COMPARATIVE ANALYSIS OF HEAVY METALS IN RED SNAPPER FISH IN

MBO AND IKO RIVER

BY

ETUKUDO, ABASIAMA ANSELEM

AK16/NAS/BIO/126

SUBMITTED TO

THE DEPARTMENT OF MARINE BIOLOGY

FACULTY OF BIOLOGICAL SCIENCE

AKWA IBOM STATE UNIVERSITY

AKWA IBOM STATE

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE AWARD OF

THE BACHELOR OF SCIENCE DEGREE (BSC) IN MARINE BIOLOGY

MAY 2023
 DECLARATION

I hereby declare that the project work entitled “Comparative Analysis Of Heavy Metals In Red snapper Fish in Mbo and Iko
River”. Submitted to the Akwa Ibom State University, is a record of an original work done by me.

…………………………………………………….

ETUKUDO, ABASIAMA ANSELEM

AK16/NAS/BIO/126

Certification

This is to certify that this project titled “Comparative Analysis Of Heavy Metals In Red snapper Fish in Mbo and Iko
River”. Carried out by ETUKUDO, ABASIAMA ANSELEM with registration number AK16/NAS/BIO/126 in the
Department of Marine Biology (B.Sc.) degree in Marine Biology, Akwa Ibom State University.

Etukudo Abasiama Anselem _________________

StudentSignature/Date
Dr. Mrs. Mary Ekanim _________________

Supervisor Signature/Date

Dr. Ini-Ibehe NabukEtim_________________

Head of DepartmentSignature/Date

_____________________ ________________

External ExaminerSignature/Date

DEDICATION

I dedicate this project work to the Almighty God for His grace, strength, and unconditional love. I also dedicate it to my
Mother Mrs. Rebecca Anselem for her immense support and tolerance.
 ACKNOWLEDGEMENTS

I wish to acknowledge Dr Mrs. Mary Ekanim my supervisor, Dr. Ini-Ibehe Nabuk my Head of Department for their
discipline and encouragement throughout the entire process of this work.

My gratitude is expressed to Mrs, Rebecca Anselem who have made this dream a reality. I also acknowledge the staff of
Marine Biology for the assistance they provided in my analysis.

Special thanks to my special friends, Samuel Usoro, Favour Bassey, Abasifreke Ibanga and Joy Linus for their love and
good cheer. You guys have made this B.Sc. journey worthwhile. And to my colleagues and friends who have in one way or
the other shown support throughout this work.

Table of Contents

Chapter one: Introduction

1.1Background Of Study

1.2Statement Of Problem

1.3Aim Of Study

1.4.Objectives Of Study

1.5.Significance Of The Research

1.6.Scope Of Research

Chapter two: Literature review

2.1Biological Classification Of Red Snapper Fish

2.2Heavy Metals
2.3 Related Literature Review

Chapter three: Materials and method

3.1 Study Area Description

3.1.1. Iko River

3.1.2.Ibaka River

3.2.Material Used

3.3.Sample Collection

3.4. Measurement Of Biological Parameters

3.5 Fish Handling and Preservation

3.6.Digestion and Analytical Procedures

3.6.1 Sample Digestion

3.6.2Analytical Procedure

3.6.3Precaution To Be Followed ToAvoid Contamination

3.6.4Statistical Analysis

Chapter four: Result and Discussion26

4.1.1 Physico-Chemical Characteristics Of Estuarine Water26

4.1.2 Ex Situ Parameter/Values28

4.2 Results Of Heavy Metal Test31

Chapter five: Conclusion and Recommendation34

5.1Conclusion34

5.2Recommendation34

References35
Appendices………………………………………………………………………………...…37

CHAPTER 1

INTRODUCTION

1.1 Background of Study

Population increase has been the major drive for industrialization and this has been

helpful to us over the years but the detrimental effects of this are gradually outweighing the

positives because of continuous pollution of the aquatic environment which makes it an

unsafe habitat.

Heavy metal is a dense metal that is most times toxic at low definitions. (Helmenstine,

2021). Heavy metals are elements that have atomic number greater than 20 and atomic

density above 5g and exhibit the properties of metal (Raychaudhuri et al., 2021). Heavy

metals may either be essential heavy metals like Copper (Cu), Iron (Fe), Manganese (Mn),

Cobalt (Co), Zinc (Zn) and Nickel (Ni). or nonessential elements like Cadmium (Cd), Lead

(Pb), Mecury (Hg) and Chromium (Cr) (Raychaudhuri et al., 2021). The emphasis of this

research will be on the heavy metals: Lead, Nickel, Cadmium, Vanadium, Arsenic, Iron and

Mercury as they are the major aquatic bodies pollutant which may be from runoffs, direct

waste disposal, etc. These heavy metals could in turn be detrimental to the end consumers

which are humans.

Fish is becoming increasingly important in the diet of Nigerian as the cost of beef

increases daily. Fish constitutes a great percentage of animal protein intakes in Nigeria at

present.
Most Red snapper are bottom feeders. In general, they may be negatively buoyant, which

means that they normally sink in place of float because of a reduced gas bladder and a heavy,

bony head (Bruton, 2009). Red snapper have a variety of body shapes, although most have

Almond -shape body with a flattened ventrum to permit for benthic feeding (Bruton, 2009)

A flattened head allows for digging through the substrate, in addition to possibly serving as a

hydrofoil. a few have a mouth which can expand to a large size and incorporates no

incisiform tooth; (Bruton, 2009)

Fish are one of the most widely distributed organisms in the aquatic environment and considered as

one of the main protein sources of food for human (Rashed, 2001). Freshwater fishes are similar to

sea water fishes which play an important role in determining resident’s diet (Ahmad et al., 2009).

