AN ASSESSMENT OF THE HEAVY METAL CONTENTS OF THE OBAFEMI AWOLOWO UNIVERSITY TEACHING AND RESEARCH POND I, ILE IFE,

, OSUN STATE.

BY

IKPE, EMMANUEL CHUKWUMA B.Sc (HONs) CHEMISTRY SCP06/07/H/1471

A RESEARCH PROPOSAL SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE AWARD OF POSTGRADUATE DIPLOMA (PGD) IN ENVIRONMENTAL CONTROL AND MANAGEMENT

THE

SUPERVISOR: PROF. I.F ADENIYI DEPARTMENT OF ZOOLOGY OBAFEMI AWOLOWO UNIVERSITY ILE IFE

AUGUST, 2007.

INTRODUCTION. As the world is ushered into the modern era of civilization, water and its management will continue to be a major issue, which will definitely have profound impact on our lives and that of our planet Earth than ever before (Herschy, 1999). Water is indeed life and the most important natural resources for life. Availability of safe and reliable source of water is an essential pre requisite for sustainable development. Deserts are not habitable because of lack of water. Continuous urban development and large solid waste pose as major environment risks because of the difficulties in disposal. Landfills and other solid wastes disposal sites are major targets of pollution because rainfall and groundwater leach these highly contaminated substances into lakes, ponds, rivers, streams, and waterways (surface waters) which are inadvertently used by people residing in such areas. Water borne diseases kill 50,000 people daily (Herschy, 1999) and yearly about 4 million children under the age of five die in developing countries due to water related problems (USAID, 1990; Warner, 1998). Water pollution is of grave consequence because both terrestrial and aquatic life may be poisoned; it may cause disease due to the presence of some hazardous substances, and hence significantly, hinder economic activities. The causes and forms of water pollution according to Strandberg (1971) include sewage and other oxygen demanding wastes,
2

infectious agents, organic chemicals, other chemicals and mineral substances, sediments (turbidity), radio-active substances and heat. Additionally, several human activities that may result to water pollution include the following, agriculture, irrigation, urbanization, mining fire and industrialization (Goudie, 1990). These activities have been documented to have impacted negatively in some specified Nigerian surface waters especially in the Niger delta region (Izonfuo and Bariweni, 2001). Heavy metals are of particular interest because they are among the most toxic pollutants. Heavy metals are metals with a density greater than 5g/cm3. They are less abundant than the light metals. One of their characteristics is their relative inertness. Because they hold electrons rather tightly, these metals do not form ions with ease, and they do not readily yield their electron to electron-hungry element like oxygen. Therefore, heavy metals tend to resist oxidation, which implies that after release into the environment they are persistent contaminants. The noble or coinage metals-Gold (Au), Platinum (Pt), and Silver (Ag) are heavy metals that keep their metallic luster for ages because oxidation occurs only slowly or not at all. Some heavy metals, mostly notably copper (Cu), Zinc (Zn), Cobalt (Co) and chromium (Cr) are essential to life in trace or small quantities. They are architecture of various proteins, enzymes and vitamins.

Natural processes such as bedrock and soil weathering, wind and water erosion, violence activity, sea salt spray, and forest fires release heavy metals into the environment. The modern age of heavy metal pollution has its beginning with the industrial revolution. The rapid development of industry, intensive agriculture, transportation, and urbanization, has been the precursor of todays environmental

contamination problems. Anthropogenic utilization has also increased heavy metal distribution by removing the substances from localized ore deposits and transporting them to other parts of the environment. Heavy metal by products result from many activities including ore extraction and smelting fossil fuel combustion, dumping and land filling of industrial wastes, exhausts from leaded gasoline, steel, iron, cement and fertilizer production, refuse and wood combustion. Heavy metal has also increased through activities such as farming, deforestation, construction dredging of harbors and the disposal of municipal sludge and industrial wastes on land. STATEMENT OF PROBLEM Heavy metals are one of the causes and forms of water pollution, which is not commonly addressed. Although these trace elements are usually present in the environment, they are potentially extremely toxic and not only would they affect the biota at a water soluble concentration at less that 1 part per million (ppm), humans can be grossly affected (Freedman,
4

1989). Therefore the high concentrations and unacceptable levels of the elements may constitute risk to health. However, the emission of airborne metallic pollutant has now reached such proportions that long-range atmospheric transport causes contamination, not only in the vicinity of industrialized regions, but also in more remote areas. AIMS AND OBJECTIVES The general aim of this study is to: assess the heavy metal levels of water in the farm pond. The specific aims are to: (i) assess the horizontal and vertical variations in the metals within the pond. (ii) show the pattern of seasonal variability in the concentration of the heavy metals. (ii) assess the suitability of the pond water for a number of applications, including for fish culture and irrigation as presently applicable. SCOPE OF STUDY To review literature on the heavy metal contents of fresh water (rivers, lakes and ponds) and the analysis of heavy metal contents of Research farm pond water collected over one annual cycle.

RESEARCH METHODOLOGY Three sampling stations will be established along the horizontal axis of the lake denoted (A, B, and C). Station A will be located towards the deepest portion of the lake close to the dam, mid-point from the shores. Station B will be established at the middle basin of the lake while station C will be located at the riverside portion of the lake. At station A, four vertical samples will be collected for heavy metal analysis from the surface, 1metre depth, 2metres depth and the bottom of the lake. At station B, three vertical samples will be collected from the surface, 1metre depth and at the bottom of the lake, while at station C, two samples will be collected, from the surface and the bottom of the lake. An improvised water sampler will be used for sampling sub-surface water at these various depths. Field survey will be conducted monthly for a period of 12 months. The following parameters of the lake water will be determined on the field: depth and transparency (using a secchi disc) and temperature (using a mercury in bulb thermometer). Heavy metals to be determined will include: (Arsenic (As), Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu), Iron (Fe), Manganese (Mn), Nickel (Ni), Lead (Pb), Zinc (Zn) All determinations shall be carried out using atomic absorption spectrometry (AAS) with adequate quality assurance and quality control measures (QA/QC).
6

THE AREA OF STUDY The Research farm pond is located at the Teaching and Research farm about 4km from the central campus. The pond was formed by the impoundment of Elerin and Omifunfun stream in 1976. Obafemi Awolowo University is located in Ile-Ife, which lies in the Southern climate belt of Nigeria. The climate of Ile-Ife area is typically humid tropical with two major seasons, that is, dry and rainy seasons. Rainy season starts from April and ends in October, while the dry season starts from November and ends in March.

REFERENCES Freedman, B. (1989). Environmental ecology, Academic press Inc., San Diego. Goudie, A. (1990). The human impact on the natural environment (3rd edition). The MIT Press, Cambridge, Massachusetts. Herschy, R.W. (1999). Hydrometry Principles and Practices. (2nd edition) John Wiley & Sons, Chichester Izonfuo, L.W.A: Bariweri (2001). The Effect of Urban Runoff water and Human Activities on some physico-chemical parameters of the Epie Creek in the Niger Delta. J. app. sci. environ. Management. 5 (1): 47 55.
7

Strandberg, C.H. (1971). Water Pollution. In: GH Smith (ed), Conservation of Natural Resources (4th edition) Wisely, New York.189 219. United States Agency for International Development (USAID) (1990). Strategies for Linking water and sanitation programs to child survival USAID, Washington, D.C Warner, D. (1998). Drinking water Supply and environmental sanitation for health. Presented at the International conference of water and Sustainable Development, Paris.

AN ASSESSMENT OF THE HEAVY METAL CONTENTS OF THE O.A.U. TEACHING AND RESEARCH POND 1,ILE-IFE,OSUN STATE.

A PGD Propositional Seminar Presented By IKPE,EMMANUEL CHUKWUMA SCP06/07/H/1471 Institute of Ecology And Environmental Studies OAU,ILE-IFE. Supervisor 10/12/2008 OAU Prof.I .F Adeniyi

Introduction
Water pollution is of grave consequence because both terrestrial and aquatic life may be poisoned; it may cause disease due to the presence of some hazardous substances, and hence significantly, hinder economic activities. Heavy metals are of particular interest because they are among the most toxic pollutants. Heavy metals are metals with a density greater than 5g/cm3.One of their characteristics is their relative inertness, which implies that after release into the environment they are persistent 10/12/2008 OAU contaminants..

Introduction contd.
Heavy metals occur naturally in the environment in rocks and ores. They cycle through the environment by geological and biological means. Anthropogenic activities have also increased the release of heavy metals into the environment, there by causing environmental pollution. Such activities include ore extraction and smelting, fossil fuel combustion, dumping and land filling of industrial wastes, exhausts from leaded gasoline, steel, iron, cement and fertilizer production, refuse and wood combustion.
10/12/2008 OAU 3

Statement of problem
Heavy metals are one of the causes and forms of water pollution, which is not commonly addressed. Although these trace elements are usually present in the environment, they are potentially extremely toxic and not only would they affect the biota at a water soluble concentration at less that 1 part per million (ppm), humans can be grossly affected (Freedman, 1989). Therefore the high concentrations and unacceptable levels of the elements may constitute risk to health. However, the emission of airborne metallic pollutant has now reached such proportions that long-range atmospheric transport causes contamination, not only in the vicinity of industrialized regions, but also in more remote areas.
10/12/2008 OAU 4

Aims and Objectives

Assess the heavy metal levels of water in the farm pond. Assess the horizontal and vertical variations in the metals within the pond. Show the pattern of seasonal variability in the concentration of the heavy metals. Assess the suitability of the pond water for a number of applications, including for fish culture and irrigation.
10/12/2008 OAU 5

Scope of study
To review literature on the heavy metal contents of fresh water (rivers, lakes and ponds) and the analysis of heavy metal contents of Research farm pond water collected over one annual cycle.

10/12/2008

OAU

Research methodology
Three sampling stations will be established along the horizontal axis of the lake denoted (A, B, and C). Station A will be located towards the deepest portion of the lake close to the dam, mid-point from the shores. Station B will be established at the middle basin of the lake while station C will be located at the riverside portion of the lake. At station A, four vertical samples will be collected for heavy metal analysis from the surface, 1metre depth, 2metres depth and the bottom of the lake. At station B, three vertical samples will be collected from the surface, 1metre depth and at the bottom of the lake, while at station C, two samples will be collected, from the surface and the bottom of the lake.
OAU 7

10/12/2008

RESEARCH METHODOLOGY CONT.

An improvised water sampler will be used for sampling sub-surface water at these various depths. Field survey will be conducted monthly for a period of 12 months. The following parameters of the lake water will be determined on the field: depth and transparency (using a secchi disc) and temperature (using a mercury in bulb thermometer). Heavy metals to be determined will include: (Arsenic (As), Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu), Iron (Fe), Manganese (Mn), Nickel (Ni), Lead (Pb), Zinc (Zn) All determinations shall be carried out using atomic absorption spectrometry (AAS) with adequate quality assurance and quality control measures (QA/QC).
10/12/2008 OAU 8

THE AREA OF STUDY

The Research farm pond is located at the Teaching and Research farm about 4km from the central campus. The pond was formed by the impoundment of Elerin and Omifunfun stream in 1976. Obafemi Awolowo University is located in Ile-Ife, which lies in the Southern climate belt of Nigeria. The climate of Ile-Ife area is typically humid tropical with two major seasons, that is, dry and rainy seasons. Rainy season starts from April and ends in October, while the dry season starts from November and ends in March.
10/12/2008 OAU 9

AN ASSESSMENT OF THE HEAVY METAL CONTENTS OF THE O.A.U. TEACHING AND RESEARCH FARM POND 1, ILE-IFE,OSUN STATE.
A PGD Final Seminar Presented By IKPE,EMMANUEL CHUKWUMA ( B.Sc. Chemistry ) SCP06/07/H/1471 Institute of Ecology And Environmental Studies O.A.U.,ILE-IFE. Supervisor Prof. I .F Adeniyi

INTRODUCTION
Water is life and indeed the most important natural resource without which life would be non-existent. Water pollution is the addition of undesirable foreign matter, which deteriorates the quality of the water. Heavy metals are of particular interest because they are among the most toxic pollutants. Heavy metals are metals with a density greater than 5g/cm3 . They occur naturally in the environment in rocks and ores. Anthropogenic activities have also increased the release of heavy metals into the environment,there by causing environmental pollution. Such activities include: ore extration and smelting, fossil fuel combustion, dumping and landfilling of industrial wastes, exhausts from leaded gasoline, steel, iron, cement and fertilizer production and refuse and wood combustion.

STATEMENT OF THE STUDY PROBLEM

Heavy metals are one of the causes and forms of water pollution, which is not commonly addressed. They are potentially toxic and not only would they affect the biota at a water soluble concentration at less than 1 ppm, humans can be grossly affected ( Freedman, 1989). Therefore the high concentrations and unacceptable levels of the elements may constitute risk to health.

AIMS AND OBJECTIVES OF STUDY

The general aim of this study is to: assess the heavy metal levels of water in the farm pond. The specific aims are to : Assess the horizontal, vertical and seasonal variations in the concentrations of the heavy metals. Assess the suitability of the pond water for a number of applications, including for fish culture, and irrigation.

SCOPE OF THE STUDY

To review literature on the heavy metal contents of fresh water (rivers, lakes and ponds) and the analysis of farm pond water samples collected over one annual cycle for heavy metals using atomic absorption spectrophotometry.

GOAL/ESSENCE/PROBABLE APPLICATION OF STUDY This work is expected to provide information on the level of heavy metal concentration or contamination of the O.A.U Teaching and Research Farm Pond I, Ile-Ife. bring to focus on the suitability of the pond water for a number of applications, including for fish culture and irrigation. provide information for O.A.U. Teaching and Research Farm Pond I authority or management to design and put in place an appropriate indicator parameters for monitoring the level of heavy metal concentration in the pond water.

THE STUDY AREA

The pond is located at the Faculty of Agriculture Teaching and Research Farm, O.A.U., Ile-Ife.Two ponds are located at the farm, this study was carried out at the one located after the poultry section. The pond was impounded for the supply of water for irrigation to the nearby Teaching and Research farms. The pond which was constructed between March and July 1967, occupies an estimate area of 11 acres at maximum fill. The two inflows to the pond are Elerin Streams which flow from between two villages, Kajola and Obagbile, and Omifunfun. They flow from a relatively higher plain and through a secondary forest.

THE STUDY AREA CONTD

Obafemi Awolowo University is located in Ile-Ife, which lies in the Southern climate belt of Nigeria. The climate of Ile-Ife area is typically humid tropical with two major seasons, that is, dry and rainy seasons. Rainy season starts from April and ends in October, while the dry season starts from November and ends in March.

THE STUDY AREA CONTD

Area = 11 Acres

Figure 1:The Teaching and Research Farm Pond 1 O.A.U.,Ile-Ife,Osun State

MATERIALS AND METHODS

Sampling Programme and Sampling Stations Method of Analysis The heavy metals were determined instrumentally using atomic absorption spectrometry (AAS) at different wavelengths, Arsenic (As) at the wavelength of 193.0 nm, Cadmium (Cd) 228.0 nm, Chromium (Cr) 429.0 nm, Cobalt (Co) 240.0 nm, Nickel (Ni) 232.0 nm, Manganese (Mn) 403.0 nm, Copper (Cu) 324.7 nm, Iron (Fe) 2248.0 nm, Lead (Pb) 283.0 nm, and Zinc (Zn) 213.0 nm. Concentrations were measured in mg/l according to Golterman et al. (1978).

RESULTS
Table 1:Summary of Descriptive Statistics of Heavy Metals Concentration (mg/l) in the Teaching and Research Farm Pond 1 O.A.U.
Heavy Metal Arsenic Cobalt Cadmium Chromium Copper Iron Manganese Nickel Lead Zinc % Detection 68.4 43.4 59.2 53.8 92.1 63.2 47.4 46.1 51.3 53.9 Maximium 4.20 0.14 2.63 0.32 10.00 20.20 2.24 2.80 0.49 6.92 Median 0.70 0.00 0.36 0.02 2.77 2.60 0.00 0.00 0.02 0.42 Mean 1.022 0.024 0.594 0.057 2.910 3.987 0.371 0.446 0.074 1.264 S.E 0.121 0.004 0.081 0.009 0.218 0.563 0.066 0.072 0.013 0.185 %C.V 103.2 143.5 119.6 133.7 65.3 123.2 153.9 140.4 149.0 127.4 Kurtosis 0.22 0.99 0.38 1.15 4.28 2.04 1.76 1.56 3.08 1.36 Skewness 0.93 1.35 1.136 1.35 1.52 1.56 1.62 1.40 1.84 1.31

Table 2:Descriptive Statistics of Heavy Metals Concentration (mg/l) in the Teaching and Research Farm Pond 1 O.A.U.
Heavy Metals Arsenic Cobalt Surface (n=30) Max 4.20 0.10 Mean 0.783 0.024 0.490 0.067 2.491 5.070 0.427 0.437 0.093 1.338 S.E 0.208 0.006 0.128 0.015 0.206 1.049 0.103 0.132 0.024 0.290 %C.V 145.9 139.1 143.2 126.28 45.2 113.3 132.2 165.9 139.0 118.8 Max 3.30 0.11 0.71 0.18 10.00 17.30 2.24 1.60 0.15 3.09 Mid-depth (n=20) Mean 1.090 0.022 0.480 0.046 3.357 3.405 0.420 0.410 0.032 1.164 S.E 0.224 0.007 0.136 0.013 0.538 1.149 0.162 0.114 0.011 0.265 %C.V 91.8 145.0 126.7 125.2 71.7 150.9 172.2 124.3 159.9 101.9 Max 2.90 0.14 2.47 0.26 10.00 11.70 1.42 1.60 0.39 6.92 Bottom (n=26) Mean 1.185 0.027 0.798 0.058 3.050 3.418 0.269 0.485 0.083 1.210 S.E 0.196 0.008 0.151 0.016 0.420 0.670 0.087 0.119 0.022 0.369 %C.V 84.5 147.0 96.2 143.0 70.2 107.3 164.3 125.1 135.6 158.5

RESULTS CONTD

Cadmium 2.63
Chromium

0.32 4.60

Copper Iron

20.2 0 Manganese 1.80 Nickel Lead 2.80 0.49 5.08

Zinc

Table 3: WHO/EU drinking water standards comparative table

Heavy Metals Arsenic (As) Cobalt (Co) Cadmium (Cd) Chromium (Cr) Copper (Cu) Iron (Fe) Manganese (Mn) Nickel (Ni) Lead (Pb) Zinc (Zn) 3.0 WHOs Standards 1993 (mg/l) 0.01 No guideline 0.003 0.05 2.0 No guideline 0.5 0.02 0.01 EUs Standards 1998 (mg/l) 0.01 Not mentioned 0.005 0.05 2.0 0.2 0.05 0.02 0.01 Not mentioned WHOs Standards (2006) mg/l 0.01 No guideline 0.003 0.05 2.0 No guideline 0.4 0.07 0.01 No guideline

Table 4: Selected Water quality Criteria for Irrigational Water (mg/l)

Elements Arsenic (As) Cobalt (Co) Cadmium (Cd) Chromium (Cr) Copper (Cu) Iron (Fe) Manganese (Mn) Nickel (Ni) Lead (Pb) Zinc (Zn) FAO 0.1 No guideline 0.01 0.1 0.2 No guideline 0.2 0.2 No guideline 2.0

Canada
0.1 No guideline 0.01 0.1 0.2 1.0 No guideline 0.2 0.2 No guideline 1.0 5.0

Nigeria
0.1 No guideline 0.01 0.1 0.2 1.0 No guideline 0.2 0.2 No guideline 0.0 5.0

Sources: FAO,1985; CCREM,1987; FEPA,1991.

