1

CHAPTER ONE

INTRODUCTION

1.1 Background of Study

Water is an essential resource in which aquatic organism depends on for

survival. When polluted, its value is lost and can become a threat to organisms

inhabiting it Uyo and Nwaniba [1]. Fresh water sources such as lake, river and

streams are open to anthropogenic activities [2]. This results in changes in the

distribution of heavy metals and hydrocarbon of water, such as Temperature,

Dissolved Oxygen, pH, Total dissolved solids (TDS), Salinity, Conductivity,

Biological Oxygen Demand (BOD) etc. Variation in these water properties greatly

influences the distribution patterns of aquatic insects, since some of them are

highly sensitive to pollution while others are somewhat tolerant or completely

tolerant to pollution and environmental disturbances.

The data of heavy metals and sediment in the present work, revealed that

there is highly significant difference between the four stations, the in increased

and decreased in values of station 1, 2, 3 and 4 may be attributed to a number of

factors such as industrial effluents, agricultural waste and municipal. Water levels

on the four stations showed higher concentrations of lead (0.31, 0.04), Cobalt

(0.03, 0,03ppm), Nickel (0.43, 0.09ppm), Copper (2.00, 0.16 ppm), Manganese

(1.42, 0.11ppm), Zinc (15.27, 016ppm) and Iron (2.69, 0.37 ppm). Meanwhile,
 2

sediment of the four stations showed higher concentrations of Lead (1.87,

0.06ppm), Cobalt (0.83, 0.07 ppm), Nickel (0.69 0.05 ppm), Copper (0.66, 0.09

ppm), Manganese (2.97, 0.09 pmm). Zinc (22.80, 0.35 ppm) and Iron (24.11, 0.18

ppm). The highest accumulated metals were Mn, Fe and Zn in both water and

sediment, Pb and Cu, exhibited moderate concentrations. Co and Ni metals were

below detectable limit at both water and sediments.

1.2 General View Of Pollution

Pollution occurs when pollutants contaminate the natural surroundings,

which brings about changes that affects our normal lifestyles adversely. Pollutants

are the key elements or components of pollutants of pollution which are generally

waste materials of different forms. Pollution disturbs our ecosystem and the

balance in the environment, with modernization and development in our lives,

pollution has reached its peak: giving rise to global warming, water toxicity,

human illness etc.

Pollution occurs in different forms, air, water, soil, noise, radioactive, light

and heat/thermal. Every form of pollution has two sources of occurrence, the point

and the non-point sources. The point source area easy to identify, monitor and

control. Whereas the non-point sources are hard to control.

Pollution can come from chemical waste dumped into rivers, factories

spewing. Toxins into the air, scavengers burning e-waste to extract valuable

component, industrial accidents and many other sources (Ademoruti, 1993).

 3

Pollution is one of the most underreported and undefined global issues. Pollution

is especially prevalent in developing economic, where rapid industrialization and

lack of regulations have resulted in unchecked toxic pollution.

Pollution is invisible in many countries where it is so much a part of daily

life. In Nigeria, no one realized that lead pollution was the cause of hundreds of

child deaths. Parents were bringing lead filled ore back to their homes for

processing. The problem was not uncovered until doctors found almost no

children in some villages on their immunization visits. Heavy metals and THC are

the sources of pollution on the environment, especially in water and sediments

which can gets into our rivers through drainage runoff.

Environmental contamination is an inevitable cause of man’s activities and

his environment, the disposal of materials into the environment by man has

characterized his activities. According to Asuquo (2001), the physical process in

the world around the cause continual change by removing, recycling and

redistribution of enormous volume and variety of materials. For instance, volcanic

eruption discharges gases; rain erodes and transporting soil particles and a wide

variety of other particles, plants remove nutrients from the soil, recycle them

through food webs and return them in different concentrations. The physical

world is into fact dynamic, constantly changing by rearranging and therefore

constantly contaminating the environment.

 4

Man as a social being has created a new order of products, which have

increased in volume fasters than population growth, and these have been

concentrated by urbanization. This disproportional increase has resulted in

increasing contamination of the environment to a point where the natural

purifying process can no longer cope, resulting in severe contamination known as

pollution. Pollution could therefore be summarized as the contamination of an

ecosystem to a level that could be detrimental to organisms including plants and

animals (Ogri, (3. R (2002), Pf Thesis, university of Uyo).

Although the discovery of a high concentration of dangerous substances

may provide a warning sign, unless it is the result of human activities and it is

damaging to the environment, it does not constitute pollution. Clark et al (1997)

regard pollution in practical terms as an example of one set of human interest such

as the use of leaded petrol in cars, burning of coal, the transportation of petroleum

products, the generation of electricity, the disposal of waste products etc. they also

view it in terms of healthy human amenities, tourism, recreation aesthetics,

scientific values, etc. environmental manipulations and other human activities are

major causes of stress on natural ecosystem.

Recently, there has been a growing concern worldwide that near shore

marine and fluvial ecosystems are being affected by man-made pollutants leading

to environmental stress (Ogri, (2002) Pf thesis university of Uyo. Furthermore, the

decomposition of dead wild life from this incidence aggravated the situation by

generating obnoxious odor and exerting high biochemical oxygen demand (BOD).
 5

Environmental pollution is clearly evident by the present pollution status of

rivers in relatively high-industrialized regions. Most of the surface waters are

endangered and some have already reached a stage in which is due to a strong

increase in the quantity of industrial waste, domestic sewage and agricultural run-

off which accumulate in the very limited river and discharge into the oceans.

