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ABSTRACT

Assessment of water quality in wells located near three abandoned indigo dyeing centers in Zaria City, Nigeria was carried out. Physicochemical parameters (pH, temperature, electrical conductivity, turbidity, colour, total dissolved solid, hardness, alkalinity, Cl- PO43-, NO3-, SO42-, dissolved oxygen, biochemical oxygen demand and chemical oxygen demand), heavy metals ( Ni, Cr, Cu, Pb , Cd) and coliform test using standard method were used to study the well water quality in dry and wet seasons. The presence of dye residue in water was determined using FTIR and UV-Visible spectroscopy. The data obtained were compared with SON standard values and discussed. The result showed physical parameters (pH, temperature, turbidity, colour, and total dissolved solid) ranged from 7.92-8.75, 24.01-24.45°C, 1.33-281.33NTU, 5-30 hazen and 617.33-3186.37 mg/dm3 for dry season and 7.40-8.57, 28.05-29°C, 1.33-66.33NTU, 5-20 hazen and 444.33-3563.33mg/dm3 for wet season respectively. The result for chemical parameters (electrical conductivity, dissolved oxygen, biochemical oxygen demand, Cl-, hardness, alkalinity, SO42-, PO43-, NO3-, chemical oxygen demand) ranged from 272.00-5840.00μʅ/cm, 0.30-0.77mg/dm30.13-0.63mg/dm3, 2017.33-44613.46mg/dm3, 276.36-2898.91mg/dm3, 313.33-1663.33mg/dm3, 73.3-438.33mg/dm3, 0.70-12.67mg/dm3, 10.83-119.20mg/dm3and 8.00-56.67mg/dm3for dry season and 933.99-4783.33μʅ/cm, 0.30-2.13mg/dm3, 0.1-0.93mg/dm3,1798.67-7277.03mg/dm3, 538.95-3046.80mg/dm3, 153.33-1160.00mg/dm3, 42.67-351.67mg/dm3, 0.43-17.37mg/dm3,3.20-105.13mg/dm3and 2.03-35.00mg/dm3 for wet season respectively. Values obtained for metal analysis (Pb, Cd, Cu, Cr and Ni) ranged from not detected-0.09mg/dm3, 0.01-0.02mg/dm3, 0.04-0.11mg/dm3, not detected-0.21mg/dm3 and not detected-0.05mg/dm3 for dry season and 0.11-0.19mg/dm3, not detected-0.02mg/dm3, 0.00-2.26mg/dm3,0.00-0.18 mg/dm3and0.01-0.04. Large numbers of bacteria were found in wet season than in dry, none of the sampled wells gave a result that fell within the permissible level for drinking water quality given by the SON (2007) for both seasons. Principal Component Analysis (PCA) was used to investigate the sources of pollution and the course of variation in the water samples for two seasons and Cluster Analysis (CA) was used to detect the similarities in the well water samples for the two seasons. The principal component analysis extracted important parameters which indicated the abandoned dyeing pits, pits toilet in close proximity to the well water, seasonal effects and domestic wastes to be the sources of pollution. Hierarchical Cluster Analysis grouped the sampled wells into three clusters for both seasons showing the similarities between sampling wells during the period under investigation. UV-Visible spectra of the extracts showed maximum absorption peaks at 465nm, 235nm and 220nm when, methanol, diethyl ether and n-hexane respectively were used for the extractions. The extracts showed the presence of C-H, CO,C-C=C, CH3 –C-H and N-H in FTIR spectra.

