IMPACT OF EWEKORO CEMENT FACTORY ON THE SURROUNDING WATER RESOURCES.

AJADI OLANIYI AKEEM MATRIC NO: 02/0670

A PROJECT REPORT SUMMITTED TO THE DEPARTMENT OF WATER RESOURCES MANAGEMENT AND AGROMETEOROLOGY COLLEGE OF ENVIRONMENTAL RESOURCES MANAGEMENT

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE AWARD OF BACHELOR OF WATER RESOURCES MANAGEMENT AND HYDROLOGY (DEGREE)

UNIVERSITY OF AGRICULTURE, ABEOKUTA, OGUN STATE, NIGERIA

This study work was carried out to determine the effect of dust effluent from Ewekoro cement factory on the surrounding water. Five samples were collected at the monitoring stations on Akinbo River while another one sample was collected from 22km away from the factory which serves as the control station. The outcome of the study analyse the conc~ntration levels of potentially heavy metals and harmful elements contained in the vicinity of the factory and 22km farther away from the factory. Moreover, from the result high levels of heavy metals were recorded within the monitoring station compared to the control station which is outside the factory. Using analysis of variance to compare, heavy metals like K, Na, Ca, Mg, Cr, Cu, Pb, Mn, Fe and Zn .were significantly higher and have a significance difference (p<O.05) between the monitoring stations and the control station. In addition, a simple bar chat is also used to compare the parameters in the monitoring station and the control station and the result shows that there is high concentration of heavy metals in the monitoring stations than the control station. Never the less, a post hoc test is also used to compare the monitoring stations and the control station with World health Organiza~ion, and the outcome shows that their is a significance difference.

TITLE CERTIFICATION DEDICATION ACKNOWLEDGEMENT ABSTRACT TABLE OF CONTENT LIST OF TABLES LIST OF FIGURES

ii iii iv v vi ix x

CHAPTER ONE 1.1 BACKGROUND 1.2 INTRODUCTION 1.3 RAW MATERIAL 1.4 CEMENT PLANT AND ITS POLLUTION 1.5 AIR POLLUTION 1.5.1 AIR POLLUTION FROM CEMENT KILN AT EWEKORO 1.6 WATER POLLUTION 1.6.1 SOURCES OF WATER POLLUTION 1.6.2 EXPOSURE TO CHEMICAL WATER POLLUTION 1.7 PROBLEM STATEMENT 1.8 JUSTIFICATION 1.9 AIM 1 1 3 3 4 5 5 5 6 6 7 7

CHAPTER TWO 2.1 LITERATURE REVIEW 2.2 ASSESSMENT OF WATER QUALITY 8 13

CHAPTER THREE 3.0 METHODOLOGY 3.1 STUDY SITE 3.2 GEOLOGICAL SETTING 15 15 16

3.3 MATERIALS 3.4 COLLECTION OF SAMPLES 3.5 PRECAUTION TAKEN DURING SAMPLING 3.6 WATER QUALITY PROCEDURES 3.6.1 Water Temperature 3.6.2 pH 3.6.3 Dissolve Oxygen 3.6.4 Electrical Conductivity 3.6.5 Total Dissolve Solid 3.6.6 Total Hardness 3.7 LABOURATORY ANALYSIS OF ALL THE HEAVY METALS

16 16 19 19 19 19 19 20 20 20 21 21 22 22 23

3.7.1 Procedure for Water Digestion 3.7.2 Atomic Absorption Spectrometer (AAS) 3.7.3 Mode of Operation of AAS 3.8 METHODS OF COMPARATIVE ANALYSIS

CHAPTER FOUR
4.1 RESULTS 4.2 DISCUSSION 4.2.1 Dissolve Oxygen (DO) 4.2.2 Electrical Conductivity (Ee) 4.2.3 Total Dissolve Solid (TDS) 4.2.4 Total Hardness (TH) 4.2.5 Potassium (K) 4.2.6 Sodium (Na) 4.2.7 Calcium (Ca) 4.2.8 Magnesium (Mg) 4.2.9 Chromium (Cr) 4.2.10 Copper (Cu) 4.2.11 Lead (Pb) 4.2.12 Manganese (Mn) 4.2.13 Iron (Fe) 4.2.14 Zinc (Zn) 4.2.15 Temperature 26 35 36 36 36 37 37 37 37 38 38 38 39 39 39 39 40

4.2.16 Degree of Hydrogen Ion (Ph) CHAPTER FIVE 5.0 CONCLUSION AND RECOMMENDATION 5.1 CONCLUSION 5.2 RECOMMENDATION

1 Percentage Waste 2 Presents the GPS co-ordinates of the Water Quality Monitoring stations on Akinbo River. 3 Analysis of variance 4 World Health Organization (WHO) Standards for drinking water quality 2006 5 Results of the physical water quality parameter of the samples collected. 6 Presents the results of the analysis of variance of water quality at significance level of 0.05.

17 23 24 26

29

Fig 1: Map of Ogun State showing the study area. Fig2: Map of study area showing locations where samples were taken from. Fig3: Temperature, pH, Dissolve oxygen (DO), Electrical Conductivity (EC) and Total Dissolve Solid (TDS) of water samples collected from five locations along Akinbo River. Fig4: Total Hardness (TH), Potassium (K), Sodium (Na), Calcium (Ca) and Magnesium (Mg) of water samples collected from five locations along Akinbo River. FigS: Chromium (Cr), Copper (Cu), Lead (Pb), Iron (Fe) and Zinc (Zn) of water samples collected from five locations along Akinbo River.

15 18

34

34

35

West African Portland Cement Company is a public limited liability company registered in Nigeria with its corporate headquarter originally located at Ikeja in Lagos state but later relocated to Ewekoro and Shagamu in Ogun state. Ewekoro Cement factory is located within the tropical lowland rainforest. It is on a latitude
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5degrees.50 inches N and longitude 3degrees.17 inches E. it is approximately 64 kilometers north of Lagos and 42 kilometers south of Abeokuta. The factory occupies approximately 0.4 hectares of land an it was incorporated by the West African Portland Cement Company in March 1959. Production started in 1960 with only one kiln. The initial production was 200,000 tons per annum. The second kiln was constructed in 1967 and this has increased the total annual production 450,000 tons.

Generally the natural environment is made up of air, water and soil. The release of emission of industrial waste into anyone causes pollution. The presence of these wastes (pollutants) i~ the surrounding tampers with the natural quality of the environmental media (air, water, and land) thus, affecting plant, animal and human life's. Air pollutants are "dust, fluns, smoke, particulate matter vapour and gas". At Ewekoro Cement factory the major air pollutant is dust which results from the activities involved in the processing of the cement. These activities include the burning of the raw material such as (limestone, gypsum, red alluvium) in the kiln and the burning of coal in the factory area which is also responsible for the phenomenon known as acid rain which causes the rainfall on the water surface to become highly acidic. Moreover, the major products that Ewekoro Cement factory produces are cement and paint and the raw materials used are limestone, gypsum, red aHuvium, clay and water. The percentage waste generated at the factory is shown in table 1. of the components of the environment

WASTE GENERATED

PERCENTAGE

CEMENT DUST

94

SLURRY

SMOKE AND SOOT

OTHERS

TOTAL

100

The dusts from the factory are concentrated around the area and decreases with distance from the factory. It is assumed that the farther the location the less the amount of particulate deposited. The various pollutant which discharges from the factory will obviously have an adverse effect on the water into which they are discharged. An example is the presence of acids or bases in a water body which alters the PH value of that water. (Irving Say, 1974). Acid lowers the PH value while bases increase the PH value of water. Lowering and increasing of the PH value of water has an adverse effect on aquatic life. In addition, excessive alkalinity and acidity should be avoided n drinking water and the normal PH value for drinking water is'usually between the range of 6.5 and 7.5. (W.H.O, 2006) Moreover, sulphate especially those of sodium, magnesium and calcium are associated with hardness of water. (Irving Say, 1974). This project will examine the effect of externalities (environment pollution) generated by the activities ofEwekoro cement factory to water resources in its environments.

