Abstract

The incidence of shipping mishaps and spills at sea and on the high seas is an unavoidable side
consequence of the international transportation of crude oil and refined petroleum products by
water, which cannot be avoided. In spite of the fact that the frequency and severity of major
catastrophes have decreased dramatically since the 1970s, oil spillages and operating discharges
from tankers continue to be a significant source of oil pollution in the maritime environment. A
huge oil spill in coastal waters has resulted in the rapid absorption of oil and polycyclic aromatic
hydrocarbons by fish and shellfish that have been exposed to the oil (PAHs). This may provide a
health concern to human consumers of fish and shellfish, as well as reducing the marketability of
fish and shellfish that have been collected. It is the purpose of this article to provide a
comprehensive analysis of the mechanisms that determine the absorption and retention of
polycyclic aromatic hydrocarbons (PAHs) in fish and shellfish, building on the knowledge
learned from earlier examples. The Exxon Valdez, the Braer, and the Sea Empress, as well as the
poisoning of local resources as a result of these disasters, are all examined in depth in this
chapter. If oil spill monitoring were more consistent, it would make it much easier to draw
comparisons across different occurrences. The use of a more standard method to oil spill
monitoring would also make it easier to analyse the kinetics and dynamics of hydrocarbons
produced in future spills, which would assist in the prediction of future spills in the first place.
The presence of PAHs in edible tissues of fish or shellfish has not been subjected to regulatory
limits or suggested levels at this time, regardless of whether the PAHs originate from oil or
combustion sources.
Introduction
Middle Eastern states, such as UAE, provide most of the world's crude oil for refinement and
use. Transporting crude oil on a massive scale throughout the world, as well as refining it on a
smaller scale and distributing it more locally, may lead to oil tanker accidents and spills. A
disproportionate majority of maritime mishaps occur close to shore, in waters with fewer
protections for marine life and consequently a bigger danger for harm to fishing resources
(International Petroleum Industry Environmental Conservation Association, 1997). (International
Petroleum Industry Environmental Conservation Association, 1997). (International Petroleum
Industry Environmental Conservation Association, 1997). The great majority of spills are created
by the loading and unloading of cargo, as well as bunkering and other activities.

Imperfect records of minor incidents may only infer a tiny proportion of the annual total amount
of oil discharged into the ocean by ships. Up to 608,000 metric tonnes per year of oil leakage
occurred between 1970 and 1996, with the bulk of the amount coming from only a few notable
events. Seven-ton leaks released 1372 thousand tonnes of oil between 1987 and 1996, whereas
nine-ton leaks spilled 992 thousand tonnes of oil. Polycyclic aromatic hydrocarbons (PAHs)
represent a concern to human health and the viability of fish and shellfish harvests when they are
consumed by farm-raised or wild fish and shellfish in coastal waters. This information on how
PAHs are absorbed and maintained in fish and shellfish would assist both fish and shellfish
farmers and consumers.

Methodology
Chemical Analysis Combustion-derived PAHs are composed mostly of parent molecules,
although alkyl-substituted homologs are also found in crude oil. Analytical methods used to
study pyrogenic PAHs (based on high-performance liquid chromatography [HPLC] or gas
chromatography [GC]) may be used to study oil-derived PAHs because of their greater
complexity (Law and Biscayan, 1994). In spite of the fact that it is still not possible to separate
all of the parent and alkylated PAH isomers, the higher resolving power of capillary GC columns
and the selectivity of MS detection maximize the amount of information that can be gained. Oil
spill data is seldom directly comparable to data from later spills due to the fact that various PAH
groups are often discovered and different methodologies may also be used. A more uniform
approach is desirable, yet this may indicate varied aims to some extent.

There is a list of PAHs (J.Klungsyr, 1998, personal communication) that may be used to identify
both com-bastion and oil sources in monitoring study (J.Klungsyr, 1998, personal
communication). Analysis of PAH concentrations and ranges using UV fluorescence
spectrometry between extraction and cleaning provides critical information, allowing more
difficult and time-consuming (and costly) chromatographic techniques to be targeted more
successfully. In order to guarantee that the sampling and analysis processes stay under the
control of the techniques, a rigorous analytical quality control strategy should be employed in the
laboratory programme. In other places, this topic has been extensively discussed. Historical
evidence shows that "blind" inter-comparison activities may improve test results by distributing
"blind" samples to participants.