Figure 2: The Mean Concentratiions of Arsenic in the Teaching & Research Farm Pond 1, O.A.U.

Figure 3 The Mean Concentratiions of Cobalt in the Teaching & Research Farm Pond 1, O.A.U.

Figure 4: The Mean Concentratiions of Cadmium in the Teaching & Research Farm Pond 1, O.A.U.

Figure 5: The Mean Concentratiions of Chromium in the Teaching & Research Farm Pond 1, O.A.U.

Figure 6: The Mean Concentratiions of Copper in the Teaching & Research Farm Pond 1, O.A.U.

Figure 7: The Mean Concentratiions of Iron in the Teaching & Research Farm Pond 1, O.A.U.

Figure 8: The Mean Concentratiions of Manganese in the Teaching & Research Farm Pond 1, O.A.U.

Figure 9 The Mean Concentratiions of Nickel in the Teaching & Research Farm Pond 1, O.A.U.

Figure 10: The Mean Concentratiions of Lead in the Teaching & Research Farm Pond 1, O.A.U.

Figure 11: The Mean Concentratiions of Zinc in the Teaching & Research Farm Pond 1, O.A.U.

Figure 12: The Concentration of Heavy metals for both Rainy and Dry Seasons in the Teaching and Research Farm Pond 1 O.A.U.

DISCUSSION
General Background Levels All the heavy metals ( As, Co, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn ) analysed in this study were detected in the pond and their mean concentrations were found to be in the order of Fe > Cu > Zn > As > Cd > Ni > Mn > Pb > Cr > Co.

DISCUSSION CONTD
Vertical Distribution Pattern Horizontal Distribution Pattern Seasonal Distribution Pattern Associated Health Risks

CONCLUSIONS
The results showed that the levels of Arsenic, Cadmium, Chromium, Copper, Iron, Nickel and Lead were well above the (WHO,1993 and 2006) and (EU,1998) standards for drinking water and water quality criteria for irrigation water. This indicates that the pond water is unsafe for human consumption. This implies that there is heavy metal contamination in the pond water. The results obtained in this study would serve as baseline data for future heavy metal monitoring of the pond.

RECOMMENDATIONS
Some suggested solutions include: The creation of water collection zones on the edges of the field to trap runoff, which would then be allowed to enter the pond after treatment. Farmers within the catchment area should be encouraged to rationalise the fertilizer applications to reduce the input of heavy metals from the farmland into the pond through runoff. To plant hyper accumulating plants on the bank of the pond for environmental clean up.

The heavy metal contents of the Obafemi Awolowo University (OAU), Teaching and Research Farm Lake, Ile-Ife, Southwest, Nigeria By Adeniyi, I.F., Ikpe, E.C., and Aduwo, A.I. Hydrobiology Section (Laboratory of Limnology) Zoology Department, OAU, Ile-Ife, Nigeria.

INTRODUCTION
1. Background Information
1.1 Nature of heavy metals Major group of aquatic pollutants Non-degradable hence tend to accumulate in the environment Accumulation leads to grave consequences to man and ecosystem Toxic, causes mobidity and diseases More toxic than radioactive wastes and trace organics

INTRODUCTION CONTD
1.2 Heavy metals in Africa
Review by Biney et al (1994), information scarce and scattered Need for information in view of increased urbanization and industrialization in many countries including Nigeria Particularly relevant for Niger Delta and SW Nigeria.

1.3 Previous studies of heavy metals in Ife area

Review by Olabanji and Adeniyi (2006) Components already covered include rain, vegetation, effluent, soils.

INTRODUCTION CONTD
1.4 Previous studies on present study lake
Imevbore et al. (1972) Aderounmu and Adeniyi. (1972)

1.5 Objectives of present study

Levels of ten heavy metals (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in the lake.

MATERIALS AND METHODS

2. Study Area
2.1 General features of Ife area Information available in several published studies e.g. Ako et al. (1990), Adeniyi (1992), Adeniyi and Olabanji (2005). Geology of Pre Cambrian Basement Complex rocks Soils are Lixoxols and Ultisols, mostly of Iwo, Egbeda, Owena (uplands), Oba and Apomu (low lands & valley bottom). Vegetation of Guinean Congolean forest (White, 1983) Climate of Equatorial Hot and wet type, rainfall mainly of conventional type, low peaks (June/July, September/October). Temperature generally high.

MATERIAL AND METHODS CONTD

2.2 The study lake Impounded March May 1967 for water supply to the farm. 07033.3081 07033.3981N, 004032.9391 003033.1431E About 4 ha (11 acres) Fertilized for fisheries development Fish include Tilapia, Hemichromis Clarias and Heterobranchus species.

MATERIAL AND METHODS CONTD

2.3 Sampling programme Monthly sampling through the column at three sampling stations (A,B,C) along the main axis of the lake. Station A (dam site, 6m deep), Station B (midlake, 4m), and Station C (inflow, <2m) Sampling for one annual cycle, 2006 2007 Sampling for heavy metals in 250ml polyethylene bottles. Other in-situ determinations include temperature, pH, Conductivity, Transparency.

MATERIAL AND METHODS CONTD 2.4 Chemical analysis

Analysis carried out at Central Laboratory OAU, Ife. By AAS/FAAS methods using commercial standards for the instrument. Statistical analysis include, Descriptive statistics, Anova, Regression and correlation, and Cluster analysis.

RESULTS
3.1 Statistical Summary
Percent detection generally less 70% except for Cu (92.1%). Distribution pattern positively skewed, i.e. mean>Median>Mode values. Cu and Pb leptokurtic (Kurtosis >3), other platykurtic (Kurtosis 3.0). Median ranking order: Cu>Fe>As>Zn>Cd>Pb>Cr Mn Ni Co. Relatively low levels of ferrous metals (Co, Cr, Mn, Ni) compared to the others (Cu, As, Cd, Pb, Zn). Occur in four long concentration levels Cu>Fe (>1.00mgl-1) As>Zn>Cd (>0.10 1.00mgl-1) Pb>Cr (0.01 0.10mgl-1) Mn>NI>Co (<0.01)

RESULTS CONTD
3.2 Spatial distribution patterns
Most of the metals (As, Cd, Co, Cr, Cu, Ni & Pb) showed an increase from surface to bottom. The degree of difference between surface and bottom values most pronounced and statistically significant based on median values. Fe, Mn and Zn tended to decrease towards the lake bottom Most of the metals showed an increased from Station C (inflow) to Station A (dam site) As, Fe, Ni, Pb, & Zn Cd & Cu showed a decrease from Station C to Station A.

RESULTS CONTD
3.3 Temporal distribution pattern
The values of metals were higher in the rainy season than in the dry season (most pronounced using median values). Ration of RS/DS also most pronounced at Station A (dam site). All metals showed dual peaks over the annual cycle. Major peaks at early rainy season = Co, Cu, As, Ni, Fe. Minor peaks, early RS: Pb, Cd, Cr, Zn Major peaks, late RS; Cd, Cr, Pb Minor peaks, late RS: Cu, Mn Major peaks: DS: Mn, Zn Minor peaks: DS: Fe, Ni, As.

RESULTS CONTD
3.4 Heavy metals and other water quality parameters

Correlation with other parameters generally low. Heavy metals showed negative correlation with pH. Heavy metals showed positive correlation mostly with conductivity, TDS, Colour, and TSS.

Figure 1: The concentration of Heavy metals for both Rainy and Dry season in the Teaching and Research Farm Lake O.A.U

Fig. 2: Cluster analysis of relationship between heavy metals

DISCUSSION
4.1 Probable sources of metals
Most probably of background terrestrial sources within the catchments. (both soil and vegetation). Inputs mainly through runoff, erosion. Agricultural practices, mainly through application of fertilizers, pesticides and herbicide, secondary sources.

DISCUSSION CONTD
4.2 Likely effect of heavy metal contents Water not safe for drinking without treatment, especially in the rainy season. Water suitable for irrigation, aquaculture and other agricultural purposes.

ACKNOWLEDGMENT
Dean Faculty Of Agriculture, O.A.U. Ile-Ife

Thank you.

AN ASSESSMENT OF THE HEAVY METAL CONTENTS OF THE OBAFEMI AWOLOWO UNIVERSITY TEACHING AND RESEARCH FARM POND I, ILE-IFE, OSUN STATE

BY IKPE, EMMANUEL CHUKWUMA. (B.Sc. CHEMISTRY) SCP 06/07/H/1471

A THESIS SUBMITTED TO THE INSTITUTE OF ECOLOGY AND ENVIRONMENTAL STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF POST GRADUATE DIPLOMA IN ENVIRONMENTAL CONTROL AND MANAGEMENT, OBAFEMI AWOLOWO UNIVERSITY (OAU) ILE-IFE, OSUN STATE, NIGERIA

JUNE, 2008

CERTIFICATION
This is to certify that this research study was carried out by Mr.Ikpe Emmanuel Chukwuma (SCP 06/07/H/1471), at the Institute of Ecology and Environmental Studies, Obafemi Awolowo University, Ile-Ife under my supervision.

----------------------Prof. I.F. Adeniyi Supervisor

-------------------------Date

Institute of Ecology and Environmental Studies O.A.U. Ile-Ife, Nigeria.

ii

DEDICATION
I dedicate this research work to God Almighty (I AM) and Prince Pat Abii. I also dedicate this research work to my late sisters Miss Francisca and Miss Monica Ikpe, may their soul rest in peace.

iii

ACKNOWLEDGEMENTS
I first of all thank God for His abundant mercy and for giving me the grace to work hard. I am grateful to Prince Pat Abii (Agu Eze), my mother, Mrs. Agatha Igbo and family and Mrs. Eugenia Marshall for their tremendous financial and moral supports. My Supervisor Prof. I.F. Adeniyi deserves no less my appreciation for his intelligent, academic and professional guidance, advice and suggestion that made this research study a success. My sincere thanks go to all the lecturers in the Institute of Ecology and Environmental Studies, Obafemi Awolowo University, for giving me the rare privilege of sharing in their wealth of knowledge and experience, especially Prof. A. Salami and Dr. O.O. Awotoye. My appreciation also goes to Mr. A.I Aduwo for his assistance and encouragement, Mr. Akinola and Mr. Kayode Adepoju for their assistance. Thanks to all my friends, who contributed in their various capacities to ensure the success of this research study. Finally I wish to appreciate the assistance and co-operation received from The Dean, Faculty of Agriculture who kindly gave us the permission to undertake studies on the farm pond.

iv

TABLE OF CONTENTS Title page Certification Dedication Acknowledgments Table of contents List of Tables List of Figures Abstract CHAPTER ONE: INTRODUCTION 1.1 1.2 1.3 1.4 1.5 1.6 Importance of Water Background to the Study Statement of Study Problem Aims and Objectives of Study Scope of the Study Goal/Essence/Probable Application of Study i ii iii iv vi viii xii xiv 1 1 2 4 5 5 5 7 7 8 9 10

CHAPTER TWO: LITERATURE REVIEW 2.1 2.2 2.3 2.4 Water quality and its importance Effects of Environment and resource use on water quality Measurement of water quality. The Effects of Water quality on Aquatic Ecosystem.
v

2.5 2.6 2.7

Previous Studies on the work Sources of Heavy Metals Distribution Pathways and Fate of Heavy Metals in the Aquatic Environment.

12 13

16 18 19 28 35 36 36 37 38 39 43 45 45 46 47 47 48

2.8 2.9

Effects of Heavy Metals in Organisms Nigerian and some African Experience

2.10 Some African Countries 2.11 Levels of Heavy Metals in Different Environment Compartments 2.11.1 Concentration of Metals in Water 2.11.2 Concentration of Metals in Sediments 2.11.3 Concentration of Metals in Aquatic Fauna 2.11.4 Concentration of Metals in Aquatic Flora 2.12 Comparison between Metal contents in Sediment and Biota 2.13 Methods of Analysis CHAPTER THREE: THE AREA OF STUDY 3.1 3.2 3.3 3.4 3.5 The Geographical Location and General Features of Ile-Ife The Climate and Meteorology of the Area The Geology of the area Soils of the Area and Land Use Vegetation of the Area

vi

CHAPTER FOUR: MATERIALS AND METHODS 4.1 4.2 Sampling Programme and Sampling Stations Method of Analysis

49 49 50 52 52 53 54 61 62 63 68 69 69 70 86 86 87 88 89 89

CHAPTER FIVE: RESULTS 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 Arsenic (As) Cobalt (Co) Cadium (Co) Chromium (Cr) Copper (Cu) Iron (Fe) Manganese (Mn) Nickel (Ni) Lead (Pb)

5.10 Zinc (Zn) CHAPTER SIX: DISCUSSION 6.1 6.2 6.3 6.4 6.5 General Background Levels Vertical Distribution Pattern Horizontal Distribution Pattern Seasonal Distribution Pattern Associated health Risks

vii

CHAPTER SEVEN: CONCLUSIONS AND RECOMMENDATIONS 7.1 7.2 Conclusions Recommendations REFERENCE List of abbreviations and acronyms used

92 92 93 95 108

viii

LIST OF TABLES Table No. Table 2.1: Title Industrial and Agricultural Source for metals in the Environment. Table 2.2: Mean metal concentrations in some industrial effluents and Landfill leachates (ug /ml). Table 2.3: Mean dissolved metal concentrations in inland and coastal Waters (ug/ml). Table 4.1: Instrument methods used in the chemical analyses of water quality parameters. Table 5.1: The Concentrations (mg/l) of Arsenic (As) in Teaching and Research Farm Pond I of Obafemi Awolowo University Table 5.2: The concentrations (mg/l) of Cobalt (Co) teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.3 The Concentrations (mg/l) of Cadmium (Cd) in Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.4 The Concentrations (mg/l) of Chromium (Cr) in Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.5 The Concentrations (mg/l) of Copper (Cu) in Teaching and Research Farm Pond I of Obafemi Awolowo University. 65 58 57 56 55 51 41 40 15 Page

ix

Table 5.6

The Concentrations (mg/l) of Iron (Fe) in Teaching and Research Farm Pond I of Obafemi Awolowo University 66

Table 5.7

The Concentrations (mg/l) of Manganese (Mn) in Teaching and Research Farm Pond I of Obafemi Awolowo University. 72

Table 5.8

The Concentrations (mg/l) of Nickel (Ni) in Teaching and Research Farm Pond I of Obafemi Awolowo University. 73

Table 5.9

The Concentrations (mg/l) of Lead (Pb) in Teaching and Research Farm Pond I of Obafemi Awolowo University. 74

Table 5.10: The Concentrations (mg/l) of Zinc (Zn) in Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.11: The Hydrogen ion concentration (pH) (pH Units) of water samples in the Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.12: The total Depth (m) of water measured in Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.13: The Total Depth (m) of Water Measured in Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.14: The Water Transparency (m) Values measured at each sampling station in Teaching and Research Farm Pond I of Obafemi Awolowo University. Table 5.15: Descriptive statistics of Heavy Metals Concentrations (mg/l)
x

75

79

80

81

81

in Teaching and Research Farm Pond I of O. A.U. Table 5.16: Descriptive Statistics of Heavy Metals Concentrations (mg/l) in Teaching and Research Farm Pond I of O. A.U. Table 5:17: WHO/EU drinking water standards comparative table. Table 5.18: Selected Water quality Criteria for Irrigational Water (mg/l)