The main raw materials for manufacturing ordinary Portland cement (OPC) are limestone or chalk, shale or clays, minor or corrective components, fuel, gypsum, and extenders. OPC clinkers are composed mainly of lime, silica, alumina, and iron compounds. Each of these components is found in the various minerals that are the raw materials for OPC. Lime is the principal constituent of limestone or chalk. The other components, silica, alumina, and iron compounds, are present in various proportions in shale or clays. Marls and other materials containing significant proportions of all the four oxides (i.e., lime, silica, alumina, and iron compounds) are frequently used. Some minor components, like magnesia, zinc, copper, fluoride, and phosphate, are also introduced through the calcareous components In some cases, corrective components are added with the, raw materials to compensate for defects. Such components may include sand (to increase the silica), iron oxide or bauxite (to increase the alumina, especially in special types of cement), and china clay (to minimize the iron in white cement). Calcium fluoride and calcium sulphate are useful in lowering the temperature required for a given combination of raw materials and may yield an improved- quality. Gypsum is added to retard setting in the finished product. Powdered blast-furnace slag may be used as an extender to reduce fuel consumption in the manufacturing process. The fuel needed for OPC manufacture is coal, gas, or oil. The choice depends on economics and the process used. Colliery waste, oil shales, domestic refuse, used tires, rice husks, and sewage sludge have also been tried as novel fuels to supplement
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to the convectional ones. The manufacturing of OPC consists of three major unit operations: raw-meal preparation, heat treatment, and cement milling.

Before 2008, smoke and dust from the Ewekoro Cement Factory had adverse impact on the atmosphere daily activities of local people. Due to pr?duction line with lots of badly treated stages and current substandard smoke and dust disposal, dust pollution still occurred. Dust polluted areas changed depending on wind's direction and speed, mainly households living around the plant and some households affected by exhaust fume from clinker kiln.

Each pollutant has its own health risk profile, which makes summarizing all relevant information into a short chapter difficult but it will focus on the problems caused by air and water pollution at the community, country, and global levels.

Estimates indicate that the proportion of the global burden of disease associated with environmental pollution hazards ranges from 23 percent (WHO-1997) to 30 percent (Smith, Corvalan, and Kjellstrom 1999). These estimates include infectious diseases related to drinking water, sanitation, and food hygiene; respiratory diseases related to severe indoor air pollution from biomass burning; and vectorborne diseases with a major environmental component, such as J11alaria. hese three types of diseases each T contribute approximately 6 percent to the updated estimate of the global burden of disease (WHO 2002). As the World Health Organization (WHO) points out, outdoor air pollution contributes as much as 0.6 to 1.4 percent of the burden of disease in developing regions especially Nigeria, and other pollution, such as lead in water, air, and soil, may contribute 0.9 percent (WHO 2002). These numbers may look small, but the contribution from most risk factors other than the "top 10" is within the 0.5 to 1.0 percent range (WHO 2002).

Air pollutants are usually classified into suspended particulate matter (PM) (dusts, fumes, mists, and smokes); gaseous pollutants (gases and vapors); and odors. Suspended PM can be categorized according to total suspended particles: the finer fraction, PMIO, which can reach the alveoli, and the most hazardous, PMz.5 (median aerodynamic diameters of less than 10.0 microns and 2.5 microns, respectively). Much of the secondary pollutants PMz.5 consists of created by the condensation of gaseous pollutants-for example, sulfur dioxide (SOz) and nitrogen dioxide (NOz).

Types of suspended PM include diesel exhaust particles; coal fly ash; wood smoke; mineral dusts, such as coal, asbestos, limestone, and cement; metal dusts and fumes; acid mists (for example, sulfuric acid); and pesticide mIsts. Gaseous pollutants include sulfur compounds such as SOz and sulfur trioxide; carbon monoxide; nitrogen compounds such as nitric oxide, NOz, arid ammonia; organic compounds such as hydrocarbons; volatile organic compounds; polycyclic aromatic hydrocarbons and halogen derivatives such as aldehydes; and odorous substances. Volatile organic

compounds are released from burning fuel (gasoline, oil, coal, wood, charcoal, natural gas, and so on); solvents; paints; glues; and other products commonly used at work or at home. Volatile organic compounds include such chemicals as benzene, toluene, methylene chloride, and methyl chloroform. Emissions of nitrogen oxides and hydrocarbons react with sunlight to eventually form another secondary pollutant, ozone, at ground level. Ozone at this level creates health concerns, unlike ozone in the upper atmosphere, which occurs naturally and protects life by filtering out ultraviolet radiation from the sun.

Air emissions from cement kilns include toxic organic chemicals such as dioxins and furans and various hydrocarbon compounds (r~ferred to as products of incomplete combustion); acid gases generated by the combustion process; and heavy metals such as lead, mercury, cadmium and chromium. These pollutants are found in both stack and fugitive emissions (i.e., dust and gas stirred up from plant operations and emitted from locations other than stacks).

Pollution of surface water can create health risks, because such waterways are often used directly as drinking water sources or connected with shallow wells used for drinking water. In addition, waterways have important roles for washing and cleaning, for fishing and fish farming, and for recreation. Another major source of drinking water is groundwater, which often has low concentrations of pathogens because the water is filtered during its transit through underground layers of sand, clay, or rocks. However, toxic chemicals such as arsenic and fluoride can be dissolved from the soil or rock layers into groundwater.

Chemicals can enter waterways from a point source or a non point source. Pointsource pollution is due to discharges from a single source, such as an industrial site. Non point-source pollution involves many small sources that combine to cause significant pollution. For instance, the movement of rain or irrigation water over land picks up pollutants such as fertilizers, herbicides, and insecticides and carries them into rivers, lakes, reservoirs, coastal waters, or groundwater. Another non point source

is stonn-water that collects on roads and eventually reaches rivers or lakes. At Ewekoro Cement Factory there are two major sources of water pollution which are the disposal of chemical waste from the factory on the surface of the water and the constant settling of dust on the surface of the water from the factory.

Drinking contaminated water is the most direct route of exposure to pollutants in water. The actual exposure via drinking water depends on the amount of water consumed, usually 2 to 3 liters per day for an adult, with higher amounts for people living in hot areas or people engaged in heavy physical work. Use of contaminated water in food preparation can result in contaminated food, because high cooking temperatures do not affect the toxicity of most chemical contaminants. Inhalation exposures to volatile compounds during hot showers and skin exposure while bathing or using water for recreation are also potential routes of exposure to water pollutants. Toxic chemicals in water can affect unborn or young children by crossing the placenta or being ingested through breast milk. Estimating actual exposure via water involves analyzing the level of the contaminant in the water consumed .and assessing daily water intake (WHO 2003). Biological monitoring using blood or urine samples can be a precise tool for measuring total exposure from water, food, and air (Yassi and others 2001).

a) The extent of pollution of water resources in the environment in which the factory is situated decreases as the distance ,from the factory increases. This rate of decreases has not been mapped before or studied. b) The consistent effluent infonn of dust that discharges into water around the factory area leads to pollution of the water resources of the area. c) The pollution of the environment might affect the water and it might cause hazard to human beings acc9rding to World Health Organization:

a) The relationship between pollution and distance from the factory will be established and mapped. This will help for pollution monitoring and remedial efforts. b) The study will determine if true there is pollution of water resources in the area as a result of continuous setting of dust from the factory into the water surface around the factory area. c) The study will also compare the result with World Health Organization standard to see if there are health hazards.

To analyse the impact of Ewekoro cement factory on the surrounding water to verify if there is any adverse effect on the surrounding water. In order to achieve this aims the study have the following objectives: i. To determine the water quality by carrying out the physical and chemical analysis on the water collected. ii. To compare the water around the factory area to neighboring area using analysis of variance and also to compare the contrel station and the monitouring stations to that of World Health organization (WHO) to determine whether there are any differences using Post Hoc Test.

According to Kirov (1982) the release of waste into the environment by industries is known as environmental pollution and we have been polluting systematically our land, air and water since the beginning of the industrial revolution. Industrialization and increased productivity are making an unprecedented demand or natural resource. Moreover, Chanlott (1979) made known that chemical research and technologies have brought about 70,000 compounds into use. It has been estimated possibly that as many as 1,000 new ones are added each year. All ofthese production anduses result in waste that are discharge d into the air, water and onto or into'the soil. Our soil, air and water 'are under constant threat of pollution (Des Wilson, 1984). From the above statement, it could be noted that as man population increases and groping and advances made in technology to meet different needs of man, the very environment on which man lives stand the danger of being increasingly polluted. Also, it is quite ironical that man's endeavor to improve and better his existence on earth has now turned round to threaten his life. In view of the trend of pollution the American Ex president, Nixon has warned that "we should not let the sunrise of technology to be the sunset of man" "There is a widespread argument that water pollution is a significant and growing national problem that must be solved ".Observation in most Australian river showed a rising trend of pollution. (S Ghost, et aI, 1985). Pollution of water would be caused if waste and or sewage effluents are discharged into a body of water. In such case the assimilative capacity of the water is usually exceeded. Scimmons et aI, (1985) made clear in his work that sewage effluent from sewage treatment work sited along the locuse of the Napeon river in Australia contains high concentration of phosphorus and it is generally accepted that phosphorus causes eutrophication in fresh waste. Entrophication result in rapid growth and increase of aquatic plant which eventually leads to exhaustation of dissolve oxygen in that lake (David Gordon Wilson, 1974). A lot of work had been done to show the negative effect of water pollution. Most pollution result in serious damage to all forms of life.

