ABSTRACT
The presence and bioaccumulation pattern of some heavy metal
concentrations in wild and farmed African catfish, Clarias gariepinus (Burchell, 1822) muscles collected from selected
rivers and fish farms in Kaduna State, Nigeria, were assessed. Fish and water
samples used for the assessment were collected during the wet and dry seasons
from River Kaduna, River Galma in Zaria; and from two fish farms in Sabon
Tasha, Kaduna and Dakace, Zaria. Physico-chemical parameters, such as Puissance
Hydrogen (pH), temperature, Turbidity etc., were also analysed. The analyses of
heavy metals, Iron (Fe), Lead (Pb), Nickel (Ni), Cadmium (Cd) and Mercury (Hg),
in all water and Clarias gariepinus
muscle samples was carried out in the Multi-User Science Research Laboratory,
Department of Chemistry, Ahmadu Bello University, Zaria, using Thermo-element
Solar S4 Atomic Absorption Spectrophotometer (AAS), while the Varian Generation
Accessory (VGA 77) with closed end cell was used for Hg determination. The
results obtained were subjected to t-test analysis to determine the level of
significance (p < 0.05) between the means, while Pearson correlation
coefficient was employed to determine the relationships. pH was highest in
River Kaduna during the wet season, in the upstream (7.04), while there was a
dip in the downstream (6.67) during the dry season. Seasonal variations in
temperature were evident, as the ranges obtained in the rivers were from
27.03°C – 30.68°C and the farms ranged from 23.76°C – 27.42°C, which were
within World Health Organization (WHO) recommended threshold (30°C – 36°C).
Dissolved Oxygen (DO) varied widely in the rivers (5.11mg/l – 7.04mg/l) as well
as in the farms (9.29mg/l – 10.74mg/l). Total dissolved solids (TDS)obtained in
this study were all very high (Rivers: 54.91mg/l – 82.09mg/l, Farms: 28.43mg/l
– 42.03mg/l), but were all lower than the WHO standardindicativeofportability
(1000 – 1600mg/l). Heavy metal concentrations in water samples and heavy metal
bio-accumulation in both wild and farmed C.
gariepinus muscles showed irregular distributions with descending order
of:Fe >Pb>Hg>Ni > Cd. Fe levels were the highest in both rivers water samples (3.23mg/l), closely
followed by Pb (0.78) and Hg (0.69mg/l), while the farms also had Fe as the
dominant element (1.31mg/l), with Pb (0.26mg/l) and Hg (0.09mg/l),
respectively. Both water bodies had Ni concentration (0.2mg/l) higher than the
WHO limits of 0.02mg/l, while the farms‟ concentration (0.03mg/l) was slightly
higher than WHO threshold limit. In the muscle of C. gariepinus, Fe concentrations were also high in rivers
(3.53mg/kg), while the Farms was 1.44mg/kg, all above the FAO recommended limit
(0.5mg/kg) in fish. Generally, only Cd didnot exceed the maximum permissible
limits in the tissues ofC. gariepinus.
However, with Fe, Hg, Pb and Ni all higher than the acceptable limits, most
especially in the rivers, this could pose a serioushealth risk to consumers.
Thus, a close periodical and regular monitoring of heavy metal pollution in the
water bodies is strongly advocated.
