STUDY ON CHEMICAL HAZARDS ASSOCIATED WITH

TRADITIONALLY SMOKED FISHES SOLD IN OWERRI

FEDERAL CONSTITUENCY

CHAPTER ONE

1.0 INTRODUCTION

Hazards could be defined as any material capable of causing

harm when consumed. They could be microbial, physical or even

chemical hazards. However chemical contaminants are those

contaminants which get into fish from synthetic materials like

packaging materials, pesticides, etc, which are introduced into

both aquatic and terrestrial environment as a result of human

activities either intentionally or unintentionally. These hazards are

capable of causing harm depending on their potential toxicity.

Chemical contaminants could be of inorganic source e.g. metals,

nitrate, asbestos, etc. or of organic sources e.g.solvent,

pesticides, herbicides etc. and other products used by man on

daily basis and they include plastics, resins, disinfectants,

electronic waste, oil spills from

crude oil, etc.

A fish is a cold blooded gill breathing, oviporous aquatic

vertebrate which lives entirely in water, however, indiscriminate

dumping of chemical contaminants in water bodies pollutes

drinking water and food ( Liu et al., 2009) as well as rendering

such water body toxic to fish. Furthermore, a high concentration

of these contaminants could result to bioaccumulation of

chemical salts in several organs of fish. Fish is a highly perishable

food product which requires a considerable amount of effort to

extend its shelf life (Abowei et al., 2011) as well as prevent post

harvest loss (Kumolu-Johnson et al., 2011) using processing and

preservation techniques such as freezing , chilling, salting ,

canning, smoking and drying. However, in Nigeria, traditional

smoking involving treating of presalted whole or filleted fish with

wood smoke in which smoke generated due to incomplete

combustion of fuel, comes in contact with fish is the most

employed techniques and it has been estimated that about 70-

80% of capture and cultured catches "are consumed in smoked

form ( Akinyemi et al., 2011).

Wood has been one of the oldest sources of energy known and

used by man and it still amount for more than 90% of national

energy consumption in some poorest African countries (Sambo,

2009). However, when wood undergoes combustion, in limited

supply of air, wood smoke is produced. Smoke can be generated

from other energy sources aside wood such as coal charcoal, cow

dung, paper, plastics, tyre and even cow dung. Hence the drying

and cooking effect of the energy source and the wood smoke

during smoking, deposit chemicals like tar, phenols, aldehydes,

sooth, carboxylics,etc which produces powerful antioxidant and

bacterio-static effects on the fish hence , prolonging fish's shelf

life (Eyo, 2001). Smoking is also commonly applied to fish

(Cardinals et al., 2007), Meat products (Modi et al., 2004) as well

as other food products like cheese (Suchanova et al., 2008).

However, the smoking techniques has developed to a point where

once common food becomes a delicacy and there is need for

concern for safety issues in smoked fish consumption (Riches,

2017).
Eyo, (2001) also stated what wood smoke also contains polycyclic

Aromatic Hydrocarbons (PAHs) which may be carcinogenic or non-

carcinogenic.

Polycyclic Aromatic Hydrocarbons are chemical environmental

contaminants which find their ways in food processed through

smoking, roasting, drying and even grilling (Rose et al., 2015) and

the actual concentration of PAH on smoked fish products depend

on several factors during the actual smoking process which

include, distance between the fish and the smoke source, the

degree of smoking and temperature ( Purcaro et al., 2013)

Olabemiwo et al., (2011) , assessed the PAHs of two smoked fish

species (Clarias gariepinus & Tilapia guineensis) available in

Western Nigeria and reported that the sum of PAHs in the smoked

fish ranged from 0.497-0.814ug/kg and 0.519-0.772 ug/kg

respectively. The Codex Alimentaruis describes international food

standards, citing/stating permitted maximum levels for

contaminants in foods based on risk assessment and scientific

evidence (FAO, 2004).

Furthermore, contaminants may get to foods through different

routes such as from the atmosphere and deposit on fruits and

vegetables (Fismes et al., 2004), contamination from packaging

materials, naturally occurring toxicants in fish feed, inclusion of

additives to improve processed fish and meat

appearances,use of pesticides on stored fishes against rodents,

cockroaches, flies, beetles (Akinola et al., 2006) and veterinary

residue in processed food could have deleterious effects on

human and animal health . However, there is dearth of

information regarding chemical contaminants in fish sold in some

markets in Rivers State hence the purpose of this study.

OBJECTIVES OF STUDY

To investigate the presence or otherwise of chemical

contaminants in processed fish sold in some markets in River

State.

Specific Objectives of study

To know what chemical hazards are

To know the allowable concentration of PAH as an environmental

contaminants from wood smoke, and fumes on processed fish

To know the implication of chemical contaminants on human

health

To know the concentration of phenols deposited on processed fish

JUSTIFICATION

The issue of food safety and chemical contamination in Nigeria is

worsened by public ignorance on the lack or inadequate

application of good fish processing practices, use of poor quality

packaging materials, uncoordinated approach to food control,

poor enforcement of legislations and regulatory limits, direct or

indirect application of pesticides on smoked fish against pests by

illiterate processors as well as unprotected display of processed

fish in the market to dust and fumes from automobiles.However,

as a result, FAO, has raised alarm over what it described as

worrisome levels contamination of foods at the point of

consumption with aflatoxis, mycotoxins, heavy metals such as

lead and pesticide residues in Lagos State and Kano State

(PremiumTimes, 2019)which could result to various ailments

ranging from gastrointestinal disorders to carcinogenesis, and

even death. However in view of the serious and negative public

health impact of chemical contaminants in traditionally smoked

fish, little or no works have been carried out on smoked fish sold

in some markets in River State, hence the purpose for the study.
 CHAPTER TWO

LITERATURE REVIEW

Fish industry in Nigeria

Fish has been a valuable and nutritious food which forms part of

human diet. Fish is an essential source of high quality and

relatively cheap source for humans. Proteins are mostly found in

meat, poultry, fish and legumes but plant protein are inferior to

animal proteins because they lack sulphur-amino acids such as

Methionine, Lysine and Tryptophan. Nevertheless, fishes are

excellent source of sulphur-amino acids, B-Vitamins an High

quality unsaturated fatty acids (Agbabiaka, 2014).