According to Akeredolu (1989) wet and semi-wet clinker production technology has been adopted by Ewekoro plant of the West African Portland Cement (WAPC PIc) since its inception in 1959. By-products from the process include gaseous and
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particulate emissions from the kilns and effluent discharges from the slurry basins. Akeredolu reported that kiln stack losses from the Ewekoro plant mostly ranged between 1 and 4% of the clinker produced. Mean atmospheric deposition rate from the factory in the early 1990s within 5 km radius was estimated to be in the neighbourhood of 67 tones kmG monthG. The authors also reported the average dustfall rates even at a distance greater than 5 km from the factory ranged between 13-16 tones kmG monthG. Depositions and discharges from Ewekoro cement plant would have had

unquantifiable negative impacts on the riparian ecosystem after over 40 years of continuous cement manufacture. Dustfall not only contaminate the soil it also form encrustations on plant leaves thereby reducing the chlorophyll content,
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impairing carbon dioxide exchange and ultimately the plant photosynthetic rate. The toxic elemental composition in the atmospheric deposition from the cement plant operations not only endanger the soil quality but also affect the flora and fauna composition (Akeredolu, F., 1989). Although, Adejumo et al. reported that cement marker element, Ca, decreased exponentially with increasing distance from the factory, some toxic heavy metals like As, Pb, Ni, Co, Zn, Cu, Cr, as well as S, P were found highly enriched in the neighbourhood compared to the control sites (Adejumo, 1994). Disseminates caused by emissions from Ewekoro cement Kilns were monitored at some terrestrial and aquatic receptor locations. High levels of total suspended particulates (TSP) and atmospheric deposition rates (ADR) were recorded within the factory compared to auxiliary locations outside the factory. The TSP and ADR levels which are location dependent were significantly higher (p<0.05) during the dry periods than in the wet season. Irrespective of seasonal variations the key elements in the emissions were Ca and Fe. The physico-chemical parameters assayed were significantly higher (p<0.05) in the factory effluent discharges than in water samples from each of the catchment's rivers. Alaguntan river which receives effluents directly from the factory had significantly higher levels (p<0.05) of the assayed ions than the other two rivers draining the cement factory catchment's area (WAPC, 2001).

Study site shows that Ewekoro cement production facility is located five kilometers North of Ewekoro town (655'N 312'E) and within the tropical rainforest belt of Nigeria. Farming settlements such as Olapeleke (West), Itori (North), Elebute and Alaguntan (East) which predate the factory are located within 10 km radius of the production facility. The settlements are perennially drained by Itori, Elebute and Alaguntan Rivers. Only Alaguntan River receives waste water directly from the cement plant. However, the water qualities of other catchment rivers are primarily influenced by non-point pollutants from run-offs and atmospheric depositions (Oluwole F., 1994). Cement dust and other particulate depositions are facilitated by an average wind speed of 1.0 and 0.72 m sG , respectively 10 m above the ground during the dry (January,

March) and wet periods (May-November) (lITA, 2000). Other significant prevailing climatic conditions over the cement plant catchment area include an average relative humidity of 651O% and an average annual rainfall of 1500120 mm. Based on the locations up-wind and down-wind of the cement factory various sites were adjudged suitable for sample collection. The selected locations for water quality and planktonic studies were the After Work Discharge Channel (AWDC), Alaguntan, Itori and Elebute Rivers. For air quality and vegetation studies within the factory area, sites selected include the main gate, the new factory site and the current overburden. Outside the factory, the Junior Staff Quarters (JSQ) (1.1 km South), Olapeleke (1.0 km West), Itori (4.8 km North), Wasinmi (9.5 km North) and Alaguntan settlements (1.5 km East) were selected as sampling points. Air and water quality, planktonic composition and the vegetation of some strata of Ewekoro cement plant catchment area were investigated between November, 1997 and August, 2000. Monthly samplings which were carried out on the selected strata accommodated the primary influence of the prevailing dry and wet tropical rainforest climatic conditions.

Duplicate sub-surface water samples were collected at designated points on sampling days with a Friedinger water sampler. A multi-probe HACH portable water laboratory was used to determine the water pH in situ. Collected water was field preserved to retard chemical changes prior to laboratory analyses. The preserved water samples were analysed for the HCO G, S 0 G NO G and PO G contents using standard methods. Na and K concentrations were determined using

flame photometry, while the Ca, Mg P, Cr, Ni, Cu, Zn, Fe concentrations were determined by Zeeman Flameless Atomic Absorption Spectrophotometer. Water samples from designated locations were evaluated for the planktonic composition. Collected water sample (30 L) which was concentrated to 20 mL by filtering through 45 11 plankton net was preserved in Lugol solution. Each preserved concentrated sample was examined through an Olympus BH2 Microscope in a Sedwick-Rafter counting chamber. Planktonic identification and enumeration were done where possible to specific level according to Adeniyi and APHA et al. Planktonic species richness and diversity were calculated according to Washington. Collected water and planktonic quality data were subjected to Analysis of Variance (ANOVA). Moreover, the qualitative result shows that the discharged factory effluents had comparatively significantly higher (p<0.05) levels of assayed ions, suspended and dissolved solid loads than samples collected from each of the catchment rivers. Also, the factory effluent and water samples from Alaguntan River had pH in the alkaline range compared to the slightly acidic nature of Elebute and !tori ~iver samples irrespective of season of collection. Location-wise and seasonal variations inclusive, the bicarbonate (HCO G), carbonate (CO G), calcium (Ca) and Magnesium (Mg) constituted the major dissolved solid components of water samples collected. The level of each of the parameter determined was also shown to be relatively higher (though, not significantly, p>O.05) during the wet than during the corresponding dry periods. Comparatively, the assayed ionic concentrations, were however significantly higher (p<O.05) in samples from Alaguntan River than in corresponding samples from Elebute and Itori River during the period of study (Akeredolu, 1989).

Particulate matter deposition constituted major atmospheric pollution problem in Ewekoro Cement Plant immediate and auxiliary environment. The very high mean Atmospheric Deposition Rate (ADR) and Total Suspended Particulates (TSP) within the factory area could be attributed to kiln stack losses which Akeredolu estimated to range between I and 4% of the clinker produced. Other sources of contamination within the factory include dust re-moblisation from vehicular traffic on unpaved and unswept paved road. Fugitive emission from wind erosion of large open air piles of clinker and winnowing of clinker fine particles while being fed by a band of conveyor are also identified source of atmospheric pollution within the factory.

Location and distance from the cement factory dictated the amount of particulate deposition within the factory auxiliary area. The farther the location, the less the amount of particulate deposited. Wind direction also plays a major role in particulate deposition. Locations down-wind had higher amount of deposition than locations upwind. Differential deposition rate occurred due to differing lifetime of aerosols with different particle size in the air. Adejumo et al. reported that particles in the range of 0.08-1.0 11mcould be airborne for a long distance from the point of origin. Large particles with diameter greater than 1.0 11mon the other hand have a life time of minutes to days. Based on such findings, locations within 1-10 km radius down-wind of the cement factory would likely be inundated with coarse cement particles whose diameters are equals to 111m. The concentration of the selected elements assayed in the suspended and deposited particulates confirmed that cement dustfall were enriched with toxic heavy metals although an exponential fall-off in concentration occurred with increasing distance from the factory. The TSP and ADR coupled with the concentration of element assayed in the particulates which was higher during the dry periods was probably due to the influence ofharmattan haze. Oguntoyinbo et al (1983) reported that harmattan dust haze constitutes the largest source of particulate matter over Nigeria between the months of November and March Simoneit et al (1985) estimated the total harmattan particle loading over Nigeria to range between 300,000 and 600,000 taG. The harmattan dust particles most probably amplified the effects ofthe emissions from the cement plant hence the high ADR and TSP during the dry.period. Sources of water for the three catchment rivers in the vicinity of the cement plant are groundwater discharges from opened-up confined aquifers and vertical flow from fractures and joints within the floor of the quarry. The physico-chemistry of water from the catchment Rivers therefore is primarily dependent on the soil characteristics, secondarily on the enriched cement dust-falls and run-offs. The enhanced nutrient status of Alaguntan River was probably due to potential im~act from direct effluent recipient from the cement Plant (Simoneit, 1988).