Heavy metals are an important group of chemical pollutants, whereby food is the main route for

entry into our body; some heavy metals irreversibly are bound to human body tissues, e.g., cadmium

to kidneys and lead to bones (Kaplan et al., 2011). Fish constitute a major source of heavy metals in

food (Sivaperumal et al., 2007). High level of metals in environment may lead to an excessive

accumulation which cause problem to human, animal and plants (Al-Khateeb and Leilah, 2005). Fish

has been found to be excellent indicator for the heavy metal contamination level in aquatic system

because it occupies different food chain levels (Karadede-Akin and Unlu, 2007). A major concern and

attention about the health effects people due to consumption of foodstuff contaminated with

metals were paid (Iwegbue et al., 2008). Heavy metals occur in the environment both as a result of

natural processes as well as contaminants from human beings activities (Franc et al., 2005). Some

heavy metals are known as potentially toxic include arsenic, lead, aluminium and cadmium, others

are essential such as nickel, zinc and chromium (Abduljaleel and Shuhaimi-Othman, 2011). Heavy

Metal has positive and negative effect on human health and surroundings (Abduljaleel et al., 2011).

The accumulation of heavy metals in fish has been extensively studied and well documented.

However, the research has been generally focused on the muscle tissue, while the distribution
pattern among other tissues, such as liver and gills have been mainly neglected (Jaric et al., 2011).

Furthermore, the contaminants also concentrate in some of the organs of fish and can cause lethal

and a range of sub lethal effects (Ozmen et al., 2008). It was known that active metabolite body

parts such as liver, gill and kidney concentrate more on an amount of heavy metal than other parts

like muscle (Dural et al., 2007). Fishes are often seen at the top of the aquatic food chain and may

accumulate large amount of heavy metals from its environment (Mansour and Sidky, 2002). In

addition, fishes are one of the most indicative aspects in freshwater ambience, for the evaluation of

heavy metals pollution and health risk potential of human consumption (Papagiannis et al., 2004)

The concentration of these heavy metals in fish and in marine ecosystems can likely

lead to the ecosystem instability and the fish affected nurseries for their reproduction. Waste

disposal in coastal waters, fuel spills and other pollutants accumulated in the marine

environment causing lack of oxygen, food, shelter or spawning ground for finger fish and

other marine life, thereby affecting to people who live on it for food and income.

1.2 Statement of Problem

Pollution of the marine environment has been a menace that has lingered around for some

time now. With industrialized, poor waste disposal and other man attributed factors has been

contributory to this pollution of the marine environment with this toxic heavy metals. The red

snapper fish is a tasty and highly sought after fish has been unfortunately affected by the

menace of this pollution and as such there is need to scrupulously understand this menace;

the root cause, management techniques as well solutions.

1.3 Aim of the Study

 The aim of this research is to compare heavy metals concentration in Red snapper fish

from Iko and Ibaka fishing terminals.

1.4 Objective of the Study

i. To compare heavy metals concentration in fish (red snapper fish) from Iko and ibaka

fishing terminals.

ii. To ascertain the extent of heavy metal pollution from these two fishing terminals.

iii. To suggest solutions on how to curtail this menace for a healthy aquatic environment

sustenance.

iv. To compare the extent of pollution in the flesh

1.5 Significance of the Research

This research is important because of the present state of pollution in the Iko and mbo

river due to improper waste disposal and other contributory factors and as such this research

will be helpful as it is timely with the aim of making sure a solution is swiftly provided to

ensure the pollution does not metamorphose to a full blown undesirable stage.

1.6 Scope of Research

This research will be limited to the analysis of heavy metal in different part of red

snapper e.g head, skin, flesh and liver.

Only red snapper fish gotten from mbo and Iko River will be analyzed

CHAPTER 2

LITERATURE REVIEW
 In this study, there will be critical evaluation of heavy metals contamination on the

marine environment. This contamination is detrimental to the populace dependent on the

aquatic bodies for food and income.

2.1 Biological Classification of Red Snapper

Kingdom: Animalia

Phylum: Chordata

Class: Actinopterygii

Order: Perciformes

Figure 2.1 The Dentition of a red snapper fish (Source: Getty Images, the Internet)
Figure 2.2 Skeleton of a Red snapper (Source: Getty Images, internet)

Figure 2.3 Red snapper fish (Source: Getty Images, the Internet)
Figure 2.4 Labelled Diagram of a Red snapper fish (Source: Getty Images, internet)

2.2 Heavy Metals

Heavy metals are environmental pollutants because of their toxic nature and bio-

accumulative nature. It can occur through natural curses like weathering of metal bearing

rocks and volcanic eruptions, while anthropogenic sources like mining and various industrial

and agricultural activities (Ali et al., 2019). Heavy metals will be detrimental to human health

as the affected aquatic animals are consumed.

In this research, the heavy metals in consideration are Lead, Nickel, Cadmium,

Vanadium, Arsenic, Iron and Silver.