82

83 84 85

xi

LIST OF FIGURES Figure No. Title Page 11

Figure 2:1: The hydrological cycle Figure 5.1: The mean concentrations of Arsenic in the Teaching and Research Farm Pond I, O.A.U. Figure 5.2: Figure 5.1: The mean concentrations of Cobalt in the Teaching and Research Farm Pond I, O.A.U. Figure 5.3: The mean concentrations of Cadmium in the Teaching and Research Farm Pond I, O.A.U. Figure 5.4: The Mean Concentrations of Chromium in the Teaching and Research Farm Pond I, O.A.U. Figure 5.5: The Mean Concentrations of Copper in the Teaching and Research Farm Pond I, O.A.U. Figure 5.6: The Mean Concentrations of Iron in the Teaching and Research Farm Pond I, O.A.U. Figure 5.7: The Mean Concentrations of Maganese in the Teaching and Research Farm Pond I, O.A.U. Figure 5.8: The Mean Concentrations of Nickel in the Teaching and Research Farm Pond I, O.A.U. Figure 5.9: The Mean Concentrations of Lead in the Teaching and Research Farm Pond I, O.A.U.
xii

59

59

60

60

67

67

76

76

77

Figure 10:

The Mean Concentrations of Zinc in the Teaching and Research Farm Pond I, O.A.U. 77

Figure 5.11: The Concentration of Heavy Metals for both Rainy and Dry season in the Teaching and Research Farm Pond I, O.A.U. 78

xiii

Abstract
The main aim of this study was to assess the heavy metal levels of water in the farm pond I at the Faculty of Agriculture Research Farm, Obafemi Awolowo University, Ile-Ife. The specific aims were to assess the horizontal, vertical and seasonal variations in the concentration of the heavy metals and also assess the suitability of the water for a number of applications, including for fish culture and irrigation with regard to their heavy metal levels. Water samples were collected monthly at three different sampling stations ( A, B, and C ) from the Teaching and Research farm pond 1, Obafemi Awolowo University (O.A.U.), Ile-Ife, from September, 2006 to August, 2007. Water samples collected from the pond were analysed for heavy metals contents. The levels of pH, temperature, depth and water transparency were also measured in the water samples. The concentrations of the heavy metals were determined with an Atomic Absorption Spectrophotometer (AAS). The results showed that the water quality in the pond has been polluted by some of the heavy metals, notably Arsenic, Cadmium, Copper, Iron and Lead. The mean concentration levels were in the order of: Fe > Cu > Zn > As > Cd > Ni > Mn > Pb > Cr > Co. The results also showed that most of the heavy metals (As, Cd, Cr, Cu, Fe, Ni and Pb) were higher than the recommended World

xiv

Health Organisation (WHO) and European Union (EU) standards for drinking water quality and the water quality criteria for irrigation water. Arsenic and manganese showed definite pattern of vertical variation in the pond, while, cobalt, cadmium, chromium, copper, iron, nickel, lead, and zinc did not show any definite pattern in their vertical variation in the pond. There was also definite pattern of horizontal variation in the concentrations of arsenic, cadmium, cobalt, copper, iron and zinc. On the other hand, there was no distinct pattern in the horizontal variation in of chromium, manganese, nickel, and lead. The concentration of most of the heavy metals (As, Co, Cd, Cr, Cu, Fe, Mn and Ni) appeared higher during the rainy season than in the dry season, while Zn was higher in the dry season. The probable source of the heavy metal into the pond was agricultural runoff, and recommendations for the control of the pollution in the pond are suggested.

xv

CHAPTER ONE
INTRODUCTION
1.1 Importance of Water Water is life and indeed the most important natural resource without which life would be non-existent. Availability of safe and reliable source of water is an essential prerequisite for sustainable development. Deserts are not habitable because of lack of water Continuous urban development and large solid waste pose a major environmental risk because of the difficulties in disposal. Landfills and other solid wastes disposal sites are major targets of pollution because rainfall and groundwater leach these highly contaminated substances into lakes,ponds river, streams and waterways (surface waters) which are inadvertently used by people residing in such areas. Water borne diseases kill 50,000 people daily (Herschy, 1999) and about 4 million children under the age of five die yearly in developing countries due to water related problems (USAID, 1990; Warner, 1998). Throughout the world, about 2.3 billion people suffer from disease that are linked to water related problems (U.N, 1997; WHO, 1997) which, continue

to kill millions of people yearly, debilitate billions thereby undermining developmental effort (Nash, 1993; Olshanshy et al., 1997). 1.2 Background to the Study The terms water pollution and air pollution imply the presence of undesirable foreign matter in an otherwise pure or natural substance. The pollution of water is thus the addition of undesirable foreign matter, which deteriorates the quality of the water. Water quality may be defined as its fitness for the beneficial uses which it has provided in the past-for drinking by man and animals, for the support of aquatic life, for irrigation of the land, for recreation and aesthetics and for industry. Any substance that prevents the normal use of water is considered a water pollutant. Pollutant (foreign) matter may be either nonliving, such as compounds of Pb or Hg, or living such as micro-organisms. Water pollution is of grave consequence because both terrestrial and aquatic life may be poisoned; it may cause disease due to the presence of some hazardous substances, and hence significantly, hinder economic activities. The causes and forms of water pollution according to Stradberg (1971) include sewage and other oxygen demanding wastes, infectious agents, organic chemicals, other chemicals and mineral substances,

sediments (turbidity), radio-active substances and heat. Additionally, several human activities that may result to water pollution include the following, agriculture, irrigation, urbanization, mining, fire and industrialization (Goudie, 1990). These activities have been documented to have impacted negatively in some specified Nigerian surface waters especially in the Niger Delta region (Izonfuo and Bariweni, 2001). Heavy metals are of particular interest because they are among the most toxic pollutants. Heavy metals are metals with a density greater than 5g/cm3. They are less abundant than the light metals, one of their characteristics is their relative inertness, which implies that after release into the environment they are persistent contaminants. The heavy metals of interest include the following Arsenic (As), Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu), Iron (Fe), Manganese (Mn), Nickel (Ni), Lead (Pb) and Zinc (Zn). Heavy metals occur naturally in the environment in rocks and ores. They cycle through the environment by geological and biological means. The geological cycle begins when water slowly wears away rocks and dissolves the heavy metals. The heavy metals are carried into streams, rivers, lakes and oceans. The heavy metals may be deposited in sediments at the bottom of the water body, or they may evaporate and be carried elsewhere as

rainwater. The biological cycle includes accumulation in plants and animals and entry into the food web. Anthropogenic activities have also increased the release of heavy metals into the environment, thereby causing environmental contamination or pollution. Such activities include ore extraction and smelting, fossil fuel combustion, dumping and land filling of industrial wastes, exhaust from leaded gasoline, steel, iron, cement and fertilizer production, refuse and wood combustion. Heavy metal has also increase through activities such as farming, deforestation, construction, dredging of harbours and the disposal of municipal sludge and industrial waste on land.

1.3

Statement of Study Problem Heavy metals are one of the causes and forms of water pollution,

which is not commonly addressed. Although these trace elements are usually present in the environment, they are potentially extremely toxic and not only would they affect the biota at a water soluble concentration at less than 1 part per million (ppm), humans can be grossly affected (Freedman, 1989). Therefore the high concentrations and unacceptable levels of the elements may constitute risk to health. However, the emission of airborne metallic pollutant has now reached such proportions that long-range atmospheric transport causes contamination
4

not only in the vicinity of industrialized regions, but also in more remote areas. 1.4 Aims and Objectives of Study The general aim of this study is to assess the heavy metal levels of water in the farm pond. The specific aims are to i. assess the horizontal and vertical variations in the concentration of the heavy metals. ii. assess the suitability of the pond water for a number of applications, which include: fish culture and irrigation.

1.5

Scope of the Study To review literature on the heavy metal contents of fresh water (rivers,

lakes and ponds) and the analysis of heavy metal contents of research farm pond water collected over one annual cycle.

1.6 Goal/Essence/Probable Application of Study This work is expected to provide information on the level of heavy metal concentration of the O.A.U Teaching and Research Farm Pond I, IleIfe. The result of this work will also bring to focus on the suitability of the pond water for a number of applications including fish culture and irrigation.

It also expected that the result of this work will provide information for O.A.U. Teaching and Research Farm Pond I authority or management to design and put in place appropriate indicator parameters for monitoring the level of heavy metal concentration in the pond water.

CHAPTER TWO
LITERATURE REVIEW
2.1 Water Quality and Its Importance Water is essential to human life and to the health of the environment. As a valuable natural resource, it comprises marine, estuarine, fresh water (river and lakes) and groundwater environment, across coastal and inland areas. Water has two dimensions that are closely linked quality and quantity. Water quality is commonly defined by its physical, chemical, biological and aesthetic (appearance and smell) characteristics. A healthy water environment is one which the water quality supports a rich and varied community of organisms and is conducive to public health. The water quality of a body of water influences its use by the riparian communities for drinking, swimming or commercial purposes. More specifically, the water may be used by the community for the following: Supplying drinking water. Recreation (swimming, boating) Irrigation crops and watering live stock Industrial processes Navigation and shipping

Production of edible fish, shell fish and crustaceans Protection of aquatic ecosystems Wildlife habitats Scientific study and education. Water quality is rated one of the highest priority environmental issues,

and it has to be improved at the very least, not further degraded. Our water resources are of major environmental, social and economic value to us, but if water quality becomes degraded water loses its values. Water quality is important not only to protect public health-water provides ecosystem habitats, is used for farming, fishing and mining and contributes to recreation and tourism. Therefore, if water quality is not maintained, it is not just the environment that will suffer- the commercial and recreational value of our water resources will also diminish. 2.2 Effects of Environment and Resource Use on Water Quality Other than in its vapour form water is never pure.This is because, water quality is closely linked to the surrounding environment and land use. It is affected by community uses such as agriculture, urban and industrial uses, and recreation. The modification of natural stream flows by dams and wiers can also affect water quality. The weather too can have a major impact

on water quality, particularly in a dry country like Australia which is periodically affected by droughts (USEPA, 2001). Generally the water quality of rivers is best in the headwaters, where rainfalls are often abundant. Water quality often declines as rivers flow through regions where land use and water use are intense and pollution from intensive agriculture, large town, industry and recreation areas increases. 2.3 Measurement of Water Quality The presence of contaminants and the pattern of water use and/or land use reflect on the quality of water. Water quality indicators can be categorized as follows: a. b. biological: bacteria, algae Physical: temperature, turbidity and clarity, colour, sanity, suspended solids, dissolved solids. c. Chemical: pH, dissolved oxygen, biological oxygen demand, nutrients (including nitrogen and phosphorus), organic and inorganic compounds (including toxicants). d. e. Aesthetic: odours, taints, colour, floating matter. Radiation: alpha, beta, gamma radiation emitters.

Measurement of these indicators can be used to determine and monitor changes in water quality, and determine whether the quality of the water is

suitable for the health of the natural environment and uses for which the water is required.
2.4 The Effects of Water Quality on Aquatic Ecosystem

An ecosystem is a community of organisms plants, animals, fungi and bacteria-interacting with one another and with the environment in which they live. Protecting aquatic ecosystem in many ways as important as maintaining water quality, for the following reasons: i. Aquatic ecosystems are an integral part of our environment. They

need to be maintained if the environment is to continue to support people. World conservation strategies stress the importance of maintaining healthy ecosystem and genetic diversity. ii. Aquatic ecosystem plays an important role in maintaining water

quality and is a valuable indicator of water quality and the suitability of the water for other uses. iii. Aquatic ecosystem is valuable resources. Aquatic life is a major

source of protein for humans. In most countries, commercial and sport fishing is economically important. Figure 2.1: below illustrates the variety of physical process related to the movement and storage of water within the environment.

10

(2001). Figure 2.1: The hydrological Cycle.

11

2.5 Previous Studies on the Work In natural aquatic ecosystem, metals occur in low concentrations, normally at the nano- gram (ng) to micro- gram (g) per litre levels. In recent times, however, the occurrence of metal contaminants especially heavy metals in excess of natural loads has become a problem of increasing concern. This situation has risen as a result of the rapid growth of population, increased urbanisation, expansion of industrial activities, exploration and exploitation of natural resources, extension of irrigation and other modern agricultural practices as well as the lack of environmental regulations. Unlike other pollutants like petroleum hydrocarbons and litter which may visibly build up in the environment, trace metals may accumulate unnoticed to toxic levels. This problems associated with trace metal contamination were first highlighted in the industrially advanced countries because of their larger industrial discharges and especially by incidents of mercury and cadmium pollution in Sweden and Japan (Kurland et al., 1960; Nitta, 1972; Goldberg 1976). In spite of the relatively low level of industrial activity in less developed regions such as Africa, there is nevertheless growing awareness of the need for rational management of aquatic resources including control of waste discharges into the environment. This becomes

12

even more important in view of the expected increases in industrial and urban activities in all parts of the country. For effective water pollution control and management there is a need for a clear understanding of the inputs (loads), distribution and fate of contaminants, including trace metals from land-based sources into aquatic ecosystems. In particular, the quantities and qualities need to be considered together with the distribution pathways and fate and the effects on biota. 2.6 Sources of Heavy Metals. Heavy metals enter the aquatic environment from both natural and anthropogenic sources. Entry may be as a result of direct discharge into both freshwater and marine ecosystems or through indirect routes such as dry and wet deposition and land runoff. Important natural sources are volcanic activity, continental weathering and forest fires. The contribution from volcanoes may occur as large but sporadic emissions, due to explosive volcanic activity or as other low continuous emissions, including geothermal activity and magma degassing (Zoller, 1984). The major sources of atmospheric mercury, for example are land and ocean degassing. In view of the toxic nature of heavy metals, the knowledge of their sources and fate in the environment is important.

13

The anthropogenic sources include: i. ii. iii. iv. v. Mining effluents Industrial effluents Domestic effluents and urban storm-water run off Leaching of metals from garbage and solid wastes dump. Metals inputs from rural areas, e.g metals contained in pesticides. Atmospheric sources, e.g burning of fossil fuels, incineration of wastes and industrial emissions. vi. Petroleum industry activities.

14

Table 2.1 Industrial and agricultural source for metals in the environment

Source
Batteries and other electricals

Metal
Cd, Hg, Pb, Zn, Mn, Ni Ti, Cd, Hg, Pb, Zn, Mn, Sn, Cr, Al, As, Cu, Fe

Pigments and paints

Alloys and solders

Cd, As, Pb, Zn, Mn, Sn, Ni, Cu

Biocides(pesticides, herbicides, As, Hg, Pb, Cu, Sn, Zn, Mn preservations) Catalysts Glass Fertilizers Plastics Dental and cosmetics Textile Refineries Fuel Ni, Hg, Pb, Cu, Sn As, Sn, Mn Cd, Hg, Pb, Al, As, Cr, Cu, Mn, Ni, Zn Cd, Sn, Pb Sn, Hg Cr, Fe, Al Ni, V, Pb, Fe, Mn, Zn Ni, Hg, Cu, Fe, Mn, Pb, Cd

Source: Biney, et al. (1991).

15

For most heavy metals, anthropogenic emission are more than or equal to natural emissions. The combustion of leaded petrol in automobiles for instance, is responsible for the widespread distribution of lead in the world. For mercury, however several reports (Hutchinson and Meema, 1987; GESAMP, 1988) suggest that natural emission are qualitatively more important than anthropogenic sources. Heavy metal concentrations in industrial effluents and landfill leachate in Nigeria are shown in Table 2.2.

16

Table 2.2 Mean metal concentrations in some industrial effluents and landfill leachates (g ml-1) Location NIGERIA Textile factory effluents Soft drinks factory effluents Steel plat effluents Oil refinery effluents <0.10 <0.10 0.12 <0.05 0.83 0.50 <0.10 <0.10 Osibanjo, 1991 Osibanjo, 1991 Hg Cd Pb Cu Zn Mn Fe Ni Co Reference

<0.10

0.02 <0.10

0.05

0.40 2.40

0.02

<0.10

n0.10 0.05 0.20

0.70 0.14

2.3 0.25 1.45

0.90

Nriagu et 0.90 al., 1987 Kakulu and Osibanjo, 1991; Osibanjo et al., 1988

Landfill leachates (fresh) Landfill leachates (aged)

0.10

0.10

0.50

13.5 87.2

2.7

1.8

Adedayo, 1990 Adedayo, 1990

0.10

0.50

3.8 31.2

2.0

2.6

Source: Biney et al., (1991)

17

2.7 Distribution Pathways and Fate of Heavy Metals in the Aquatic Environment: Once in the aquatic environment, metals are partitioned among various aquatic environmental compartments (Water, suspended solids, sediments and biota). The metals in the aquatic environment may occur in dissolved, particulate and complexed form. The main processes governing distribution and partition are dilution, advection, dispersion, sedimentation and adsorption/desorption. The speciation under the various soluble forms is regulated by the instability constants of the various complexes and by the physico-chemical properties of the water (pH, dissolved ions, Eh and temperature). Adsorption could be the first step in the removal of metals from water. In the course of distribution, permanent or temporary storage of metals take place in the sediments of both fresh-water and marine environments. Microbial activity and redox processes may change the properties of sediments and affect the composition of interstitial water. As a result, iron and manganese oxides may be converted to carbonates or sulphides, leading to a decrease in the adsorption capacity of the sediments. Reworking of the sediments by organisms will also bring sediments to the surface where a significant fraction of the metal will be released (Biney, et al., 1991).

18

Many transformations of heavy metals in aquatic environments occur as bio-chemically mediated reduction, methylation, demethylation and oxidation of single species. Redox reactions may also facilitate some transformations. The biochemical processes are carried out by microorganisms and algae. According to Jernelov (1975), methylation of mercury takes place when micro-organisms, while consuming organic substances, happen to come into contact with mercury ions. This may also be true for As, Sn and Pb (Biney, et al.,1991). Heavy metals are taken up by both fauna and flora. This uptake could provoke an increase in the concentration of the metal in the organism; if the excretion phase is slow, this can lead to the bioaccumulation phenomenon. A few metals such as mercury have been shown to undergo biomagnification through the food chain (Biney, et al., 1991).