According Smith et al (1996), urban effluents always contain heavy metals and

some hydrocarbon from waste-oil. Their concentration in water is related to the

source of water and activities in the urban environment. Heavy metals are widely

used in industrial processes and so are hydrocarbons, especially as fuel oils. The

discharges of untreated effluents from industriesand Nwanibaas a whole are

generally the case in this study area. The lack of waste treatment facilities

inNwaniba, the main urban area here is probably responsible for (possible)

increase in the levels of toxicants in rivers and eventually the marine environment.

Some of the important rotential heavy metal pollutants from industrial sources are

Cd, Cr, Co, Cu, Hg, Pb, Ni, Mo, Sn, B and Zn (Ogri, (2002), Pf Thesis, university

of Uyo).

These pollutants are transported through runoffs, streams and rivers to the

estuary. Besides, the atmospheric fall outs introduce metals into estuary and sea

(WHO, 1994). Other sources of pollution include direct discharge into the rivers

and the estuaries of Nwaniba waste (WHO, 1994). The singular most important

source of hydrocarbon and heavy metals is petroleum.

 6

These introduces large quantities of heavy metals and hydrocarbons into

the estuarine water (WHO, 1994). River-borne metals tend to settle to the bottom

of the coastal water/estuaries or to be, incorporated into living matter before

eventual transportation into the open sea (WHO, 1994). The estuarine and coastal

areas have been polluted with heavy metals by sedimentation of the pollutants

while some fractions of the hydrocarbons are transformed and dissolved in

sediments.

1.3 Aims and Objectives

The apparent lack of information on the level and distribution of heavy metals and

THC in water and sediments along Uyo main drainage system spurred this study,

which is aimed at;

2 Determining the level of pollution in water and sediments in Nwaniba main

drainage in order to discover the extent of pollution of the river by heavy

metals and THC.

3 Determining the level of pollution on the drainage and the level of

contamination in the aquatic and the ecological environment.

4 To determine the distribution of the metals and their pollution

concentration in the area.

 7

1.4 Specific Aims

2 To determine the concentration of heavy metal (Pb, Ni, Fe, Zn, Mn, Co,

and Cu) in water.

3 To determine the level and concentration of the heavy metal (Pb, Ni, Fe,

Zn, Mn, Co, and Cu) in sediment.

4 To determine the concentration of total hydrocarbon content in water and

sediment of the drainage.

 8

CHAPTER TWO

LITERATURE REVIEW

Water and sediment for heavy metals and total hydrocarbon has been used

for detecting pollution sources and for selecting criteria site for routine water

sampling for contaminants for over decades now.

Hydrocarbon levels assessment of water and sediment has been prompted

of water the increasing rate of hydrocarbon exploration exploitation. However, the

rate of discharge of effluent water has also heightened the tear of degradation

getting out of control.

Ntekim (1987) has studied the heavy metal concentration in water and

sediment of Qua Iboe River. His result shows that there is a non-uniform

distribution of heavy metals in the river. His results however revealed that Qua

Iboe River have, Zn (720.00ppm), Cd (2.5ppm) and Cu (40.00ppm) have mean

concentrations, which are higher than averages.

Concentrations of these metals according to him were above toxicological

tolerance limits of 19.4, 0.16 and lppm respectively. He therefore advised that

these results should be viewed with concern.

In the other parts of the parts of the river, Ntekim (1987) and Ekpo and Ibok

(1998) in their study of sediment and water of Uyo River compared the index of
 9

geo-accumulation with previous research and found that Nwaniba river sediments

were polluted.

Azmatullah and Ekwere (1985) reported the heavy metal distribution in

Cross River estuary sediments. Their study revealed that high concentration of

Cu, Zn and Mn. These elements are known to be very toxic i f they exceed the

tolerable limit.

Esu et al (1995) also assessed petroleum hydrocarbon pollution of upper Uyo

river sediment. Their results revealed that soluble organic matter content (668.3-

702.8ppm) found in the area corresponds to an overall pollution resulting from

different sources inputs.

Many studies have been carried out internationally on the levels and

assessment of petroleum hydrocarbon in certain services using sediments as geo-

chemical indications. Farran et al (1957) studies the Coatzacoals River in Mexico

using water and sediments samples collected to assess the extent of total

hydrocarbon pollutions in the river. Their results revealed that high levels of

petroleum were found in the whole of the study area, with no definite trend. This

corresponds to an overall pollution by crude oil products

Chester and Stoner (1993) have reported an abnormal concentration of Sn,

Pb and Zn in water sample and sediments and came to a conclusion that water and

sediments samples are important heavy metal “traps”, particularly in estuaries.

Macknight (1984) has detected an appreciable anthropogenic input of heavy

 10

metals in water of the Courtenay bay area of St. Jon Barbour in Canada.

Salomon et al (1977), have reported a high magnitude pollution of the Rlinemeuse

River in Holland with respect to Cu, Zn, Pb, and Cd inputs

Ekpo et al, (1992) carried out an investigation on the Uyo River to determine the

abundance and distribution of heavy metals in trash water and fish using samples

collected from the river.