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Abstract
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Table
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List of
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List of Figures
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List of
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xv
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CHAPTER ONE
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1
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1.0
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INTRODUCTION
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1.1
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Background of the Study
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Statement of Research Problem
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Justification of the Study
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Aim and Objectives of the Study
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1.5
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Hypotheses
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CHAPTER TWO
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2.0
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LITERATURE REVIEW
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2.1
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Water Pollution
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2.2
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Health – Environment Nexus
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2.3
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Sources of Heavy Metals
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Distribution Pathways and Fate of Heavy Metals in
Aquatic Biomes
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2.5
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Bio-magnifications and Bioaccumulations of Heavy
Metals in Fish-
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2.6
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Selected Heavy Metals and their Toxicity -
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2.6.1
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Mercury
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2.6.2
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Lead
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2.6.3
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Cadmium
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2.6.4
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Nickel
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2.6.5
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Iron
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2.7
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Heavy Metal Contamination of Fish in Nigeria
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22
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2.8
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Ecological Distribution of Clarias gariepinus (Burchell, 1866)
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25
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CHAPTER
THREE -
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28
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3.0
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MATERIALS AND METHODS
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3.1
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Study Area
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3.1.1
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River
Kaduna, Kaduna
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3.1.2
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River
Galma, Zaria
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3.2
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Sample Collection
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3.2.1
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Water
collection
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3.2.2
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Fishcollection
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3.2.3
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Digestion
procedures
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3.3
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Analytical Technique
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3.3.1
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Calibration
of instrument
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3.3.2
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Validation
of analytical methodology (Recovery test)
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3.3.3
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Precautions
followed to prevent contamination
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3.4
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Techniques for Determining Physico-chemical
Characteristics
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3.4.1
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phmeasurement
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3.4.2
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Temperaturemeasurement
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3.4.3
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Dissolved
oxygen measurement
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3.4.4
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Turbidity
measurement
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3.4.5
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Biological
oxygen demand
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43
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3.4.6
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Determination
of total dissolved solid
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3.4.7
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Electrical
conductivity measurement -
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44
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3.5
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Data Analysis -
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44
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CHAPTER FOUR
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45
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4.0
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RESULTS
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45
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4.1
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Physico-chemical Parameters of Water Samples
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4.2
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Analysis of Heavy Metals in Water Samples
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58
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4.2.1
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Analysis
of heavy metals in water samples from River Kaduna
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58
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4.2.2
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Analysis
of heavy metals in water samples from River Galma
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62
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4.2.3
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Analysis
of heavymetals in water samples from Farm 1
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67
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4.2.4
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Analysis
of heavy metals in water samples from Farm 2
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69
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4.3
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Analysis of Heavy Metals in Fish Samples -
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71
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4.3.1
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Physical parameters of fish specimen
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71
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4.3.2
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Analysis
of heavy metals in fish samples from River Kaduna
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74
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4.3.3
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Analysis of heavy metals in fish samples from River Galma
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76
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4.3.4
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Analysis
of heavy metals in fish samples from Farm 1
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78
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4.3.5
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Analysis
of heavy metals in fish samples from Farm 2
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80
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4.4
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Comparative Analysis of Heavy Metals in Water
Samples
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82
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4.5
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Comparative Analysis of Heavy Metals in Fish
Samples -
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97
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4.6
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Correlation between Heavy Metal Concentrations
and
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Physico-chemical Parameters
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110
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CHAPTER FIVE
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119
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5.0
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DISCUSSION
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119
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5.1
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Physico-chemical Parameters of Water Samples
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119
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5.2
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Heavy Metals in Water Samples
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123
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5.3
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Heavy Metals in C. gariepinus
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129
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CHAPTER SIX
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134
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6.0
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SUMMARY, CONCLUSIONS AND RECOMMENDATIONS -
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134
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6.1
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Summary
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134
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6.2