Researchers may be able to get a better understanding of their findings if they can accurately
count the PAHs present. It may be required to apply sophisticated chemical fingerprinting
technologies to separate pollution from other probable sources even in sites with a history of oil
spills or substantial natural oil inputs. Astonishingly, comparing data from previous spills to get
advantage from the vast quantity of knowledge that has been acquired throughout the world is
quite challenging. Many different PAH suites are explored, and concentrations may be reported
either as dry weight or as wet weight. Oil spill records are seldom (if ever) published in their
entirety. This is due to a variety of factors.

Taint Assessment
Even in coastal locations where extensive farming is going place, toxicology studies of local
seafood may be crucial in oil disaster response. Sensory rather than analytical approaches can
only be used to investigate taint since there is a lack of knowledge of the hydrocarbons that
induce taint and the levels at which they do so. Torrey Research Station in the UAE (SOAEFD,
Aberdeen) taint assessment approach was shown reliable via laboratory studies in which oil taint
from fish was absorbed and depuration analyzed (Martine et al., 1992; Davis et al., 1995). It was
discovered that the tainting threshold for trout exposed to diesel fuel in ambient water was 0.08
mg/L (Davis et al., 1992), however amounts in the range of 1–100 mg/L are often observed. For
example, following the Braer and Sea Empress tanker catastrophes in the UAE, researchers
employed similar strategies. Setting up, training, and maintaining an effective taint-testing panel
is costly, but the panels can examine a large number of samples (in the case of the Braer , 12,800
individual assessments were made for salmon alone; Whittle et al., 1997). When oil refineries or
other businesses are present in coastal areas, there may be a notion that contamination is the
usual, even if this may not be the case.

Sampling of Fish and Shellfish for Analysis

In the aftermath of an oil spill, it is common practice to monitor the removal process and record
the return to baseline concentrations. The most important commercial species may be sampled
even if resources are restricted, since sampling should take into account all probable exposure
and absorption pathways. In order to get to the laboratory faster (within 24–48 hours), samples
may be transported on ice, but they should otherwise be frozen and stored in a freezer. It may be
essential to rent a boat for sample purposes as a consequence of the commercial fishing ban.
Considering contamination levels and analytical resources when deciding how frequently
samples should be collected for fisheries management decisions is crucial. As long as it may take
for PAH depuration to take place, it is possible for bi-valves to absorb PAHs quite quickly.
Analysis of cockles and mussels from commercial beds was used to trace the removal of PAHs
from the Sea Empress catastrophe.

Fishery closures following oil spills

Global fishing takes place mostly in waters close below continental shelves, which are rich in
marine life. We've already shown that a large oil spill in coastal waterways will likely
contaminate fish and shellfish stocks. Damage to fisheries and shellfish is most probable if they
can't escape oil, and pollution is most likely in areas with significant inshore shellfisheries
(International Petroleum Industry Environmental Conservation Association, 1991). The Braer,
the Aegean Sea, the Exxon Valdez in Alaska, the Amoco Cadiz in France, the m; farmed mussels
and oysters in France, and m; farmed salmon in Shetland, among other sites, were discovered to
be polluted [Whittle and Alvarez-Pinero et al., 1997]. Whittle and Alvarez-Pinero (2007)
Because of their extensive aquaculture practices, Japan and Korea's seafood has been impacted in
ways akin to the 225,000-ton Amoco Cadiz disaster in France (Moller et al., 1989). Crustaceans
and mollusks are more vulnerable to pollution than fish, yet wild fish populations may still be
contaminated. A year after the Exxon Valdez tragedy in Alaska, biologists discovered con-
termination in the nearby Pollock (Pollachius virens) 400 miles away (Collier et al., 1993). A
main source of food for Alaskan fishermen is Pollock, a deep-sea fish that feeds in the water
column. In the open sea, there is little indication that an oil spill has had any effect on adult fish
populations, and even if larvae have perished, this has seldom been seen in adult populations.
Plagued by the Amoco Cadiz spill in 1978, North Brittany's worst-hit sections of Pleuronectes
platessa and Solea vul-garis perished. (National Oceanic and Atmospheric Administration,
1981). Oyster fishing was banned for seven years and the oyster population was poisoned by oil
hidden in aerobicsubtidal sediments in the Ambers (inlets) (Berthou etal., 1987). Polluted or
threatened fish and shellfish populations are often the trigger for action. It is possible to
terminate a thesis in the UAE under the Food and Environment Protection Act (1985). In
addition to safeguarding the fisheries markets, fishing activity is controlled to prevent human
consumers from consuming polluted food. Because they may accumulate in the body even at
quantities that are hundreds of times lower than those of the low MWPAH alkylated derivatives
present in crude oil, oil-derived carcinogens (like some of the high MWPAHs) are of special
concern. Epidemiological studies show that eating seafood from areas impacted by oil spills does
not enhance the risk of cancer or other ailments in people (GESAMP, 1993).