The result of this investigation or study showed that the Nwaniba River is

moderately polluted by Fe, Zn and Cd. While Cu, Mn, Cr, and Pb are well below

the WHO maximum permissible limits. These results, however, serve as a base

line data against which future impact assessment will be based. The lack of trend

in the spatial distribution of heavy metals and THC in Nwaniba drainage,

indicated random distribution from diverse sources as: industrial activities,

agricultural inputs and atmospheric fallout, whose direct impact were not

quantitatively assessed in the study. The result of the analysis of heavy metals and

THC level studies show moderate levels of the metals that do not pose health

hazards.

Ede et al. (1996) carried out a study on level and distribution of heavy

metals and THC in drainage, which they discovered that enhanced concentration

of Cd, Ni, Pb and Cu were present in surface water of Akwa Ibom State-Nigeria.

This was attributed to rapid development in terms of agricultural practices and

 11

industries in South Eastern Nigeria. In the Southern part of the state, there was

anomalous concentration of these metals indicating migration of sea water into

fresh water aquifer and pollution due to activities of oil companies in the

localities. They also proposed that one approach which may be useful interpreting

the extent of anomalous heavy metal concentration in water from drainage is to

assess their magnitude of relation to background or natural values.

According to their study, the presence of heavy metals and THC in review

is mostly attributed to oil pollution while metals like Zn, Mg, Co and Fe are in

water as a result of discharge of industrial effluents into the ecosystem, because

water is dynamic, the metallic substance discharge into water is ultimately

incorporated into the sediments which is static.

Also they revealed that the entrance of heavy metals in water and

sediments is not necessarily fixed for all times but may be recycled via biological

and chemical agent both within the sedimentary compartment and also back to the

water column.

In the work of Ezeanyim and Okereke (1995). The effect of petroleum

activities in the Nigerians soil environment. Their work has expose the hazard and

pollution in the oil environment and trace it opt the origin of some of the heavy

metal concentration in the body of water and sediment and their effect on the

living organisms in rivers.

Olalade Lajide and Amoo (2008) examined the distribution of heavy metals in
 12

stream bed sediment from an oil-producing region in Nigeria in the two seasons

(dry and wet) of the year. Comparison of sediment with guidelines values

indicated anthropogenic enrichment and it was considered that only copper, cu

and lead Pb, posed potential threats to the area.

Adefemi, Olaofe and Abaolu (2007) studied the seasonal variation in heavy metal

distribution in the sediment of major deems in Ekiti state, Nigeria. The

concentration of most metals appears higher in dry season than those recorded for

the wet season.

Adekola, Eletta and Atanda (2002) carried out the determination of levels

of some heavy metals in urban run-off sediments and water in Illorin and Lagos,

Nigeria. Zn, Fe, and Cd were found in very high concentrations in the urban

sediments from the cities while Pb had the lowest level.

Adejare and Odeyemi (2007) investigated the levels of total hydrocarbon content,

in surface soils and water from the vicinity of Agbabu bitumen field. The research

showed that some stations have high concentration of THC except one, which

contains a small quantity.

2.1 Meaning Of Heavy Metals

Fleavy metals are known as metals with density greater than 5g/m 3 and atomic

number > 20. With these; I will note that, heavy metals are metals which have

adverse effect on human beings and other organisms.

 13

Heavy metals are also refers to as heavy metals, and they are in good proportion

on the earth. Hg Co, Cd, Cr, Pb, Ni, Mn, Ag etc.

Heavy metals which are normal concentration are essential components of

biochemical functions (Cu, Zn, Fe, Hg) are toxic when present in higher

concentration.

They are known as heavy metals because, they are toxic to the body and the

environment, though some are required or considered essential to the body

Cu, Zn, Co Fe) but can be toxic in large amounts or certain forms. (Baldwin £

Marshall, 1999).

Heavy metals occur as natural constituent of the earth crust, and are

persistent environmental contaminants, since they cannot be degraded or

destroyed (Forstner & Salsons, 1991).

Metals occur naturally on the earth curst as stated above, and are release to

the soil and water during physical and chemical weathenng of rocks (igneous and

metamorphophic). The background concentration of these metals are mainly

controlled by the geologic characteristic of water shed, some of this metals are

naturally abundant and have high concentration, examples are (Iron and

Manganese) other metals are rare and have low background solenium, lead,

cooper, cadmium, zinc etc), this rare metals are refer to as toxic metals at low

concentration in sediment and water (Nriagu, 1978), they serve as micronutrient

 14

or nutrient to plants and sea animals, as such essentials when in high

concentration, they are toxic and harmful to human health ( Hawkes, 1999).

Wastes are being discharge to drain areas untreated, which accumulates in gutters

and drainage channels: these heavy metals and other extraneous materials which

include sand, salt and dry particles are transported or carriedby run-off process

into rivers and even the soil which in turn contaminate the water we used and also

causes plants tinted growth (Lentech, 2004, UNEP/GPA, 2004).

Though, these heavy metals are found naturally in the earth crust, it can be

increase by human activities such as industrialization, over population and

increase ambient temperature among other factor, and have become major

environmental issues in recent years.

Most heavy metals are released from food chain and potentially cause

adverse effects on human health (Hutton & Symon, 1986). Discharge of industrial

wastes and the various tropic levels of animal's result to these metals and these

metals endanger the environment say they ultimately find their way into food

chain albeit in small doses (Mitchell, 1990).

However, run-off which is one of the ways these metals get into the rivers is

influenced by soil type, water storage capacity, amount of rainfall, slope of the

land and the amount of waste accumulation (Asuquo, 2001).