2.3 Related of Literature Review

Firstly, Kumar et al (2013) researched on A Review on the Detection of Heavy

Metals in Water Bodies, Fish Organs, and Sediment River Bed of which it was highlighted
that the growth of industries near or along the banks of water bodies as a result of

technological advancements is one of the most significant sources of pollution causing the

population’s health to be jeopardized ingesting tainted water and other harmful substances

eatables that are connected. The consumption of highly contaminated water and eatables may

prove lethal to the human being and may bring genetic disorders. Toxic heavy metals are

continuously released to the aquatic bodies in Allahabad as a rapid industrialization. Metals

are the problem of magnitude and of ecological significance due to their high toxicity and

ability to accumulate in living organisms. Many toxicologists have worked on the analysis

and detection of heavy metals in the water bodies, soil, sediments, plankton, fish organs, etc.

Kumar et al., in conclusion stated that there is a need to maintain control on disposal

of industrial waste in water bodies and to bio-monitor the trace elements in the water and

other eatables. The practice of trace element detection should be continued to avoid possible

consumption of contaminated eatables. It is recommended that awareness should be spread

among the people regarding the hazards on consumption of polluted water and related

eatables. It is also essential that farmers should be educated to reduce such contamination and

should be encouraged to use the controlled amount of pesticides, to avoid the leaching of

waste water and cultivating in a field far away from industrial area as well as areas prone to

contamination.

Another research by Varol et al., (2019) On Evaluation of Health Risks from

Exposure to Arsenic and Heavy Metals through Consumption of Ten Fish Species stated that

the levels of 11 heavy metal (loid)s (HMs) were determined in ten different fish species

(wild, farmed, freshwater, and marine) frequently consumed in Turkey and compared with

the maximum permissible limits (MPLs) established by international standards. Also, human

health risks for the consumers were assessed. Among 11 HMs, only Al and Cr levels did

notshow significant differences among fish species. The highest concentrations of As were
found in red mullet, which is a demersal fish. The average concentrations of Cd, Cr, Cu, and

Pb in all fish species were below the MPLs, whereas those of Zn in European anchovy and

Mediterranean horse mackerel, and that of inorganic As in red mullet exceeded the MPLs.

The highest and lowest toxic metal contents (Al, As, Cd, and Pb) were recorded in red mullet

and farmed rainbow trout, respectively. The estimated daily intakes of HMs in each fish

species were very lower than their corresponding tolerable daily intakes, suggesting the daily

intake of HMs through fish consumption would not pose health risks for the consumers. The

target hazard quotient for individual HMs and hazard index for combined HMs in fish species

were below 1, which indicated that non-carcinogenic health effects are not expected. The

carcinogenic risk results revealed that there was a carcinogenic risk from exposure to

inorganic As via the consumption of red mullet. Among all investigated fish species, rainbow

trout and common carp were safer in terms of both non-carcinogenic and carcinogenic risks

from exposure to HMs.

In conclusion to the research by Varol et al., they stated the average concentrations of

Zn in European anchovy and Mediterranean horse mackerel, and that of inorganic As in red

mullet were higher than the maximum limits set by international standards. Except arsenic in

red mullet, European anchovy and Atlantic salmon, and Pb in Atlantic salmon, the levels of

HMs in fish species were lower than or comparable with those found in other studies. The

lowest and highest toxic metal contents were recorded in rainbow trout and red mullet,

respectively, while the lowest and highest essential metal contents were found in red mullet

and European anchovy. The mean As content of red mullet was higher 209.8 times than that

of rainbow trout. The human health risk assessment indicated that individual and combined

metals in fish species would not pose non-carcinogenic risks to people. However, inorganic

As in red mullet would cause potential carcinogenic risk to consumers.

 Pazou et al., (2020) highlighted in their research on Assessment of Heavy Metal’s in

Atlantic Sea Fish Sold in Benin that Marine space is constantly threatened by various sources

of pollution that may reduce its economic potential and have negative repercussions on

human health. This study aims to assess heavy metals contamination of eight fish species and

their impact on human health. Heavy metals such as cadmium, lead, copper and zinc were

determined by atomic absorption spectrophotometry in fresh, cooked and fried fish.

The results found in fresh fish from Pazou et al’s research (cadmium: 0.002 to 0.005

mg / kg, lead: 0 to 0.031 mg/ kg, copper: 0.0045 to 0.305 mg / kg, zinc: 0.1245 to 0.6195

mg / kg), in cooked fish (cadmium: 0.0035 to 0.005 mg / kg, lead: 0 to 0.01 mg / kg, copper:

0 to 0.021 mg / kg, zinc: 0.171 to 0.327 mg / kg) and in fried fish (cadmium: 0.004 mg / kg,

lead: 0 to 0.007 mg / kg, copper: 0 to 0.016 mg / kg, zinc: 0.0875 to 0.5065 mg / kg) showed

that heavy metal levels are all below the standard values accepted by FAO / WHO. The

consumption of these fish could therefore have no negative effect on the population’s health.

Both types of cooking have both positive and negative effects on the heavy metal reduction in

fish species. They stated that although the concentrations of heavy metals are not worrying,

the vigilance of the populations and a variation of the diet are important to guarantee a better

health.

A research on Heavy Metal Concentration in Fishes from the Coastal Waters of Kapar

and Mersing, Malaysia by Bashir et al., (2013) brought to light although fish is a significant

source of protein; they are currently affected by rapid industrialization and mechanized

agricultural activities, resulting in increased concentrations of heavy metals in fishes.