In addition to all this, is an "illustrative case of cumulative exposure and chronic long term effect of toxicants in the open environment is that of Mercury in the resident
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population in Minamata and Nigata, Japan. Mercury was a waste discharge from chemical plants. The mercury underwent biological information/transformation to methylated mercury which became resimilable by fish. This result in about 121 people suffering mercury poisoning, 40 deaths 23 cases of cerebral paisy-like attution which became known as the Minamata disease .(Emil T Chanlott, 1979). Never the less, Des Wilson (1984) made clearly in his research that for thousand of years lead (Pb) has been used by humans for such purpose as pipes, vessels, paints, cosmetics and solders. Lead is a neurotoxin: it attacks the nerve and brain and it has been known for nearly four decades that children who have recovered from lead poisoning may still be left with permanent brain damage. The above mention cases is indicative of how dangerous a mortal polluted water body could be .Other observed causes are those of cadmium and boron. "Cadmium (Cd) of course is a cumulative toxic element with a biological half life in man of 16 to 33 years ". (L Huyah Ngoc et aI, 1988). "The pollution characteristics of industrial waste waters are of extremely varied nature: suspended matter and dissolved solids metal and chemical, strong acids, and alkalis, oil, dips and smeil". Air pollutants are dust, flame, smoke particulate matter, vapour, gas, odocous Substance or any combination thereof but shall not include encombined water vapour. Sulphur-dioxide results from the burning of oil and coal and is one of the groups of substance responsible for the phenomenon on of acid rain which is currently weakening havoc on ecosystem in several countries. Repeated doses of acid causes the water to become highly acidic and this causes dissolution of metals from the underlying rocks, including aluminium which is highly toxic to fish the condition described. Fish population is some 9,000 Swedish lakes have suffered varying degrees of damage, many of them dying out completely (Des Wilson, 1984).

The utility of water is limited by its quality which makes it unsuitable for particular uses. Assessment of water quality is therefore an important aspect of water resources evaluation. As part of water resources survey, water samples will be collected and analysed. The quality of surface water, however, often varies throughout the year as

the rate of flow varies. Water quality depends on the physical, chemical and biological composition of water. The most important characteristics that determine water quality are as follows:
1.

Physical characteristics - colour, clarity, taste, odour, temperature, amount of suspended solid, content.

ii.

Chemical characteristics - reaction, amount of dissolved solid, hardness, amount of nitrogenous matter, degree of acidity (pH), presence of toxic substances, and other substances such as copper, iron, magnesium, manganese, zinc and sulphate.
,

Hi.

Biological characteristics - bacteriological content, amount of dissolve oxygen and biological oxygen demand

Ewekoro is one of the sites of West Afrioan Portland Cement Company (WAPCO) blessed with large deposits of limestone - the major raw material in the production of cement. The Ewekoro plant of WAPCO is located in Ewekoro local government area of Ogun State in the south west Nigeria. The local government area is bounded in the North by Abeokuta, in the East by Obafemi - Owode, in the West by Yewa South and in the South by Ado-Odo Ota. Moreover, Ewekoro cement factory it is on a latitude 5.50' N and longitude 3.17 E.
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Also it is approximately 64 kilometers north of Lagos and 42 kilometers south of Abeokuta. Majority of the inhabitants are farmers and the area is largely rural. Most of these farmers engaged in the planting of sugar cane, cassava, maize and vegetable. Cash crops such as cocoa, kolanut and oil palm are also cultivated. These farmers also engaged in the rearing of livestocks like small ruminants, poultry and pigs .
. I~ '" C } j)

T~ )~ qo Fig. 1: Map of Ogun State showing the study area

According to Kehinde-Phillips (1992), geology of Ogun state in which Ewekoro the study area is a part, comprises of sedimentary rocks which underlie approximately three-quarters of the whole surface area of the state stretching from the northwest to the southeast and Basement complex rocks which underlie the remaining one-quarter of the surface of the state. The basement complex according to Jones and Hockey (1964) is made up ofmagmatite-gneiss complex, the schist belt and the older granites which are 800 to 500 million years in age (Hurley et aI, 1967). These rocks are well displayed in Odeda, Abeokuta, Igbo-ora, and Ijebu Igbo etc. The sedimentary rocks of Ogun state consist of Abeokuta formation (Rayment, 1965; Adegoke, 1969) later known as Abeokuta group consisting ofIse Formation, Afowo formation and Araromi formation (Omatsola and Adegoke, 1981). The Abeokuta group which is Neocomian to Maastrichtian in age is overlain by Ewekoro formation which is Paleocene in age and Haro formation of Eocene age. Ewekoro formation is highly fossiliferous and consists of economic deposits of limestone that is presently quarried by WAPCO in Ewekoro and Sagamu, respectively.

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The materials used include, Tape rule, Thermometer, pH meter and batteries, D.O meter with batteries, Electrical conductivity meter, Conical Flask, Burette, beakers and measuring cylinder, Atomic absorption spectrometer (AAS).

A hand held GPS is used to geo-position the location at each of the sampling points which provides the altitude, longitude and the latitude as shown in table 2 and also an ,. Arc view GIS is used to project a Map of the study area indicating the sampling points as also shown in Figure 2.

Table 2: Presents the GPS co-ordinates of the Water Quality Monitoring stations on

Akinbo River.
Stations Altitude Longitude Latitude

(m) 500m Upstream (M1) Meeting Point (M2) 500m Downstream (M3) 1000m Downstream (M4) 2000m Downstream (M5) 22km control (e1) Six water samples of about 2 liters each were collected at the monitoring stations on Akinbo River while one sample was collected on Itori River using a systematic sampling method for carrying out the lab$>ratoryanalysis. The water samples were taken as far as from the bank as possible and about 20cm below the surface. Moreover, on Akinbo River the first sample was collected 500m upstream from the meeting point and after this a sample was also collected at the meeting point which marks the point at which the upstream and downstream flow meets. Also on the river samples were collected !it 500m, 1000m, 2000m downstream while the last sample which serves as the control station was collected at 22km away from the factory. Furthermore, all bottles are marked individually with w;rterproof marker (project code, location, date, sample number, collector's name, type of analysis needed) the information which is been cross-checked with the field notebook and the sample collection sheets. 41m 06.90026 003.18805 42m 06.89285 35m 06.89650
.

27m

06.90141

003.22916

40m

06.89941

003.20467

51m

06.89759

003.20640

003.20957

003.21278

Never the less, the samples are being transported to the departmental laboratory where it is being preserved in a refrigerator at a temperature between 00 C and 40 C. When cooled to this temperature and stored in the dark, most samples are normally stable for up to 24 hours.

"a'

"s'"
N

"g'

_.

,'li'

(1"

'~~'

0
i

25KM

N
::.~ 2#13'

,-,r.' .
I

Control station Mon~oringstations Railway N River N Minor road OJ Settlement/V Majer road
.~\I"

,'f'pl

" 3"'

!~(

3'0'

l lfr

1. The selection of the sampling container, such that it must have high resistance to breakage, good sealing efficiency, ease of reopening, good resistance to temperature extremes, practicable size, shape and mass, good potential for cleaning and re-use availability and cost. 2. The water samples were taken as far from the bank as possible and about 20cm below the surface. 3. Filling to top of container before capping to prevent loss of dissolved gases. 4. Samples are Stored in darkness to stop photosynthesis.