19

2.8 Effects of Heavy Metals in Organisms Some heavy metals such as Zn, Cu, Mn and Fe are essential for the growth and well-being of living organisms including man. However, they are likely to show toxic effects when organisms are exposed to levels higher than normally required. Other elements such as Pb, Hg and Cd are not essential for metabolic activities and exhibit toxic properties (Biney, et al.,1991). Metals contamination of the aquatic environment may lead to deleterious effects from localised inputs which may be acutely or chronically toxic to aquatic life within the affected area. Most published data on the effects of metals on aquatic organisms, however, report adverse effects at concentration higher than usually found in the environment (GESAMP, 1985; 1988). Metals may be taken in the inorganic or organic form. For some elements, such as arsenic and copper, the inorganic form is the most toxic. For others, such as Hg, Sn and Pb, the organic forms are the most toxic. At low concentrations many heavy metals including Hg, Cd, Pb, As and Cu, inhibit photosynthesis and phytoplankton growth. Effect at higher tropic level include delayed embryonic development, malformation and reduces growth of adults of fish, molluscs and crustaceans (Biney, et al., 1991).

20

The major routes of heavy metal uptake by man are food, water and air. For example, aquatic fauna, especially fish, are the most important source of mercury and arsenic for human beings. 2.9 Nigerian and some African Experience Studies on the occurrence and distribution of metals in Nigeria have been conducted on all the major environmental matrices (water, sediments, fauna and flora) but again with more emphasis on sediments (Biney, et al., 1991). Statistical treatment of the result of metal analysis of 176 stream sediments samples from the Ife-Ilesa area (1800 km2) of southern Nigeria (Ajayi, 1981) showed that all the elements have density distribution close to natural background levels. Ojo (1988) also used various statistical methods for the interpretation of the geochemical data obtained from analyses of Cu, Pb, Zn, Co, Ni, Fe, Mg, Mn and Ca in 374 stream sediment samples collected over an area of 700 km2 within Upper Benue Trough and concluded that these elements exhibit various patterns of association depending on their nature and prevailing environmental conditions. Other studies in the area (Kakulu and Osibajo, 1988, 1991) revealed elevated levels of Pb, Cr, Ni, V and Zn in Port Harcourt and Warri sediments which suggest that effluents from petroleum refineries located in these cities have

21

contributed significantly to the heavy metal pollution of the respective aquatic ecosystem. Okoye et al., (1991) reported anthropogenic heavy metal enrichment of Cd, Co, Cu, Cr, Fe, Mn, Ni, Pb, and Zn in the Lagos lagoon and implicated land based urban and industrial wastes sources. Pollution studies on 26 rivers in some southern and northern states in Nigeria (Ajayi and Osibanjo, 1981), on rivers in the Niger Delta (Kakulu and Osibajo, 1991) on the cocoa growing area of Ondo state (Ogunlowo, 1991) and the Lagos waters (Okoye, 1991a) showed that, with the exception of iron, the concentrations of most trace metals in the surface water are generally lower than the global average levels for surface water and the international drinking water standards. Ndiokwere and Guinn (1982) determined As, Cd, Cr, Hg, Mn, Mo, Ni, Se and Sb in two Nigerian rivers and two harbours and attributed high metal concentrations to local pollution sources. In their studies of streams and lakes around Ibadan, Mombesshora et al. (1983) reported much higher levels of lead in sediments than in water. The highest levels of lead coincided with areas of high traffic density. Analyses of sediments and fish from the Niger Delta area of Nigeria (Kakulu and Osibajo, 1986) revealed that the area was relatively unpolluted

22

with mercury compared to some European areas (Mediterranean, Baltic sea and North-East Atlantic). Report from the same area (Kakulu et al, 1987a) indicated that the levels of Cd, Cu, Fe, Mn, Pb, and Zn were higher in shell fish than in finfish. With the exception of the level in some shellfish, levels of these metals were generally lower than the WHO recommended limits in foods. Concern about the high level of lead in Lagos lagoon fish has also been expressed (Okoye, 1991). Other Nigerian studies included that of Ntekim et al. (1992), they studied the concentration and area distribution of selected metals (Pb, Zn, Cu, Cd, Ni, Fe, and Cr) in the sediments of the Calabar River to determined the extent of anthropogenic input and to estimate the effects of dumping industrial waste materials into the river. Ntekim et al. (1992) found that the concentration of Pb, Zn, and Cu indicate relatively moderate pollution mainly on the left- hand side of the river while Ni, Cr, Co, Cd and Fe levels are below value found to have adverse effects on the lives of marine biota. Ntekim et al. (1992) discovered that high metal contents are found close to industrial establishments. So, they suggested/states that enhanced metal concentrations are related to industrial sewage and metal leaching from garbage and solid waste dumps.

23

Asonye, et al. (2007) collected water samples of 72 rivers, streams and waterways in southern Nigeria. Asonye, et al. (2007) carried out the following physico-chemical analyses on the samples - tesmperature, colour, taste, turbidity, pH, total dissolved solids (TDS), conductivity and also assessed the heavy metal profiles (Pb, Cr, Cd, Fe, Zn, Mn, Cu) among the entire samples they have collected. Asonye, et al. (2007) discovered that the turbidity (NTU) of 93 % of all the samples was higher than World Health Organisation (WHO) and European Economic Community (EEC) standards. Asonye, et al. (2007) found that 57 % of the entire samples had conductivities above normal limits, and the pH of 81 % of the entire samples are above WHO and EEC guide limits. The profiles of the heavy metals Pb, Cd, Cr, Zn and Mn levels in some of the samples are above the guidelines of WHO and EEC (Asonye, et al. (2007)). Fe had 55 % of all the samples exceeding recommended 0.05 ppm, Cd had 11 % exceeding 0.03 ppm while 7 % of both Zn and Pb exceeded 3 ppm and 0.10 ppm respectively (Asonye, et al. (2007)). From their results, they indicated the heavy metal pollution and toxicity might pose serious risks to the health of communities residing around and using these surface waters for domestic, commercial and sociocultural purposes.

24

Edet and Offong (2004) studied the evaluation of water quality pollution indices for heavy metal contamination monitoring. Edet and Offong (2004) evaluated two documented methods, contamination index (Cd) and the heavy metal potential index (HPI) for their suitability for contamination monitoring of surface water in parts of south-eastern Nigeria. The results of (Edet and Offong 2004)), showed that the final classification gave two extreme results, despite the significant correlation between the data generated from these indices. Therefore, Edet and Offong (2004) developed a third model (Heavy Metal Evaluation Index, HEI) to accommodate this deficiency. The HEI values show significant correlation with Cd and HPI but categorised into semi quantitative classes for proper assessment of pollution level. Edet and Offong (2004) found that the HEI values show that 65.5 % of the sites are classed as low with value lower than the mean and the remaining 34.5 % with values greater than the mean are classed as medium. In contrast, Edet and Offong (2004) classified water samples from all the 32 locations as high and low using the Cd and the HPI respectively. Edet and Offong (2004) reclassified the Cd and HPI categories using the mean values as a criterion which show good comparison with the HEI. Edet and Offong (2004) suggested that the difference in the former can be attributed to the

25

variations in the concentration of the heavy metals used for the different evaluation schemes. Wegwu and Akaninwor (2005) carried out studies on the assessment of heavy-metal profile of the New Calabar River and its impact on juvenile Calrias gariepinus. Wegwu and Akaninwor (2005) determined the heavymetal status of the lower reaches of the New Calabar River in the Niger Delta region over a 40-km-long distance, and its impact on the development of catfish (juvenile Claris gariepinus). Wegwu and Akaninwor (2005) also determined the total mean concentrations of dissolved trace metals in the river to be 0.01, 0.85, 0.56, 2.08, 0.05, 12.0 and 6.59mg/1 for Hg, Pb, Cd, Cu, Cr, Fe and Zn, respectively. Wegwu and Akaninwor (2005) examined the accumulated concentration of trace metals in the muscles of different mature fish caught from the river, and their results fell within the action levels adopted in most countries. Wegwu and Akaninwor (2005) hatched eggs of C. gariepinus in dilution water spiked with the total mean metal levels determined in the river water, in order to evaluate the contributions of trace metals to fisheries depletion. The results of Wegwu and Akaninwor (2005) showed even at very low concentrations of the majority of the trace metals studied with mortality rates well above 50% after 216hrs of exposure. From their findings, they suggested that trace metals (except for Zn), even at

26

very low concentration, negatively affect fish hatch and fry rearing, implying that aquatic milieus contaminated by trace metals are not suitable as nursery grounds for fish cultures. Ekpo and Ibok (1999) worked on the temporal variation and distribution of trace metals in freshwater and fish from Calabar River, S.E Nigeria. Ekpo and Ibok (1999) investigated on the abundance and distribution of trace metals (Fe, Cu, Zn, Mn, Cr, Cd and Pb) in water, and nine species of fish samples from Calabar River. Ekpo and Ibok (1999) determined the concentrations of iron to be (6.0-7.24 mg/1), Zinc (4.91-7.23 mg/1), and Cadmium (0.003-0.007 mg/1). The results of Ekpo and Ibok (1999) showed moderate pollution while that of copper (0.42-0.63 mg/1), manganese (0.023-0.048 mg/1), Chromium (<0.01-0.02 mg/1) and Lead (<0.001-0.01 mg/1) in water were well below WTO permissible levels. Ekpo and Ibok (1999) obtained significant seasonal changes (0.001>p <0.25) for iron, copper, zinc, manganese and in water. Furthermore iron, zinc, and cadmium showed statistically significant spatial changes (0.005>p<0.10) they found that of the nine fish species studied, no statistically significant relationship between body weight and the concentrations of the metals was observed. They also discovered that the concentrations of the metals per mean total body weight apparently decreases in the order

27

Fe>Zn>Cu>Mn>Pb>Cd=Cr and were within the limits that were safe for consumption. Oyewale and Musa (2006), studied the pollution assessment of the lower basin of lakes Kainji/Jebba, Nigeria; heavy metal status of the waters, sediments and fishes. They examined the heavy metal status of the lower basin of Kainji dam (used for hydroelectricity generation), which includes lakes Kainji/Jebba, Nigeria and the potential for human exposure to heavy metals from eating fish caught in the lakes. Oyewale and Musa (2006) assessed/evaluated water, sediments and fish samples from the lakes for As, Cu, Co, Cr, Fe, Hg, Mn, Ni, Pb, Sb, Ti, V and Zn using the EDXRF technique. Oyewale and Musa (2006) discovered Fe and Mn to be present at high mean concentrations in the water (0.013 and 0.019 mg/l), sediments (7.092 and 0.376mg/g) and fish (0.0114 and 0.004.6 mg/g) samples. Oyewale and Musa (2006) also found Sb (0.0032mg/1), Ti (0.0041 mg/1), Cr (0.0022 mg/1) Co (0.0012 mg/1), Cu (0.0013 mg/1) and Pb (0.0012 mg/1) in the water samples and Sb (0.029 mg/l), Ti (0.027 mg/1), V (0.027 mg/1), Cr (0.027 mg/1), Co (0.04 mg/1), Ni (0.033 mg/1), Cu (0.025 mg/1), Zn (0.059 mg/1) and Pb (0.019 mg/1), in the sediment samples to be of medium mean concentrations. Oyewale and Musa (2006) discovered that As and Hg are present at trace levels (<0.001 mg) in the fish and sediment

28

samples. From their results, Oyewale and Musa (2006) discovered an appreciable increase in metal concentrations in going from the water to the sediment samples. Oyewale and Musa (2006) suggested that the probable source of the pollutants is anthropogenic, a rising from agricultural activities, corrosion/abrasion of the ferrous steel material and additives in the lubricants and insulation used for auxiliary services on the turbine floor of the dam constructed on the lakes. They attributed the high levels of Fe and Mn in the sediments samples to natural geological sourcing from the underlying lake rock. They also suggested that, the potential risk for human exposure to these metals emanates from the fish caught in the lakes and subsequently consumed, as there are already significant levels of these metals in the two fish species they analysed, Tilapia (Oreochromis niloticus) and Chrysicthys (Chrysithys auratus). Adefemi, et al., (2007), studied the seasonal variation in heavy metal distribution in the sediment of major dams in Ekiti State. They found iron to be the most abundant out of all the metals examined for both seasons for the two years, with an average value of 6.48 and 4.801/100g (2001) and 6.51 and 3.62mg/100g (2002) for dry and wet season respectively. Adefemi, et al. (2007) discovered that the average metal concentration increased yearly.

29

Adefemi, et al. (2007) also discovered that the concentration of most of the metals appears higher in the dry season than for the wet season and the values of the metals are below the standard limits of World Health Organization, (WHO). 2.10 Some African Countries Studies of heavy metals in Northern Africa have been concentrated on Egyptian inland waters and coastal zones, particularly on the river Nile and its two branches (Rosetta and Damietta), as well as on the Delta lagoons. However, many studies have been conducted within the framework of the 1975 Action Plan for the protection of the Mediterranean and have therefore focused on the coastal zones. Advanced investigation on the dynamics and speculations of trace metals are also being conducted in different Egyptian inland and coastal waters. Bernhard and Renzoni (1977) differentiated between natural and anthropogenic sources of mercury pollution in the Mediterranean by reviewing concentrations in pelagic fishes and benthic organisms as well as sediments. Studies on the surface sediments of El-Mex region of the Mediterranean in front of Alexandria (Saad et al, 1981) revealed two zones, one of which showed high concentrations of Mn, Cu, Cd, Zn and Fe, as a

30

result of discharges of industrial effluents. Their findings also suggested incorporation of similar proportions of Fe and Mn into the sediments and the co-precipitation of Cu and Zn by iron oxides. The seasonal distribution of dissolved and particulate heavy metals in the water column of the Damietta, El-Rayis and Saad (1985) estimated the contribution of trace metals from the River Nile to the eastern Mediterranean by determining the concentrations of dissolved metals in the surface and subsurface water along the Rosetta branch. The relative abundance was Zn > Fe > Cu > Mn > Cd. Saad and Fahmy (1985) studied the occurrence of trace metals in surficial sediments from the Damietta estuary of the Nile and concluded that the eastern side of the estuary was exposed to more pollution than the western side. Also, areas of maximum aver ages of Cu, Zn and Cd coincided with the discharged sites of sewage wastes. Heavy metal pollution in lake Mariut has been further investigated by El-Rayis and Saad (1990), based on the distribution of Cu, Zn, Fe, and Mn in water, suspended matter and sediments. The contribution of metals from this lagoon to the Mediterranean Sea via Umum Drain (contaminate landbased source) was also estimated.

31

In other parts of Africa, the concentrations of major and minor ions, including Cu Mn and Fe in river Jong, Sierra Leone, was determined by Wright (1982), who found a clear relationship between metal concentrations and seasonal variations in rainfall. In Ghana, one of the earliest studies (Amasa, 1975) examined various matrices, including drinking water, from the Obuasi Gold mining area and found that arsenic concentrations occurred above normal values. A more recent study (Akoto Bamford et al, 1990) in which heavy metal pollution from gold mining activities was assessed by analysing gold ore, tailings, sediments and water for Cr, Mn, Fe, Cu Zn, As, Pb, Rb, Sr, Y, Zr and Nb revealed the presence of all the elements in sediments within a concentration range o f 0.08 to 49000 (g/mg) whereas only iron and zinc were detected in water at levels of 0.08 -2.4(g/ml). Total mercury concentrations in commercial fish from different coastal sites of Ghana have been determined by Ntwo and Khawaja (1989) who concluded that all values were well below the 0.5g/mg action level adopted in many countries. Biney and Beeko (1991) conducted a survey of metals in fish sediments from the River Wiwi in Kumasi and found a positive correlation between mercury concentration and body weight of fish. They also reported higher levels of cadmium and mercury in fish than in

32

sediments. Studies on the distribution of Hg, Cd, Pb, Zn and Fe in water, finfish and shellfish macrophytes and sediments from Kpong headpond and lower Volta river (Biney, 1991) showed the highest concentration of iron and lead in sediment and of manganese and cadmium in macrophytes. Finfish had the lowest concentrations of the metal, except for lead. In Cote dIvoire Marchand and Martin (1985) and Kouadio and Trefy (1987) have studied sediments of the Ebrie lagoon and reported metal concentrations in excess of background levels, this was attributed to the disposal of untreated sewage and industrial effluents. A comparative study by Metongo (1991) of Cd, Cu, Hg, and Zn in samples of oysters (Crassotrea gasar) from urban and rural lagoon areas of Cote dIvoire revealed higher but background of the metals in the urban area. Likewise, other studies of heavy metals in Callinectes amnicola (Metongo and Sankare, 1990) and in Thunnus albacares (Metongo and Kouamenan, 1991) gave concentrations lower than internationally acceptable limits for seafood. In Senegal, analyses by Gras and Mondain (1978) of fish and crustaceans from coastal waters revealed lower mercury concentrations than the generally acceptable limits (0.5g/g), except in sword fish and sharks weighing more than 5kg.