 15

2.2 Sources Of Heavy Metals

Most of the major sources of heavy metals pollution along drainage are

anthropogenic in urban areas while the natural sources predominately in the rural

areas.

Anthropogenic sources (cause by human) of heavy metals pollution include

those associated with fossil fuel and coal combustion, industrial efficient, solid

waste disposal, fertilizer application and mining at present, the impact of these

pollutants is contained mostly in the urban centers with large population, high

traffic density and consumer-oriented industries. Natural sources of heavy metals

pollution include weathering of mineral deposits brush burning and wind-blown

dust (Hutton & Symon, 1986).

Among the heavy metals, the most serious effect of pollution is presently

associated with lead (Pb) emission. Heavy metals also come from industrial and

municipal wastes, which accumulate on land and estuaries particularly during

tidal incursion sediment perturbation and biochemical (ingestion/defecation)

activities.

Similarly, pasture grasses growing along traffic highways and industrial

layouts are also sources of heavy metals such as cooper (CN), Nickel (Ni) and

cobalt (Co). (Odoemena &Akpabio, 1997).

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2.3 Factors Affecting Heavy Metals Pollution

Several factors are reported to affect heavy metals pollutions. Heavy metals

depend on the nature or state of the metal (particulate, colloidal and solution). The

speciation of these metals especially in natural water is determined by the

physiochemical hydrodynamic characteristics and the biological state of the water

(Lauren, 1986). Most heavy metals are more toxic in free ionic states, which are

more toxic in pH below neutral example, cooper (Cu).

The various processes taking place in the drainage systems affect heavy

metals pollution eliciting these metals to amalgamate of inorganic and organic

ligands which precipitate out of solution or settle out of the water column. The

presence of completing agents such as bicarbonates, carbonates and hydroxide

ions have a marked effect on heavy metals pollution (Scerbo and Barghigiani,

1998). Heavy metals pollution also depends on the nature of the water. High water

hardness may increase 96-lc50 of heavy metals. Furthermore, the rate of

absorption of heavy metals depends also on the type of sediment, pH, completing

cations and the presence of dissolved and particulate chemical species.

Another factor affecting heavy metal pollution is the lack of treatment of

industrial wastes before being discharged into the drainage, which in turn flows

into rivers, sea (Johansen et al, 1980). These deadly and toxic wastes have

densities different from that of the natural sea water and also such denote mix,

rather settle down at the bottom of the river as sludge, which may be several
 17

meters as sludge, which may be several meters and with time undergo fluxing,

especially at regions of high rate of organic carbon-demineralization (Forster &

Wiltman, 1983).

2.4 Meaning Of Total Hydrocarbon Content (Thc)

Total Hydrocarbon Content (THC) is used to describe the quantity of the

measured hydrocarbon impurities present in a substance, example water. Usually

expressed as methane equivalents. However, hydrocarbons are compounds of

carbon and hydrogen. Total hydrocarbon content gets into water and sediment

through oil and grease content around that area, in small amount but posse’s

serious health issues to humans (Bayne, 1985).

Drainages contain these THC which are being discharged into rivers from

industrial wastes, especially along Nwaniba industrial layouts or lane and in the

coasted environment. THC can also be passed into the coastal environment

through run-off (which includes, poorly treated effluent, oil spillages) (Blumer,

1976). THC has been given less attention especially in water and sediments in

time past, but studies on the level and distribution of THC have improved in

recent years.

The degree of contamination may be significant where frequent spillages

occur. Such spillages may lead to damage and loss of biodiversity, depletion of

arable land, and depletion of available portable water and blockage of water ways

(UNDP, 2006, Luisellu et al, 2004).

 18

2.5 Sources Of Total Hydrocarbon Content

The sources of THC have been traced by environmental chemist from

petroleum (crude oil fuel oils). Low molecular weight aromatic compounds are

constituents of the crude and fuel oils known to be sources of hydrocarbons.

THC can be gotten from dredge metals which are known to contain

hydrocarbon containments (Jarvis and Clarke, 1990). This report was a result of

their analysis of dredged materials by United States Army engineering along the

water ways experiment stations (WES) in 1987.

Crude oil and its pollutants are rich in hydrocarbon its derivatives are also

rich sources of hydrocarbons consisting of low molecular weight and volatile

compounds. Also tar balls are good sources of hydrocarbon and tar balls are

particulate hydrocarbons. (Asuquo, 1997).

2.6 Factors affecting total hydrocarbon content pollution

Several factors have been reported to be responsible for THC pollution, these

include, spreading capability dissolution evaporation, photo-oxidation,

sedimentation and biodegradation capabilities of the hydrocarbon (Asuquo, 1997,

Floodgate, 1973).
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2.7 Toxicity Of Heavy Metals On Man

Metals are particularly toxic to the sensitive and rapid developing system

of the fetus, infants and young children. According to Johansen et al (1980) some

metals such as Pb and Hg, easily cross the placenta and damage the foetal brain

Similarly, Paludan-Miller et al (1993) maintain that childhood exposure to

some metals can result in learning difficulties, memory impairment, damage to the

nervous system and behaviours problem such as aggressiveness and hyper-

activity,

At higher dose Vary et al (1989) maintained that heavy metal can cause

irreversible brain damage. Humans generally have been reported to be exposed to

heavy metal through inhalation of polluted air consumption of contaminated soils

or industrial or consumption of contaminated food (Johansen et al (1950), and

Paluden-miller et al (1993). Food source such as vegetable gains, fruits fish and

shellfish can become contaminated from surrounding soil and water (WHO 1991).