Concentrations of heavy metals, namely, Cd, Cu, Mn, and Zn, were estimated in the muscle,

liver, and gills of two commercially important marine fishes, namely, Arius thalassinus and

Johnius belangeri. The fish samples were collected from Kaparand Mersing, which are the

west and east coastal waters of Peninsular Malaysia, respectively.

 The results by Bashir et al., showed that the muscle had the lowest metal

concentrations compared with the liver and gills. Among the estimated heavy metal

concentrations, those of Zn and Cd were the highest and the lowest, respectively, for both

species in muscle, liver and gills. Moreover, our results indicate that A.thalassinus has higher

metal concentrations than J. belangeri in both areas. None of the values in the muscles

exceeded the standard guideline values and hence would not pose any health hazard to

consumers.

In conclusion, Bashir et al., stated that the knowledge of heavy metal concentrations in fishes

is important in order to regulate the consumption of fish. In this study, the highest metal

concentrations were found in the liver and gills, while the muscle had less accumulation of

heavy metals. The accumulation of metals in liver, gills and muscle was established and

decreases in the order of Zn>Cu> Mn> Cd. The concentrations of Zn were the highest in all

organs of two species from both study areas. Moreover, species from Merging site have

higher Zn and Cu concentrations than those from Kapar. The mean concentrations of heavy

metals analysed in the muscles of both species were lower than the maximum permitted

concentrations recommended by FAO/WHO (1984), and Malaysian Food Regulation act

(1985). The concentrations of these metals in muscle tissues of the samples were not risky to

human health. These data provide a useful baseline to measure any future changes in local

pollution.

In addition, a research by Adeyeye et al., (2017) on Quality Attributes, Polycyclic

Aromatic Hydrocarbon, and Heavy Metal Profile of Traditional Drum-Smoked Guinean

Barracuda Fish from Lagos State, Nigeria stated their study was carried out to assess the

quality attributes, polycyclic aromatic hydrocarbon (PAH), and heavy metal profile of

traditional drum smoked Guinean barracuda fish from Lagos State, Nigeria. Fresh Guinean

barracuda fish (60) samples were obtained from 20 different fish-processing centers. The
fresh fish samples were smoked with traditional drum kiln. The fresh and smoked fish

samples were analyzed for proximate composition, quality indices (peroxide value (PV),

thiobarbituric acid (TBA), total nitrogen base-nitrogen (TVB-N), trimethylamine acid

(TMA), and free fatty acid (FFA)), PAH, heavy metals, and microbiological (coliform, fungi,

Listeria monocyte-genes (LM), Salmonella paratyphi (SP), and Staphylococcus aureus (SA))

analyses. The results revealed that the mean moisture, protein, fat, crude fibre, ash, and

carbohydrate contents of traditional drum-smoked fish samples were in the range 10.93–

14.15%, 51.97–60.96%, 11.34–15.99%, 1.74–2.99%, 1.12–1.56%, and 7.70–17.99%,

respectively. The values of PV, FFA, TBA, TVB-N, and TMA were in the range of 8.21–

10.19 meq.peroxide/kg, 1.13–1.80%, 1.03–1.19 mgMol/kg, 17.29–19.36 mgN/kg, and 2.12–

2.68 mgN/kg, respectively. The results of PAH compounds in the traditional drum-smoked

fish samples showed that 10 of the 16 PAH compounds detected were above the 5.0 μg/kg B

(α) P maximum permissible levels stipulated by EU Regulation 1881/2006. The

concentrations of Hg, Pb, Cd, and Cr in the smoked fish samples ranged from 0.001 to 0.0027

μg/g, 0.0013 to 0.0028μg/g, 0.0014 to 0.0028 μg/g, and 0.0621to 0.0796 μg/g, respectively.

The results of microbiological analysis revealed the presence of LM and SA in the traditional

drum-smoked fish samples. The study concluded that traditional drum-smoked fish may

constitute higher risks (chemical and microbiological) and public health concerns to

consume.

Ekanim et al., (2016) in their research: Comparative Study Of Heavy Metal Concerntrations

In Tissues And Shells Of Tympanotonus Fuscatus From Okoro Ete River, Eastern Obolo Local

Government Area Of Akwa Ibom State, Nigerian stated that water pollution by heavy metals is an

emerging problem in both developed and undeveloped countries. This research was carried out to

determine the concentration of Ni, As, Cu, Fe, Pb and Cd in periwinkle (T. fuscatus) tissues and shell

from Okoro Ete River, Eastern Obolo, Akwa Ibom State, using UNICAM 629 Atomic Absorption
Spectrometer. The mean concentrations of each heavy metals: Ni (0.72 ± 0.20 mg/kg); Cu (9.23 ±

5.60 mg/kg); Fe (56.98 ± 32.03 mg/kg); Pb (17.64 ± 4.00mg/kg); Cd (22.46 ± 5.50 mg/kg) in

Tympanotonus fuscatus tissues were higher than the concentration of metals: Ni (BDL); Cu (0.41 ±

0.23 mg/kg); Fe (33.17 ± 12.80 mg/kg); Pb (1.49 ± 0.20 mg/kg); and Cd (2.21 ± 1.00 mg/kg) in shell

samples and also higher than the WHO and FAO permissible standards of 0.5 mg/kg (Ni); 0.2 mg/kg

(Cu); 5.0 mg/kg (Fe); 5.0 mg/kg (Pb); and 2.0 mg/kg (Cd) indicating higher levels of accumulation of

these metallic contaminants by the test organisms implying that these organism may pose high risk

upon human consumption due to high pollution of the study area by heavy metals contaminating

from both point source and non point source. The result of this study revealed a very high

concentration of Lead both in the tissues and shell of T. fuscatus. This indicated that T, fuscatus from

Okoro Ete River, Eastern Obolo, Akwa Ibom State is unfit for human consumption.