TABLE OF CONTENTS

Title Page …………………………………………………………………………………………………………………. i
Cover Page ……………………………………………………………………………………………………………….. i
Title Page ………………………………………………………………………………………………………………… ii
Cover Page ………………………………………………………………………………………………………………. ii
Declaration ……………………………………………………………………………………………………………… iii
Certification ……………………………………………………………………………………………………………. iv
Dedication ……………………………………………………………………………………………………………….. v
Acknowledgement …………………………………………………………………………………………………… vi
Abstract…….. ………………………………………………………………………………………………………… vii
Table of Contents…………………………………………………………………………………………………….. ix
List of Figures ……………………………………………………………………………………………………….. xiv
List of Plates …………………………………………………………………………………………………………. xvi
List of Appendices ………………………………………………………………………………………………… xvii
CHAPTER ONE …………………………………………………………………………………………………….. 1
1.0 Introducton …………………………………………………………………………………………………. 1
1.1 Justification ………………………………………………………………………………………………… 2
1.2 Aim of Study ……………………………………………………………………………………………… 3
1.3 Objectives of the Study ………………………………………………………………………………… 3
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CHAPTER TWO ……………………………………………………………………………………………………. 4
2.0 LITERATURE REVIEW ………………………………………………………………………….. 4
2.1 Water Pollution Indicators ……………………………………………………………………………. 6
2.1.1 Heavy metals ………………………………………………………………………………………………. 6
2.1.1.1 Copper …………………………………………………………………………………………………………. 6
2.1.1.2 Lead …………………………………………………………………………………………………………….. 7
2.1.1.3 Chromium ………………………………………………………………………………………………….. 7
2.1.1.4 Cadmium ……………………………………………………………………………………………………… 8
2.1.1.5 Nickel…………………………………………………………………………………………………………… 9
2.1.2 pH 9
2.1.3 Electrical conductivity ……………………………………………………………………………….. 10
2.1.4 Turbidity ………………………………………………………………………………………………….. 10
2.1.5 Temperature ……………………………………………………………………………………………… 10
2.1.6 Colour ……………………………………………………………………………………………………… 11
2.1.7 Total dissolved solid ………………………………………………………………………………….. 11
2.1.8 Water hardness ………………………………………………………………………………………….. 11
2.1.9 Alkalinity …………………………………………………………………………………………………. 12
2.1.10 Dissolved oxygen …………………………………………………………………………………………. 12
2.1.11 Chemical oxygen demand …………………………………………………………………………… 13
2.1.12 Biochemical oxygen demand ………………………………………………………………………….. 13
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2.1.12 Chloride……………………………………………………………………………………………………. 14
2.1.13 Nitrates………………………………………………………………………………………………………… 14
2.1.14 Sulphate……………………………………………………………………………………………………. 15
2.1.15 Phosphate …………………………………………………………………………………………………….. 15
2.1.16 Bacteriological analysis ……………………………………………………………………………… 16
2.2 Instruments ……………………………………………………………………………………………….. 17
2.2.1 Principle of atomic absorption spectroscopy ………………………………………………… 17
2.2.2 Principle of ultraviolet–visible spectroscopy ……………………………………………………… 17
2.2.3 Principle of fourier transform infra-red spectroscopy …………………………………….. 18
CHAPTER THREE ………………………………………………………………………………………………. 20
3.0 MATERIALS AND METHODS ………………………………………………………………. 20
3.1 Description of the Study Area ……………………………………………………………………… 20
3.2 Sample Collection …………………………………………………………………………………….. 20
3.2.1 Sampling locations …………………………………………………………………………………….. 20
3.2.2. Water sampling techniques ……………………………………………………………………………… 29
3.3 Preparation of Solutions ……………………………………………………………………………… 29
3.3.1 Manganous sulphate solution ………………………………………………………………………. 29
3.3.2 Alkali iodide-azide reagent …………………………………………………………………………. 29
3.3.3 Sodium thiosulphate solution …………………………………………………………………………… 29