However, the FAO estimates that about 1billion people world-wide

rely on aquaculture as a main source of animal protein (FAO,

2000). In most countries of the world, individuals derive more

than 40% of their daily animal protein from fish (Eyo, 2001;

Abolagba & Melle, 2008) fish do not only contribute to the

populace of a country as a source of cheap quality protein but as

a source of employment for both capture and culture fishers in

Nigeria.
Africa as a continent has over 5% of her populace depending

completely or partially on fisheries for their income(Guillen et

al.,2000)

DOMESTIC FISH PRODUCTION AND SOURCES:

Nigerian's dependences on fish as cheap source of quality animal

protein in order to meet the demand of her increasing population

is greatly increasing. Nigeria's fish supplies come from major

sources such as importation, inland estuaries and coastal

artisanal fishery, industrial trawl fishery and aquaculture.

However, Nigeria's total fish supply in 2004 was 1,600mts,

according to (FAO, 2013). In 2010, the capture fisheries

production was 600,000MTs and aquaculture is 200,000MTs

respectively. Overall production of fish from capture fisheries

increased from 1995- 2006, and slightly decreased in 2007 due to

problems of piracy and militant groups the marine waters.

Aquaculture production increased geometrically from year 2000

due to increased awareness in fish farming especially in the area

of catfish & Tilapia production using flow through and water

recirculatory culture systems.

Some fish species commonly smoked in Nigeria

Aside fish being an excellent source of cheap quality animal

protein its oil also has been very useful in lowering blood

cholesterol and as well richer in iodine than any other food

(Agbabiaka, 2014). Omodara et al. (2012), noted that poorly

processed fish especially in the tropics, go bad when stored at

ambient temperatures. Therefore the need of the widely used

traditional method employed for processing & preservation of fish

for centuries. However, in sub-Sahara Africa and Nigeria

practically all species of fish can be processed using traditional

method of processing. Eg Mackerel (Scomber scombrus), Herring

(Clupea sp),Catfish (Clarias gariepinus) and it has been estimated

that about 70-80% of domestic marine and freshwater catches

are consumed in smoked form (Akinyemi et al.,2011)

Domestic Fish Demand and Consumption in Nigeria

Fish has been playing a crucial role in the diets of Nigerians with

an estimated population of about 186 million people (World Bank,

2016). A recent study estimated that Nigeria ranks third globally

for the number of people dependent on coastal fisheries for food

and nutrition security however, household fish consumption in

Nigeria measured at 13.3kg/capital year is low compared with the

world's average of 20.3kg/Capital year (FAO, 2018). The majority

of household in Nigeria (58%) suffer from chronic food insecurity

(Ogundari, 2017). Nigeria's vast inland water bodies and coastline

measures over 800km and supports nearly 1.5 million people

engaged in fish-based livelihood (FAO 2007; World fish 2017b).

However, as of 2012, over 13,000 people were employed in

aquaculture, which is mostly monoculture of large species of fish

like catfish, tilapia etc is seen as a pathway through which the fish

demand and consumption gap can be bridged.

Current trends in fish demand and consumption

The demand for fish has been existing centuries ago, though the

trend of its demand and the strategies to supply them have been

constantly evolving, trending now is the consumption of charcoal-

gilled and oven-broiled tilapia (Mangala) due to its increased

availability and affordability. Lately fish is becoming the

predominate protein served at events and parties, it is gradually

replacing meat in urban centres due to high satisfaction obtained

from its consumption, it’s relatively cheaper than poultry as well

as healthier when compared to beef,mutton and even pork and

it’s highly patronized by the middle class. Therefore, increasing

popularity of this has provided a favorable market for fish hence

aquaculture is now seen as an essential aspect of the food sector

development agenda. An aquaculture policy which has been

proposed has much focus on increasing yields and improving

market access with a view to raise production and thus grows

income for poverty alleviation (Directorate of Fisheries, 2004).

Nutrient value of fish in diet

Since fish is one of the most affordable animal protein, it has been

playing the role of providing quality protein in the diets of both

the young old. When compared to meet protein, fish protein has

lower fat content and is more easily digested, therefore more

preferred. Fatty acid from some fish belong to the omega-3-

group, thus possessing desirable health benefits for consumers

particularly children and the aged (Bourer, 2011). The low fat

content of fish, makes consumers, stand a lower risk of

cardiovascular disease and obesity. Generally, sea food is

regarded as a rich source of minerals which is especially good for

children. Therefore, it is recommended that fish be incorporated

into diets of children (infants) during formulation in order to

facilitate development and growth.

Fish handling and steps of fish spoilage

Handling of fish involves all activities from the catch until the

product (fish) gets to the final consumer. Handling of fish could be

grouped into wet fish handling and processed fish handling Wet

fish handling involves all the activities such as grading or sorting,

removal of scales, gutting etc. Good handling entails adopting

techniques that will halt or delay the natural spoilage of fresh fish.

It is therefore expedient to process fish immediately it is caught

or perserved until it is retailed fresh or processed because high/

warm temperatures of typical tropical environment can enhance

and hasten the rate of fish spoilage due to autolytic and bacterial

actions. Furthermore, bad handling such as leaving the fish in the

sun allowing fishes get in contact with filthy or unhygienic

materials or bruises specially the pelagic species enhances fast

spoilage (Agbabiaka , 2014).

Signs of fish spoilage

Soft muscles leading to permanent indentation, on the body of

fish when pressed, pale or white coloured gills, copious or plenty

slime on the body of fish, putried or offensive odours , sunken or

cloudy eyes a dull or discoloration of the skin are all signs

(physical) of fish spoilage

Water activity and its role in fish spoilage

Micro-organisms have an obligatory demand for water, for without

water no growth can occur. Each microorganism has a maximal,

optimal and minimal water requirement represented as a w.

Fish is an extremely perishable food commodity due to its high

water content. as the available water or water activity (a w) is

reduced below the optimal level, there is a lengthening of the lag

phase of growth, a decrease in changes occurring in the organism

or cell and a decrease in the amount of solute concentration in

the solvent employed to reduce the water activity or water

content of the fish (Nwachukwu and Nwaka, 2015). Therefore, an

increase in water activity (aw) or water content in fish favour quick

fish spoilage while a decrease retards spoilage.