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Conclusion
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134
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6.3
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Recommendations
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135
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REFERENCES
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137
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APPENDICES
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151
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LIST OF TABLES
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Table
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Page
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3.1
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Sample Water Sources and GPS Coordinates
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29
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4.1
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Physico-chemical
Water Parameters of River Kaduna
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46
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4.2
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Physico-chemical Water Parameters of River Galma
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48
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4.3
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Mean
Physico-chemical Parameters of Rivers Kaduna and Galma
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51
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4.4
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Mean
Physico-chemical Parametersbetween Rivers
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Kaduna
and Galma
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53
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4.5
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Physico-chemical
Parameters of Water in Farms 1 and 2
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55
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4.6
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Physico-chemical
Parameters of Water between Farms 1 and 2
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57
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4.7
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Morphometric
parameters of C. gariepinusCollected
in River Kaduna
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and
River Galma
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72
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4.8
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Morphometric
parameters of C. gariepinusCollected
in River Kaduna
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and
River Galma
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73
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4.9
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Analysis
of River Water Samples
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93
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4.10
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Analysis
of Farm Water Samples
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96
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4.11
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Analysis
of Fish Muscle Samples between Rivers
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101
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4.12
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Analysis
of Fish Muscle Samples between Farms
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107
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4.13
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Correlation
of Physico-chemical Parameters of River Kaduna
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111
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4.14
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Correlation
of Physico-chemical Parameters of River Galma
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113
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4.15
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Correlation
of Physico-chemical Parameters of Farm 1
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115
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4.16
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Correlation
of Physico-chemical Parameters of Farm 2
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117
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LIST OF FIGURES
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Figure
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Page
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3.1
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River
Kaduna and Sampling Points
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31
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3.2
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River
Galma and Sampling Points
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33
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4.1
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Heavy
Metals in River Kaduna – Dry Season
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-
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-
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59
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4.2
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Heavy
Metals in River Kaduna – Wet Season
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-
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-
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59
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4.3
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Average
Concentration of Heavy Metals in River Kaduna
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-
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-
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61
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4.4
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Heavy
Metals in River Galma – Dry Season -
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-
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-
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63
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4.5
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Heavy
Metals in River Galma – Wet Season -
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-
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-
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64
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4.6
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Average
Concentration of Heavy Metals in River Galma
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-
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-
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66
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4.7
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Heavy
Metals Concentration in Farm 1
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-
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-
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-
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68
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4.8
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Heavy
Metals Concentration in Farm 2
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-
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-
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-
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70
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4.9
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Heavy
Metals Concentration in C. gariepinus
– River Kaduna
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-
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75
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4.10
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Heavy
Metals Concentration in C. gariepinus
– River Galma
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-
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-
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77
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4.11
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Heavy
Metals Concentration in C. gariepinus
– Farm 1
|
-
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-
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-
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79
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4.12
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Heavy
Metals Concentration in C. gariepinus
– Farm 2
|
-
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-
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-
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81
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4.13
|
Heavy
Metals Concentration in R. Kaduna and River Galma in
|
|
|
|
|
Water
Samples –Wet Season -
|
-
|
-
|
-
|
-
|
-
|
-
|
83
|
4.14
|
Heavy
Metals Concentration in R. Kaduna and River Galma
|
|
|
|
|
Water
Samples – Dry Season -
|
-
|
-
|
-
|
-
|
-
|
-
|
84
|
4.15
|
Heavy
Metals Concentration in Farm 1 and 2 Water Samples
|
|
|
|
|
– Wet
Season
|
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
86
|
4.16
|
Heavy
Metals Concentration in Farm 1 and 2 Water Samples
|
|
|
|
|
– Dry
Season
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
88
|
4.17
|
Heavy
Metal Concentrations in Water Samples fromBoth Rivers
|
|
|
|
|
and
Ponds
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
90
|
4.18
|
Heavy
Metals Concentration in R. Kaduna and R. Galma Fish
|
|
|
|
|
Samples
– Wet Season
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
98
|
4.19
|
Heavy
Metals Concentration in R. Kaduna and R. GalmaFish
|
|
|
|
|
Samples
– Dry Season
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
99
|
4.20
|
Heavy Metals Concentration in
Farm 1 and 2 Fish Samples
|
|
|
|
|
– Wet
Season
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
103
|
4.21
|
Heavy
Metals Concentration in Farm 1 and 2 Fish Samples
|
|
|
|
|
|
– Dry
Season -
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
-
|
105
|
4.22
|
Heavy
Metal Concentrations in Both Rivers and Farm Fish Samples-
|
-
|
109
|
|
|
|
|
|
|
|
|
|
|
|
|
LIST OF APPENDICES
|
|
|
|
Appendix
I
|
WHO
Recommended Limits of Physico-chemical Parameters for Water -
|
151
|
Appendix
II
|
WHO
Recommended Limits of Heavy Metal for Water
|
-
|
-
|
151
|
Appendix
III
|
FAO Threshold Limits of Heavy Metals for Fish-
|
-
|
-
|
152
|
CHAPTER ONE
1.0 INTRODUCTION
1.1 Background of the Study
In recent years the concentrations of toxic metals
in many ecosystems are reaching unprecedented levels. The increasing use of
metals in industry and mining activities have led to serious environmental
pollution through effluents and emanations (Güven et al., 1999). Under certain environmental conditions, heavy metals
may accumulate and cause serious ecological damage. The aquatic ecosystem is
often seen as the ultimate recipient of almost everything including heavy
metals (Ogoyi et al., 2011).