3.3.4 Potassium dichromate digestion solution………………………………………………………. 30
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3.3.5 Standard ferrous ammonium sulphates solution ……………………………………………. 30
3.3.6 Standard EDTA solution …………………………………………………………………………….. 30
3.4 Determination of Physico-chemical Parameters of Water Samples ………………… 30
3.4.1 Temperature measurement ………………………………………………………………………….. 30
3.4.2 Measurement of pH……………………………………………………………………………………. 30
3.4.3 Determination of conductivity …………………………………………………………………….. 31
3.4.4 Determination of turbidity ………………………………………………………………………….. 31
3.4.5 Determination of total dissolved solid ………………………………………………………….. 31
3.4.6 Determination of dissolved oxygen …………………………………………………………….. 31
3.4.7 Determination of biochemical oxygen demand ……………………………………………… 32
3.4.8 Determination of chemical oxygen demand ………………………………………………….. 32
3.4.9 Determination of total hardness …………………………………………………………………… 33
3.4.10 Determination of alkalinity ………………………………………………………………………… 34
3.4.11 Determination of chlorides …………………………………………………………………………. 34
3.4.12 Determination of phosphates ………………………………………………………………………. 35
3.4.13 Determination of sulphate …………………………………………………………………………… 35
3.4.14 Determination of nitrate …………………………………………………………………………….. 35
3.5 Elemental Analysis by Atomic Absorption Spectrophotometer ……………………….. 36
3.5.1 Sample pre -treatment ………………………………………………………………………………… 36
3.5.2 Preparation of standard solution for cadmium ……………………………………………….. 36
xii
3.5.2 Preparation of standard solution for chromium ……………………………………………… 36
3.5.3 Preparation of standard solution for lead ………………………………………………………. 37
3.5.4 Preparation of standard solution for copper …………………………………………………… 37
3.5.5 Preparation of standard solution for nickel ……………………………………………………. 37
3.6 Determination of Coliform Bacteria …………………………………………………………….. 37
3.6.2 Serial dilution ……………………………………………………………………………………………. 38
3.7 Spectrophotometric Analysis of Dye Residue in Water Sample ………………………. 38
3.7.1 Uv-visible spectrophotometric determination of dry residue ………………………….. 39
3.8.2 FTIR spectrophotometric determination of dry residue …………………………………… 39
3.8 Statistical Treatment of Results …………………………………………………………………… 39
3.8.1 Principal component analysis …………………………………………………………………………… 40
3.8.2 Cluster analysis ………………………………………………………………………………………………. 41
CHAPTER FOUR ………………………………………………………………………………………………… 43
4.0 RESULTS ……………………………………………………………………………………………….. 43
4.1 Descriptive Summary of Data ……………………………………………………………………… 43
4.2 Statistical Treatment of Data ………………………………………………………………………. 43
4.3 Coliform Test ……………………………………………………………………………………………. 43
4.4 Spectroscopic Studies of Dye Residue in Water…………………………………………….. 43
xiii
CHAPTER FIVE ………………………………………………………………………………………………….. 72
5.0 DISCUSSION …………………………………………………………………………………………. 72
5.1 Statistical Treatment of Data ……………………………………………………………………… 75
5.1.1 Principal component analysis ……………………………………………………………………… 75
5.1.2 Cluster analysis …………………………………………………………………………………………. 79
5.2 Coliform Bacterial Density ………………………………………………………………………… 80
5.3 Spectroscopic Studies of Dye Residues for Water ………………………………………… 81
CHAPTER SIX …………………………………………………………………………………………………….. 82
6.0 SUMMARY, CONCLUSION AND RECOMMENDATION ……………………… 82
6.1 Summary ………………………………………………………………………………………………….. 82
6.2 Conclusion ……………………………………………………………………………………………….. 83
6.2 Recommendations ……………………………………………………………………………………… 84
References …………………………………………………………………………………………………………….. 85
xiv