Signs of fish spoilage

Rancidity

This is the process of complete or incomplete oxidation or

hydrolysis of fats and oils when exposed to air, light or moisture

or by bacterial action, resulting in unpleasant taste and odours. It

is the hydrolysis or oxidation of fats into short chain aldehydes

and ketones, which are objectionable in taste and odour (Erich

and Gert-Wolfhard, 2002).

When these processes occur in food, undesirable odours and off

flavour can result. However, in certain cases, these rancid favors

can be desirable (as in aged chesse). Alfred, (2005), in processed

meats, these flavours are collectively known as warmed-over

flavor. Rancidity can also detract from the nutritional value of

food as some vitamins are sensitive to oxidation (Termes, 1990)

there are three recognized pathways for rancidity of interest to us

and they are; hydrolytic rancidity, oxidative rancidity & microbial

rancidity.

Methods of fish processing

Traditional methods of fish processing in Nigeria

Cooking or boiling

Boiling or cooking of fish is another technique in fish processing

which can prolong the shelf of the fish. The fish to be boiled is

first gutted, scaled if any then gills and fins are removed. The fish

is also thoroughly washed with sufficient clean water, cunt into

chucks prior boiling (Nwachukwu and Nwaka, 2015).Fish is cooked

to produce changes in the texture, flavour, water content of the

fish, and to kill pathogenic organisms (FAO, 2005).

Heating fish to an internal temperatures above 66°c or 150°C is

sufficient to kill most spores of the thermophilic bacterial (Pigott,

2015). However, the heating duration should be regulated to

prevent excessive loss of nutrients by much heat, oxidation etc

(FAO, 2005).

Frying

Frying as a techniques in fish processing, is one of the oldest

technique of prolonging the shelf life of fish through the use of

heat and oil by convection. This technique's popularity is related

to the ease and speed of food preparation and sensory features

such as unique aroma, flavor, taste (Ngadi and Xuc, 2009). Frying

as a traditional technique of fish processing is a cheap and fast

process of simultaneous heat and mass transfer that changes the

sensory and nutritional characteristics of the fish as a result of

complex interactions between food and oil (Trazzani and Trystam,

2008). Furthermore, trying is an efficient method of processing

because it reduces the moistures content of the fish as well as

stop microbial action on the fish (Nwachukwu and Nwaka, 2015)

however, frying is known to introduce PAHs into fish since it

involves the use of vegetable oil.

The production of these oils in the industry involves processes

that may result in PAHs formation in the oils which may be used

in frying the fish (Bartle, 1991). Moreover, the vegetables used to

manufacture the oils may be contaminated by environmental

PAHs from the soil.

High temperatures, employed in frying the fish, is sufficient to

start the pyrolysis of fat and proteins in the fish and of the

vegetable oil, leading to PAH formation. However, extended

surface frying (30- 40 mins), has been found to generate

mutagens. At moderate temperatures,deep-frying for short

periods is the best way to fry fish.

Grilling

Grilling as a technique of processing is characterized by the

application of dry heat directly to the surface of the food, either

below or above it. It uses direct radiant energy (heat) for the rapid

cooking of meat or fish. However smoking and grilling are similar

techniques in processing except that in grilling , only dry heat is

used without smoke , while smoking combines the use of both

heat and smoke to cook fish (European Commission, 2002). Fish

can be grilled using a griddle.

Smoking

Smoking is a popular traditional method of fish processing and

preservation in Nigeria and most developed countries. Smoking

combines the effect of the destruction of bacterial present in the

fish by compounds in the smoke (e.g, phenol) and the cooking of

the fish's flesh since high temperatures will be utilized and

generated from the energy source (wood, saw dust, charcoal etc

(Nwachukwu and Nwaka, 2015). Smoked fish products have long

shelf- life which has been attributed to the drying, antimicrobial,

antioxidant and cooking effect of the smoke and energy source.

During smoking the wet surface of the fish, absorbs the smoke

and obtain a characteristics aroma (Tawari and Abowei, 2011). As

it is frequently seen in fish markets properly smoked fish products

tend to possess a characteristics dark brown coloration, hence

ensuring the product gets to the final consumer in relatively good

state with a prolonged shelf (FAO, 2005).

Furthermore, smoking can be cold smoking or hot smoking

(Agbabiaka, 2014).

Hot smoking

Hot smoking is a traditional smoking method using both heat and

smoke. It is a common practice in developing countries in Africa

which involves placing the fish on the wire gauze and placed in

direct contact with the heat source, hence the fish is cooked

(Agbabiaka, 2014). The fish is smoked at temperatures that is

high enough and for a period sufficient to obtain heat and

eliminate microbial contaminants. However, since hot smoking

entails addition of flavours to the fish as well as thoroughly

cooking its flesh, the fish can be consumed without further

cooking (Blackwell, 2014).

However, the partial combustion of wood due to limited supply of

air, results in the production of smoke, which contain many

chemicals from the wood including PAHs. The PAHs formed from

the wood during incomplete combustion, deposit on the flesh of

the fish from the smoke passing over it. Smoking is also employed
in Portugal in the production of dry fermented sausages and to

obtain unique sensory properties as a result of the phenol

derivatives such as carbonyls and organic acids in foods.

Combustion or Burning

Combustion or burning is a high temperature exothermic redox

chemical reaction between a fuel (the reductant) and an oxidant,

usually atmospheric oxygen, that produces oxidized, often

gaseous products , in a mixture termed as smoke . fuels for

combustion can be sold (wood coal), or liquefied gases e.g

(propane)or liquid (ethanol, petrol, kerosene diesel etc). However,

during combustion, the smoke may contain toxic substance

Combustion can be classified into;

Carbon monoxide

Carbon monoxide (Co) is one of the product from incomplete

combustion (Greenfact, 2001) carbon is released in the normal

incomplete combustion reaction, forming soot. Since carbon

monoxide may lead to respiratory troubles when inhaled since it

takes place of oxygen and combines with haemoglobin to form

decarboxyhaemoglobin in the blood.

Wood smoke and its composition

Smoke applied to fish and other foodstuff is a physical process

which involves diffusion, absorption and dissolution

(Douben,2003). The chemical processes involved in smoking

facilitate the interaction of the smoke with food components

(Zakaria et al., 2002). Several analyses over the years have

established a few fundamental concepts of the formation of

smoke and its application. The energy source mostly used for

smoking (wood) is made up 3 basic polymer, cellulose,

hemicellouse and lignin (Douben, 2003). Chemical bonds hold

these three polymers together and the formation of smoke is

imitated by the breakdown of these chemical bonds using

chemicals energy (Amos et al., 2013).