33

Other studies on the occurrence of trace metals have been conducted as part of the joint FAO/IOC/WHO/ IAEA/UNEP project on monitoring of pollution in the marine environment of the West and Central African region. Within this framework, concentrations in marine biota have been reported for Cameroon (Mbome et al, 1985; Mbome, 1988), Ghana (Biney, 1985; Biney and Ameyibor, 1989) Cote dIvoire (Metongo, 1985, 1988) and

Senegal (Ba et al, 1985; Ba, 1988). On the basis of these studies, Portmann et al (1989) reviewed the levels of contaminants in the marine environment of the region and concluded that there was little input of mercury and other metals into the coastal zone from land. Early studies in Eastern Africa focused on Lake Nakaru in Kenya, one of a number of Soda lake in the Great Rift Valley which was made a national park in 1986 because of its world-famous flamingo population. The effect of copper ions on the photosynthetic oxygen production of phytoplankton, on the growth rate of blue-green algae (Sprirulina platensis) and populations of rotifers (Brachionus sp) in water from Lake Nakuru was experimentally investigated by Kallqvist and Meadows (1978). The rotifers were less sensitive to copper than algae. Other studies by Lewin (1976) showed that Lake Nakuru water contained 0.08 mg/1 mainly from pesticide containing run-off from the surrounding agricultural lands. This value was

34

thus higher than the critical value of 0.02 mg Cu/1 which may significantly reduce algal growth (Kallqvist and Meadows, 1987). Observations by Ochumba (pers.comm.) have shown that, during the dry season, flamingos which feed on the algae migrate away from the lake. This may negatively affect the tourism industry. Earlier studies on sediments, water and biota of the second largest natural lake in the world, Lake Victoria (Alala, 1981; Onyari, 1985; Ochieng, 1987) showed no significant heavy metal pollution. However, more recent studies in the same area revealed increased lead levels largely due to increased shipping traffic and associated problems, car washing and discharge from local industries (Wandiga and Onyari, 1987; Onyari and Wandiga, 1989). Ochumba (1987) studied physico-chemical parameters, dissolved oxygen and heavy metal concentrations in Lake Victoria as the possible causes of periodic fish kills. The author attributed the fish kills to dissolved oxygen depletion. In other East African areas, copper ion distribution in the surface waters of lakes George and Edward in Uganda was studied along other chemolimnological parameters (Bugenyi, 1979). Concentrations ranged from 0.07 to 0.13g/ml in Lake George and from 0.006 to 0.02g/ml in Lake Edward, A direct relationship was established between cooper, water

35

hardness, alkalinity and total dissolved solids. Bugengi (1982) studied the occurrence of Cd, Cu and Fe in sediments of the same lakes and concluded that the concentrations, although distinct in the different water bodies, did not show much variation within each of the lakes. Studies of dissolved metals in the marine environment were conducted by Norconsult (1977) concluding that the concentrations for Tudor creek fell within the normal range of unpolluted natural sea water. Oteko (1987) studied the Mombasa creek and suggested crustal sources to be responsible for copper concentrations and increased anthropogenic sources from automobile exhausts for cadmium and lead concentrations. The concentrations and distributions of metals amongst other chemical contaminants were investigated by Greichus et al. (1977) in two South African lakes, Hartbeespoort dam, which receives industrial and municipal waters from Johannesburg and Voelvlei dam, situated in mainly agricultural area. Water, sediments, aquatic plants and insects, fish, fisheating birds and their eggs were analysed for As, Cd, Cu, Mn, Pb, Zn, and Hg. The results indicated higher levels in Hartbeespoort dam than in Voevlei for all metals in sediments and birds, except for copper in bird carcasses. Mercury levels in birds were 2 to 5-fold greater than in fish, whereas lead values were 2 to 10-fold greater.

36

Greichus et al. (1978) investigated metals among other contaminants in Lake Mcllwaine, a eutropic water body near Harara, Zimbabwe. Water, sediment, plankton, bottom fauna and fish were analysed. The data gave intermediate levels of metals between those found in Hartbeespoort dam and Voelvlei dam. Watling and Emmerson (1981) identified areas of metal input to the River Papenkuils which was considered to be a serious source of pollution to the marine environment around Port Elizabeth. In contrast, the estuary of River Swartkops was found generally unpolluted on the basis of metal concentration in water, surface sediments and sediments cores (Watling and watling, 1982). Similar studies also showed that the estuary of River Knysna as well as the Bushmans, Kariega, Kowie and Great Fish Rivers were unpolluted (Watling and Watling, 1982a, 1983). 2.11 Levels of Heavy Metals in Different Environmental Compartments A more detailed discussion will be presented on the quantitative aspects based on concentration levels in the various environmental compartments. Most studies on the levels and its distribution of heavy metals in Nigeria and some parts of Africa have concentrated on urban and industrialized areas.

37

2.11.1 Concentration of Metals in Water Mercury showed the lowest concentrations (<1.0 g/m1), followed by cadmium (0.2-21.0 g/m1), iron gave the highest level in most waters with a considerable wide range of variation, from 2.5 g/m1 in the river Nile, Egypt (El-Rayis and Saad 1985), to 14, 400g/m1 in Shasha stream, Nigeria (Martins, 1978). The other metals are generally arranged in the following order of abundance: Mn>Zn>Pb> Cu>As. The levels of metal in the coastal waters were markedly lower than those found in most inland waters. This reflects the direct influence of pollution on the lakes and rivers. Undoubtedly, the very high concentrations of certain metals found in specific waters are as a result of acute pollution. 2.11.2 Concentration of Metals in Sediments Most water bodies showed low-to-moderate metal concentration except for Hartbeespoort dam and river Papenkuils in South Africa, the Niger Delta in Nigeria and lakes George and Edward in Uganda. Lakes Nozha, MAriut and Manzaleh and River Nile in Egypt as well as Lake Mcllwaine in Zimbabwe also showed elevated concentrations of some metals which clearly indicate considerable anthropogenic inputs.

38

Most concentration in inland water sediments thus pose no environmental concern for the continent except for the above-mentioned areas which may be considered as hot spots within their respective regions. Heavy metal concentrations in the Africa marine and coastal sediments fell within the ranges given for Hg, Cd, Pb and As by GESAMP (1985, 1988) but higher values occurred in some areas. For example, sediments from Lagos lagoon in Nigeria had high concentrations of lead and iron while the Ebrie lagoon in Cote dIviore had high mercury, zinc and iron concentrations. The result revealed largely anthropogenic heavy metal enrichment implicating urban and industrial runoff into coastal lagoons which have poor water exchange (Okoye, 1989; Koudio and Trefry, 1987). 2.11.3 Concentrations of Metals in Aquatic Fauna Some differences between water bodies were observed with respect to the levels of certain elements in finfish. For example, zinc showed relatively higher values in samples from lakes Nakuru, Kenya, followed in decreasing order by those from Zimbabwe and South Africa, Egypt, Nigeria and Ghana. Likewise, copper concentrations were higher in samples from Egypt and lakes Nakuru and Mcllwaine. However, on the whole, the levels of metals in inland water fish muscle were below WHO limits, except for lead in

39

Macrobrachium sp from Niger Delta, Nigeria and Lower Volta River, Ghana. As for Inland water, the levels in marine organisms were generally below WHO limits except for some hot-spot. Cadmium and mercury for example showed the same low trends in both fin-and shell fish. In contrast, marine organisms from Nigeria had lead levels which exceeded the WHO limit. This may be attributed to a higher state of contaminations from the use of leaded gasoline. In support of what has been reported in several studies (Hellawell, 1986; Kakulu and Osibanjo, 1986; Kakulu et al., 1987a; Institute of Aquatic Biology, 1990), shellfish had higher concentrations of most metals. The higher concentrations of cadmium, copper and zinc occurred in Crassostrea sp, which has a great capacity to accumulate contaminants and is a biological indicator of pollution. 2.11.4 Concentration of Metals in Aquatic Flora Aquatic plants have been shown to accumulate heavy metals in their tissues and therefore have been used as biological indicators for metals pollution monitoring in the aquatic ecosystem. Generally, the levels in aquatic plants from inland waters were higher than in those form coastal waters. The variability in the levels of heavy metals in different regions

40

could be ascribed to biological variation between the species rather than environmental factors. Nonetheless, higher concentrations of cadmium were found in Ceratophyllum from industrial areas in Egypt compared to relatively unpolluted areas. (Fayed and Abd El-Shafy, 1985). Furthermore, it is significant that an excessively high value of lead (78.0g/g) was found in blue-green algae from Lake Mcllwaine, Zimbabwe (Greichus et al., 1978) compared to the rest of the region. 2.12 Comparison Between Metal Contents in Sediment and Biota In Egypt all metals except cadmium showed higher values in sediments than in fish (Saad, 1985a, 1987). In Ghana only iron and lead followed this pattern, whereas the other metals have higher values in certain floral and fauna (Biney, 1991a). In Kenya the metals accumulated in higher concentrations in sediments than in fish (Wanda and Onyari, 1987). In South Africa the same pattern occurred with exception (Greichus et al., 1977). The levels of accumulation of metals in the different flora and fauna did not follow the same pattern.

41

Table 2.3 Mean dissolved metal concentrations in inland and coastal waters (ng ml-1) Location INLAND WATERS River Nile, Egypt Lake Mariut, Egypt Nozha Hydrodome, Egypt Kpong Headpond, Ghana Groundwater, Ghana Kaduna River, Nigeria Oyi River, Nigeria Ora River, Ibadan, Nigeria IITA Lake, Ibadan, Nigeria Agodi Lake, Ibadan, Nigeria Ogunpa Str., Ibadan, Nigeria Shasha Str., Lagos, Nigeria Calabar River, Nigeria Warri River, Nigeria Lake Nakuru, Kenya <1.0 0.40 0.95 0.84 0.38 5.0 1.3 4.9 13.1 100 1.35 13.9 Hg Cd Pb As Cu Zn Mn Fe Reference

0.4 0.22 0.2

1.3 10.6 20.5

8.18 18.3 17.1

0.46

2.5 42.5 40.1

El-Rayis and Saad, 1985 Saad, 1985 Saad, 1987

<1.0 <1.0

<10 <10

<20 92

<20 17.5 240 100 8.0 0.8 2.3 8.9 900 3.2

<20 80 200

45

90 Biney, 1991 924 Pelig-Ba et al., 1991 Martins, 1978 Ajayi and Osibanjo, 1981 Mombeshora et al., 1981 Mombeshora et al., 1981 Mombeshora et al., 1981 Mombeshora et al., 1981 Martins (1978) Kakulu and Osibanjo, 1991 Kakulu and Osibanjo, 1991 Greichus et al., 1978a

<20

1,300 3800 300 1800

7.5 1.5 4.7

450 1247 212 436

774 1375

5.8 1,155 2213 70 10.3 2,900 14400 188

2.3 21

17.9 5 6

23.1 2

42.9 49 24

625

42

Lake Victoria, Kenya * Lake George, Uganda Lake Edward, Uganda Lake Mcllwaine, <1.0 Zimbabwe Hartbeespoort <1.0 Dam, S.Afr. Voelvlei Dam, <1.0 S. Africa Knysna River, S. Africa* COASTAL WATERS Southwest. Mediterranean Red Sea, Egypt Accra, Ghana Lagos Lagoon, Nigeria BACKGROUND Rivers Coastal Waters <0.002

28

793.6 6 1.1

557.6 100 15 3 1 3 10 3

25 50 125 3,276

Ochieng, 1987 Bugenyi, 4830 1982 Bugenyi, 89 1982 Greichus et al., 1978

1 1 2

10 4 12

12 36

32 45

0.01 <0.1 <0.1 0.19 10 8

Greichus et al., 1977 Greichus et 13 25 38 al., 1977 Watling and <0.1 <0.1 1.1 40510 Watling, 2.4 26 40 1982a

0.024 5.1

0.83

9.0

3.0

15

21

Bernhard, 1988 Saad and 16.2 Kandeel, 1988 Portmann et al., 1989 Okoye, 86 1991a 40 2 Burton and Liss, 1976; Martin and Whitfield, 1983

0.02 0.01

1.7 1.5

7 1

20 2.5

0.03

0.4

Source: Biney et al., (1991)

43

2.13 Methods of Analyses Several methods have been used to determine trace elements in environmental matrices. In early studies, gravimetric, volumetric and colorimetric techniques were employed. The more common colorimetric method involved formation of soluble metal complexes, chelates with such organic compounds as dithizone, o-phenathroline and ammomium pyrolidine dithiocarbamate (APDC). Modern methods such as anodic stripping voltametry (ASV) and the use of non-selective electrodes (ISE) are based on electrochemical principles. Other methods employ nuclear related technique. These include proton-induced X-ray emission (PIXE), instrumental neuron activation analysis (INAA), X-ray fluorescence (XRF) and inductively coupled plasma mass spectrometry (ICP-MS). Most of these methods are however very expensive, and only a few recent studies in Africa (Kakulu et al., 1987; Akoto Bamford et al., 1990; Onwumere and Oladimeji, 1990) have reported using them. The most common methods for determination of heavy metals is atomic absorption spectrophotometry (AAS). It has the advantage of speed, sensitivity, simplicity and ability to analyse complex mixtures without prior separation. For most of the heavy metals the basic technique involvess flame

44

atomisation, while for some of them at very low concentrations the graphitefurnace technique involving electro thermal atomisation is used. Vapourgeneration methods may be used for a few metals, such as As, Se and Sb, whereas mercury is analysed by the cold vapour technique.

45

CHAPTER THREE
THE AREA OF STUDY
3.1 The Geographical Location and General Features of Ile-Ife. The pond is located at the Faculty of Agriculture Teaching and Research Farm, Obafemi Awolowo University, Ile Ife. Two ponds are located at the farm; this study was carried out in Pond 1, which is located after the poultry section. The pond was impounded for the supply of water for irrigation to the nearby Teaching and Research farms. Teaching and Research farm Pond 1, O.A.U, lies approximately between latitudes 070 33.3081 N 070 33.3981 N of the Equator and longitudes 0040 32.9391 E 0030 33.1431 E of the prime meridian, on an elevation of 122.4m above the sea level in the North to North East of the University. The pond which was constructed between March and July 1967, occupies an estimate area of 1,100 square metres at maximum fill. The two inflows to the pond are Elerin Stream which flow from between two villages, Kajola and Obagbile, and Omifunfun both of which flow from a relatively higher plain and through a secondary forest.

46

3.2 The Climate and Meteorology of the Area The area completely falls within the humid Semi-Hot Equatorial climate zone (Ojo, 1977). It is dominated by two major air masses: the warm and dry continental wind from the Sahara, called north-East Trade Wind (Harmattan Wind), and the hot humid tropical maritime South West Trade Wind from the Atlantic zone (South Monson Wind) (Ojo, 1977). The wet season starts from around mid March to late October and rainfall pattern is bimodal with peak periods in July and September. The dry seasons runs from November to March, with a dry spell in August called August break. The average annual rainfall at Ile-Ife is 1433 256.3 mm in over 22 years survey (Olabanji, 2002). The relative humidity follows the rainfall pattern. It is high during the wet (rainy) season with an average 86.1 4.0% and low during the dry season with an average of 75.8 6.9%. The highest value usually occurs in July (91.5%) while the lowest is in December (69.0%), (Asibor, 2001). Atmospheric temperature is moderately high at Ile-Ife throughout the year, with low range between the monthly mean

47

maximum temperatures. The peak of the maximum temperature is usually between February and March (32.2-34.40C) just before the onset of rains while the lowest minimum temperature is usually between July and September (27.1 27.90) during the peak period of rainfall (Olabanji, 2002). 3.3 The Geology of the Area. The rocks of Ile-Ife constitute part of the Precambrian basement complex of Nigeria, which in turn, is part of the African crystalline shield. They consist of various gneisses, schist and quartzite into which granites and basic rocks have intruded. Outcrops do occur, and vary from place to place depending on their resistance to erosion, and are usually found forming minor falls and rapids along the river. 3.4 Soils of the Area and Land Use The soil types of the area range from sandy clay to those with rocky fragments, which may either poorly drained or well drained. The soils of the area vary from moderately to strongly leached, and have low to medium humus contents, weakly acidic to neutral on surface layers and moderately to strongly acidic sub-soils (Smith and Montgomery, 1962). The soil type in the area is suitable for growing crops such as cocoa, kola, banana, cassava, yam, maize etc.

48

3.5

Vegetation of the Area The natural vegetation of the area was a typical rain forest

characterised by emergent trees with multiple canopies and lianas. However, widespread and persistent rotational bush farming, coupled with widespread cultivation of food crops and drug research around the dam area has led to the destruction of the original vegetation. However a leftover of the forest vegetation can still be noticed around the mechanical spill way and towards the south of the pond.

49

CHAPTER FOUR
MATERIALS AND METHODS
4.1 Sampling Programme and Sampling Stations Three sampling stations were established along the horizontal axis of the lake, denoted A, B and C. Station A is located towards the deepest portion of the lake close to the dam, mid-point from the shores. Station B is established at the middle basin of the lake while station C is located at the riverside portion of the lake. At Station A, four vertical samples were collected for heavy metal analysis from the surface, 1metre depth, 2 metres depth and the bottom of the lake. At Station B, three vertical samples were collected from the surface, 1metre depth and at the bottom of the lake, while at Station C,two samples were collected from the surface and the bottom of the lake. An improvised water sampler was used for sampling subsurface water at these various depths. Field survey was conducted monthly for a period of 12 months. The following parameters of the lake water were determined on the field: depth and transparency (using a secchi disc) and temperature (using mercury in bulb thermometer). Heavy metals determined

50

include: Arsenic (As), Cadmium (Cd), Chromium (Cr), Cobalt (Co), Copper (Cu), Iron (Fe), Manganese (Mn), Nickel (Ni), Lead (Pb), Zinc (Zn). All determinations were carried out using atomic absorption spectrometry (AAS) with adequate quality assurance and quality control measures (QA/QC). 4.2 Method of Analysis The heavy metals were determined instrumentally using atomic absorption spectrometry (AAS) at different wavelengths, Arsenic (As) at the wavelength of 193.0 nm, Cadmium (Cd) 228.0 nm, Chromium (Cr) 429.0 nm, Cobalt (Co) 240.0 nm, Nickel (Ni) 232.0 nm, Manganese (Mn) 403.0 nm, Copper (Cu) 324.7 nm, Iron (Fe) 2248.0 nm, Lead (Pb) 283.0 nm, and Zinc (Zn) 213.0 nm. Concentrations were measured in mg/l according to Golterman et al. (1978) (Table 4.1).