Tawio et al., (2017) did an Assessment of heavy metal concentrations in the muscles

of ten commercial fish species from Lagos lagoon, Nigeria. In the research, it was gathered

that the study was undertaken to assess the concentration of five heavy metals (zinc (Zn), lead

(Pb), copper (Cu), iron (Fe) and manganese (Mn)) in the muscles of Tilapia zilli, Hydrocynus

fiscalis, Parapristipoma humile, Caranx hippo, Cynoglossusa caudatus, Chrysichthys

nigrodigitatus, Letjanus sp, Portunus validus, Sardinella maderensis, and Sphyreana sp. from

Lagos Lagoon. There were significant differences (P<0.05) in the concentration of heavy

metals in fish muscles. There was no specific pattern in the levels of heavy metals among the

fish species. P. validus had the highest concentration of Zinc in the fish sampled with a mean

value of 14.45mg/g while T. zilli had the lowest concentrations of Zn and Mn. Sphyreana sp

had the highest concentrations of Lead and Copper and Manganese in the muscles. Iron

concentration was highest in the muscle of S. maderensis. In this study, the overall average

concentrations of metals in fish muscles were in the order of Zn> Fe > Pb> Cu> Mn. The

values of Zn and Cu were within or lower than the acceptable limits FAO/WHO (in fish
while levels of Pb, Fe and Mn in the muscles of the various fishes were beyond the safe limit

in foods. Close monitoring of heavy metal pollution of Lagos Lagoon is strongly advocated,

in view of possible risks to the health of consumers.

In conclusion Taiwo et al., stated that heavy metals are toxic to both humans and fish,

therefore, these compounds should be monitored regularly in the Lagoons. The overall

average concentrations of Zn, Pb, Cu, Fe, and Mn in the muscles of the fish species studied

gave a ranking of: Zn > Fe > Pb > Cu > Mn. These metals are essential in human diets in

minute quantities; their consumption should not exceed the limits set by FEPA, WHO and

FAO. The high concentration of these metals in the fish species studied calls for caution in

their consumption. However, if eaten in moderation, the fish are safe for consumption. The

concentration of heavy metals in the fish species is an indication of the level of pollution in

the Lagos Lagoon. This level of pollution could be due to industrialisation and inadequate

monitoring of dumping into the lagoon. It is essential to monitor disposal of industrial

effluents and dumping of domestic sewage.

However, this research is needful as it will analyse same situation for the fishing

terminals: Iko and Ibaka in the southern state of Nigeria, Akwa Ibom, outline the possible

cause of the heavy metals pollution as well as suggest ways to check mate it.

General Description on Vanadium

Vanadium (V) is a bright white ductile metal belonging to group V of the periodic system of

elements. It forms compounds mainly in valence states +3, +4 and +5. In the presence of oxygen, air

or oxygenated blood, or oxidizing agents, vanadium is always in the +5 oxidation state. In the
presence of reducing agents, vanadium compounds are in the +4 oxidation state ( Erdmann, et

al,2009) Vanadium forms both cationic and anionic salts, and can form covalent bonds to yield

organometallic compounds which are mostly unstable.

Source

Vanadium is an ubiquitous metal. The average concentration of vanadium in the earth’s

crust is 150 μg/g; concentrations in soil vary in the range 3-310 μg/g ( Waters, 2007). It’s may reach

high values (up to 400 μg/g) in areas polluted by fly ash. The concentration of vanadium in water is

largely dependent on geographical location and ranges from 0.2 to more than 100 μg/litre in

freshwater and from 0.2 to 29 μg/litre in seawater (Waters, 2007). The ocean floor is the main long-

term sink of vanadium in the global circulation . The concentrations of vanadium in coal and crude

petroleum oils vary widely (1-1500 mg/kg).

The world production of vanadium was about 35 000 tonnes in 1981 (Galloway, J.N. et al.,

2006). The major producing countries being Chile, Finland, Namibia, Norway, South Africa, USSR and

the United States.

Most of the vanadium produced is used in ferrovanadiurn and, of this, the majority is used in

high-speed and other alloy steel (usually combined with chromium, nickel, manganese, boron and

tungsten).

It has been estimated that around 65 000 tonnes of vanadium annually enter the

environment from natural sources (crustal weathering and volcanic emissions) and around 200 000

tonnes as a result of man’s activities (Lahmann, E. et al, 2008). The major anthropogenic point

sources of atmospheric emission are metallurgical works (30 kg per tonne of vanadium produced),

followed by the burning of crude or residual oil and coal (0.2-2 kg per 1000 tonnes and 30- 300 kg

per 106 litres) (Anderson,2003).