After the oil spill from the Exxon Valdez, Alaskan subsistence fishermen investigated whether
oil-contaminated fish could be eaten by humans. In this study, fish metabolism and removal of
PAHs resulted in a minimal danger of ingesting flesh from fish exposed to PAHs, and the FDA
supported this finding in an advisory opinion (Collier et al., 1996). Food and Drug
Administration officials said the danger of cancer from eating spill-area finfish is so minimal that
it can't be quantified and is thus essentially nonexistent (Bolger et al., 1996). Even if you ate
shellfish from the most damaged area for the rest of your life, you had a very low risk of
acquiring cancer, according to research. It's possible that the levels of carcinogenic PAHs in
shellfish contaminated by combustion-derived PAHs rather than oil-derived PAHs are greater,
hence these tests may not apply to such shellfish. Three recent large-scale oil spills in the United
Kingdom and the United States demonstrate the contamination of fish and shellfish caused by oil
spills. A sample's total PAH content is determined by multiplying the number of PAHs and
groups in the sample by the number of samples.
Exxon
Approximately 38,000 metric tonnes of crude oil spilled from the Alaskan North Slope when the
Exxon Valdez went aground in Prince William Sound, Alaska, on March 24, 1989 People who
rely on Alaskan seafood for their nourishment have expressed anxiety after the state's abrupt halt
of commercial fishing. Fishing is essential to the local economy and way of life (Means and
Yonder, 1997). Despite testing showing that the great majority of fish were free of PAHs and
otherwise undamaged, residents in the region refused to accept the results (Fall and Field, 1996).
Longlines and pots were not used for many days after the accident because black cod (Sablefish
[Anoplopoma fimbria] and shrimp) may have contaminated their skin (Spies et al., 1996).
Fisheries in the near-shore zones were contaminated because of shoreline cleaning activities,
which resulted in the fouling of fishing gear and merchandise. This trend persisted for the rest of
the year... PAH levels in pink salmon were observed to differ three to one across oiled and
uncontaminated portions in 1989, according to research. 181 6 28 dry weight m gig 2 1 dry
weight PAH concentrations (S PAH concentrations). In 1990, PAH concentrations were the same
in both oiled and unoiled regions. Researchers (Curls et al; Koran et al; Marty et al., 1997).
Untreated mussel beds (Milieus trossulus) showed pollution levels of up to 8000 mg kg 21 dry
weight after three or four years (Babcock etal., 1996; Harris et al., 1996). S PAH levels in these
mussels had grown to 100,000 mg kg 2 1 dry weight within six weeks after the occurrence,
illustrating the severity of the oiling (Short and Babcock, 1996). Protected from the effects of
nature are the best places to sleep when it comes to pollution. Mussels had access to an unlimited
supply of hydrocarbons since the remaining oil had not been organically weathered or
discharged.

Braer
Braer was stuck by strong winds owing to the spill's accompanying severe weather. Despite the
difficulties of spreading the 84,700 tonnes of crude oil using chemical dispersants, around half of
the shipment was spontaneously dispersed following discharge (Davies et al., 1997). In Europe,
the Shetland Islands' economy is heavily reliant on the seafood industry, making it one of
Europe's most fisheries-dependent areas (Good-lad, 1996). Three days after the Braer was
grounded, a fishing closure order was issued. At 14,000 mg kg 2 1 wet weight, muscle tissue S
PAH concentrations in Shetland Pansy salmon were quickly absorbed (compared to 30 mg kg 2
1 in the background). As a result, 2650 mg/kg of PAHs in wild finfish muscle was the highest
concentration ever recorded for wild smelt harvests in 1993 and 1992, resulting in the loss of half
of the intended 1993 harvest and the whole 1992 intake (in whiting sampled in January 1993).
Four months after the grounding, the exclusion zones for wild fish were removed, allowing them
to return to their natural habitats (Top-ping et al., 1997). In September 1994 and February 1995,
the limitation on crustaceans other than Nephrons was eased. The Clam (Pectin Maximus) Six
years after the disaster, it is still illegal to collect mussels and Nephrons in specific portions of
the closure zone due to oil contamination in upper votes (inlets) in the impacted region (similar
to the situation on the north coast of Brittany following the Amoco Cadiz spill in 1978)