Furthermore quiet a number of compounds existent in wood are

released during combustion (Yusuf et al., 2015). It has been

shown that about 300 compounds exist in wood and a number of

these are deposited into smoked foods (Fleter, 2004).

Some of the most important compounds to be found in woods are

phenols, alcohols, lactones, carbonyls, furans, esters and

polycyclic aromatic hydrocarbons (Zakarai et al., 2002). Smoking

imparts some desirable characteristics into food namely; flavour

and colour.

However , some volatile compounds such as formaldehyde,

phenols etc. have been proven to posses bactericidal effects,

making it adavantegous. efficacy against bacteria, moulds and

some viruses has been attributed to formaldehydes though

smoke components are not effective against spore forming

bacteria and has been reported that the lingering effect is

stronger against bacteria than moulds (Zakaria et al., 2002)

Polycylic Aromatic Hydrocarbons (PAHs)

Polycyclic Aromatic hydrocarbons, can be defined as a group of

chemicals produced during incomplete combustion of organic

substance such as wood, coal oil, garbage etc. they are composed

of a group of organic compounds which posses at least one or

more aromatic rings joined together (Simko, 2002) PAHs are fat

soluble and chemically stable compounds which may be

carcinogenic or non carcinogenic. Furthermore, they are

pollutants of the environment and greatly affect the food chain.

PAHs found in diets usually originates from processing and

preparation of foods, if it involves smoking, drying and cooking

(Cypel et al., 2012). PAHs from the environment and various

treatment used in food preparation may be of other source (Yusuf

et al., 2015). The characteristic low solubility of PAHs in water is

due to their lipophilic nature. Moreso, they have the ability to be

absorbed on surfaces, thus explaining how they adhere to

smoked meat and fish. However, upon absorption or dissolution,

PAH undergo photodecomposition in the environment, using the

ultraviolet radiation from the sun (Goulas et al., 2015). Data from

warshawsky (1999) concerning PAHs have shown that they trigger

numerous health hazards such as haemotological, hepatic,

immunological, genotoxic and carcinogenic effects.

Formation and nature causes of PAHs

At temperatures of 100-150°C, PAHs can be formed as a result of

natural aromatization (Liu et al., 2009). A variety of activities

involving the incomplete burning of organic matters, however can

result in their artificial synthesis. Various PAHs are formed

differently based on the environmental conditions and organic

matter involved. Polycyclic Aromatic Hydrocarbons are generally

synthesized with organic matters or raw materials via the process

of aromatization. Subjection of organic matter to strong heat and

pressure will evolve PAH. Therefore, it is worth noting that PAHs

can be artificially synthesized .

Furthermore, PAH can spontaneously form in nature without

human interferences. Therefore a high deposit of organic matter

can be generated as waste due to human activities, however

upon the accumulation of these organic matter or waste in hot

parts of the earth's crust , which is characterized by high

temperatures and pressures called pyrolysis (Cypek et al.,

1995),these unstable molecules, combine to form much more

stable compounds named PAH. A process known as

pyrosynthesis.
Sources of PAHs

The source of PAHs vary coming from natural and man-made

activities that prompt their creation, hence they can be ordered

according to how they are produced. Whether natural or artificial

occurrence in the environment. Forests are composed of natural

matter (trees, grasses etc) and upon partial burning of the natural

matter by flames (fire), there is a possibility of the production of

PAH which could be dispersed into the atmosphere through air as

agent of dispersal or buried in the soil as fossil.

One noteworthy ecological source of PAH is petroleum and fossil

fuels. This is because of urbanization and industrialization which

demands on the provision of energy. However not only is fossil

(petroleum) an energy source, it also serves as a raw material for

plastic industries. therefore an incredible extent of plastics

recycling in the environment is made from petroleum source and

in this manner a potential source of PAHs.

In the presence of high temperatures or ionizing radiation, for e.g

microwaves, these plastics forms radicals and can recombine with

oils in food they contain to produce PAHs. Contaminant levels of

PAHs, were found to also be produced from exhaust of vehicles

(IKINS, 1994)

Classification of PAHs

PAHs are classified based on a couple of factors such as size and

genotoxicity. PAH is made up of a maximum of four benzene rings
fused together which are known as light polycyclic Aromatic
Hydrocarbons whereas those characterized by benzene rings
greater than four are described as heavy PAH. Light PAH when
compared to the heavier ones, are more volatile, water soluble
and less lipophilic (Ferrarese et al., 2008). However heavy
polycyclic Aromatic Hydro carbons are more stable and toxic than
the light ones. Furthermore, in risk assessments, PAHs are mostly
treated as being similar because they are usually found as
mixtures and their structures and toxicity are related.

Although PAH are mostly discussed as group, the individual

chemicals are isolated when it comes to risk characterization
genetoxicity - based classification comprises four groups B2, N/a,
D and E with the group B2 having carcinogenic activity . The
USEPA has named seven chemicals to be of the B2 group (EPA,
1993) with the classification of the system adapted by the
international Agency for research on cancer (IARC) in agreement
to the outcome to the outcome of various research. However it
must be noted that PAH which are unclassified may be
carcinogenic also hence must not be assumed as non-
carcinogenic (USEPA class E).

Health implication of Polycyclic Aromatic Hydrocarbons

A carcinogen is any chemical that can cause mutation and lead to

cancer. PAHs have turned out to be a menace due to

carcinogenicity. Carcinogens are known for their ease in forming

free radicals which initiate chain reactions of radical formation in

the cell leading to destruction of the control mechanism of the

cells ultimately resulting in metastasis. The destruction of the

cells control mechanism results in uncontrolled cell growth

leading to the formation of cancerous tumors and lesions.

B2 - classified PAHs have been implicated in a number of cancer

cases and have become a priority in the discourse of food safety

and quality management. Cancer management is difficult

particularly in the advanced stages and quiet expensive as well.

Health effects of polycyclic Aromatic Hydrocarbons

Though the immediate health effect of PAHS are unclear in

humans, observations have been made concerning occupational

contact with high levels of pollutant mixtures containing these

group of chemical these include nausea, vomiting , diarrhea, eye

irritation etc.