 Effect of Vanadium on Human

Both acute and chronic poisonings have been described in workers engaged in the industrial

production and use of vanadium. Most of the reported clinical symptoms reflect irritative effects of

vanadium on the respiratory

There is insufficient evidence that vanadium causes generalized systemic effects except at

extremely high concentrations (Waters, 2007). Several observers described only vague, general signs

or symptoms and reported nervous disturbances, neurasthenic or vegetative symptoms, occasionally

tremors, palpitation of the heart, high incidence of extrasystoles, changes in the blood picture

(anaemia, leukopenia, punctatebasophilia of the erythrocytes), reduced level of cholesterol in the

blood, etc. (Vouk et al, 2004)

Numerous studies have reported acute and chronic respiratory effects mainly due to

exposure to vanadium pentoxide (Vouk et al, 2004). Most of the reported clinical symptoms reflect

irritative effects of vanadium on the upper respiratory tract. Only at high concentrations (above 1 mg

vanadium per m3) were more serious effects of the lower respiratory tract observed, such as

bronchitis and pneumonitis,(Water 2007). Respiratory effects after acute or chronic expo- sure to

low levels of vanadium are summarized in Table 1.

Acute changes in lung function in workers exposed to vanadium compounds during cleaning

of boilers were reported (time-weighted average concentration of respirable dust 523 μg/m3, 15.3%

of vanadium, giving a value of 80 μg vanadium per m3) (Lee’s,2002). In spite of the fact that the

workers wore respirators, the changes in lung function developed within 24 hours and pre-exposure

levels had not returned by the eighth day; however, the efficacy of the respirators was low (about

9% leakage).
 Respiratory effects after acute exposure to vanadium pentoxide dust were also observed in a

clinical study in which healthy volunteers were exposed to levels of 100, 200 and 1000 μg vanadium

pentoxide per m3 for 8 hours (Zeno et al,2001). It was found that 98% of the particles were smaller

than 5 μm. Coughing, which persisted for several days, was the most characteristic symptom at all

three levels of exposure.

Chronic inhalation of vanadium pentoxide dusts in industry has resulted in rhinitis,

pharyngitis, bronchitis, chronic productive cough, wheezing, shortness of breath and fatigue.

Pneumonitis and bronchopneumonitis have also been observed (Waters, 2007). It has been reported

that vanadium workers are more susceptible to colds and other respiratory illnesses than others.

(Anderson, 2003)

CHAPTER 3

MATERIALS AND METHODS

3.1 Study Areas Description

3.1.1 Iko River

Figure 3.1 Satellite Map of Iko Town and the River (Source: Google Maps)

Iko town lies on the geographical coordinates Latitude 4º52’ N; Longitude 7º72’E; Altitude

16.00m/52.49ft. The Iko river estuary is located in the Niger Delta region in the southern part

of Nigeria and this zone is one of the coastal regions where there is massive oil exploration,

exploitation, production and refining (Adiaobo et al., 2016).

3.1.2 Ibaka River

Figure 3.2 Satellite Map of IbakaTown and the River (Source: Google Maps)

Ibaka fishing terminal is located at the banks of the Ibaka river which is one of the significant

streams in Akwa Ibom State, Nigeria. The Ibaka River in Mbo is situated at Latitude 4º39’

North and Longitude 8º19’ East on the South-Eastern Region of the Nigerian Shoreline. It

discharges into the Cross River Estuary at Ibaka in the Bight of Bonny and assumes a

significant part in the fisheries assets of Akwa Ibom State (Essien-Ibok et al., 2010)

3.2 Materials Used

i. Polyethylene bag

ii. Measuring tape

iii. Weighing balance

iv. Oven

v. Buck Scientific Atomic Absorption Spectro-photometer, Model 225/23x

vi. Meter Toledo Weighing Balance

vii. Conical flask

viii. Nitric acid

ix. Distilled water

x. Electric stove

xi. Stopper

xii. Catfish

3.3 Sample Collection

The red snapper fish were be purchased from the Iko and Ibaka fishing terminals of which

there was adequate provision for preservation of the fish during transit in an ice box. The

samples to be used was transported to the central laboratory of the Akwa Ibom State

University.

3.4 Measurement of the Basic Biological Parameters

After the transit and transfer of the fish under case study to the laboratory, it is necessity to

take note of the basic biological which are likewise physical parameter of the fish sample.

These parameters will include the size and weight. The table below will show the breakdown

of the measurement of the parameters:

Table 3.2 Table Showing the Biological Parameters of the Fish Samples from Iko and
Ibaka River

—————————————————
Sample No. Weight (kg). Length

—————————————————
Sample A (Ibaka) 1.3. 54 Cm
————————————————————————————————————-
Sample B (Iko) 1.35. 54 cm

—————————————————
Source: From this Study

3.5 Fish Handling and Preservation

This process comes next as the parameters have been taken. The fish will be washed with de-

ionized water and preserved in a freezer in poly-ethylene bags with temperature of -4ºC.

3.6 Digestion and Analytical Procedures

3.6.1 Sample Digestion

Sample digestion is a process of decomposing a solid sample into a liquid state by dissolving

it using reagents such as strong acids, alkalis, or enzymes. Digestion is aimed at reducing or

changing the state of the fish from solid to liquid this will make it easier for the analysis

process. In the course of this research wet digestion method will be used.