Pollution of heavy metals in aquatic environment is a growing problem worldwide
and currently it has reached an alarming rate. There are various sources of
heavy metals; some originates from anthropogenic activities like draining of
sewage, dumping of hospital wastes and recreational activities. Conversely,
metals also occur in small amounts naturally and may enter into aquatic system
through leaching of rocks, airborne dust, forest fires and vegetation
(Fernandez and Olalla, 2000). As heavy metals cannot be degraded, they are
continuously being deposited and incorporated in water, sediment and aquatic
organisms (Linnik and Zubenko, 2000), thus causing heavy metal pollution in
water bodies.
Heavy metal is any metallic chemical element that has a relatively high
density and is toxic or poisonous at low concentrations (Ngumbu, 2014).
Examples of heavy metal include mercury, cadmium, arsenic chromium, thallium
and lead. As trace elements, some heavy metals (e.g. copper, iron, zinc,
manganese and selenium) are essential to maintain the metabolism of the human
body. However, at higher concentrations they can lead to poisoning (Lenntech,
2014). Heavy metals can enter the human food through water, air, soil, plants
and animals. The pollution of the environment by heavy metals is viewed as an
international problem because of its effects. In recent years, the pollution of
aquatic environment with heavy metals has become a worldwide problem because of
their potential toxic effect and also most of them accumulate in tissues and
organs of aquatic organism (Goldstein and Hewitt, 1990andGledhill et al., 1997). However, the amount of
absorption and bioaccumulation of the heavy metals depends on ecological,
physical, chemical and biological condition and the kind of element and
physiology of organisms (Jaffer et al.,
1988). Heavy metals are considered the most important form of pollution of the
aquatic environment because of their toxicity and accumulation by marine
organisms (Eletta et al., 2003;
Malik, 2004; Obasohan et al., 2006 and Igwemmar et al., 2013). There is increasing concern
about the quality of foods in several
parts of the world. The determination of toxic elements in food has prompted
studies on toxicological effect of these elements in food. Fish as an important
component of the human diet, is generally appreciated as one of the healthiest
and often times referred to as the “cheapest” source of protein, as its amino
acid compositions are richer in Cysteine than most of the other sources of
protein (Eletta et al., 2003).
In Nigeria, limited surveys on heavy metals in fish have been reported.
Tawari-Fufeyin (1998) working on whole body tissues of fishes from Ikpoba
reservoir in Benin-City reported the concentration of vast amounts of Cadmium
(Cd), Chromium (Cr), Copper (Cu), Lead (Pb), Manganese (Mn), Nickel (Ni) and Zinc
(Zn). Also Nwaedozie (1998) noted that heavy metals such as Hg, Cd, Pb, Cr, Zn
and Fe were identified in appreciable quantities in the fish samples from
Kaduna River. Obasohan et al. (2006)
examined the concentrations of Cu, Mn, Zn, Pb, Cr, Ni and Cd in fish tissues of
two tropical fish species from Ogba River, Nigeria.While Alinnor and Obiji
(2010) investigated the level of heavy metals – Pb, Fe, Cd, Mn, Hg, Cu and Zn
in fish samples from Nworie River in Imo State.
Specifically, aquatic systems are more sensitive to
heavy metal pollutants and the gradual increase in the levels of such metals in
the aquatic environment, mainly due to anthropogenic sources have now become a problem of primary concern (Oluyemi and
Olabanji, 2011). This is due to their
persistence as they are not usually eliminated either by biodegradation or by
chemical means, in contrast to most organic pollutants. Moreover, the decay of
organic materials in aquatic systems together with detritus formed by natural weathering
processes and uncontrolled mining activities provides a rich source of
nutrients in both the bottom sediments and overlaying water body (Jafari and
Gunale, 2006and Wade et al., 2008),
with microorganisms, microflora and algae capable of incorporating and
accumulating these metal species into their living cells from the various
supply sources (Jaffar et al., 1988).
Consequently, fishes become enriched with the accumulated substances,
and eventually man, consuming these fishes inevitably suffers from the results
of an enrichment process which have taken place at different trophic levels
(Zhuang et al., 2013). However, it
has been noted that heavy metal concentrations vary according to demographic
climates. Heavy metals concentration are reported in industrialized nations
such as China, United States of America (USA), Germany, Russia and Japan, where
most imported fishes are cultured before sold to Nigeria(Huang, 2003; USEPA,
2009; Molina, 2011; FAO, 2012; WHO, 2012;Zhuang et al., 2013 and Abubakar et al.,
2015). For instance, Huang (2003) reports that heavy metals entering the
aquatic ecosystems in the coastal waters of Eastern Taiwan, are deposited in
aquatic organisms continually, which through the effects of bioaccumulation via
the food chain becomes potentially toxic to humans as the accumulation can
reach substantially high levels, with resultant lethal effects such as renal
failure, autism in children, premature births, heart failures etc.