51

Table 4.1: Instrumentation methods used in the chemical analyses of water quality parameters.
Water parameter Instrument used Wavelength (nm) Arsenic (As) Cadmium (Cd) Chromium (Cr) Cobalt (Co) Nickel (Ni) Manganese (Mn) Copper (Cu) Iron (Fe) Zinc (Zn) Lead (Pb) Atomic absorption spectrophotometer Atomic Atomic Atomic Atomic Atomic Atomic Atomic Atomic Atomic absorption 228.0 absorption 429.0 absorption 240.0 absorption 232.0 absorption 403.0 absorption 324.7 absorption 248.0 absorption 213.0 absorption 283.0 mgl-1 mgl-1 mgl-1 mgl-1 mgl
-1

Unit

Reference

193.0

mgl-1

Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978) Golterman et al. (1978)

spectrophotometer spectrophotometer spectrophotometer spectrophotometer spectrophotometer mgl-1 mgl-1 mgl-1 mgl-1 spectrophotometer spectrophotometer spectrophotometer spectrophotometer

52

CHAPTER FIVE
RESULTS
The results of this study are presented in Tables 5.1 to 5.17 and Figures 5.1 to 5.11. 5.1 Arsenic (As): The concentrations of arsenic in the water samples from the pond ranged from 0.00 to 4.20 mg/l (Table 5.1), with an overall mean standard error of mean (s.e.m) of 1.022 0.121 mg/l, mode value of 0.00 mg/l and a medium value of 0.70mg/l. The highest recorded concentration of arsenic was found on the surface of the pond in Station A in April 2007. The detection limit of arsenic was 0.005 mg/l and arsenic was detected in 68.4% of the entire samples. The mean values through the vertical profile of the pond were 0.783 0.208 mg/l, 1.090 0.224 mg/l and 1.185 0.196 mg/l on the surface, at mid- depth and at the bottom of the pond respectively (Table 5.16). The mean concentrations of arsenic through the horizontal profile was found to be highest in Station C, followed by Station B and lowest in Station A (Figure 5.1). It was also observed that the mean concentrations of arsenic were higher during the rainy season (1.1220.162 mg/l) than the dry season (0.841 0.172 mg/l), (Figure 5.11). The mean concentration of arsenic in the pond was higher than World Health Organisation (WHO, 1993 and 2003)
53

standard and European Union (EU, 1998) standards for drinking water quality (Table 5.15 and 5.17). 5.2 Cobalt (Co): The concentrations of Cobalt were detected in 43.4% of the entire samples and the detection limit of cobalt was found to be 0.005 mg/l. The concentrations of cobalt varied over a range of 0.00 to 0.14mg/l (Table 5.2), with overall mean standard error mean (s.e.m) of 0.0240.004 mg/l and the median/ mode values of 0.00 (Table 5.15). The highest recorded concentration of cobalt was found in the bottom of the pond in Station B in May, 2007. The mean values of cobalt through the vertical profile of the pond were 0.024 0.006mg/l on the surface, 0.022 0.007mg/l at the mid-depth, and 0.027 0.008mg/l in the bottom of the pond (Table 5.16). The mean concentration of cobalt through the horizontal profile of the pond was highest in Station A, followed by Station B and lowest in Station C (Figure 5.2). Figure 5.11, reveals that the mean concentration of cobalt was higher during the rainy season (0.0300.006 mg/l) than the dry season (0.014 0.005 mg/l).

54

5.3 Cadmium (Cd): Cadmium was detected in 59.2% of all the samples and the detection limit of Cadmium was 0.002 mg/l. Cadmium concentrations in water samples from the pond varied from 0.00 to 2.63mg/l (Table 5.3), with overall mean s.e.m of 0.594 0.081mg/l, a mode of 0.00 mg/l and a median value of 0.36mg/l. It was noted that the highest value of cadmium was found in the surface of the pond in Station C in January 2007. The mean values of cadmium through the vertical profile of the pond were 0.490 0.128 mg/l on the surface, 0.480 0.136 mg/l at the mid-depth and 0.798 0.151 mg/l at the bottom of the pond (Table 5.16). The mean concentrations of cadmium along the horizontal profile was highest in Station C, followed by Station B and lowest in Station A (Figure 5.3). It was also observed that the mean concentration of cadmium was higher during the rainy season (0.6620.102 mg/l) than the dry season (0.4700.134 mg/l), (Figure 5.11). Also it was observed that the concentration of cadmium in the pond was higher than the 0.003 mg/l WHOs (1993) and (2006) standards and 0.005 mg/l EUs (1998) standards recommended for drinking water quality (Tables 5.15 and 5.17).

55

Table 5.1: The concentrations (mgl-1) of Arsenic (As) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 0.00 1.80 0.80 A 1 1.70 0.00 0.60 2 0.00 0.00 0.60 B 2.90 2.00 0.00 S 0.80 1.00 0.00 B 1 2.00 1.40 0.90 B 1.00 1.70 0.00 C S 0.00 2.20 0.00 B 2.30 0.00 2.70 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 0.40 1.80 0.00 0.40 4.20 0.90 2.20 0.40 ND ND ND 0.50 ND ND ND ND ND ND 0.00 2.40 1.40 ND 1.50 1.30 2.10 0.00 1.70 ND 0.40 0.00 1.30 ND ND ND ND ND 0.00 0.00 ND ND ND 1.90 2.00 0.00 ND ND ND ND 1.00 ND ND ND ND ND June 14 0.60 0.00 ND 0.20 0.10 ND 1.20 ND ND July 13 0.00 2.40 3.30 2.00 0.00 2.80 2.80 3.90 0.50 Aug. 17 0.00 0.60 0.60 0.00 0.00 0.50 0.80 0.00 1.20 Mean 0.91 0.93 0.90 1.15 0.55 1.48 1.04 1.16 1.28 S.E. 0.35 0.31 0.61 0.33 0.23 0.33 0.32 0.59 0.42 %CV 134.1 101.1 152.2 93.9 138.2 55.4 93.3 134.5 81.3

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 1.01, S.E. = 0.12

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 105.0

56

Table 5.2: The concentrations (mgl-1) of Cobalt (Co) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). Station Depth Sept. (m) 14 S 0.00 A 1 0.07 2 0.00 B 0.04 S 0.00 B 1 0.00 B 0.00 C S 0.00 B 0.03 2006 Oct. Nov. 12 16 0.07 0.00 0.00 0.00 0.05 0.05 0.00 0.00 0.00 0.00 0.02 0.06 0.00 0.10 0.00 0.04 0.00 0.00 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 0.00 0.03 0.02 0.00 0.00 0.07 0.01 0.00 ND ND ND 0.02 ND ND ND ND ND ND 0.00 0.03 0.00 ND 0.00 0.11 0.00 0.00 0.00 ND 0.00 0.09 0.00 ND ND ND ND ND 0.00 0.00 ND ND ND 0.14 0.05 0.00 ND ND ND ND 0.00 ND ND ND ND ND June 14 0.00 0.05 ND 0.01 0.00 ND 0.06 ND ND July 13 0.07 0.00 0.00 0.00 0.08 0.00 0.04 0.10 0.00 Aug. 17 0.05 0.11 0.00 0.07 0.05 0.00 0.01 0.00 0.05 Mean S.E. %CV 0.03 0.03 0.02 0.02 0.02 0.01 0.04 0.03 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.02 0.01 100.0 133.3 150.0 200.0 200.0 200.0 125.0 133.3 200.0

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 0.02, S.E. = 0.003

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 150.0

57

Table 5.3: The concentrations (mgl-1) of Cadmium (Cd) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 0.00 2.01 0.00 A 1 0.62 0.00 0.00 2 0.00 0.00 1.63 B 1.51 0.55 0.00 S 0.31 0.26 0.00 B 1 0.83 0.82 0.00 B 1.28 1.44 0.83 C S 0.00 0.00 0.00 B 2.47 0.74 0.00 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 0.00 0.00 0.43 0.00 1.79 0.15 0.62 0.00 ND ND ND 1.33 ND ND ND ND ND ND 0.00 0.49 0.62 ND 0.00 0.00 0.37 0.00 0.00 ND 0.49 0.62 1.41 ND ND ND ND ND 1.78 0.00 ND ND ND 0.25 0.85 2.63 ND ND ND ND 1.03 ND ND ND ND ND June 14 0.00 0.00 ND 0.00 1.44 ND 0.25 ND ND July 13 0.83 0.37 0.00 1.36 0.00 1.71 1.14 0.72 0.40 Aug. 17 0.00 0.00 0.28 0.34 0.37 0.00 2.41 1.47 1.86 Mean S.E. %CV 0.43 0.33 0.38 0.44 0.35 0.80 1.04 0.81 1.08 0.21 0.15 0.32 0.17 0.13 0.29 0.26 0.37 0.38 169.8 139.4 186.8 125.0 120.0 87.5 76.0 121.0 86.1

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 0.59, S.E. = 0.08

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 120.3

58

Table 5.4: The concentrations (mgl-1) of Chromium (Cr) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 0.18 0.04 0.00 A 1 0.18 0.00 0.14 2 0.02 0.00 0.03 B 0.08 0.00 0.21 S 0.00 0.32 0.00 B 1 0.08 0.17 0.05 B 0.00 0.09 0.07 C S 0.18 0.12 0.17 B 0.00 0.03 0.00 S = Surface, B = Bottom, ND = No Data S.E. = Standard Error, %CV = Percentage Coefficient of Variation 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 0.12 0.00 0.01 0.00 0.00 0.14 0.03 0.00 ND ND ND 0.00 ND ND ND ND ND ND 0.00 0.00 0.13 ND 0.19 0.00 0.00 0.00 0.02 ND 0.00 0.00 0.00 ND 0.00 ND ND ND 0.10 0.00 0.00 ND ND 0.00 0.00 0.10 0.00 ND ND ND 0.00 ND 0.00 ND ND ND Overall: Mean = 0.06, %CV = 133.3 June 14 0.17 0.00 ND 0.06 0.00 ND 0.08 ND ND July 13 0.03 0.07 0.00 0.26 0.18 0.08 0.00 0.02 0.25 Aug. 17 0.09 0.06 0.05 0.00 0.03 0.00 0.00 0.14 0.01 Mean S.E. %CV 0.07 0.05 0.02 0.08 0.05 0.06 0.04 0.10 0.05 0.02 0.02 0.01 0.03 0.03 0.02 0.02 0.03 0.04 100.0 140.0 100.0 125.0 200.0 100.0 125.0 70.0 200.0

S.E. = 0.01

59

Figure 5.1:The Mean Concentrations of Arsenic in the Teaching & Research Farm Pond 1 O.A.U.
1.4

1.2

Concentration (m g/l) of Arsenic

0.8 Concentration of Arsenic in the pond 0.6

0.4

0.2

0 A B Different Stations at which Samples were taken C

Figure 5.1: The Mean Concentrations of Arsenic in the Teaching and Research Farm Pond 1 O.A.U.
Figure 5.2:The Mean Concentrations of Cobalt in Teaching & Research Farm Pond 1 O.A.U.
0.03

0.025

Concentration (mg/l) of Cobalt

0.02

0.015

Concentration of Cobalt in the pond

0.01

0.005

0 A B Different Stations at which samples were taken C

Figure 5.1: The Mean Concentrations of Cobalt in the Teaching and Research Farm Pond 1 O.A.U.

60

Figure 5.3:The Mean Concentrations of Cadmium in Teaching & Research Farm Pond 1 O.A.U.
1

0.9

0.8 Concentration (m g/l) of Cadm ium

0.7

0.6

0.5

Conc. of Cadmium in the pond

0.4

0.3

0.2

0.1

0 A B Different Stations at which samples were taken C

Figure 5.3: The Mean Concentrations of Cadmium in the Teaching and Research Farm Pond 1 O.A.U.

Figure 5.4:The Mean Concentrations of Chromium in Teaching & Research Farm Pond 1 O.A.U.
0.08

0.07

Concentration (mg/l) of Chromium

0.06

0.05

0.04

Conc. of Chromium in the pond

0.03

0.02

0.01

0 A B Different Stations at which samples were taken C

61

The mean values of cadmium through the vertical profile of the pond were 0.490 0.128 mg/l on the surface, 0.480 0.136 mg/l at the mid-depth and 0.798 0.151 mg/l at the bottom of the pond (Table 5.16). The mean concentrations of cadmium along the horizontal profile was highest in Station C, followed by Station B and lowest in Station A (Figure 5.3). It was also observed that the mean concentration of cadmium was higher during the rainy season (0.6620.102 mg/l) than the dry season (0.4700.134 mg/l), (Figure 5.11). Also it was observed that the concentration of cadmium in the pond was higher than the 0.003 mg/l WHOs (1993) and (2006) standards and 0.005 mg/l EUs (1998) standards recommended for drinking water quality (Tables 5.15 and 5.17). 5.4 Chromium (Cr): Chromium was detected in 53.8% of all the samples analysed and the detection limit of chromium was 0.002 mg/l. The concentrations of chromium in the water samples from the pond were in the ranged of 0.00 to 0.32 mg/l (Table 5.4), with overall mean s.e.m of 0.057 0.009 mg/l, and a median value of 0.02 mg/l (Table 5.15). The highest recorded level of chromium was at the surface of the pond in Station B in October 2006. The mean concentrations of chromium through the vertical profile of the pond were 0.067 0.015 mg/l at the surface, 0.046 0.013 mg/l at mid-

62

depth and 0.058 0.016 mg/l at the bottom of the pond (Table 5.16). Also the mean concentrations of chromium along the horizontal profile of the pond was highest in Station C, followed by Station A and lowest in Station B (Figure 5.4). It was also higher during the rainy season (0.0690.012 mg/l) than in the dry season (0.0380.012 mg/l). (Figure 5.11). The mean concentrations of chromium in the pond was slightly higher than the 0.05 mg/l WHOs (1993) and (2006) standards and EUs (1998) standards recommended for drinking water quality (Tables 5.15 and 5.17). 5.5 Copper (Cu): Detectable concentrations of copper occurred in 92.1% of the entire samples analysed and the detection limit of copper was 0.001 mg/l. The range in the water samples was 0.00 to 10.00 mg/l (Table 5.5), with overall mean s.e.m of 2.910 0.218 mg/l, a median value of 2.77 mg/l and a mode value of 0.00 mg/l (Table 5.15). The highest recorded level of copper was found at the mid-depth and in the bottom of the pond in Station A in May 2007 (Table 5.5). The mean concentrations of copper through the vertical profile of the pond were 2.491 0.206 on the surface, 3.357 0.538 mg/l at mid-depth and 3.050 0.420 mg/l in the bottom of the pond (Table 5.16). The mean concentrations of copper along the horizontal profile of the pond were highest in Station A, followed by Station B and lowest in Station C (Figure

63

5.5). The mean concentration was higher during the rainy season (2.9420.741 mg/l) than the dry season (2.3300.184 mg/l), (Figure 5.11). It was also observed that the concentrations of copper in the pond were mostly higher than the 2.00 mg/l WHOs and EUs standards recommended for drinking water quality (Tables 5.15 and 5.17). 5.6 Iron (Fe): Iron was detected in 63.2% of the entire samples and the detection limit of iron was found to be 0.003 mg/l. Table 5.6, shows that the iron values ranged from 0.00 mg/l to 20.20 mg/l, with the highest value found on the surface of the pond in Station B, in May 2007. It was also noted that iron was found to be the dominant metal measured during this study. The overall mean s.e.m of iron was 3.987 0.563 mg/l, the median value was 2.60 mg/l (Table 5.15) and the mode value was 0.00 mg/l. The mean concentrations of iron through the vertical profile of the pond were 5.070 1.049 mg/l on the surface, 3.405 1.149 mg/l at mid-depth and 3.418 0.670 in the bottom of the pond (Table 5.16). Figure 5.6, reveals that the mean concentrations of iron along the horizontal profile of the pond was highest in Station A, followed by Station B and lowest in Station C. Figure 5.11, shows that the mean concentration of iron was higher during the rainy season (4.2690.741 mg/l) than the dry season(3.4740.850 mg/l). It was

64

also observed that the mean concentrations of iron in the pond was mostly higher than the 0.2 mg/l EUs standards recommended for drinking water quality (Tables 5.15 and 5.17).