3.6.2 Analytical Procedures

i. Fishes were purchased from both stations and stored in a black polyethylene bags and taken to the

laboratory.

ii. The length and weight of the fishes were measured; the length measurement of the fish was taken

from the mouth to the tail.

iii. The fishes were placed on a chop board and taken and cut to smaller pieces.
iv. The chopped fish samples were washed thoroughly and oven dried at 100◦C temperature; the

samples were each treated as a whole Flesh were dried and together they made a homogenous

sample.

v.

vi. After that a portion of both fishes were taken and weighed with a Melter Toledo

weighing balance of which the weight for both samples were 0.5g.

vii. The weighed samples were digested in a conical flask. 10ml of Nitric acid and 2.5ml

of distilled water was added to each sample and mixed thoroughly by shaking.

viii. The conical flask was heated on an electric stove to further dissolve it and get a clear

solution. It was left to boil with a stopper covering it.

ix. The essence of covering the Conical flask is to stop the vapour from escaping while

boiling so that the metals are still retained in the sample as keeping it open would lead

to lose of the metals through evaporation.

x. A clear sample was gotten for each fish sample and further analysis was done using a

Buck Scientific Atomic Absorption Spectro-Photometer.

3.6.3 Precautions to be followed to avoid Contamination

There will be list of precautions that are sacrosanct to be followed so as to guard against

contaminations during investigation. The fish samples are to be washed with deionized water

prior to cutting to take away absorbed metals from the skin. the deionized water is to be used
to prepare all aqueous solution. All plastics and glass used in the process will be rinsed and

soaked in 10% (v/v) HNO3 overnight. They are to be further rinsed with deionized water and

dried prior usage.

3.6.4 Statistical Analysis

Pearson’s correlation (r) matrix among the parameters was computed to show the

association among the parameters. Descriptive statistics of the parameters were also computed to

show their average behaviors and dispersions. All statistical analyses were performed using IBM

SPSS Statistics.
 CHAPTER FOUR
RESULTS AND DISCUSSION

Table 4.1: Concentration of heavy metals on two fish sample (MRS and
IRS) collected from two different locations (Mbo and Iko rivers)
respectively.
Sample ID Cd Cr Fe Pb V Hg Ni As

MRS 1 0.426 0.04 2.836 0.218 0.001 0.001 2.640 0.001

(mg/kg)

IRS 2 0.248 0.04 3.218 0.647 0.001 0.001 1.246 0.001

(mg/kg)

Note: Cadmium (Cd); Chromium (Cr); Iron (Fe); Lead (Pb);

Vanadium (V); Mercury (Hg); Nickel (Ni); Arsenic (As)

3.5
3.25
3
2.75
2.5
2.25
2
1.75
1.5
1.25
1
0.75
0.5
0.25
0
MRS 1 (mg/kg) IRS 2 (mg/kg)

Cadmium (Cd) Chromium (Cr) Iron (Fe) Lead (Pb)

Vanadium (V) Mercury (Hg) Nickel (Ni) Arsenic (As)

Figure 4.1: Column chart showing the concentration of heavy metals on fish sample MRS and IRS
collected from Mbo and Iko rivers respectively.
Table 4.2: Maximum permissible limit of heavy metals in fishes according
to DPR, FMENV, FAO and WHO
Parameter limits DPR limits FMENV FAO limits WHO limits
Limits

Cadmium (Cd) mg/l 1.000 1.000 0.200 0.500

Chromium (Cr) mg/l 0.050 0.050 0.150 0.150

Iron (Fe) mg/l 0.020 0.025 0.500 0.300

Lead (Pb) mg/l 0.050 0.050 0.200 0.500

Vanadium (V) mg/l <0.001 <0.001 0.200 0.200

Mercury (Hg) mg/l <0.001 <0.001 0.020 0.200

Nickel (Ni) mg/l 0.200 0.500 0.500 0.200

Arsenic (As) mg/l 0.200 0.500 1.400 1.400

Table 4.3: Concentration of heavy metal with their standard deviation and
percentage (%) occurrence for Mbo Red Snapper
Samples Unit (mg/kg) SD % WHO standard of
Occurrence Heavy metals in
fishery resources
(mg/kg)
Cadmium (Cd) 0.426 ±1.224 6.912 0.050

Chromium (Cr) 0.040 ±1.217 0.649 0.150

Iron (Fe) 2.836 ±1.268 46.016 5.000

Lead (Pb) 0.218 ±1.037 3.537 0.200

Vanadium (V) 0.001 ±1.143 0.016 2.000

Mercury (Hg) 0.001 ±1.244 0.016 0.150

Nickel (Ni) 2.640 ±1.320 42.836 0.500

Arsenic (As) 0.001 ±1.165 0.016 0.050

Table 4.4: Concentration of heavy metal with their standard deviation and
percentage (%) occurrence for Iko Red Snapper
Samples Unit (mg/kg) SD % WHO standard of
Occurrence Heavy metals in
fishery resources
(mg/kg)
Cadmium (Cd) 0.050
0.248 ±1.118 4.024
Chromium (Cr) 0.150
0.040 ±1.104 0.649
Iron (Fe) 5.000
3.218 ±1.152 52.215
Lead (Pb) 0.200
0.647 ±0.500 10.498
Vanadium (V) 2.000
0.001 0.539 0.016
Mercury (Hg) 0.150
0.001 0.587 0.016
Nickel (Ni) 0.500
1.246 0.623 20.217
Arsenic (As) 0.050
0.001 0.000 0.016
Table 4.5: Summary of heavy metal concentration
Groups Count Sum Average Variance
Cadmium (Cd) 2 0.674 0.337 0.01584
Chromium (Cr) 2 0.08 0.04 0
Iron (Fe) 2 6.054 3.027 0.07296
Lead (Pb) 2 0.865 0.4325 0.09202
Vanadium (V) 2 0.002 0.001 0
Mercury (Hg) 2 0.002 0.001 0
Nickel (Ni) 2 3.886 1.943 0.97162
Arsenic (As) 2 0.002 0.001 0