CHAPTER ONE

Project Topics

1.0 INTRODUCTON
Water is absolutely essential to life. It is undoubtedly one of the most precious natural resource that exists on our planet. Humans may survive for several weeks without food, but barely few days without water because constant supply of water is needed to replenish the fluids lost through normal physiological activities, such as respiration, perspiration, urination (Murray, 2003). The essential role played by water in supporting human life, makes it a great potential for transmitting diseases and illnesses if contaminated (Yakasaiet al., 2004). Adequate supply of safe and potable water assist in preventing the spread of gastrointestinal diseases, supports domestic and personal hygiene, and improves the standard of living (Ike and Ugodulunwa, 1999). Access to safe drinking water is a basic human need and a fundamental human right. Even at that, 1 billion people worldwide live without access to safe and potable drinking water and nearly 50% of them, suffer from health problems due to lack of safe drinking water sources and sanitation (Giwaet al., 2008). Ground water is the most suitable fresh water resource with nearly balanced concentration of the salts for human consumption. It is generally less susceptible to contamination and pollution when compared to surface water bodies (Zaman, 2002). Over burden of the population pressure, unplanned urbanization, unrestricted exploration policies and dumping of the polluted water at inappropriate place enhance the infiltration of harmful compounds to the ground water (Sandeep and Shweta, 2009). Furthermore, the natural impurities in rainwater, which replenishes groundwater systems, get removed while infiltrating through soil strata (Veslind, 1993).
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In the last few decades, there has been a tremendous increase in the demand for fresh water due to rapid growth of population and the accelerated pace of industrialization (Ramakrishnaiah, 2009). The quality of water is vital concern for mankind since it is directly linked with human welfare. Due to inadequate supply of pipe –borne water in towns and cities in Nigeria, many people have been sourcing their daily water need from wells in order to meet the daily water demand (Adejide and Ajibade, 2005). The major substitutes for pipe borne water are shallow hand dug wells in areas of low and average income (Akinleye,2008). Groundwater contamination is responsible for water related and water borne diseases. The source of ground water contamination could be natural through ground water -rock interaction or through anthropogenic sources which involve human activities. Ground water pollution which is man-made is worse than natural pollution as it eventually renders water unsuitable for use (Abimbolaet al., 2005). Ground water pollution due to toxic organic compounds is a serious problem which has necessitated the legal regulations concerning disposal of chemicals into the natural environment being more and more restrictive (Pieter and Nazar, 2011). In Zaria, due to scarcity of drinking water, people collect water from surface streams and shallow wells. Therefore majority of the populace rely heavily on untreated well water and boreholes (Musa et al., 2004).
1.1 Justification
Kaduna State was famous for its traditional indigo dyeing pits, during the trans Sahara trade in northern part of the country. Local industries like the dyeing industry, proved vital to Nigeria’s socio-economic development, apart from providing employment to a good number of people, it serves as source of tourist attraction. These local industries used a local technology of dyeing and discharge of waste. Ideally citing industries should strike a balance between socio-
3
economic and environmental considerations. This was not the case with local dyeing industries in Zaria, they were mostly located within the city walls and surrounded by settlements. The mode of disposal was usually in pits dug for that purpose. Previous studies, when the dyeing activities were functional have shown contamination of ground water in close proximity to the dye wastes well in Zaria (Ajibola and Rilwanu, 1998). The findings show environment-related ailments ranging from skin and eye problems to cancerous tumours and methaemoglobinaemia in children which were attributed to the disposal of dye wastes in these areas.Even though most of these dyeing pits have long been abandoned, their impacts on the settlements around them are still persisting.
1.2 Aim of Study
The overall aim of this study is to assess the water quality in wells located near abandoned indigo dyeing pits in Zaria City, Kaduna State, Nigeria.
1.3 Objectives of the Study
The above aim will be achieved by the following objectives:
i. To determine the level of some heavy metals (Ni, Cd, Cu, Pb, Cr) concentration in the well water during wet and dry seasons.
ii. To determine some physiochemical properties of well water during wet and dry seasons.
iii. To determine the level of coliform in the water samples.
iv. To determine qualitatively, the presence of dye residues using FTIR and UV-Visible Spectroscopies.

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