65

Table 5.5: The concentrations (mgl-1) of Copper (Cu) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). Station A 2006 Depth Sept. Oct. Nov. (m) 14 12 16 S 4.08 1.93 3.19 1 5.37 2.12 1.70 2 5.32 2.33 1.74 B 3.57 1.48 2.95 S 3.10 3.64 2.51 1 2.88 0.97 3.02 B 5.02 5.06 1.51 S 2.74 2.50 2.10 B 2.72 0.24 2.66 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 3.45 3.01 1.70 0.00 0.00 0.00 0.00 3.32 ND ND ND >10.00 ND ND ND ND ND ND 2.03 2.93 1.66 ND 0.00 >10.00 1.89 2.52 2.01 ND 1.54 2.36 4.06 ND ND ND ND ND 3.25 1.80 ND ND ND 7.10 1.88 3.19 ND ND ND ND 2.83 ND ND ND ND ND June 14 3.87 7.86 ND 2.56 4.60 ND 5.07 ND ND July 13 2.74 2.84 4.55 3.76 2.40 0.25 2.44 2.89 2.71 Aug. 17 2.05 3.13 2.80 2.91 3.10 2.87 3.05 3.74 0.00 Mean 2.17 4.04 3.35 3.08 2.71 2.34 3.81 2.72 1.36 S.E. 0.43 1.06 0.68 0.76 0.26 0.58 0.62 0.24 0.55 %CV 69.1 78.5 45.4 82.1 32.1 61.1 48.8 23.5 99.3

B C

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 2.91, S.E. = 0.22

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 65.3

66

Table 5.6: The concentrations (mgl-1) of Iron (Fe) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 0.00 0.00 8.80 A 1 0.00 7.00 4.40 2 0.00 0.00 1.20 B 0.00 0.00 8.50 S 1.90 5.20 18.00 B 1 0.00 2.60 0.00 B 3.10 3.50 0.00 C S 4.60 4.00 0.00 B 0.00 3.90 6.00 2007 Dec. Jan. Feb. March April May June July Aug. 13 11 13 13 19 18 14 13 17 6.40 3.90 0.00 10.80 12.60 15.80 7.80 11.80 3.10 0.00 0.00 ND ND ND 0.00 4.10 6.30 16.60 ND ND ND ND ND ND ND 17.30 2.50 5.10 7.00 5.00 ND 0.00 8.00 11.70 0.00 0.00 0.00 2.60 1.50 ND 1.90 20.20 5.90 3.10 0.80 0.00 ND ND ND ND ND ND 2.40 3.70 4.60 0.00 ND ND ND 2.70 7.10 0.00 1.20 0.00 0.00 ND ND ND ND ND 1.40 0.00 0.00 ND ND ND ND ND ND 5.40 0.00 Overall: Mean = 3.99, S.E. = 0.56 S.E. = Standard Error, %CV = Percentage Coefficient of Variation %CV = 123.1 Mean 6.75 4.27 4.20 4.12 5.55 1.45 2.47 1.43 2.55 S.E. 1.56 1.81 3.31 1.36 2.09 0.67 0.81 0.77 1.18 %CV 80.2 127.4 176.2 104.9 125.1 113.8 98.4 142.0 112.9

S = Surface, b = Bottom, ND = No Data

67

Figure 5.5:The Mean Concentrations of Copper in Teaching & Research Farm Pond 1 O.A.U.
3.5

Concentration (m g/l) of Copper

2.5

2 Conc.of Copper in the pond 1.5

0.5

0 A B Different Stations at which samples were taken C

Figure 5.5: The Mean Concentrations of Copper in the Teaching and Research Farm Pond 1 O.A.U.
Figure 5.6:The Mean Concentrations of Iron in Teaching & Research Farm Pond 1 O.A.U.
6

Concentration (mg/l) of Iron

Conc. of Iron in the pond

0 A B Different Stations at which samples were taken C

Figure 5.6: The Mean Concentrations of Iron in the Teaching and Research Farm Pond 1 O.A.U.

68

5.7 Manganese (Mn): Manganese was detected in 47.4% of the entire samples; the detection limit was 0.001 mg/l. The concentrations of manganese in the water samples from the pond ranged from 0.00 mg/l to 2.24 mg/l (Table 5.7), with overall mean s.e.m of 0.371 0.066 mg/l and the median/mode of 0.00 mg/l (Table 5.15). The highest recorded concentration of manganese was found at the mid-depth of the pond in Station A in July 2007. The mean concentrations of manganese through the vertical profile of the pond were 0.427 0.103 mg/l on the surface, 0.420 0.162 mg/l at the mid-depth and 0.269 0.087 mg/l at the bottom of the pond (Table 5.16). It was noted that the mean concentrations of manganese through the horizontal profile of the pond was highest in Station A, followed by Station C and lowest in Station B (Figure 5.7). It was also observed that the mean concentrations of manganese were slightly higher during the rainy season (0.3820.090 mg/l) than the dry season (0.3510.087 mg/l), (Figure 5.11). Tables 5.15 and 5.17, revealed that the mean concentrations of manganese in the pond were lower than the 0.50 mg/l WHOs (1993) standards, higher than the 0.05 mg/l EUs (1998) standards and slightly lower than the 0.40 mg/l WHO,s (2006) standards recommend for drinking water quality.

69

5.8 Nickel (Ni): The detection limit of nickel was 0.05 mg/l and it was detected in 46.1% of the entire samples. The nickel values in the water samples from the pond ranged from 0.00 mg/l to 2.80 mg/l (Table 5.8), with overall mean s.e.m of 0.446 0.072 mg/l and the median/mode = 0.00 mg/l (Table 5.15). The highest recorded concentration of nickel was found on the surface of the pond in Station A in August 2007. The mean concentrations of nickel through the vertical profile of the pond were 0.437 0.132 mg/l on the surface, 0.410 0.114 mg/l at the middepth and 0.485 0.119 mg/l in the bottom of the pond (Table 5.16). The mean concentrations of nickel through the horizontal profile of the pond were highest in Station C, followed by Station A and lowest in Station B (Figure 5.8). It was observed that the mean concentration of nickel was higher during the rainy season (0.5080.096 mg/l) than the dry season (0.3330.101 mg/l),(Figure 5.11). It was also higher than the 0.02 mg/l WHOs (1993) standards and EUs (1998) standards as well as 0.07 mg/l WHOs (2006) standards recommended for drinking water quality. 5.9 Lead (Pb): Lead was detected in 51.3% of all the samples and the detection limit of lead was 0.004 mg/l. The concentrations of lead in the water samples from the pond ranged from 0.00 mg/l to 0.49 mg/l (Table 5.9), with overall mean s.e.m of 0.074 0.013 mg/l, a mode value of 0.00

70

mg/l and a median value of 0.02 mg/l (Table 5.15). The highest recorded value of lead was found on the surface of the pond in Station A in October 2006. The mean values of lead through the vertical profile of the pond was 0.093 0.024 mg/l on the surface, 0.032 0.011 mg/l at the mid-depth and 0.083 0.022 mg/l at the bottom of the pond (Table 5.16). The mean concentrations of lead along the horizontal profile of the pond were highest in Station A, followed by Station C and lowest in Station B (Figure 5.9). It was observed that there was no significant seasonal variation in the concentrations of lead in the pond, 0.0750.016 mg/l (rainy season) and 0.0710.021 mg/l (dry season), (Figure 5.11). It was also noted that the mean concentrations of lead in the pond was higher than the 0.01 mg/l WHOs (1993) and (2006) standards and EUs (1998) standards recommended for drinking water quality. 5.10 Zinc (Zn): Zinc values in the water samples from the pond were in the ranged of 0.00 to 6.90 mg/l (Table 5.10), with overall mean s.e.m of 1.264 0.185 mg/l and a median value of 0.42 mg/l (Table 5.15). The highest recorded value of zinc was found at the bottom of the pond in Station B in June 2007. Zinc was detected in 53.9% of the entire samples and the detection limit was 0.006 mg/l.

71

The mean values of zinc through the vertical profile of the pond were 1.338 0.290 mg/l on the surface, 1.164 0.264 mg/l at the mid-depth and 1.210 0.369 mg/l in the bottom of the pond (Table 5.16). Also the mean values of zinc through the horizontal profile of the pond was highest in Station C, followed by Station B and lowest in Station A (Figure 5.10). It was observed that the mean concentrations of zinc were higher during the dry season (1.6670.021 mg/l) than in the rainy season (1.0090.213 mg/l),(Figure 5.11). It was also observed that the mean concentration of zinc in the pond was lower than the 3.00mg/l WHOs (1993) standards recommended for drinking water quality.

72

Table 5.7: The concentrations (mgl-1) of Manganese (Mn) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 1.14 0.00 0.61 A 1 0.00 0.00 0.25 2 2.07 0.00 0.00 B 0.62 0.00 0.00 S 1.47 0.01 0.00 B 1 1.44 0.00 0.25 B 0.76 0.00 0.00 C S 1.73 0.18 0.00 B 0.00 0.25 0.00 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 0.00 0.70 1.80 0.00 0.00 0.00 0.41 0.42 ND ND ND 0.00 ND ND ND ND ND ND 0.77 1.42 0.34 ND 0.00 0.00 0.42 0.50 0.42 ND 0.11 0.00 0.00 ND ND ND ND ND 0.51 0.00 ND ND ND 0.00 0.00 0.65 ND ND ND ND 0.00 ND ND ND ND ND June 14 0.00 0.05 ND 0.00 0.04 ND 0.00 ND ND July 13 0.00 0.00 2.24 0.00 1.31 0.00 0.00 0.00 0.00 Aug. 17 0.18 0.00 1.26 1.33 0.50 0.00 0.00 1.04 0.99 Mean S.E. %CV 0.37 0.13 1.11 0.41 0.43 0.28 0.14 0.51 0.21 0.17 0.06 0.48 0.17 0.16 0.24 0.10 0.25 0.16 159.5 138.5 97.3 134.1 120.9 207.1 207.1 131.4 190.5

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 0.37, S.E. = 0.07

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 154.1

73

Table 5.8: The concentrations (mgl-1) of Nickel (Ni) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). Station A Depth (m) S 1 2 B S 1 B S B Sept. 14 0.00 0.20 0.20 1.30 1.00 0.00 0.00 0.00 0.50 2006 Oct. Nov. 12 16 0.00 0.00 0.00 0.70 1.00 0.00 0.90 0.00 1.70 0.00 0.70 1.30 0.00 0.00 0.00 0.00 1.60 0.00 Dec. 13 0.70 0.00 ND 1.00 0.80 0.00 0.00 0.00 0.00 Jan. 11 0.10 1.60 ND 0.00 0.00 ND 0.00 1.50 ND 2007 Feb. March April May 13 13 19 18 0.00 0.00 0.00 0.00 ND ND ND 0.50 ND ND ND ND 1.00 ND 0.00 0.30 0.30 ND 0.00 0.90 ND ND ND ND ND ND ND 0.80 ND ND ND ND ND ND ND ND June 14 0.00 1.10 ND 0.70 0.00 ND 0.00 ND ND July 13 0.30 0.00 0.00 0.00 0.00 0.00 0.00 1.90 1.40 Aug. 17 2.80 0.20 0.70 1.50 1.10 0.00 1.60 0.00 0.00 Mean 0.33 0.48 0.38 0.61 0.53 0.33 0.27 0.49 0.58 S.E. 0.23 0.19 0.20 0.17 0.18 0.22 0.19 0.32 0.30 %CV 245.5 116.7 118.4 93.4 113.2 166.7 211.1 171.4 127.6

B C

S = Surface, B = Bottom, ND = No Data S.E. = Standard Error, %CV = Percentage Coefficient of Variation

Overall: Mean = 0.45, S.E. = 0.07 %CV = 140.0

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Table 5.9: The concentrations (mgl-1) of Lead (Pb) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 0.00 0.49 0.00 A 1 0.00 0.07 0.13 2 0.03 0.00 0.00 B 0.11 0.06 0.00 S 0.00 0.12 0.00 B 1 0.00 0.00 0.00 B 0.00 0.00 0.27 C S 0.00 0.03 0.29 B 0.14 0.00 0.00 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 0.00 0.00 0.11 0.00 0.05 0.37 0.15 0.00 ND ND ND 0.14 ND ND ND ND ND ND 0.01 0.00 0.00 ND 0.05 0.28 0.19 0.10 0.10 ND 0.00 0.08 0.00 ND ND ND ND ND 0.39 0.07 ND ND ND 0.24 0.00 0.10 ND ND ND ND 0.00 ND ND ND ND ND June 14 0.00 0.06 ND 0.00 0.05 ND 0.06 ND ND July 13 0.35 0.03 0.03 0.22 0.05 0.00 0.00 0.10 0.19 Aug. 17 0.22 0.00 0.00 0.07 0.00 0.00 0.00 0.00 0.00 Mean 0.13 0.06 0.01 0.07 0.06 0.00 0.11 0.07 0.06 S.E. 0.05 0.02 0.01 0.03 0.02 0.00 0.05 0.04 0.04 %CV 138.5 100.0 200.0 142.9 100.0 0.00 136.4 157.1 150.0

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 0.07, S.E. = 0.01

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 157.1

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Table 5.10: The concentrations (mgl-1) of Zinc (Zn) in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 2.25 0.44 0.00 A 1 0.00 0.00 2.47 2 2.12 2.25 0.00 B 0.00 0.00 3.03 S 0.00 0.00 5.08 B 1 2.38 2.38 1.80 B 0.00 0.00 0.00 C S 0.00 0.32 0.00 B 0.00 1.13 1.63 2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 3.07 4.07 0.00 0.69 0.00 0.37 0.00 0.00 ND ND ND 0.48 ND ND ND ND ND ND 2.40 3.79 0.00 ND 1.89 0.09 3.50 1.11 4.70 ND 1.90 3.02 0.00 ND ND ND ND ND 0.00 0.00 ND ND ND 0.00 2.41 2.89 ND ND ND ND 4.04 0.00 ND ND ND ND June 14 0.00 2.41 ND 0.00 2.30 ND 6.92 ND ND July 13 0.92 3.09 0.00 0.93 0.70 0.00 0.00 0.00 5.66 Aug. 17 0.00 2.40 0.00 1.17 0.40 1.50 0.00 0.00 0.00 Mean S.E. %CV 0.98 1.21 0.87 1.21 2.06 1.01 0.77 0.80 2.08 0.40 0.45 0.54 0.42 0.55 0.42 0.77 0.48 0.94 140.8 110.7 137.9 114.0 88.3 101.0 300.0 158.8 110.6

S = Surface, B = Bottom, ND = No Data

Overall: Mean = 1.28, S.E. = 0.19

S.E. = Standard Error, %CV = Percentage Coefficient of Variation

%CV = 126.6

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Figure 5.7:The Mean Concentrations of Manganese in Teaching & Research Farm Pond 1 O.A.U.
0.6

0.5 Concentration (m g/l) of M anganese

0.4

0.3

Conc. of Manganese in the pond

0.2

0.1

0 A B Different Stations at which samples were taken C

Figure 5.7: The Mean Concentrations of Manganese in the Teaching and Research Farm Pond 1 O.A.U.
Figure 5.8:The Mean Concentrations of Nickel in Teaching & Research Farm Pond 1 O.A.U.
0.6

0.5

Concentration (mg/l) of Nickel

0.4

0.3

Conc. of Nickel in the pond

0.2

0.1

0 A B Different Stations at which samples were taken C

Figure 5.8: The Mean Concentrations of Nickel in the Teaching and Research Farm Pond 1 O.A.U.

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Figure 5.9:The Mean Concentrations of Lead in Teaching & Research Farm Pond 1 O.A.U.
0.07

0.068

0.066

C n e tra n(m /l) o L a o c n tio g f ed

0.064

0.062

0.06

Conc. of Lead in the pond

0.058

0.056

0.054

0.052

0.05 A B Different Stations at which samples were taken C

Figure 5.9: The Mean Concentrations of Lead in the Teaching and Research Farm Pond 1 O.A.U.

Figure 5.10:The Mean Concentrations of Zinc in Teaching & Research Farm Pond 1 O.A.U.
1.6

1.4

1.2 Concentration (mg/l) of Zinc

0.8

Conc. of Zinc in the pond

0.6

0.4

0.2

0 A B Different Stations at which samples were taken C

Figure 5.10: The Mean Concentrations of Zinc in the Teaching and Research Farm Pond 1 O.A.U.

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Figure 5.11: The Concentration of Heavy metals for both Rainy and Dry Seasons in the Teaching and Research Farm Pond 1 O.A.U.