1.2 Statement of Research Problem
Although, Kaduna State is not a heavily
industrialized city (Nnaji et al.,
2011), it still has its fair share of pollutants within her surrounding, due to
the presence of several cottage industries and activities of the Nigerian Bottling
Company, Nigeria Breweries, Sunseed Oil Mill, Zaria Industries Limited and the
Kaduna Refinery, whose effluents, containing heavy and trace metals are
continually being discharged into River Kaduna, River Kubanni, River Galma and
other surrounding water bodies (Nwaedozie, 1998; Uzairu et al., 2009; Nnaji et al., 2011; Abubakar et al., 2012). Thus, it is pertinent to examine the levels of
heavy metals concentrations in wild
fish species in river bodies used for aquaculture in Kaduna state, in order to
determine the contamination levels.
Also because of the growing aquaculture practice in Nigeria, Kaduna
inclusive,farmers are constantly seeking ways to improve and manage fish farms
despite water shortages, especially in the northern part of Nigeria (FAO, 2007;
Galadima et al., 2011; WHO, 2012)
there‟s is a growing concern that the water sourced from hand dug wells and
boreholes contain heavy metals as a result of sustained practice of illegal
mining of solid minerals, urban sewage runoff and inadequate waste management
practices (Sakai et al., 1996;
Dimuna, 2004; Dan-Azumi and Bichi, 2010; Galadima et al., 2011; Galadima and Garba,
2012; Agwu, 2012). These locally cultured fish speciesmay often contain
contaminants, including heavy metals, above acceptable levels. Thus, there is a
need to analyse heavy metal concentrations in both wild and locally farmed
fishes in Kaduna State, to establish their suitability for human consumption.
1.3 Justification of the Study
Although many studies have been done on the levels of heavy metals in
fish samples along theWest African Sub-region (Sodomou et al., 2005; Voegborlo et al.,
2006; Christopher et al.,2009; Voegborlo and Adimado, 2010and
Kwaansa-Ansah, 2012), very little work has
beenconducted in Kaduna, Nigeria, especially in relation to an analysis of
heavy metals in wild and locally farmed fish species.
Heavy metals are persistent environmental
contaminants, and are at least five times denser than water, and as such they
cannot be metabolized by the body and thus becomes bio-accumulative (Es‟haghi,
2011), thus heavy metal contamination of water bodies has been of major concern
regarding their toxicity, persistence and non-degradability in the environment
(Onianwa, 2001; Butu, 2013; Iguisiet al.,
2001; Udiba et al., 2014).
Also, the role of aquaculture and fisheries to the
Nigerian economy is significant but consumers‟ safety must not be toyed with,
but for now it has not reached any appreciable level, primarily due to improper
management, inadequate quality control measures and inadequate waste management
systems. These have been highlighted as some of the major problems of fish
consumption in Nigeria(Kudiet al.,
2008; Adewuyi et al., 2010; Galadima
and Garba, 2012 andOforka et al, 2012).
1.4 Aim and Objectives of the Study
This study is aimed at investigating the presence
andbioaccumulation pattern of heavy metals in wild and farmed Clarias gariepinus inKaduna to establish
theirsuitability for human consumption.
The specific objectives of this
study are as follows:
i.
To analyse the water quality parameters of the
selected rivers and fish farms.
ii.
To determine the concentration
levels of heavy metals in the selected rivers and fish farms.
iii.
To determine the concentration
levels of heavy metals in wild and farmed C.
gariepinus in the selected rivers and
fish farms.
1.5 Hypotheses
The following null hypotheses
would be used in this study:
i.
There is no significant
difference in water quality parameters of the selected rivers and fish farms.
ii.
There is no significant
difference in heavy metals concentrations in the selected rivers and fish
farms.
iii.
There is no significant
difference in heavy metal concentrations in wild and farmed C. gariepinus
in the selected rivers and fish farms.
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