It has not been established which of the constitutions of the

mixture were responsible for that effects. The fact that PAH

mixtures can cause skin irritation and inflammation has been

established in humans and animal. Anthracite, benzo (a) pyrene,

and benzo (a)pyrene cause allergic reactions in animals and

humans (skin sensitizers).

Exposure to PAHs on a long term basis have known effects such

as damage to the liver, kidney and jaundice. Prolonged skin

contact with PAHs may cause inflammation and reddening of skin.

Naphthalene, if ingested or inhaled in large quantities can cause

haemolysis. Lung cancer and cancer of the stomach resulting

from the long period of exposure through inhalation and ingestion

respectively have been observed in animals (Nisbet etal, 1992).

Furthermore, lung dysfunction, chronic bronchitis and lowered

immune response are known to be implicated to exposure to PAH

mixture and other workplace chemicals over a long term study of

workers.

Incidence of skin cancer, long cancers gastrointestinal and

bladder cancers have been observed (Ramesh et al.,2004).

Determination of PAH in facts

The traditional approach to determining the occurrence of PAHs in

fish samples is a three step approach which begins with
extraction, followed by purification then finally, analysis.

SOURCES & ROUTES OF CHEMICAL CONTAMINATION IN

FISH AND OTHER NON-FISH PRODUCTS

Toxic and non toxic chemical contaminants end up in our states

water bodies in different ways. Industrial and municipal

discharges, obnoxious fishing practices and storm water runoff

can all put harmful sub stances into water bodies. It is however,

useful to consider the sources of contaminant in order to

understand their pathways into food and water sources for

consumption. Other sources or routes such as soil properties,

activities of people and point sources as listed above, affect the

accumulation of metals in the aquatic environment. For e.g

mining may result in release of substance such as arsenic or

mercury (smedley et al., 2002: Bortey_sam et al., 2015)

Rainfall can also wash down agricultural chemicals or fertilizer

from arable land or air into streams rivers, lakes etc. Hence, fish

in these water bodies, absorbs these chemicals through their skin,

hills and are accumulated In their muscles. Therefore routes or

sources of chemical contamination in fish & non-fish product are

through the following.

Mining of Metals and Metalloids

Metals and metalloids in the environment have various sources.

One source of mercury and lead in the aquatic and terrestrial

environment is artisanal gold mining. For example, the gold

mining area of tongguan & china, concentration of these metals in

locally produced grains and vegetables exceeded governmental

tolerance limits and posed a potential health risk to people from

consumption (Xiao et at., 2017)

Lend and cadmium from iron mine in morocco, resulted in

concentration of cadmium in livestock organs higher than

acceptable limits (Nairi et al., 2016) Likewise, in Spain sheep near

a mine were found to have lead contamination with levels 87. 5%

liver samples above European union Maximum Residue level

(MRL) (Pareja_carrera et al., 2014) Arsenic, selenium, lead and

other metal and metalloid contaminants were found near a coking

plant in china, contaminating the soil and food and detected in

blood samples from children (Cao et al., 2014)

In that case, ingestion of food was determined to be the major

exposure pathway for local children. Thallium from a steel plant in

south china was found to contaminate soil and vegetables, hence

exceeding German standard, for the maximum permissible level

and showing hyper accumulation in plants such as lettuce, chard

and pak choi ( Liv et al., 2017)

However, in the global arena, methylmercury has been detected

in fish and other sea foods around the world (Frery et al., 2001;
peng, 2016)

Various metals have been detected in fish from Sicily, with some
concentrations exceeding European regulation limits (Copat et al.,
2012). The side effects of these chemicals depend on the
chemical concentration, length of exposure and the contaminated
species); these chemicals for example may have effects on the
reproductive or immune systems or increase risks of cancer (Li et
al., 2006).

Organochlorine pesticides such as Dichlorodiphenyl

trichloroethane (DDT) has been used in agriculture and vector-
transmitted disease control for decades, though their use is
restricted due to known persistence in the environment and toxic
effects such as neurological dysfunction and endocrine disruption
(UNEP,2001).

Permethrin and deltametrin are widely used for control of vectors

and aircraft disinfection as they are relatively safe for people
(WHOPES, 2005) However, their use near foods can result in
contamination and studies are ongoing to reduce potential toxic
effects.

POLYCHLORINATED BIPHENYLS (PCBs) have a variety of uses

in industry, including in transformers, as heat exchange fluids, or
paint additives or in plastics. Ingestion of PCB residue
contaminated food -especially meat, fish and poultry is the main
source for people with ready absorption from the gastrointestinal
tract (WHO; ATS DR, 2000)

ACRYLAMIDE occurs in many foods-generally associated with

high heat cooking processes (e.g in bread and baked or fried
potatoes) and acrylamide is also manufactured for commercial
and industrial use (such as in paper and dye production, in waste
water treatment and as a chemical grouting agent (kumar et al.,
20018).

The international Agency for Research on cancer (IARC) has

classified acrylamide as a probable human carcinogen, placed in
group 2A since 1994 (IARC, 2018).

PHARMACEUTICALS AND PERSONAL CARE PRODUCTS.

This includes a wide range of substances that may find

themselves in the environment and hence food or water sources.

Antimicrobials and other drugs may originate from use in both

humans and animals. For example, swine wastes, containing
antimicrobials, may contaminate both water and sea food (FIE,
Ying and Liu, 2016).

RADIOACTIVE ELEMENTS

Most radioactive elements do not exist naturally and hence soil

contamination with materials have only become a problem since
by a development of nuclear ammunitions (Walker etal., 2013)

Furthermore, after the fukushima nuclear plant was wrecked by a

tsunami in Japan, in 2011, monitoring of food & water samples
detected contamination above provisional regulation values and
restrictions were put in place (Flamada et al., 2012)
Radionudeotides have also been detected in sea food in india,
various foods in Balkans and food and drinking water in
Switzerland (Khan et al., 2011; Carralhoet et al., 2011).

Risk assessments are conducted to ensure that levels remain

within acceptable limits. In the US, there is an FDA rule pertaining
to uranium, radium, alpha particles etc in bottled water (FDA,
2003). Indiscriminate dumping of these wastes in classified area
of the sea, can result to radioactive, contamination of aquatic
lives, accumulate in their tissues and flesh over time and can be
taken up by man when such fish is caught and eaten.