3.6.1 Water Temperature Water temperature plays a very important role in the health and quality of a water body. Temperature can affect the biological, chemical and physical features of a river. The amount of oxygen that can be dissolved in water, the rate of photosynthesis by
,

plants and algae and also the sensitivity of aquatic organisms to toxic wastes and disease can all be influenced by water temperature. The temperature of the samples collected was measured at the site with the use of a thermometer by placing the thermometer into the stream water collected and recording the value in e. 3.6.2 pH

When we measure pH we measure how acidic or alkaline the water is. pH is a measure ofthe hydrogen ion (H+) concentration. The pH scale is from 1-14, pH of 7 is neutral, zero is the most acidic and 14 is the most alkaline. After the calibration step has been performed, the pH meter probe is placed into the sample collected. The display on the pH meter is allowed to stabilize before the reading is taken. 3.6.3 Dissolve Oxygen Dissolved Oxygen is essential for a healthy and diverse water body. Aquatic organisms and plants need oxygen to survive just as we do. Waters with consistently high dissolved oxygen Jevels (between 80 and 100%) are considered healthy and stable, capable of supporting a large variety of aquatic organisms. The DO meter

probe is placed into the sample collected. The display on the DO meter is allowed to stabilize before the reading is taken. 3.6.4 Electrical Conductivity

Conductivity measures the amount of dissolved ions such as, Calcium, Magnesium, Potassium, Chlorides and Bicarbonates that are present in a water body. It is measured by placing a conductivity probe in the sample and measuring the flow of electricity between the electrodes. The EC meter probe is placed into the sample collected. The display on the EC meter is allowed to stabilize before the reading is taken. 3.6.5 Total Dissolve Solid

This is the total amount of dissolve solid found in a given sample. They are also the amount of soluble substance that has dissolved into solution. The TDS meter probe is placed into the sample collected. The display on the TDS meter is allowed to stabilize before the reading is taken. 3.6.6 Total Hardness

Total hardness is a measure of the concentration of calcium or magnesium ions in a water sample. The combination of the calcium and magnesium hardness and other ions hardness of water occur due to the presence of ions or dissolved particles in the water. Hardness can result due to the sources of the water, water from boreholes and wells can have greater hardness than rain water because it has pass through different layers of rock and soil. Soil particles and ions easily dissolve into the water thereby making it to have greater hardness. Total hardness can be tested as follows: Equipments: Conical Flask, Burette, beakers and measuring cylinder Procedure: SOmlof each ofthe water sample was added into a conical flask, 2ml of Ammonia Buffer solution was added, Also not more than 1 ml of Eriochrome Black T indicator was added to give a purple colour. The solution was then titrated against EDTA until the colour changes from purple to blue.

Moreover, the titre value was multiplied by 20 to give the total hardness value in mg/l

20

- Z

Where X is the titre value. For example record from titration Initial reading Final reading Titre value
=

0.00 2.00 final reading - initial reading

= =
=
=

2.00 - 0.00 2.00

x 40mg/1

20

The heavy metals which include K, Na, Ca, Mg, Cr, Cu, Pb, Mn, Fe, Zn were analyzed by determining the trace metal concentration of each work water sample

using Atomic absorption spectrometer

(AAS). The water samples were first digested

,

and later analyzed in water laboratory and chemistry laboratory. Two parameters were measured in water laboratory and five in chemistry laboratory.

Take 5ml of the water sample, dispense it and pour into Teflon tube. Place into the digestion tube block in a fume cupboard. Then add 20ml of Nitric acid (Cone. HN03)

+ 20ml of Hcl (Cone. Hcl). Leave for some time or switch on the digestion block to
heat the sample to dryness. Bring it out and add distilled water to wash the tube. Make it up to 100ml with distilled water using 100ml volumetric metals using atomic absorption spectrophotometry Mathematically, Slope MR flask. Read for various

(BUCK 200 model).

= metal

reading i.e. the result obtained from the machine (AAS).

1 (constant)

DF = dilution factor = Volume ofH~O OdOml) 5ml (volume of sample taken)

Therefore, MR

slope

DF = 100 = 20ml 5

The wavelength used is as follows: Ca Zn Pb Fe Mn Mg K Cu Cr Na

= = = = = = = =

422 213 313 275 279 285 283 327 355 279

This is a technique for determining the concentration of metallic element in a solution of inorganic or organic materials. The analytical technique is specific and characteristic ofthe element under consideration. Atomic absorption spectrometry resembles flame emission photometry in that a sample is aspirated into a flame and atomized. The major differences is that in flame photometry the amount -of light emitted by excited ground state atom is measured, while in Atomic absorption spectrometer a light beam is directed to the flame or non flame atomizer into a monochromator and to a detector that measures the light absorbed by unexcited - ground state atom. Quantitatively one element at a time can be identify by the use of a single hallow cathode lamp for that particular element.

If a solution containing a metal is aspirated in the form of an aerosol into a hot flame, the solvent is evaporated from the droplets and the metal vapourized mainly as atoms. Alternatively, an atomic vapour could be produced by rapid electrothermal heating of graphite rod or tube on which a drop of the sample has been placed. A beam of electromagnetic radiation characteristic of a particular element can be passed through

the atomic vapour and monitored by a photomultiplier detector. If the sample contains that particular element, its atom will selectively absorbed some of the radiation thereby attenuating the beam and causing the detector signal to fail. This absorbance
,

is proportional to the concentration of that element in the vapour and hence in the original sample.

Analysis of variance is used to compare the monitoring stations with the control station and also with W.H.O standard of drinking water. i = 1,2 j = 1,2
k n

k
n

X=LLXij
i j

The total corrected sum of squares SSTis

SSe = n L (X i-X) kn SSE = L L ( X i j

ij -

X)

Degree of Freedom (df) Between treatment Within treatment Error Kn-l k (n-l ) (k-l )

Sum of Square (SS)

Mean Square

SSe

SSe k-l

SSE

SSE k (n-l )

SST

F ratio =

SSe k-l

k (n-l) SSE

= MS Treatment
MS Error

Ho: This means there is no significant different. HI: This means there is a significant different. So therefore, if Fe > 5%, then we reject HI and accept Ho if Fe < 5%, then we reject Ho and accept HI Never the less, a simple Bar Chat is also used to compare the monitoring the control station to check ifthere is any significance different. Table 4: World Health Organization (WHO) Standards for drinking water quality 2006 Element/substance Symbol/formula Normally found in Fresh water/surface water/ground water Health based guideline by the WHO stations with

Aluminum Ammonia

Al NltJ
,

O.2mg/l <0.2mg/1 (up to 0.3mg/1 in aerobic waters) No guideline

Antimony Arsenic Asbestos Barium Beryllium Boron Cadmium Electrical conductivity

Sb As

<4J.lg/I

0.02mg/1 O.Olmg/1 No guideline

Ba Be B Cd EC <1J.lg/1 <1J.lg/1 <1J.lg/1

0.7mg/1

No guideline 0.5mg/l 0.003mg/1 900(J.lscm-1)

Chromium Colour Copper Cyanide Dissolved oxygen Fluoride Hardness

Cr+J ,Cr+()

<2~g/1

0.05mg/1 3.0TCU

Cu CN-

2mg/1 0.07mg/1 No guideline <1.5mg/1 (up to 10)

,

O2
F Mg/I CaC03 H2S Fe Pb Mn Hg Mb Ni N03, N02
,

l.5mg/1 lOOmg/1

Hydrogen sulfide Iron Lead Manganese Mercury Molybdenum Nickel Nitrate and nitrite Turbidity pH at 20C Selenium Silver Sodium Sulfate Inorganic tin TDS Uranium Zinc

No guideline 0.5-50mg/1 lmg/l O.Olmg/1

o Amg/l
<0.5~g/1 <O.Olmg/1 <0.02mg/1 0.006mg/1 0.07mg/1 0.07mg/1 50mg/1 and 3mg/1 5.0NTU 7.0-8.9

Se Ag Na S04 Sn

<O.Olmg/1 5-50~g/1 <20mg/1

O.Olmg/1 No guideline

250mg/1 Not mentioned 500mg/1

U Zn .

0.Ol5mg/1 O.Olmg/1

The results of the water quality parameter and the analysis of variance of the water quality are presented in table 5 and table 6.'
Table 5: Results of the physical water quality parameter of the samples collected.
DO (mgL' I)

SEASON

LOCATION

TEMP

pH

(OC)
WET 500M UPSTREAM 26.01 6.80

EC (IlScm' I)

TDS (mgL1)

2.76

100

40

DRY

500M UPSTREAM

26.70

5.90

5.32

70

30

WET

MEETING POINT

26.50

6.30

2.94

80

30

DRY

MEETING POINT

26.90

6.50

5.71

80

40

WET

500M DOWNSTREAM 500M DOWNSTREAM 1000M DOWNSl:REAM 1000M DOWNSTREAM 2000M DOWNSTREAM 2000M DOWNSTREAM 22KM CONTROL

25.20

7.00

2.57

290

140

DRY

25.80

7.30

5.82

300

150

WET

24.90

6.90

2.77

300

150

DRY

25.30

6.50

5.86

140

110

WET

26.01

7.50

2.89

310

150

DRY

26.10

7.60

5.62

290

140

WET

25.92,

6.40

2.82

70

30

DRY

22KM CONTROL

26.20

6.80

5.85

60

30

"

SEASON

LOCATION

TH (mgL-1)

K (mgL1)

Na (mgL-1)

Ca (mgL-1)

Mg (mgL-1)