Heavy metal according to Wagnor (1974) & Johansen et al (1980) cause

serious health damages in man which include reduced growth and development,

center organ damage, nervous system damage and in extreme cases (when WHO

limit is exceeded) death.

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2.8 Toxicity Of Total Hydrocarbon Content On Man

High level of THC level in water causes fish tainting and cloggs the gills of

fish and fishing gears. Floating particulates (floating tars) contribute to increased

turbidity of aquatic system causing danger to juvenile fish species and sometimes

the adult fish are affected since the fishes can ingest the juvenile fish directly as

food (Clark 1982), Asuquo (1997).

Viddow et al (1982) reported that many physiological response e.g. rate of

oxygen consumption, teaching, excretion and scope for growth, cellular Reponses

(e.g. specific lysobomal latency and digestive cells) and biochemical responses

(e.g. specific activities of enzymes) is significantly altered when exposed to

hydrocarbon contamination.

This was confirmed by Nadeau & Berquisi (1997) on their report on the
i4
zoe colcotronic” oil spill hear Cabo Rajo, Puerto Rico. It was also studies that, it

impairs vision in humans which can sometimes lead to blindness (Clark 1982).
 21

CHAPTER THREE

MATERIALS AND METHODOLOGY

3.1 Study Area

Nwaniba River lies between (5o51/ N, 8o 41/ E; Figure 1) of longitude of

south-south Nigeria (Figure. 1). The area has an annual rainfall of about 2500mm

with a mean annual temperature of 32 0C and a relative humidity of 75%. The

main source of this river is the Uyo- Itu River which runs from the Atlantic

Ocean. During high tides it flows to Oron River and returns during low tides. The

River has a beach called Nwaniba beach which serves as habour for logging

activities, peasant fishing and other domestic activities like bathing and laundry.

The bank of the river is mostly covered with grass such as elephant grass

(Pennisetum purpureum) and watercress (Nasturtium officinale). Mangrove

swamp vegetation also included shrubs and trees such as white mangrove

(Laguncularia racemosa), screw pine (Pandamus spp), mangrove palm (Nypha

fruticans), and other pneumatophorous plant with prop roots. Tropical

hydrophytes include Emegent, Free-floating and submerged aquatic plants, such

as; Water hyacinth (Eichhorina crassipes), Water lilies (Nymphaea lotus),

hornwort (Ceratophyllum demersum,) and Bladderwort (Utricularia spp). Located

along the river is the Le Meridian Hotel and Tourist Resort (Ibom Five Star Hotel)

which attracts foreigners to the locality.

 22

Figure 1. Map of Nwaniba River showing sampling stations

Source: Department of Geography, University of Uyo.

3.2 Water Sampling

Four water samples were collected at each site of the drainage. The

samples were collected on 23rd of November, 2019 at 7 o’clock to 9 o’clock in the

morning. Samples were collected using a beaker of 50ml into well labeled bottles

ABCD and filtered in the laboratory using Whatman filter 45vm pore size and

preserved in a temperature at 50°C until analysis.

3.3 Sediment Sampling

Four (4) sampling sites were collected along a stretch of 5km between each
 23

sampling site. Sediments were collected at a depth of 0.2cm using mini spade

sampler (Bradco mini, model 2030).

Samples were collected within a triangular grid (2cm), demarcated at each side of

the four parts of the drainage and thoroughly mixed to form composite sample.

Samples were taken in a cold bucket at 4°c to the laboratory for pre-treatment and

analysis.

Water Pre Treatment

The water samples were preserved by acidifying to pH 3 with HNO3 (Who,

2004). A pH meter (model 2601) was used to measure the pH level of each of the

samples, and kept under a temperature of 50°C to 60°C before analysis.

Total hydrocarbon content in water was determined using a Vis

spectrophotometer. Meter, sky Ray, 9501 model after solvent extraction using a

mixture of xylene and Hexane of ratio 60:40 (ICES, 1991). The water sample was

FILTERED THROUGH Whatman filter (45mm) and placed in a 500cm 3

separating tunnel and preserved until the analysis is done.

Sediment Pre-Treatment

Sediment samples (5g each) were derived in an oven in a temperature of 50°c for

two days crushed and passed through 2mm mesh sieve to remove course

materials. The resulting materials were recrushed, homogenized and split into sub
 24

samples.

The filtered samples were taken for digestion mixed with 40% concentrated

Hydrofluoric acid (HF) and 70% nitric (v) acid (2cm 3), and the mixture was

placed on the heating plates (hot plates) between a temperature range of 150°C to

200°C. heating continued until complete digestion to ash- gray residues and then

completely transferred to a 50cm3 with distilled water measured in volumetric

cylinder of 100ml. boric acids crystals (2.8) were added (to reduce excessive

corrosion by HF) shaken briefly to dissolved made to 50cm mark with distilled

water. The solution was allowed to settle for two (2) days and analyzed for heavy

metal concentration by atomic absorption spectrophotometer (AAS).

Apparatus

• Atomic absorption spectrophotometer (AAS), Unicam model 919

• 500ml volumetric flask

• Test tube

• 250ml glass beaker

Precautions

The test tubes and the volumetric flasks were washed and rinsed before used. And

the AAS was working properly without errors before it was used.
 25

3.4 Heavy Metals Analysis

These were performed using atomic absorption spectrophotometer (AAS),

Unicam model 919 solar spectrometer equipped with a universal burner, air

acetylene fame.

