01 18.0 0.6 10.0 2.2 0 0.2 0 0.4 4.5 0.6 0 0
APR 02 1.7 0.13 0.4 0.7 0.45 1.7 0.02 2.1 20.4 0.23 0.07 0
JUL 00 0 0.4 0.2 0 1.5 0 44.0 1.3 6.3 0 0 0
Tarut SHRIMP OCT 00 6.0 0.3 0.15 0 2.2 0 0 0.2 26.6 0 0 0
JAN 01 0 0.8 0 3.99 0 0 0 3.07 7.4 0.4 0 0
APR02 5.0 0.85 0.2 1.36 0.22 1.73 0.37 1.45 31.4 0 0.06 0.2
*: Mean levels average of 3 replicates with % RSD Ranging between (1.5 - 11.5)

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 Table 6. Exchangeable(E) to Total (T) Heavy Metal Content in sediments of Manifa and Tarut Regions (mg/ kg dry wt)

Metal V Cd Ni Zn Co Pb Cr Cu Fe* Mn As Hg
E T E T E T E T E T E T E T E T E T E T E T E T
Exchangeable 111 9 15 43 80 43 37 218 885 201 0 0.5
Manifa
Total 208 40 33 50 178 148 64 263 1390 269 4.8 1.3
Exchangeable 92 14 ND 99 48 44 22 282 360 70 0.2 2.2
Tarut
Total 158 40 ND 99 89 129 30 327 608 89 6.2 2.6
Ratio E/T Manifa 0.53 0.23 0.46 1 0.45 0.29 0.58 0.83 0.64 0.75 0 0.38
Ratio E/T Tarut 0.58 0.35 ND 1 0.54 0.34 0.73 0.86 0.59 0.79 0.03 0.85

*:[Fe]×10 - 1

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Figure 1. Sampling Areas

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Figure 2. Nemipterus tolu (Cuvier and Valencienne ) : Local Arabic Name : Bassi (Notched Threadfin Bream)

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 Figure 3. Gerres argyreus: Local Arabic Name : Badah

Figure 4. Local Arabic Name : Sheiri (Lethrinus nebulosus)

Figure 4. Lethrinus nebulosus: Local Arabic Name : Sheiri

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Figure 5. Penaeus semisulcatus: Local Arabic Name : Rubyan

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Figure 6. Chemical components of Gill fatty Material in fish species from
Arabian Gulf

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 80
70 M
G
60
50
W% 40
30
20
10
0
BASSI BADAH SHIERI SHRIMP SHRIMP

Fish Species

Figure 7. Moisture Content in Fish Muscles (M),Gills (G) and Shrimp Tissues in
Manifa and Tarut Regions of The Arabian Gulf (%w/w)

??
 April JULY
OCT JAN

25
20
JAN
15
(ppb) OCT
10
JULY
5
April
0
S B S B S B S B S B S B S B S B S B S B S B S B
V Cd Ni Zn Co pb Cr Cu Fe Mn As Hg
Metals

Figure 8(a): Metals in Arabian Gulf Surface(S) and Bottom(B) Seawater

of
of Manifa
Monifa Costal Region (ppb)

April JULY
OCT JAN

20
15
(ppb) 10 JAN
5 OCT
0 JULY
S B S B S B S B S B S B S B S B S B S B S B S B April
V Cd Ni Zn Co pb Cr Cu Fe Mn As Hg
Metals

Figure 8(b) : Metals in Arabian Gulf Surface(S) and Bottom(B) Seawater

of Tarut Costal Region (ppb)

??
 Manifa

35

30

25

(pbb)
20

15
APR 02
JAN 01
OCT 00

10
JUL 00
APR 02
JAN 01

5
OCT 00
JUL 00
APR 02

SHIERI
JAN 01

0
OCT 00
JUL 00

M G M G M G M G M G M G M G M G M G M G M G M G
BADAH
V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg
BASSI Metals

Tarut

50
45
40
35
30

(pbb)
25
20
APR 02
JAN 01

15
OCT 00
JUL 00
APR 02

10
JAN 01
OCT 00

5
JUL 00
APR 02
JAN 01

0
OCT 00
JUL 00

SHIERI M G M G M G M G M G M G M G M G M G M G M G M G

BADAH V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg

BASSI Metals

Figure 9. Distribution of heavy metals in fish muscles (M), Gills (G) in

Manifa and Tarut regions of the Arabian Gulf (mg/kg dry
weight)

??
 Manifa

JUL 00 OCT 00
JAN 01 APR 02

25

20

15
(ppb) APR 02
10
JAN 01
5 OCT 00
JUL 00
0
V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg

Metals

Tarut

JUL 00 OCT 00
JAN 01 APR 02

35
30
25
20 APR 02
(ppb)
15 JAN 01
10
OCT 00
5
JUL 00
0
V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg
Metals

Figure 10. Distribution of Heavy Metals in Shrimp in Manifa and Tarut Regions
of The Arabian Gulf (mg/kg Dry weight)

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 1400
1200
mg/kg Dry Wt

1000
800 Tarut Total
600 Tarut Exchangeable
400 Monifa
Manifa Total
200
Manifa
Monifa Exchangeable
0
V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg

Metals

Figure 11a. Exchangeable & Total Metal Content in Sediments of Manifa And Tarut
(mg/kg Dry Weight).

1
0.8
mg/kg Dry Wt

0.6
0.4

0.2 Ratio E/T Tarut

Ratio E/T Manifa
Monifa
0
V Cd Ni Zn Co Pb Cr Cu Fe Mn As Hg

Metals

Figure 11b. Ratio of Exchangeable toTotal Metal Content in Sediments of Manifa And
Tarut (mg/kg Dry Weight).

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