WET

500M UPSTREAM

54

1.38

9.23

6.59

2.97

DRY

500M UPSTREAM

18

2.44

10.43

6.09

2.68

WET

MEETING POINT

62

1.98

9.33

65.21

9.82

DRY

MEETING POINT

16
"

1.07

10.13

84.05

5.06

WET

500M DOWNSTREAM

94

2.18

8.77

59.62

8.51

DRY

500M DOWNSTREAM

78

1.12

10.35

77.29

4.20

WET

1000M DOWNSTREAM

186

2.30

9.33

59.02

8.01

DRY

1000M DOWNSTREAM

10

1.12

10.52

79.89

4.18

WET

2000M DOWNSTREAM

150

1.72

8.95

51.31

8.00

DRY

2000M DOWNSTREAM

74

1.05

10.32

80.11

4.76

WET

22KM CONTROL

28

1.82

6.55

4.01

1.11

.
2 1.34 6.02 3.08 1.01

DRY

22KM CONTROL

SEASON

LOCATION

Cr (mgL-1)

Cu (mgL-1)

Pb (mgL-1)

Mn (mgL-1)

Fe (mgL-1)

Zn (mgL-1)

WET

500M UPSTREAM

0.005

0.24

0.80

0.129

0.80

1.65

DRY

500M UPSTREAM

0.003

0.27

0.73

0.191

0.73

1.05

WET

MEETING POINT

0.006
r

0.17

0.64

0.038

0.64

1.38

DRY

MEETING POINT

0.004

0.14

0.82

0.Q35

0.82

0.98

WET

500M DOWNSTREAM

0.004

0.26

0.67

0.119

0.67

1.49

DRY

500M DOWNSTREAM

0.008

0.13

0.98

0.054

0.98

0.87

WET

1000M DOWNSTREAM

0.001

0.19

0.72

0.102

0.72

1.34

DRY

1000M DOWNSTREAM

0.002
r

0.10

1.10

0.060

1.10

1.64

WET

2000M DOWNSTREAM

0.000

0.15

0.49

0.061

0.49

1.19

DRY

2000M DOWNSTREAM

0.003

0.16

0.77

0.053

0.77

0.92

WET

22KM CONTROL

0.007

0.20

0.58

0.090

0.58

0.95

DRY

22KM CONTROL

0.001

0.23

0.086

0.071

0.086

1.01

Table 6: Presents the results of the analysis of variance of water quality at significance level of 0.05.

DO

Between Groups Within Groups Total

Sum of SQuares .128 25.485 25.613 1025686 13550.000 1039236 327342.9 1000.000 328342.9 17687.429 20548.000 38235.429 .317 2.574 2.891 20.021 4.075 24.096 11226.649 966.643 12193.292 446.673 33.247 479.921 3.714E-03 3.500E-05 3.749E-03 .187 1.390E-02 .201 1.222 .300 1.522 1.804E-02 5. 134E-03 2.317E-02 .564 .300 .864 2.805 .535 3.340 3.348 .621 3.969 2.269 .635 2.904

df 6 5

Mean SQuare 2.134E-02 5.097 170947.619 1935.714 54557.143 142.857 2947.905 2935.429

F .004

Sig. 1.000

11 6 7 13 6 7 13 6 7 13 6 5 11 6 5 11 6 5 11 6 7 13 6 7 13 6 7 13 6 7 13 6 7 13 6 7 13 9.406E-02 4.287E-02 .467 7.649E-02 .558 .124 4.490 .060 6.111 .016 2.194 .164 3.006E-03 7.334E-04 4.099 .043 .204 4.287E-02 4.751 .030 3.115E-02 1.986E-03 15.685 .001 6.190E-04 5.000E-06 123.795 .000 74.446 4.750 15.674 .001 1871.108 193.329 9.678 .012 3.337 .815 4.094 .072 5.289E-02 .515 .103 .992 1.004 .490 381.900 .000 88.312 .000

EC

Between Groups Within Groups Total

TDS

Between Groups Within Groups Total

TH

Between Groups Within Groups Total

Between Groups Within Groups Total

Na

Between Groups Within Groups Total Between Groups Within Groups Total

Ca

Mg

Between Groups Within Groups Total

Cr

Between Groups Within Groups Total

Cu

Between Groups Within Groups Total

Pb

Between Groups Within Groups Total

Mn

Between Groups Within Groups Total

Fe

Between Groups Within Groups Total

Zn

Between Groups Within Groups Total

6 7 13 6 5 11 6 7 13

TEMP

Between Groups Within Groups Total

PH

Between Groups Within Groups Total

.378 9.071E-02

4.168

.042

Moreover, the result of the post Hoc Tests is presented below which helps to compare the monitoring stations and the control station with World Health Organization (WHO) standard of drinking water.

grouping control mtp 500 ups 1000ds 500ds 2000ds who standard Sig.

N 2 2 2 2 2 2 2

Subset for alpha 2 1 65.0000 80.0000 85.0000 220.0000 295.0000 300.0000 .674 , .124

= .05
3

900.0000 1.000

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

Qroupin!:j control 500 ups mtp 1000ds 500ds 2000ds who standard Sig.

N 2 2 2 2 2 2 2

Subset for aloha 1 2 30.0000 35.0000 35.0000 130.0000 145.0000 145.0000 .699 .266

= .05
3

500.0000 1.000

Means for groups in homogeneous subsets are,displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

Subset for alpha =.05 grouping control 500 ups mtp 500ds 1000ds who standard 2000ds Sig. Means for groups in homogeneous

N
2 2 2 2 2 2 2

1 15.0000 36.0000 39.0000 86.0000 98.0000 100.0000 112.0000 .138 subsets are' displayed.

a. Uses Harmonic Mean Sample Size = 2.000.

Subset for alpha = .05 grouping control 500 ups 1000ds 500ds 2000ds mtp who standard Sig. Means for groups in homogeneous

N 2
2 2 2 2 2 2

1 1.0600 2.8250 6.0950 6.3550 6.3800

2 2.8250 6.0950 6.3550 6.3800 7.4400

20.0000 .057 .088 1.000

subsets are displayed.

a. Uses Harmonic Mean Sample Size = 2.000.

Subset for aloha = .05 oroupino 1000ds 2000ds 500 ups control mtp 500ds who standard Sig. Means for groups in homogeneous

N
2 2 2 2 2 2 2

1 1.500E-03 1.500E-03 4.000E-03 4.000E-03 5.000E-03 6.000E-03

5.000E-02 .103 1.000

subsets are displayed.

a. Uses Harmonic Mean Sample Size = 2.000.

grouping 1000ds 2000ds mtp 500ds control 500 ups who standard Sig.

N 2 2 2 2 2 2 2

Subset for aloha .05 2 1 .1450 .1550 .1550 .1950 .2150 " .2550 .5000 .056 1.000

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

grouping who standard control 2000ds mtp 500 ups 500ds 1000ds Sig.

N 2 2 2 2 2 2 2

Subset for alpha = .05 1 2 3 1.000E-02 .3330 .3330 .6300 .6300 .7300 .7300 .7650 .7650 .8250 .8250 , .9100 .163 .062 .243

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

grouping mtp 2000ds control 1000ds 500ds who standard 500 ups Sig.

N 2 2 2 2 2 2 2

Subset for aloha .05 1 2 3.650E-02 5.700E-02 8.050E-02 8. 100E-02 8.650E-02 .1000 .1000 .1600 , .062 .066

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

grouping control 2000ds mtp 500 ups 500ds 1000ds who standard Sig.

N 2 2 2 2 2 2 2

Subset for alpha = .05 1 2 .3330 .6300 .6300 .7300 .7300 .7650 .7650 .8250 .8250 .9100 1.0000 .062 .139

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

aroupina who standard control 2000ds mtp 500ds 500 ups 1000ds Sig.

N 2 2 2 2 2 2 2

Subset for aloha .05 1 2 1.000E-02 ':9800 1.0550 1.1800 1.1800 1.3500 1.4900 1.000 .129

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

groupina 500 ups mtp control 1000ds who standard 500ds 2000ds Sig.

N 2 2 2 2 2 2 2

Subset for alpha 2 1 6.3500 6.4000 6.4000 6.6000 6.7000 7.0000 6(6000 6.7000 7.0000 7.1500 .053

= .05
3

.084

7.0000 7.1500 7.5500 .122

Means for groups in homogeneous subsets are displayed. a. Uses Harmonic Mean Sample Size

= 2.000.