Zinc (Zn)

10ml of the sample was standardized in a stock solution corresponding to lOmg/L

of zn at wavelength of 213.9nm.

The sample was analyzed using atomic absorption spectroscopy (Unicam model

919) and the values were taken.

Manganese (Mn)

10ml of the sample was prepared to a standard solution of 0.1-5.0/rg/g for Mn

(279.5nm) to overcome matrix interferences.

Atomic absorption spectroscopy, (AAS), Unicam model 919 was used for

readings.

Lead (Pb)

10ml of the pretreated sample was analyzed using atomic absorption sectrophoeter

(AAS) Unicam model 919. On a wave length of 283.3nm

 26

Nickel (Ni)

About 10ml of the pretreated samples was prepaid to a standard solution of 0.001-

0.0606 figlg for Nickel with wave length 232.Onm. Then, atomic absorption

spectrophotometer was used to analyze the sample.

Copper (Cu)

10ml of the pretreated sample was analyzed using atomic absorption spectrometer

(AAS) Unicam model 919, on 324.8nm wave length.IRON, Fe

10ml of the pretreated sample was prepaid to a standard solution of 0,1 - 5.006 |

ig/g with wave length 248.3nm.

Atomic absorption spectrophotometer was used to analyze the samples to take

readings.

Total Hydrocarbon Content In Sediment

THC concentration was determined by UV.VIS spectrophometer, Sky Ray 9501

model, 100ml of the sample was transferred into a separating funnel, plus 50ml of

extracting xylene and shake vigorously for two (2) minutes and left to settle. The

process was repeated four (4) times; the lower layer of xylene was collected and

centrifuged. The aqueous layer volumes were read with UV.VIS

spectrophotometer sky ray 9501 model at the wave length of 450nm.

 27

Total Hydrocarbon In Water

THC was determined at 450nm using UV VIS-spectrophotometer and placed in a

500cm3 separating funnel.

The solvent mixture (100cm) was added and shaken several times to obtain a clear

separation. The individual hydrocarbon concentrations in the extract were

determined using UV VIS spectrophotometer.

Insitu Field Analysis

Temperature

Temperature was determined using a thermometer single probe Handheld-p-100

high precision. This was done by inserting the probe into the sample of water in a

beaker and sediment samples in polyethylene bottles.

PH

The PH was determined with colour matched system. This was done by dipping a

part of the colours paper into the samples

 28

CHAPTER FOUR

RESULT AND DISCUSSION

Table 4.1 Determination of Metal Content in the Sediment Samples Collected

At Four Stations

Elements

Lead (Pb)

Nickel (Ni)

22.850 23.177

From the above result Iron and Zinc is recorded the higher level of sediment. Due

to municipal wastes and discharge of domestic wastes into the drainage from

industrial affluent this is above the tolerable limit WHO, 2004. Manganese and

Copper are moderately low but slightly above the tolerable limit while lead,

cobalt, and Nickel, are extremely low.

 29

Table 4.2 Determination of Mineral Metal in Water Sample Collected From

Four Different Stations of the Drainage

S/N Elements Station 1 Station 2 Station 3 Station 4

Lead (Pb)

Nickel (Ni)

Zinc is recorded the highest metal that is highly contaminated in the water sample

analyzed, Iron is second Manganese which can be attributed to municipal wastes

from industries. Copper and Nickel are moderately low while lead and Cobalt are

extremely low.
 30

Table 4.3 Mean Concentration of Heavy Metal in Water Samples of Uyo

main Drainage
 31

Metals
18

16

14

12

10 Metals

0
Pb Co Ni Cu Mn Zn Fe

Fig. 4.3 Mean concentration of heavy metals in water from Uyo main

Drainage system

Series 1
25

20

15
Series 1

10

0
Pb Co Ni Cu Mn Zn Fe

Fig. 4.3.1 Graph of Heavy Metals content in Water of Uyo main Drainage
 32

Table 4.4 Mean Concentration of Heavy Metals in Water Samples of Uyo

main Drainage
 33

Series 1
30

25

20
Series 1
15

10

0
Pb Co Ni Cu Mn Zn Fe

Fig. 4.5 Mean concentration of heavy metals in sediments from Uyo main
Drainage

Metals
30

25

20
Metals
15

10

0
Pb Co Ni Cu Mn Zn Fe

Fig. 4.5.1 Graph of Heavy Metals content in Sediments of Uyo main Drainage
 34

Table 4.6 Mean concentration of THC in Samples Sediments Using

Spectrophotometer Unicam Models 919

Fable of Absorbance for Sediment Vis Spectrophotometer Readings

 35

Table 4.7 Mean concentration of THC in Samples Sediments Using

Spectrophotometer Unicam Models 919

Table of Absorbance for Sediment Vis Spectrophotometer Readings

 36

CHAPTER FIVE

DISCUSSION, CONCLUSION AND RECOMMENDATIONS

5.1 Discussion

5.1.1 Heavy Metals in Water and Sediments

This study shed light on some of the environmental factors that might have

an impact on directly or indirectly on the concentration ability of heavy metals

and total hydrocarbon content in our drainage system which flows all the way into

rivers. The concentration and the distribution of heavy metals and THC has

become a matter of great concern over the last few decades and a lot of studies

have been published on the heavy metals and THC at all levels of aquatic

ecosystem. Many authors associated the heavy pollution in water with industrial

and municipal discharges. These heavy metals may be taken up by living

 37

organisms, deposited in the sediments or remain for some period in the water

itself.