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Table 5.11: The Hydrogen ion concentrations (pH) (pH Units) of water samples in the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). Station Depth (m) S A 1 2 B S B 1 B C S B Sept. 14 6.75 6.55 6.35 6.30 6.70 6.35 6.00 6.75 6.30 2006 Oct. Nov. 12 16 6.65 6.75 6.55 6.60 6.20 6.25 6.15 6.10 6.55 6.70 6.30 6.65 6.10 6.30 6.50 6.55 6.35 6.40 Dec. 13 6.65 6.60 ND 6.20 6.70 6.60 6.30 6.75 6.35 Jan. 11 6.85 6.80 ND 6.60 6.80 ND 6.50 6.80 ND 2007 Feb. March April May 13 13 19 18 6.80 6.15 6.15 6.75 ND ND ND 6.25 ND ND ND ND 6.70 ND 6.05 6.00 7.60 ND 6.20 6.70 ND ND ND ND ND ND ND 6.10 ND ND ND ND ND ND ND ND June 14 6.75 6.65 ND 6.60 6.80 ND 6.35 ND ND July 13 6.25 6.20 6.10 6.05 6.30 6.25 6.10 6.55 6.45 Aug. 17 6.50 6.60 6.35 6.20 6.60 6.55 6.25 6.60 6.20 Mean S.E. %CV 6.58 6.53 6.25 6.27 6.70 6.45 6.22 6.64 6.34 0.08 0.06 0.05 0.08 0.11 0.07 0.05 0.05 0.04 4.0 2.9 1.8 4.0 5.4 2.6 2.6 1.8 1.4

S = Surface, B = Bottom, ND = No Data; Overall: Mean = 6.38, S.E. = 0.09 %CV = 12.1 %CV = Percentage Coefficient of Variation

S.E. = Standard Error,

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Table 5.12: The Water Temperature (0C) values from the Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007). 2006 Station Depth Sept. Oct. Nov. (m) 14 12 16 S 29.0 31.0 29.0 A 1 27.0 28.0 28.5 2 26.5 27.0 28.0 B 26.0 26.0 27.5 S 30.0 29.0 31.0 B 1 27.0 28.0 29.0 B 26.0 26.0 28.0 C S 31.0 32.0 31.5 B 27.0 28.0 29.0 S = Surface, B = Bottom, ND = No Data %CV = 7.1 S.E. = Standard Error,
0

2007 Dec. Jan. Feb. March April May 13 11 13 13 19 18 28.5 26.0 30.0 31.0 33.0 31.0 28.0 25.0 ND ND ND 30.0 ND ND ND ND ND ND 27.5 24.0 29.0 ND 31.5 29.0 29.0 26.0 29.5 ND 33.5 32.0 28.0 ND ND ND ND ND 28.0 25.0 ND ND ND 30.0 30.5 28.0 ND ND ND ND 28.5 ND ND ND ND ND Overall: Mean = 28.3, S.E. = 0.2,

June 14 29.5 28.5 ND 28.0 30.5 ND 28.5 ND ND

July 13 27.5 27.0 26.5 26.0 29.0 28.0 27.0 30.0 27.0

Aug. 17 27.0 26.5 26.0 26.0 27.5 26.5 26.5 29.5 27.0

Mean S.E. %CV 29.4 27.6 26.8 27.3 29.7 27.8 27.2 30.4 27.8 0.6 0.5 0.4 0.6 0.6 0.4 0.5 0.5 0.4 6.8 5.1 3.0 7.3 7.1 3.2 5.5 4.3 3.2

C = Degree Celsius

%CV = Percentage Coefficient of Variation

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Table 5.13: The Total Depth (m) of water measured in Teaching and Research Farm Pond 1 of Obafemi Awolowo University (September, 2006-August, 2007) Station A B C Sept. 14 4.07 3.44 2.20 2006 Oct. Nov. 12 16 3.40 3.38 3.00 2.85 2.10 1.69 Dec. 13 3.21 2.74 1.50 Jan. 11 2.60 2.00 0.80 2007 Feb. March April May June July Aug. 13 13 19 18 14 13 17 0.86 0.70 1.46 2.10 2.32 3.68 3.60 0.16 ND 0.92 1.46 1.88 2.94 2.85 ND ND ND ND ND 1.76 1.75 Overall: Mean = 2.25, %CV = 44.89 S.E. = 0.18 Mean S.E. %CV 2.62 2.20 1.69 0.33 43.51 0.31 46.36 0.17 27.22

ND = No Data, m = meters, S.E. = Standard Error; %CV = Percentage Coefficient of Variation

Table 5.14: The Water Transparency (m) values measured at each sampling station in Teaching and Research Farm Pond 1 of Obafemi AwolowoUniversity (September, 2006-August, 2007) Station Sept. 14 A 0.64 B 0.55 C 0.65 2006 Oct. Nov. 12 16 0.75 1.12 0.75 0.90 0.60 0.92 Dec. 13 1.10 0.97 0.97 Jan. 11 0.87 0.91 0.80 2007 Feb. March April May 13 13 19 18 0.20 0.18 0.65 0.65 0.16 ND 0.50 0.66 ND ND ND ND Overall: Mean = 0.69, June 14 0.53 0.55 ND July 13 0.55 0.50 0.55 Aug. 17 0.95 0.85 0.84 Mean S.E. %CV 0.68 0.64 0.76 0.09 44.12 0.07 35.29 0.06 21.05

ND = No Data, m = meters, S.E. = Standard Error; %CV = Percentage Coefficient of Variation

S.E. = 0.05

%CV = 36.23

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Table 5.15: Descriptive Statistics of Heavy Metals Concentration (mg/l) in the Teaching and Research Farm Pond 1 O.A.U. Heavy % Maximum Median Mean S.E %C.V Kurtosis Skewness Metal Detection Arsenic 68.4 4.20 0.70 1.022 0.121 103.2 0.22 0.93 Cobalt Cadmium Chromium Copper Iron Manganese Nickel Lead Zinc 43.4 59.2 53.8 92.1 63.2 47.4 46.1 51.3 53.9 0.14 2.63 0.32 10.00 20.20 2.24 2.80 0.49 6.92 0.00 0.36 0.02 2.77 2.60 0.00 0.00 0.02 0.42 0.024 0.594 0.057 2.910 3.987 0.371 0.446 0.074 1.264 0.004 0.081 0.009 0.218 0.563 0.066 0.072 0.013 0.185 143.5 119.6 133.7 65.3 123.2 153.9 140.4 149.0 127.4 0.99 0.38 1.15 4.28 2.04 1.76 1.56 3.08 1.36 1.35 1.136 1.35 1.52 1.56 1.62 1.40 1.84 1.31

S.E = Standard Error;

% C.V= Percentage Coefficient of Variation;

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Table 5.16: Descriptive Statistics of Heavy Metals Concentration (mg/l) in the Teaching and Research Farm Pond 1 O.A.U. Heavy Surface (n=30) Mid-depth (n=20) Bottom (n=26) Metals Max Mean S.E %C.V Max Mean S.E %C.V Max Mean S.E %C.V Arsenic 4.20 0.783 0.208 145.9 3.30 1.090 0.224 91.8 2.90 1.185 0.196 84.5 Cobalt Cadmium Chromium Copper Iron 0.10 2.63 0.32 4.60 0.024 0.490 0.067 2.491 0.006 139.1 0.128 143.2 0.11 0.71 0.022 0.480 0.046 3.357 3.405 0.420 0.410 0.032 1.164 0.007 0.136 0.013 0.538 1.149 0.162 0.114 0.011 0.265 145.0 126.7 125.2 71.7 150.9 172.2 124.3 159.9 101.9 0.14 2.47 0.26 10.00 11.70 1.42 1.60 0.39 6.92 0.027 0.798 0.058 3.050 3.418 0.269 0.485 0.083 1.210 0.008 0.151 0.016 0.420 0.670 0.087 0.119 0.022 0.369 147.0 96.2 143.0 70.2 107.3 164.3 125.1 135.6 158.5

0.015 126.28 0.18 0.206 45.2 1.049 113.3 0.103 132.2 0.132 165.9 0.024 139.0 0.290 118.8 10.00 17.30 2.24 1.60 0.15 3.09

20.20 5.070 0.427 0.437 0.093 1.338

Manganese 1.80 Nickel Lead Zinc 2.80 0.49 5.08

Max = Maximum concentration; S.E = Standard Error; % C.V = Percentage Coefficient of Variation.

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Table 5.17: WHO/EU drinking water standards comparative table Heavy WHOs Standards EUs Standards WHOs Standards Metals 1993 (mg/l) 1998 (mg/l) (2006) mg/l Arsenic 0.01 0.01 0.01 (As) Cobalt No guideline Not mentioned No guideline (Co) Cadmium 0.003 0.005 0.003 (Cd) Chromium 0.05 0.05 0.05 (Cr) Copper 2.0 2.0 2.0 (Cu) Iron (Fe) No guideline 0.2 No guideline Manganese 0.5 0.05 0.4 (Mn) Nickel (Ni) 0.02 0.02 0.07 Lead (Pb) 0.01 0.01 0.01 Zinc (Zn) 3.0 Not mentioned No guideline Sources: WHO,1993; EU, 1998; WHO, 2006.

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Table 5.18: Selected Water quality Criteria for Irrigational Water (mg/l) Elements FAO Canada Nigeria Arsenic (As) Cobalt (Co) Cadmium (Cd) Chromium (Cr) Copper (Cu) Iron (Fe) Manganese (Mn) Nickel (Ni) Lead (Pb) Zinc (Zn) 0.1 No guideline 0.01 0.1 0.2 No guideline 0.2 0.2 No guideline 2.0 0.1 No guideline 0.01 0.1 0.2 1.0 No guideline 0.2 0.2 No guideline 1.0 5.0 0.1 No guideline 0.01 0.1 0.2 1.0 No guideline 0.2 0.2 No guideline 0.0 5.0

Sources: FAO, 1985; CCREM, 1987; FEPA, 1991.

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CHAPTER SIX DISCUSSION

6.1 General Background Levels All the heavy metals (As, Co, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) analysed in this study were detected in the pond and their mean concentrations were found to be in the order of Fe > Cu > Zn > As > Cd > Ni > Mn > Pb > Cr > Co. This is slightly similar to that of the typical freshwater ranking order of Fe > Zn > Mn > Cu > Pb > Cr > Ni > As > Co > Cd (Freedman, 1989). Iron was the dominant metal measured during this study and this result is similar to that of other workers (Asuquo et al., 1999). The high iron content (compared with other metals) in the pond water is expected because it has been reported that iron occurs at high levels in Nigerian soils (Asaolu et al., 1997; Asaolu and Olaofe, 2004 and Nwajei and Gagophien, 2000). Another notable observation on the metal ranking order is the enhanced positions of Cu, As and Cd in the pond water as compared to the typical freshwater, this situation may be due to the effect of agricultural activities in the study area. Heavy metals occurs as impurities in fertilizers (Cd, Cr, Pb and Zn), pesticides (As, Cu, Pb and Zn), desiccants, wood preservatives (As and Cu), waste from intensive pig and poultry production

87

(As and Cu), composts and manures (As, Cd, Cu, Ni, Pb and Zn), sewage sludge (Cd, Cu, Ni, Pb and Zn) } and corrosion of metal objects (Cd and Zn ) (Alloway and Ayres, 1993 ) in the area. Among the heavy metals determined cobalt has the lowest concentration. When compared with the recommended expected and permissible standards for drinking water quality set by World Health Organisation ( WHO, 1993 and 2006 ) standards and European Union (EU, 1998), the levels of arsenic, cadmium, chromium, copper, iron, nickel and lead recorded in this study were higher, indicating that the pond water is not safe for drinking/human consumption. However, the levels of manganese and zinc detected in the pond water were lower than the WHOs (1993 and 2006) and EUs (1998) standards. The levels of zinc are also within the limiting level of water quality criteria for irrigation water, while that of manganese is higher. 6.2 Vertical Distribution Pattern Among the heavy metals investigated, it was only arsenic and manganese that showed distinct pattern of vertical variation in the pond water. There was an increase in arsenic concentrations from the surface to the bottom of the pond. This observation is similar to that of other workers (Oyewale and Musa, 2006), that, there was an appreciable increase in metal concentrations towards the water to the sediment. On the other hand,

88

manganese concentrations showed a decrease from the surface water to the bottom of the pond. This observation is in contrast to those of most other workers and this may be as a result of anthropogenic activities arising from agricultural activities in the study area. The concentrations of Co, Cd, Cr, Cu, Fe, Ni, Pb and Zn did not show any definite pattern in the vertical variation. Rather Cr, Fe, Pb and Zn levels occurred highest on the surface of the pond, Cu occurred highest at the middepth of the pond while Co, Cd and Ni occurred highest at the bottom. The probable cause of this alteration is probably anthropogenic, arising from agricultural activities and corrosion/abrasion of the ferrous steel materials. 6.3 Horizontal Distribution Pattern Among the heavy metals investigated, arsenic, cadmium, cobalt, copper, iron and zinc showed distinct pattern of horizontal variation in their concentrations. There was an increase in the concentrations of arsenic, cadmium and zinc from Station A to Station C, while that of cobalt, copper and iron showed a decrease in concentrations from Station A to Station C. There was no definite pattern in horizontal variation in the concentrations of chromium, manganese, nickel and lead. In general, the concentrations of manganese and lead were highest in Station A, while that of chromium and nickel were highest in Station C.

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6.4 Seasonal Distribution Pattern Figure 5.11 shows the heavy metal concentrations for both rainy and dry season. All the elements examined were detected in both seasons. It was observed that there was a higher mean concentration of almost all the heavy metals in the rainy season compared to dry season. That is, the mean concentration of As, Co, Cd, Cr, Cu, Fe, Mn and Ni were higher in the rainy season than in the dry season. This observation is similar to the observation of other workers (Vivek et al., 2005). This is expected, because in the rainy season, runoff from open contaminated sites and agricultural field directly comes into the pond without any treatment. The concentration of Zn was higher during the dry season than in the rainy season and there was no distinct or significant seasonal variation in the mean concentration of lead. These observations did not correspond to the observation of other workers. 6.5 Associated Health Risks The use of contaminated pond water for agricultural irrigation, fish culture and livestock watering would be one of the possible pathways for causing human hazards partly due to the bioaccumulation of heavy metals. Arsenic is carcinogenic and may cause lung, bladder, liver, renal and skin cancers. Chronic symptoms include fatigue, gastritis, anorexia and hair

90

loss; with long term exposure producing hyperkeratosis ( thickening of the skin ), cardiovascular disease, disturbances in the peripheral vascular and nervous system, circulatory disorders and liver and kidney disorders. Arsenic is deposited in the hair, nail, bones and skin; and is readily excreted through urine after three to four days. The body can detoxify (to an extent) arsenic compounds by methylation to reduce its affinity for human tissue. Cadmium has a long biological life of 20 30 years in the kidney (WHO, 1992). Chronic exposure may eventually accumulate to toxic levels; one of the consequences may be Itai itai Byo disease, which is characterised by anaemia, damaged proximal tubules, severe bone pain and mineral loss (Hodgson and Levi, 1987). Chromium, though an essential trace nutrient and vital component for the glucose tolerance factor. Chromium toxicity damages the liver, lungs and causes organ haemorrhages (WHO, 1998; OFlaherty, 1995). Copper though widely distributed and an essential element, acute toxicity of copper results to hypotension, coma and death. Copper poisoning also causes haemolytic anaemia (Manzer and Shreiner, 1970). Iron is also an essential metal but due to frequent acute and chronic iron over load which may result to renal failure and hepatic cirrhosis, it is worthy

91

to note its adverse effects which is usually common ( Muller Eberhard et al., 1977 ). Manganese is an essential element and cofactor for several enzymatic reactions. Toxicity from manganese manifests with profound increase in the incidence of respiratory diseases. In chronic cases, there may be a neuro psychiatric disorder characterised by irritability, difficulty in walking, speech disturbance, compulsive behaviour that may involve running, fighting and singing. If there is chronic manganese toxicity, it results to Parkinson like syndrome (Mena et al., 1967). This neural manifestation is due to the easiness at which manganese crosses the blood brain barrier and its half life in the brain is longer than in the whole body. Lead may impair renal function, red blood cell production, the nervous system and causes blindness. Water, especially lead polluted water is a major source of lead toxicity. Children are very susceptible to lead poisoning resulting to clinically overt encephalopathy.

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CHAPTER SEVEN CONCLUSIONS AND RECOMMENDATIONS

7.1. Conclusions The results of this study show that there was distinct pattern in vertical variation in the concentration of arsenic and manganese in the pond, while there was no definite pattern in the vertical variation of cobalt, cadmium, chromium, copper, iron, nickel, lead and zinc. The results also reveal that, there was definite pattern in horizontal variation in the concentrations of arsenic, cadmium, cobalt, copper, iron and zinc across the pond, while there was no definite pattern in horizontal variation in the concentrations of chromium, manganese, nickel and lead. The results also reveal that the concentrations of Arsenic, Cobalt, Cadmium, Chromium, Copper, Iron, Manganese and Nickel were higher in rainy season than in dry season, while Zinc levels was higher in dry season. The results also show that the levels of Arsenic, Cadmium, Chromium, Copper, Iron, Nickel and Lead were well above the (WHO, 1993 and 2006) and (EEC, 1998) standards for drinking water (Tables 5.15 and 5.17), and water quality criteria for irrigation water (Table 5.18). This indicates that the pond water is unsafe for human consumption. This implies that there is heavy

93

metal contamination in the pond water. The results obtained in this study would serve as baseline data for future heavy metal monitoring of the pond. 7.2 Recommendations From the study conclusions state above, there is heavy metal contamination in the pond water, which should be given adequate attention and response. The heavy metal contents of the pond are probably affected by agricultural management practices and environmental conditions in the catchment area. Future studies should also look at the possible sources of heavy metals in the pond. The impacts of agricultural runoff can be ameliorated through the encouragement of farmers to practise Best Management Practices (BMP) on their farms. Some suggested solutions may include the creation of water collection zones on the edges of the field to trap runoff, which would then be allowed to enter the pond after treatment. Furthermore, farmers within the catchment area should be encouraged to rationalise the fertilizer applications to reduce the input of heavy metals from the farmland into the pond through runoff. The use of contaminated pond water for agricultural irrigation, fish culture and livestock watering would be one of the possible pathways for causing human hazards partly due to the bioaccumulation of heavy metals. It

94

is therefore recommended that efforts should be made to reduce the heavy metals pollution in the pond. One possible way would be to plant hyper accumulating plants on the bank of the pond for environmental clean up. Lastly, it has been suggested by many workers that pH, salinity, temperature and redox potential all affect uptake and retention of heavy metals in the water and sediments of ponds. This aspect should be investigated further, to fully account for heavy metals in the aquatic environment of the investigated pond.

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List of Abbreviations and Acronyms Used

et al. = et alli ( and others ) As = Arsenic Cd = Cadmium Co = Cobalt Cr = Chromium Cu = Copper Fe = Iron Mn = Manganese Ni = Nickel Pb = Lead Zn = Zinc CCREM = Canadian Council of Resource and Environment Ministers ed. = edition EEC = European Economic Community EPA = Enviromental Protection Agency, United States of America. FAO = Food and Agriculture Organisation of the United Nation. FEPA = Federal Environmental Protection Agency, Nigeria. pp. = Page Vol. = Volume EU = European Union WHO = World Health Organisation

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