ELECTRONIC WASTE

Our society has become grossly loaded with various types of

electrical devices as well as electronic waste has become a major
problem.

Inappropriate disposing of electronic wastes by combustion

instead of recycling of such electronic wastes, could lead to the
release of a variety of pollutants such as PBDEs, (Polybrominated
biphenyl ethers), dioxins, furans, PAFIs, PCBs, metals and
metalloid into the environment (WONG et al., 2007) Furthermore
indescrimate dumping of these electrical gadgets into water
bodies could contaminate drinking water and food (Liu et al.,
2009) hence the need for recycling.
PLASTICS

Recently, due to rapid development in science and technology,

there is excessive reliance on packaging materials-in particular
plastics to transport and help preserve food. These packaging
materials are not inert and may themselves contaminate food and
drinks as multiple chemicals from these plastics are released into
the food and non food products they contain. Such chemicals
include phthalate plasticizers, have been detected in bottled
water (Zara et al.,2015) However, factors such as higher storage
temperatures and prolonged contact time with the packaging
materials were linked to higher levels of contamination, but a
health risk assessment showed that the risks for consumers was
low (Zare et al., 2015)

QUALITY AND SAFETY STATUS OF TRADITIONALLY SMOKED

FISH

Traditionally smoking involves treating of pre-salted, whole or

filleted fish wood smoke in which smoke from incomplete wood
burning comes into direct contact with the product. This has been
found to contaminate smoke fish with polycyclic aromatic
hydrocarbons (PAHS) if the process is not adequately controlled or
if very intense smoking procedures are employed (WHO, 2006).

Several analyses of charcoal roasted / grimed common fish have

proven the presence of PAHs(Linda et al., 2011) some of the PAHs
have been found to be carcinogenic while some are not
(Borokovcova et al., 2005) Emerole et al (1982) screened for the
presence of PAH in local foodstuff available in the Nigerian
Market. They discovered that appreciable amounts of Benzo [a]
anthracene and Benzo [a] pyrene were found present three
varieties of smoked fish and smoked meat (suya) purchased from
a popular market in Ibadan, Nigeria.

In a recent study carried out by Olabemiwo et al. (2011) to

assesses the PAHs content of two smoked fish species available in
Western Nigeria, it was found out that the sum of all PAHs in the
smoked fish (Clarias garriepinus and Tilapia guineensis ) ranged
from 0.497- 0.814pg/kg and 0.519- 0.772 pg/kg, respectively.

High levels of PAHs have been reported to be associated with the

dark colorations in intensively heated products and this was
supported by ova and Onaran (1998), who reported that PAHs
values were higher on fish skins than the flesh.

Adeyeye et al. (2015b) also reported that traditional drumO

smoked samples had high B a P and PAH levels of which 5, out of
the 6 major PAHs, Exceeded the EU maximum permissible level of
5.0 pg/kg for BaP). In addition, the hazardous effect of aflatioxin
contaminated feeds on fish health and production have been
documented (Zaki et al., 2008).

Inspite of the available data on aflatoxin contamination of various

foodstuffs and other livestock feeds, and the associated health
implication little or scanty data exists on the occurrence of
Aspergillus specie and Aflatoxins in fishes in Nigeria and South
Africa the fact that fishes are widely consumed in Nigeria due to
their high nutrient profiles Adebayo-Tayo et al. (2006) had
reported the presence of Aflatoxigenic fungi in high
concentrations in smoked dried fish for sale in Uyo markets in
Akwa-Ibom State.

FOOD SAFETY-RISK ANALYSIS

A food safety-risk analysis is essential not only to produce high

quality product to ensure safety and protect public health but also
to comply with international and National standards as well as
market regulations. Food safety risk analysis focused on major
safety concerns in production premises,sometimes especially for
complex analysis, regular staff hygiene (Government of Alberto,
2012).

Important Concepts in Risk Assessment

Risk: Risk is a function of the relative likelihood of the occurrence

of an adverse health effect and the severity of that effect, as a
result to a hazard(s) present in that food (FAO, 2004)

Risk Analysis: Risk analysis according to Codex Alimentarius

Commission, is a process consisting of three components, viz risk
management, risk assessment and risk communication (WHO,
2010;FAO,2010).
RISK ANALYSIS FRAMEWORK

Risk management

For the purpose of Codex Alimentarius Commission, risk

management is the process,distinct from risk assessment, of
weighing policy alternatives, in consultation with all interested
parties, considering risk assessment and other factors relevant for
the health protection of consumers and for the promotion of fair
trade practices and if needed, selecting appropriate prevention
and control options (WHO/FAO, 2010).

Risk Assessment

As stated by the Codex Alimentarius Commission and adopted by

the International Food Safety Commissions(IFSCs), food safety risk
assessment is the scientific evaluation of known or potential
adverse health effects resulting from human exposure to food
borne hazards(WHO, 2015).A proper risk assessment consists of
the following

Hazard Identification:

This is the identification of biological, chemical and physical

agents capable of causing adverse health effects and which may
be present in a particular food or groups of food. Hazard
identification is often considered as the most inportant step in a
risk assessment as an Unidentified hazard in the early stage of
processing products can cause devastating effects (NFSA/WHO,
2010).

Hazard Characterization

Hazard Characterization is the quantitative, qualitative or a

combination of the both's evaluation of the nature of the adverse
health effects associated with biological, chemical and physical
agents which may be present in food. For chemical, biological or
physical agents, a dose response assessment should be
performed if the data are obtainable. In this stage of
characterization, risk assessors should describe the nature and
extent of the adverse health effects known to be associated with
the specific hazard. Using toxicity studies and epidemiological
data, a response relationship should be established between
different levels of exposures to hazard and the probability of
different adverse health effects (NFSA/WHO, 2010). Further more,
the Directorate of Fisheries in Iceland has started work on risk
categorization of the fish industry and of other establishments.
The evaluation was done according to a Danish model
(Fodevarestyrelsen, 2006)and its based on six categories.

Exposure Assessment

Hazard exposure assessment is the qualitative and/or quantitative

evaluation of the likely intake of biological, chemical and physical
agents via food as well as exposures from other sources if
relevant. This assesement assessment characterizes the amount
of hazards that is consumed by various members of the exposed
population. Taking into account the food consumption patters of
the target populace and levels of hazard in all steps of the
production process. And exposure assessment examines the
exposure to the hazard over a particular period of time in foods
that are actually consumed (NFSA/WHO, 2010)

Risk Characterization

Is the qualitative and/or quantitative estimation, including

attendant uncertainties of the probability o the occurrence and
severity of the known or potential adverse health implication on a
given population based on hazard identification, hazard
characterization and exposure assesement (NFSA/FAO, 2010).