In the present study, concentrations of heavy metals in water and sediments

from four (4) stations of Uyo main drainage were determined the highest

concentrations for all studied heavy metals were recorded in station two (2) and

four (4) when compared with station one and three (3). The differences in heavy

metals between station 2, 4 and 1, 3 might be attributed to the highly discharge of

mixture of industrial, municipal and agricultural waste into the drainage (gutter),

this agrees with Ademoroti (1993) on water contaminants, he reported that the

variation in heavy metals concentration in water might be attributed to the

contaminated sediment.

The results obtained shows that there are extremely low levels of heavy

metals in water compared to those in sediment. This is obvious as it reflects the

general expectation since sediments are sinks for pollutants. The general

distribution pattern for heavy metals followed the sequence

V<Hg<Cd<Ni<Cu<Zn<Mn<Pb<Fe for water.

Generally, the fluxes of heavy metals in sediments rather than water should reflect

the extent to which fluvial and coastal areas have been impacted by

industrialization and other anthropogenic activities (Asuquo et al 1999).

The data of heavy metals in water and sediment in the present work, revealed that

there is a highly significant difference between the four stations, the in increased
 38

and decreased in values of station 1, 2, 3 and 4 may be attributed to a number of

factors such as industrial effluents, agricultural waste and municipal. Water levels

on the four stations showed higher concentrations of lead (0.31,0.04 ppm), cobalt

(0.03, 0,03 ppm), nickel (0.43, 0.09 ppm), copper (2.00, 0.16 ppm), Manganese

(1.42, 0.11 ppm), Zinc (15.27, 0.16 ppm) and iron (2.69, 0.37 ppm). Meanwhile,

sediment of the four stations showed higher concentrations of lead (1.87, 0.06

ppm), cobalt (0.83, 0.07 ppm), nickel (0.69, 0.05 ppm), copper (0.66, 0.09 ppm),

Manganese (2.97, 0.09 ppm), zinc (22.80, 0.35 ppm) and iron (24.11, 0.18 ppm).

The highest accumulated metals were Mn, Fe and Zn in both water and sediment.

Pb and Cu, exhibited moderate concentrations. Co and Ni metals were below the

detectable limit at both water and sediments.

The observations made in the correlation between the mean concentration

of heavy metals in water and sediment (Table 4.2) may be due to the constant

remobilization of the metals because of the dynamics of particulate matter

between sediments and water caused by waves of tidal action bioturbation and

other factors prevalent in the marine environment could prevent normal settlement

and significant correlation of metals between the two (water and sediment).

However, the concentrations of metals are generally higher in sediments them due

to overall settlement of the suspended particulate (Ekpo and ibok, 1998). The

significant correlation of Mn and Pb between water and sediment may be due to

high desorption due to change in salinity of the water (Forstner and Mullen 1985,

Clark et al 1997).
 39

The high level of Zn and Fe in sediments samples have been attributed to

municipal wastes in general specifically domestic waste discharge into gutters

from industrial effluent. This is similar to the work done by Ntekim et al (1993)

on the concentration of heavy metals in most sediments in the region. The

sequence of level of the heavy metals in sediment from the drainage was

Ni<Co<Cu<Pb<Mn<Zn<Fe.

From bar chart of the mean concentration of water, it is observed that Zinc (Zn) is

extremely high, then Iron (Fe) compared to Ni, Mn and Pb which has moderate

and lowest concentration respectively. While in the bar chart of mean

concentration of sediments, Zn and Fe maintains the same level as in water but Fe

is much higher in sediment than in water. Metals like Co, Ni and Cu have the

same level which is below the tolerable limit.

The analysis of the various tables shows that Zn and Fe concentration is

high in both water and sediment, Manganese is moderately high while Pb, Co, Ni

and Cu has the lowest concentration as shown in table 4.1 and table 4.2.

The dynamics, variability and availability of heavy metals also depend on the

metal species and sediment characteristics (Asuquo et al 1999).

The spatial variations (mean trends) in the concentration of heavy metals in

water were as follows: Zn was highest (15.27 ±0.16 ppm), followed by Fe (2.69

±0.37 ppm), Cu (2.00 ±0.16 ppm), Mn (1.42 ±0.11 ppm), Ni (0.43 ± 0.09 ppm),

Pb (0.31 ± 0.04) and Co (0.03 ± 0.03 ppm). Station 2 and 4 were the most
 40

contaminated zones. These were stations of the study area which receive direct

run-off from the municipality (especially the university complex). Spatial

variations (mean trends) in the concentration of heavy metals in sediments were as

follows: Fe (24.11 ± 0.18 ppm), Zn (22.80 ± 0.35 ppm), Mn (2.97 ± 0.09 ppm),

Pb (1.87 ± 0.06 ppm), Co (0.83 ± 0.07 ppm, Ni (0.69 ± 0.05 ppm) and Cu (0.66±

0.09ppm).

These levels of heavy metals could have wide environmental implication

bordering on bioaccumulations in organisms whose adverse contamination could

be harmful to organisms (including plants and animals). In some cases, the high

level off metal concentrations in another place can be readily available resulting in

considerable accumulation.