Sea Empress
The Sea Empress ran aground in Milford Haven, southwest Wales, on February 15, 1996,
spilling a mixture of 1940s crude oil and heavy fuel oil. Environmental Assessment Committee
(Sea Empress) to protect the amount of fish and shellfish, a fishing closure zone has been created
off the coast of South and West Wales (Law et al., 1997, 1998). Species- and geographic-based
limitations were gradually lifted one at a time. Following a three-month grounding, finfish
restrictions were eased since fish absorbed low MW PAHs in relatively low concentrations. In a
sample of bass, the maximum concentration of S PAH was 259 mg kg 2 1 wet weight; all other
measurements were below 100 mg kg 2 1 wet weight. As in fish, low molecular weight PAHs
prevail in crustaceans, as they do in finfish. Fish and crustaceans acquired considerably less PAH
than mollusks (especially mussels). Six thousand milligrams of oil per kilogram me of muscle
tissue and 100,000 milligrams of S PAH were discovered in muscle tissue within nine days after
the grounding. Only intertidal mussels were affected by these restrictions, which were repealed
on September 12, 1997, 19 months after the ship was stranded.

Removal of fishery restrictions

Before fishing can resume again, restrikes must be halted. Even both the Braer and Sea Empress
instances occurred in separate sections of the United Kingdom, the same procedure was used to
determine closures. Samples of fish and shellfish taken within the exclusion zone before the spill
did not contain crude oils or petro-lemur fractions, and hydrocarbon and PAH concentrations
were within the range established for reference sites outside the exclusion zone or for similar
samples taken within the exclusion zone but before the spill. Since oil is spilt from natural seeps,
no fish or shellfish will ever be completely free of PAHs, which are ubiquitous environmental
pollutants. All species and locations impacted by a spill aren't usually included in pre-spill data.
In the event of a leak, environmental monitoring programmes like the National Status and Trends
programme may be able to give valuable information. Mollusk tissue PAH concentrations do not
vary seasonally since the samples are obtained at the same time each year (Jacob et al., 1997,
personal communication).

Environmental runoff from urban and industrial areas is a major threat to calm beds in
economically exploited estuaries and coastal waterways. Government regulations or
recommendations do not apply to PAHs found in fish and shellfish tissue samples. To define
such values in countries where seafood is a substantial element of the diet is a challenge that
varies greatly from nation to nation. Assuming that the oil leak was responsible for the pollution
or tainting, what should be done? Fisheries should be permitted to continue if these pollution
levels existed before to the incident and were approved at the time. Maintain the closure as
though the spill had been responsible for it. Long-term shutdowns pose a danger of employment
losses since there are no restrictions or guideline values. A higher PAH content in seafood from
beyond the spilled area may be more prevalent in commercially available seafood.
Study limitation

Conclusion
Maritime disasters occur at a disproportionately high rate near to shore, in seas with less
safeguards for marine life and hence a greater risk for damage to fishery resources. The vast
majority of spills are generated by the loading and unloading of goods, as well as bunkering and
other operations. A significant threat to human health and the viability of fish and shellfish
harvests, polycyclic aromatic hydrocarbons (PAHs) are emerging as a result of climate change.
A significant piece of information is provided by the analysis of PAH concentrations and ranges
using UV fluorescence spectrometry between extraction and cleaning. It may be necessary to use
advanced chemical fingerprinting methods in order to distinguish pollution from other possible
sources.

Surprisingly, comparing data from prior spills in order to gain benefit from the large amount of
information that has been accumulated around the globe has shown to be quite difficult. Sensory
rather than analytical methodologies can only be used to analyse taint since there is a dearth of
understanding about the hydrocarbons that cause taint as well as the amounts at which they occur
in the environment. A boat rental may be necessary for sampling reasons as a result of the
commercial fishing prohibition, if the situation continues. When determining how often samples
should be collected for fisheries management decisions, it is critical to take into account
contamination levels and analytical resources. It is most likely that fisheries and shellfish will be
damaged if they are unable to escape oil, and that pollution will occur in places where there are
major inshore shellfisheries.

Crustaceans and mollusks are more prone to pollution than fish, yet wild fish populations may
still be affected as a result of industrial contamination. In the open sea, there is no evidence that
an oil spill has had any impact on adult fish populations, and even if larvae have died, this has
only been seen in a small number of adult populations in the past.

Acknowledge
For the work carried out by CEFAS, the Ministry of Agriculture, Fisheries, and Food in the
United Arab Emirates provided funding. Department of Fisheries and Oceans, Dartmouth, for his
assistance with the preparation of the manuscript; Ian White, Deborah Ansell, and other
colleagues from the International Tanker Owner's Pollution Federation for information from their
Oil Spill Data Base and for helpful comments on an earlier draught of this paper; Colin Moffat of
the Fishes and Wildlife Conservation Society for his assistance with the preparation of the
Reference

Appendix