Table 4.6: ANOVA Result

Source of
Variation SS df MS F P-value F crit
Between Groups 18.121 7 2.588 17.970 0.00027 3.500
Within Groups 1.152 8 0.144

Total 19.274 15
SS – Sum of squares; df – degree of freedom; MS – Mean squared; fcrit – Fcritical

DISCUSSIONS

The data provided in Tables 4.3 and 4.4 show the concentration of heavy metals

in red snapper fish samples collected from Mbo and Iko Rivers, respectively.

The heavy metals considered in the study were Cadmium (Cd), Chromium (Cr),

Iron (Fe), Lead (Pb), Vanadium (V), Mercury (Hg), Nickel (Ni), and Arsenic

(As).

From Table 4.3, it can be observed that the highest concentration of heavy metal

in Mbo red snapper fish samples was Iron (Fe) with an average value of 2.836

mg/kg and a percentage occurrence of 46.016%. This is followed by Nickel (Ni)

with an average value of 2.640 mg/kg and a percentage occurrence of 42.836%.

The heavy metal with the lowest concentration was Vanadium (V) with an
average value of 0.001 mg/kg and a percentage occurrence of 0.016%. The

concentration of other heavy metals, such as Cadmium (Cd), Chromium (Cr),

Lead (Pb), Mercury (Hg), and Arsenic (As), were also relatively low.

Similarly, from Table 4.4, it can be observed that the highest concentration of

heavy metal in Iko red snapper fish samples was Iron (Fe) with an average value

of 3.218 mg/kg and a percentage occurrence of 52.215%. This is followed by

Nickel (Ni) with an average value of 1.246 mg/kg and a percentage occurrence

of 20.217%. The heavy metal with the lowest concentration was Arsenic (As)

with an average value of 0.001 mg/kg and a percentage occurrence of 0.016%.

The concentration of other heavy metals, such as Cadmium (Cd), Chromium

(Cr), Lead (Pb), Mercury (Hg), and Vanadium (V), were also relatively low. It

is noteworthy that the concentration of some heavy metals in both Mbo and Iko

red snapper fish samples exceeded the WHO standard of heavy metals in fishery

resources. For instance, the concentration of Lead (Pb) in Mbo and Iko red

snapper fish samples were 0.218 mg/kg and 0.647 mg/kg, respectively, while

the WHO standard is 0.200 mg/kg. Similarly, the concentration of Nickel (Ni)

in Mbo and Iko red snapper fish samples were 2.640 mg/kg and 1.246 mg/kg,

respectively, while the WHO standard is 0.500 mg/kg.

In conclusion, the comparative analysis of heavy metals in red snapper fish in

Mbo and Iko Rivers revealed that both rivers have similar trends in terms of the

concentration of heavy metals in the fish samples. Iron (Fe) and Nickel (Ni)
were the most prevalent heavy metals in both rivers, while Cadmium (Cd),

Chromium (Cr), Vanadium (V), Mercury (Hg), and Arsenic (As) were found in

low concentrations. However, the concentration of some heavy metals, such as

Lead (Pb) and Nickel (Ni), exceeded the WHO standard of heavy metals in

fishery resources, indicating potential health risks associated with the

consumption of red snapper fish from these rivers. Table 4.4 presents the results

of an ANOVA test, which is a statistical test used to determine if there are

significant differences between the means of two or more groups. In this case,

the ANOVA test was used to compare the concentrations of various heavy

metals in the red snapper fish from the Mbo and Iko Rivers.

The results of the ANOVA test are presented in Table 4.5. The "Between

Groups" row shows the sum of squares (SS) and mean squared (MS) values for

the differences between the means of the two groups (Mbo and Iko red

snapper). The "Within Groups" row shows the SS, degrees of freedom (df), and

MS values for the differences within each group. The "Total" row shows the

overall SS and df for the entire dataset.

The F-test was performed to determine if the differences between the groups

were significant. The F-value is 36.804, and the P-value is less than 0.05,

indicating that there are significant differences between the means of the two

groups. Table 4.3 and 4.4 show the concentrations of various heavy metals in

the Mbo and Iko red snapper fish, respectively. The results show that the
concentrations of heavy metals such as cadmium, lead, and nickel are higher in

the Mbo red snapper than in the Iko red snapper. The concentrations of iron are

higher in the Iko red snapper than in the Mbo red snapper. The concentrations

of other heavy metals such as chromium, vanadium, mercury, and arsenic are

very low and almost negligible in both groups.

In conclusion, the ANOVA results indicate that there are significant differences

between the concentrations of various heavy metals in the Mbo and Iko red

snapper fish. The concentrations of some heavy metals are higher in the Mbo

red snapper, while others are higher in the Iko red snapper. However, it is

important to note that some of the concentrations are still within the WHO

standards for heavy metals in fishery resources, while others exceed the

recommended limits. Therefore, further monitoring and regulation of heavy

metal concentrations in fishery resources are necessary to ensure the safety of

consumers.
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