5.1.2 Total Hydrocarbon Content (THC) In Water and Sediments

The concentration in water range from 101.825 mg/1 to 33.27 mg/1 while

in sediments, it ranges from 40.475 to 121.315 mg/1 indicating a wide variation.

High concentration of THC (above the 10 mg/kg limit recommended for surface

sediment by DPR (1991) and above the tolerable WHO limit of 0,01 mg/1 in

water were obtained. THC concentration was higher in sediments than in water.

The result also showed a decreased in THC level with depth of sediment, but there

was no significant difference between its concentrations in water.

According to Ogri (2002), PH.D thesis, university of Uyo, materials

extracted from sediments at depths greater than 7.5 cm contain relatively little or
 41

no fuel derived hydrocarbons. While sediments contained relatively high level of

hydrocarbons. This observation is valid with the result obtained in this study with

a general increase in THC concentration in sediments (Table 4.5).

Therefore, the drainage system is highly contaminated since the

concentration of THC in water and sediments were above permissible limits

(WHO, 1984, DPR, 1991). High concentration in aquatic environment (water and

sediment) exposes the aquatic organisms to bioaccumulation with serious

environmental implications (Clark et al, 1997).

High accumulation of hydrocarbons in organisms can cause tainting of organisms

which reduces their economic value and also it’s impair respiration of aquatic

organisms.

5.2 Conclusion

Heavy metals and THC concentration in water and sediments has indeed become

a subject that many environmental scientists still try to solve and possibly reduce

their concentration in the aquatic ecosystem. From the observations made in this

study, there is high concentration of both heavy metals and THC in sediment than

in water. This is because of the ability of the sediments to accumulate much of

these metals compared to water.

The present study monitored heavy metals and THC levels and their

distributions in water and sediment in Uyo drainage system, particularly, Uyo

 42

main Drainage. It was observed that the high level of heavy metals and THC in

water and sediment is due to agricultural waste that are been thrown into the

gutter, municipal wastes thrown into the gutter, industrial waste from the

industrialized areas of the city, and also discharge of untreated domestic wastes

into the drainage. High accumulation of these metals and THC level may flow

into the river and cause serious damage to the aquatic organisms and to human.

5.3 Recommendations

Heavy metals and THC high concentration and distribution in water and

sediments can reduce to minimum if monitored and handled properly to stop

damage of the river, sea and probably the ocean which habitats the aquatic

organisms such as fishes, etc. It is recommended that;

1. Constant monitoring of the aquatic ecosystem is needed to update its

pollution status in view of the growing commercial and industrial activities

in the capital.

2. The discharge of untreated domestic and municipal effluents into the rivers

should be controlled. These measures are necessary to curb the excesses of

petroleum companies and municipal scavengers from continual abuse of

the environment.

3. Anthropogenic activities, especially those of the petroleum industry,

perceived as a major source of pollutants here should be controlled.

 43

4. Legislation and regulation, and effective monitoring should be made

5. by the government.
 44

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 51

APPENDIX 1

Who recommendations for drinking water quality (extract) 1984 (chemical and

sensory parameter).

Parameter Normal Value Remarks

Colour (TUC) 15
Taste and odour none
Turbidity (NTU) 5 If possible 1 on
disinfection
pH 6.8-8.5
Dissolved solids (mg/I) 1000
Hardness as CaC03 500
(mg/I)
Chloride (mg/I) 250
Sulphate (mg/I) 400
Hydrogen sulphide Not detected
Sodium (mg/I) 200
Iron (mg/I) 0.3
Manganese (mg/I) 04
Aluminum (mg/I) 0.2
Copper (mg/I) 1
Zinc (mg/I) 5
(b)
Arsenic (mg/I) 0.05
Cadmium (mg/I) 0.005
Chromium (mg/I) 0.05
Cyanide (mg/I) 0.1
Lead (mg/I) 1.5
Mercury (mg/I) 0.001
Nitrate (mg/I) 4.5
Selenium (mg/I) 0.01
 52

APPENDIX 2

Minimum requirements for flowing water system in the EEC (on so called water

class II/III) bases.

Parameter Minimum Requirement Purification necessary

Max temperatures (°C)

(a) Cool summer water 25 25

(b) Warm summer waters 28 28

Oxygen (mg/I) 4 4

pH 6-9 6-9

Annonium (NEU +-N) (mg/I) 1 2

BOD without nitrification

inhibition 7 10

(mg/I)

COD (mg/I) 20 30

Phosphorus (mg/I) 0.4 1

Iron (mg/I) 2 3

Zinc (mg/I) 1 1.5

Copper (mg/I) 0.05 0.06

Chromium (mg/I) 0.07 0.1

Nickel (mg/I) 0.05 0.07

 53

APPENDIX 3

“Average shale” or Pre-civilization metal concentration in sediment (taken as

background level)

Metals Average shale (background) level

Iron 46,700

Manganese 850

Strontium 300

Zinc 95

Chromium 90

Nickel 68

Lithium 66

Copper 45

Lead 20

Cobalt 19

Mercury 0.4

Cadmium 0.3

Source: Adapted from Turekian & Wedepohl, (1961) as cited by Forstner

and Muller, (1981)

 54

APPENDIX 4

Formula for deriving the mean and standard deviation for both water and

sediments as shown in table 4.1 and 4.2.

Mean X=
∑X
n

Standard Deviation, SD ∑ √¿ ¿ ¿ ¿

Source: Chemistry journal of environ, study.com (2012/2013)