Risk Communication

Risk communication is the interactive exchange of information

and opinions throughout the risk analysis process concerning
hazards and risks, risk - related factors and risk persceptions
among assessors (WHO/FAO, 2010)

HAZARD ANALYSIS AND CRITICAL CONTROL POINT

(HACCP)
 Is a systematic preventive approach (concept) to food safety
from biological, chemical and physical hazards in food
production processes to ensure the safety of food by
reducing these hazards to acceptable safe level. Thus, this
approach emphasises the prevention of hazards at all the food
production stages of a food chain rather than the tradition of
analyzing the finished food product (i.e. postmortem
approach). It therefore focuses on microbial/hazard control of
foods from farm to table (a total quality management
approach). HACCP was conceived in the 1960s when the US
National Aeronautics and Space Administration (NASA) asked
Pillsbury (a major food company in the US) to design and
manufacture the first foods for space flights. Since then,
HACCP has become adopted by the food industries and
recognized internationally by government regulatory agencies
and FAO/WHO (Efiuvwevwere, 2012; FAO, 2014).

FOOD PRESERVATIVES/ADDITIVES

These substances (additives) that are used as food

preservatives must be approved by regulatory agencies (e.g.
the Joint FAO/WHO Codex Alimentarius Commission of the
United Nations, US Food and Drug Administration, NAFDAC
and others). They are often referred to as “Generally
Regarded As Safe” (GRAS). They are added to food to
serve as essential aids in food processing, making food more
attractive (e.g. Chicken, bacon), enhancing the keeping
quality and shelf-life, reducing microbial growth and
minimizing food safety risks (public health hazards etc). The
necessity for use of preservatives in foods is better captured
by this quote “Food, one assumes, provides nourishment: but
Americans eat it fully aware that small amounts of poison
(preservatives) have been added to improve its appearance
and delay its putrefaction (spoilage)” (Cage, 1990 American
avant-gardecomposer,1912-1992).
(www.quotesdaddy.com/author/John+cage). Thus, the choice
between consumption of approved preservatives versus
consumption of harmful/toxic microorganisms is bcoming
clearer in the light of more recent scientific findings.
However, most consumers prefer consuming food containing
small amounts of approved and effective preservatives. This
was the main reason for introduction of sodium nitrite in
the production of bacon and some other meat products
(although its use has been questioned recently due to its
carcinogenic potential).

Some examples of food preservatives, their

concentrations and usage
Preservatives Usage Food Affected
level

Sorbic acid/sorbates 0.2% cake-syrups, Salad

dressing cheese

Benzoic acid/benzoates 0.1% tomato-paste, soft-

drink,margarine,Salad
dressing

Sulphur dioxide/sulfintes 200- Molasses,fruits,wine

300ppm products

Ethylene/propylene 700ppm Fumigants,spice, nuts

oxide

Sodium Nutrition, 120ppm Meat curing, smoked fish

(sodium berizoate or
potassium sorbate

Source: Jay, 1996

NATIONAL AND GLOBAL PERSPECTIVES ON FOOD SAFETY

The importance of food microbiology in national and global food
standardization is effected through the working of the Codex
Alimentarius Commission (CAC) of the joint FAO/WHO Food
standards programme of the United Nations. CAC was established
in 1962 by FAO and WHO and held its first session in 1963 in
Rome. The main goals of the commission are to protect the
health of consumers and ensure fair practices in the international
food trade {WHO/FAO, 2008}. CAC is recognized by the World
Trade Organization as an international reference point for the
resolution of disputes concerning food safety and consumer
protection especially in the twenty- first century (FAO/WHO,
2008).Nigeria is a signatory to this commission by the virtue
of her membership of the United Nations. The country is
usually represented by delegates from the National Agency
for Food and Drug Administration and Control (NAFDAC) and
the Standard Organization of Nigeria (SON). Harmonalisation
of respective national food standards by the CAC is one of
her major responsibilities. However, foodborne diseases are
widespread and growing public health problems with the
recognition that food is a major vehicle of food borne illness
both in developed and developing countries (WHO, 2005). In
industrialised countries, the percentage of people suffering
from foodborne diseases each year has been reported to be
about 30% (WHO, 2005). Several guidelines (Articles) have
been adapted to help minimize or prevent incidences of food
borne illness on global scale (CAC, 2010).
The international food trade is on the increase as countries rely
on the harmonization of food standards by CAC and other
agencies such WTO. However, the United States is not sitting on
its oars (laurels) especially since the incidence of food borne
diseases is 1 in 6 Americans suffers from food borne illness
annually resulting in 128,000 hospitalizations and 3,000 deaths
per annum (CDC, 2011). This is marked improvement because the
earlier statistics was 76 million cases of foodborne diseases
resulting in 325,000 hospitalisations and 5,000 deaths per annum
(WHO, 2005) and this could be attributed to the creation by
President Barak Obama in 2009 of Food Safety Working Group
(FSWG) as a central coordinating mechanism for the United States
Federal Government Food Safety activities headed by the
Departmentt of Health and Human Services with other agencies
such as USFDA, Food Safety

and Inspection Service (FSIS), Centres for Disease Control

(CDC) and Prevention, EPA etc.

FOOD STANDARDS/SAFETY: INTERNATIONAL FOOD TRADE

AND GLOBALIZATION

The issue of food standards, food safety and globalization is

now a major concern to the global community (WHO, 2014).
Whereas the US encourages free international food trade, the
regulatory agencies ensure that the standards are not
compromised. As a result of the FSMA, USFDA will now focus
on import safety tool which states that “Food importers will
be responsible for providing documented assurances to
USFDA that the food they import has been produced under
the same prevention-oriented standards as domestic food’’.
This is to prevent occurrence of food borne illnesses and
ensure food safety. Furthermore, US Congress has directed
USFDA to establish new prevention oriented standards for the
food industry that imported food meets the SAME MODERN
STANDARDS as domestically produced food. Whereas
globalization has its own merits and demerits, most
developing countries appear to be disadvantaged since
international trade (including trade in foods) and cross-border
investment flows are the main elements for this integration
(globalisation). However, some major challenges are apparent
for developing countries as indicated in USFDA requirements
based on the Food Safety Modernisation Act for food imports.
This is particularly obvious when quality assurance system in
the food sector (i.e involving food producers and
manufacturers) are not in place. Thus, much needs to be
done so that all countries can take full advantage of the
new opportunities (liberalization) for international food trade
in order to achieve the comparative advantages in each
country.