Never the less, figures 3, 4 and 5 presents the result of the comparism between the monitoring stations and the control station using a simple Bar Chat.
350

300

250

200

150

100

50

0 Temp"C

Figure 3: Presents temperature, pH, Dissolve oxygen (DO), Electrical Conductivity (EC) and Total Dissolve Solid (TDS) of water samples collected from five locations along Akinbo River.
200

180

160 /I'" 5lnJps IIdry5lnJps C mt point 120 C dry mt paint II'" 500ds 100

140

o dry 500ds
II'" 1000ds Cdry 1000ds

80

II'" :DXlds
II dry

:DXlds

60

C 22krn dry 22krn

40

20

0 TH K
He

Figure 4: Presents Total Hardness (TH), Potassium (K), Sodium (Na), Calcium (Ca) and Magnesium (Mg) of water samples collected from five locations along Akinbo River.

ewet .dry

500ups 500upe

o wet mt point o dry mt point .wet 500ds

o dry 500ds .wet odry .wet 1000ds 1000ds 2000ds

ISdry 2000ds ewet 22km

lJdry 22km

Figure 5: Presents Chromium (Cr), Copper (Cu), Lead (Pb), Manganese (Mn) Iron (Fe) and Zinc (Zn) of water samples collected from five locations along Akinbo River

From the result of the analysis of variance presented above, each parameter's of the monitoring stations is compared with their corresponding control station using analysis of variance in which the F ratio is calculated and the significant difference drawn. If the significant different of each parameters when multiplied by 100 is greater than 5, then each parameters at the monitoring stations together with their corresponding control station is the same and if otherwise it is not the same. p > 5 = means there is no significance difference. p < 5 = means there is a significance different. Moreover a Post Hoc Test is being used to compare the control station and the monitoring stations for each parameters to that of World Heal.thorganization (WHO) to determine whether there are any differences. Also, a simple Histogram is used to compare the monitoring stations with the control station.

Comparing the monitoring stations together with the control station for dissolve oxygen (DO) content, the analysis showed that there is no significant difference, df (6,5) = 0.004, P > 5 which means the DO content of the monitoring stations and the control station is the same, but there are no'guidelines in comparing both stations with WHO standard of water. Also from the figures presented above, it shows that there is really no differences between the monitoring stations and the control station.

When comparing the monitoring stations with the control station the result shows that there is a significance difference, df (6,7) = 88.312, P < 5 indicating that the monitoring stations is different from the control station. Also the Post Hoc Test shows that the Electrical Conductivity at the control station, meeting point and ~pstream are less than that of the downstream, indicating that the high downstream Electrical Conductivity of the river emanated from the Mg2+ and Ca2+ ions from the factory water. Moreover, comparing both monitoring stations and control station with WHO standard of water, the analysis showed that there is a significant different. Moreover from the figures presented above, it shows that there is a differences between the monitoring stations and the control station.

When comparing the monitoring stations with the control station the outcome shows that there is a significance difference, df (6,7) = 381.900, P < 5. Also the Post Hoc Test shows that the Total Dissolve Solid at the control station, meeting point and upstream are less than that ofthe downstream, indicating that the high Total Dissolve Solid was as a result of the wind direction that blown the dust particle from the factory to that settle on the water surface. Moreover, when comparing both monitoring stations and control station with WHO standard of water, the analysis showed that there is a significant difference. Also from the figures presented above, it shows that there is a differences between the monitoring stations and the control station.

Comparing the monitoring stations with the control station, the result made clear that there is no significant difference, df (6,7) = 1.004, P > 5. Also the Post Hoc Test shows that the Total Hardness at the control station, meeting point and upstream are less than that of the downstream, indicating that the water is softer than that of the downstream and this is as a result of the waste water emanating from the factory which contains calcium and magnesium ions. Furthermore, in the case of comparing both stations with WHO standard of water, the test showed that there is no significant difference. Also from the figures presented above, it shows that there is a differences between the monitoring stations and the control station.

When comparing the potassium content of the monitoring stations together with the control station, the outcome of the result showed that there is no significance difference, df (6,5) = 0.103, p> 5. Moreover there is no guideline in comparing both stations with WHO standard of water. Also from the chats presented above, it shows that there is really no differences between the monitoring stations and the control station.

Also in comparing the sodium content of the monitoring stations together with the control station, the analysis of the result showed that there is no significance difference, df (6,5) = 4.094, p> 5 and this is due to the discharge of the cement waste into the near by streams. Moreover, there is no guideline in comparing both stations with WHO standard of water. Also from the chats presented above, it shows that there is little or no differences between the monitoring stations and the control station.
"

From the result of the analysis of variance, the monitoring stations and the control station both shows a significance difference, df (6,5) = 9.678, P < 5 and this is due to the fact that the rock raw material for example Dolomite used in the factory for the generation of cement contain calcium. Moreover, there is no guideline in comparing

both with the standard. Also from the chats presented above, it shows that there is adifferences between the monitoring stations and the control station.

From the result it is being shown that there is a significance difference when comparing the monitoring stations with the control station, df (6,7) = 15.674, p < 5 and this is as a result of the fact that the roc k raw material, for example Dolomite used in the factory for the generation of cement contain magnesium. Furthermore, the Post Hoc Test showed that the Magnesium at the control is lower than that of the upstream and downstream, but they are all lower than the meeting point and when comparing both the monitoring stations and the control station with WHO standard of water, there is a significant difference. Also from the chats presented above, it shows that there is a differences between the monitoring stations and the control station.
"

Comparing the monitoring stations with the control station, the analysis of the result showed that there is a significant different, df(6,7) = 0.000, p < 5. The Post Hoc Test also made clear that when comparing both stations with WHO standard of water there is a significant difference and this indicates that both the monitoring stations and the control station are being polluted as a result of dust effluent from the factory. Also
,

from the chats presented above, it shows that there is little or no differences between the monitoring stations and the control station.

When comparing the copper content of the monitoring stations together with the control station, the outcome of the result showed that there is a significance difference, df (6,7) = 0.001, p < 5 and this is considered to be directly related to the heavy traffic pattern for trucking and automobiles transporting raw and finished materials in and out of the cement factory. Furthermore, the Post Hoc Test also made clear that when comparing both stations with WHO standard of water there is a significant difference. Also from the chats presented above, it shows that there is a differences between the monitoring stations and the control station.

Comparing the lead content of the monitoring stations together with the control station, the outcome of the result showed that there is a significance difference, df (6,7) = 4.751, P < 5 and this is considered to be directly related to the heavy traffic pattern for trucking and automobiles transporting raw and finished materials in and out of the cement factory. Furthermore, the Post Hoc Test also made clear that when comparing both stations with WHO standard of water there is a significant difference. Also from the chats presented above, it shows that there is a differences between the monitoring stations and the control station.

From the result being analysed it is being shown that there is a significance difference when comparing the monitoring stations with the control station, df (6,7) = 4.099, P < 5 and this is as a result of the fact that most of the dust effluent settle in the nearby surrounding streams. Moreover, the Post Hoc Test shows that 500m upstream is in the range of the WHO standard while the rest'of the station are different. Also from the chats presented above, it shows that there is a differences between the monitoring stations and the control station. 4.2.13 Iron (Fe) Also in comparing the _iron content of the monitoring stations together with the control station, the analysis of the result shows that there is no significance difference, df(6,7) = 2.194, p> 5 and this is due to anthropogenic activities that take place in the control area. Also the Post Hoc Test showed that the iron content at the control is less than that at the monitoring stations and the control station. Moreover from the chats presented above, it shows that there is little differences between the monitoring stations and the control station.

When comparing the zinc content of the monitoring stations together with the control station, the result shows that there is a significance difference, df (6,7) = 6.111, P < 5 and this is considered to_be directly related to the discharge of waste water from the cement factory into the monitoring stations. Furthermore, the Post Hoc Test also made

clear that the monitoring stations and the control station are both less than the WHO standard or water. Also from the chats presented above, it shows that there is a differences between the monitoring stations and the control station.
4.2.15 Temperature

As a result of the analysis comparing the monitoring stations with the control station shows that there is no significance difference, df(6,5) = 4.490, P < 5 and this indicates that the temperature at both the monitoring stations and the control station are the same. Also from the chats presented above, it shows that there is really no differences between the monitoring stations and the control station.

Comparing the monitoring station with the control station shows that there is a significance difference, df (6,5) = 4.168, P < 5 and this is due to the burning of the raw material such as (limestone, gypsum, red alluvium) in the kiln at the factory area which is responsible for the phenomenon known as acid rain which causes the rainfall on the water surface to become highly acidic. The Post Hoc Test also shows that the control station is also acidic and this may be as a result of anthropogenic activities. Also from the chats presented above, it shows that there is a little differences between the monitoring stations and the control station.