FOOD SAFETY LEGISLATION IN NIGERIA

The key determinants of food safety and safety of those

producing and processing food are “the procedures, standards
and regulations (or lack of) for food production,
manufacturing and packaging” (Ericksen, 2008). Therefore,
controlling food safety is an important component of urban
food system governance. Like many other developed
countries, Nigeria is facing the challenges of supplying its
affluent population with adequate food supplies. To this end,
there is successful promotion of policies and programs aimed
at boosting agricultural and food production. The food safety
problem, however, presents a more d aunting challenge. Like
several other nations, Nigeria has to deal with the issue of
foodborne diseases with the related social, economic and
health cost s. The lack of or insufficient use of Good
Agricultural Practices (GAP) and the exploitation or misuse by
farmers of agrochemicals and during storage in developing
countries had serious health effects on the population.
Certain unsafe practices include the use of pesticides for
farming, improper application of pesticides to stored goods
such as beans and gr ains to avoid infestation by insects,
inappropriate use of chemicals to ripen fruits such as
bananas or vegetables such as carrots and cabbages for
insec t infestation control (Omojokun, 2013). Similarly,
improper use of food additives such as artificial sw eeteners,
butylated hydroxyl anisole (BHA), nitrates, nitrites, food
colours, etc. may contribute to various conditions ranging
from gastrointestinal dis cancer and death. Many packaging
materials are still used in rural Africa with toxic degradable
products that are no longer in use in developed countries.
Another issue of concern during food processing is the
partial or complete loss or elimination of nutrients. Another
cause of health concern is the inadequate digestibility or use
of nutrients a nd the development of new potentially harmful
chemicals resulting from poor processing and handling
practices (Omojokun, 2013). Therefore, to ensure food safety
and quality for domestic consumption and export, necessary
and proactive steps must be taken. This is because food was
recognized internationally not only as a biological necessity,
but also as an economic and political necessity. In cultures
and countries, it is always a potential source of socio-
political problems. Consequently, an effective national food
safety policy would ensure that the food supplied to
consumers is sufficient, nutritious, of good quality and
balanced (Omotayo and Denloye, 2002). The Federal
Government of Nigeria initiated the National Policy on Food
Hygiene and Safety in 2000 as an integral part of the
Nigerian National Health Policy in recognition of the value of
food safety as an important factor in achieving a high level
of health for all Nigerians. The overall objective of this policy
is to achieve high level food hygiene and safety practices
that promote health, control food borne diseases, reduce
and eliminate the risk of illnesses associated with poor food
hygiene and sa fety. The policy aims at stimulating and
encouraging food laws in the areas of
production,storage,handling, manufacturing, preservation,
transportation, transport and marketing. It also seeks to
improve the quality of healthcare by ensuring that all food
consumed in Nigeria, whether imported or exported, is
wholesome, safe and contaminant free to consumers. The
implementation of the policy is aimed at addressing the
unsatisfactory level of food hygiene and safety practices that
are largely responsible for the prevalence of foodborne
diseases. in Nigeria (Omotayo and Denloye, 2002). The National
Food Safety Policy provides for the establishment of a National
Committee on Food Safety that draws its membership from the
public and private sectors related to the production, storage,
processing/preparation, distribution, transportation and sale of
food intended for consumption.

Key Actors in Regulating and Monitoring of Food Safety

Standards and Pactices

 The Federal Ministry of Health (FMH)

 The National Agency for Food and Drug Administration and
Control (NAFDAC)
 Standards Organization of Nigeria (SON)
 Federal Competition and Consumer Protection Commission
(FCCPC)
 CHAPTER THREE

MATERIALS AND METHODS

Study area and samples procurement:

The research work will be conducted in the Department of

Fisheries Technology in Federal Polytechnic Nekede, Owerri West

L.G.A Imo State.

Collection and transportation of fish samples

Two species of fish ( Clariasgariepinus and Scomber scumbrus)

will be procured and used for this research.

A total of 48 traditionally smoked fish samples (a pair of Clarias

and Scomber each) will be purchased from six (6) notable fish

markets (Orji, Akwakuma, Ihiagwa, Ekeonuwa, Emekuku and

Obinze) in Owerri,Imo State.

Fish samples will be placed in aseptic containers, immediately

after procurement. The aseptic containers containing the

procured fish samples will be placed in coolers containing ice

flakes in order to prevent interaction of atmospheric oxygen with

fat in fish which may result to rancidity and spoilage prior

transportation to the lab for analysis.

Method for Analysis

- The smoked fish procured and collected will be analyzed for

the determination of the concentration of PAHs using the gas

chromatographic system.
- Other relevant procedures undertaken in determining the

levels of PAHs in smoked fish will be detailed and results from

samples outlined in tabular form.

Samples Preparation

The smoked fish samples will be prepared in two stages.

The first stage will involve extraction using a laboratory blender

while the second stage will entail the use of chemical reagents for

dissolution of homogenized samples prior analysis.

Gas chromatographic analysis

The solution prepared from the various fish samples using

standard chemical reagents, will be assessed for PAHs, using the

gas chromatographic separation techniques on an Agilent 7890A

gas chromatograph system, coupled with a flame ionization

detector (FID).

luL of the solution prepared from the various fish samples will be

injected into the inlet split less mode onto a 30m X 320iym fused

capillary column.
Furthermore, Helium gas will be used as a carrier gas at constant

pressure of about 27psi. The injection temperature will be set at

about 270°C, while the temperature of the column will be initially

held at 60°C per minute. Ramp 1 & 2 will clock 210 °C at 12 °C/

min and 320°C at the rate of 8°C/min according to (AOAC, 2010)

Statistical Analysis

Data to be collected will be subjected to one-way Analysis of

Variance (ANOVA) procedure using SPSS 20.0 for Windows. And

difference between means value of treatment determined at

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