The result of the physical and chemical analysis of the water samples collected was presented in Table 5. The concentration of heavy metals showed a wide range in concentrations within the monitoring stations, which are closer to the factory and a low concentration in the control station which is further away from the factory. The average concentration levels of selected heavy metals (k, Na, Ca, Mg, Cr, Cu, Pb, Mn, Fe and Zn) within the monitoring stations and the control station are shown in Figure 4 and figure 5. Moreover the result of the water quality parameter of the water samples collected was used to project a Bar Chat which shows that the temperature at the monitoring station and the control station are almost the same. Also the physical water quaity analysis shows that the pH value at 500m upstream 'an at the meeting point, are a little smaller than at the downstream stations (pH>7) and this is due to the effluent resulting from the factory, that causes acid rain. As a result of this, acid rain makes the water less portable for human consumption and at a certain level kill aquatic animals. Moreover, the dissolve oxygen for all stations at the wet season is less than the dry season and this is as a result of high rate of respiration of plants during the dry season. Also from the result it is being shown that Electrical Conductivity content at the upstream station and control station are lesser than that of the downstream station and this is as a result of the fact that, the downstream station contains more amounts of dissolved ions such as calcium, magnesium, potassium and chlorides but there is no evidence that hardness in water has any effect on human health. Never the less, the same thing applies 'to Total Dissolve Solids, in which the downstream station contains high soluble substance that has dissolved into solution and this makes the water unavailable for use because it may leads to many acute diseases. Furthermore, the control station shows a very minimal amount of Total hardness which makes the water to be soft in the area, together with the upstream station and the meeting point, while the downstream stations shows a high concentration of calcium and magnesium ions as a result of the factory and may lead to cancer, diabetes, respiratory diseases or other health problems in hard water areas. From figure 4, the potassium content is almost the same in both the monitoring stations and the control station, also Potassium shortages are relatively rare, but may lead to depression, muscle weakness, heart,rhythm disorder and confusion. Potassium loss may be a consequence of chronic diarrhoea or kidney disease, because the

physical potassium balance is regulated by the kidneys. The intake of a number of potassium compounds may be particularly harmful. At high doses potassium chloride interferes with nerve impulses, which interrupts with virtually all bodily functions and mainly affects heart functioning. Also the sodium content is almost the same for both station and Contact of sodium with water, including perspiration causes the formation of sodium hydroxide fumes, which are highly irritating to skin, eyes, nose and throat. This may cause sneezing and coughing. Very severe exposures may result in difficult breathing, coughing. Contact to the skin may cause itching, tingling, thermal and caustic bums and permanent damage. Contact with eyes may result in permanent damage and loss of sight. Moreover, calcium and magnesium ions of the monitoring stations are higher than that at the control station. Magnesium and calcium often perform the same functions within the human body and are generally antagonistic, when one takes up large amounts of calcium this may negatively influence human health, and also large amount of magnesium may cause vomiting and diarrhoea. Chromium content also shows significant different between the monitoring stations and the control station, with no indication of it at 2000m downstream (O.OOOmgC1). Hexavalent chromium is known for its neg~tive health and environmental impact, and its extreme toxicity. It causes allergic and asthmatic reactions, but Chromium (III) toxicity is unlikely, at least when it is taken up through food and drinking water. It may even improve health, and cure neuropathy. Moreover, the figure also shows that even the control station has a high copper content and a long-term_exposure to copper can cause irritation of the nose, mouth and eyes and it causes headaches, stomachaches, dizziness, vomiting and diarrhoea. Intentionally high uptakes of copper may cause liver and kidney damage and even death. Also, the lead content of the control station is not really different from the monitoring stations and this is due to anthropogenic activities. Symptoms over overexposure to lead include colics, skin pigmentation ~nd paralysis. Generally, effects of lead poisoning are neurological or teratogenic. Organic lead causes necrosis of neurons. Inorganic lead causes axonal degeneration and demyelination. Both species of lead may cause cerebral oedema and congestion. Manganese content of the control station also do not vary that much to the monitoring station and Because manganese is an essential element for human health shortages of

manganese can also cause health effects and the following effects includes fatness, glucose intolerance, blood clotting, skin problems, lowered cholesterol levels, skeleton disorders, birth defects, changes of hair colour, neurological symptoms. Chronic Manganese poisoning may result from prolonged inhalation of dust and fume. The central nervous system is the chief site of damage from the disease, which may result in permanent disability. Symptoms include languor, sleepiness, weakness, emotional disturbances, spastic gait, recurring leg cramps, and paralysis. During the dry season the iron content really shows a very minimal amount of about 0.086mgL1) and the wet season do not really show and differences in the iron content. In addition, Iron deficits lead to anaemia, causing tiredness, headaches and loss of concentration. The immune system is also affected. In young children this negatively affects mental development, leads to irritability, and causes concentration disorder. Young children, pregnant women and women in their period are often treated with iron (II) salts upon iron deficits. When high concentrations of iron are absorbed, for example by haemochromatose patients, iron is stored in the pancreas, the liver, the spleen and the heart. This may damage these vital organs. Healthy people are generally not affected by iron overdose, which is also generally rare. It may occur when one drinks water with iron concentrations over 200 ppm. Finally, zinc content of the control station is lesser than at the control station and this is due to the effluent that comes out from the cement factory. Many people drink mineral water rich in zinc. Symptoms of zinc deficiencies are tastelessness and loss of appetite. Children's immune systems and enzyme systems may be affected. Higher zinc application appears to protect people from cadmium poisoning. Zinc may also decrease lead absorption. The relation copper to zinc in the human body is an important characteristic. One may also absorb zinc overdoses. This does not occur very regularly. Symptoms include nausea, vomiting, dizziness, colics, fevers and diarrhoea and mostly occur after intake of 4-8 g of zinc. Intake of 2 g of zinc sulphate at once causes acute toxicity leading to stomach aches and vomiting.

The overall high concentrations of the heavy metals in the monitoring stations are representative of the current cement plant operations that dominate the air quality in the city. Moreover it can also be concluded that the Temperature, Degree of hydrogen ion (pH) and Dissolve Oxygen of the monitoring stations and the control station are of the same value while the Electrical Conductivity (EC), Total Dissolve Solid (TDS) and Total Hardness (TH) of the monitoring stations are higher than that of the control station and this is as a result of the effluent emanating from the cement industry.
,

Moreover, the major source of surface water pollution in Ewekoro is the indiscreet discharge of untreated industrial effluents directly into the ground surface or the surface water bodies resulting in serious surface and ground water pollution. This loss of water quality is causing health hazards and death of human beings in the area. Furthermore, this problem is aggravated by lack of awareness, lack of wastewater treatment facilities, lack of financial resources and the inefficient environmental laws. From this research study, it can be concluded that the results are different from the standard set by the WHO for drinking water, 2006. Although some of the parameters like Total Hardness (TH), Degree of Hydrogen ion (pH) and Iron (Fe) are some what inline with the safe limits of WHO but the toxic level of harmful materials can aggravate due to the continuous generation ofthe effluents.

It is of primary necessity to evaluate the air quality around any industrial unit in order to emphasize the adverse effects to ecological system and human health. For cement production activity, the dust deposition network should be set up in the surrounding of cement plants. It is also recommended that complete analysis of cement dust containing all the toxic pollutant should be carried out in detail, eventually, with such types of study, it would be possible to recommend plants for use a screen or green belts in industrial areas and adverse urban locations in order to mitigate dust and improve air quality.

Further study is needed not only to assess the distribution of metals in water but also to examine variations on a small scale. More intensive sampling and examination will be required to know any changes or increase of metals in the investigated area. To improve the working conditions and promote health in this company, a multifaceted approach needs to be adopted, including engineering measures directed towards reduction of the dust in the worker's microenvironment, monitoring ofthe exposed employees. In addition, it is important that the industry continues and expand on its work to harmonize incident reporting requirements so that data can be collected and analyzed to identify the underlying causes of accidents and ill health. This will provide a better basis for industry benchmarking and enable health and safety improvements to be targeted where they will be most effective. Never the less, on the basis of the result obtained in the present study and previously published reports, it may be concluded that in the cement factory, where the workers are exposed to cement and other dusts, there may be significant haemotoxic and genotoxic changes which need to be elucidated so that the after-effects of toxicant contamination may be monitored and eliminated. This will not only help in the protection of the genetic material of future generation, but also in the prevention of malignant diseases in the present populations working in the factories as well as those residing in the industrial areas.
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