CHAPTER ONE

INTRODUCTION

1.1 Background of the Study

Water pollution majorly arises from anthropogenic inputs above natural

background concentration within a specified environment. The presence

of environmental toxicants or pollutants in any ecological environment

whether aquatic or terrestrial reduces not only the quality of such

environment but also its use or applicability by natural dwellers (both

plants and animals) within such locality (Krishna et al., 2009; Ibrahim et

al., 2016). Global attention has greatly shifted to the contamination of

aquatic environments by heavy metals. This not only because of its

toxicity, but also its persistence and abundance in the environment (Islam

et al., 2015). Natural factors and human activities affect the concentration

or abundance of heavy metals in the environment (Khan et al., 2008).

Rapid increase in the number of industries and population drift to urban

centres has led to increased levels of heavy metals and organic pollutants

in the environment (Sedky et al., 2013).

Heavy metals are considered as important intermediates of pollution in

aquatic environments and public health studies (Khaled et al., 2012). This

1
is due to the fact that they can induce certain disease conditions and also

when they are released, they get deposited on sediment and can later be

immobilized depending on the prevailing condition within the environment

(Marcus and Edori, 2016). Heavy metals sometimes are found at trace

concentrations. They can be immobilized within the sediment through re-

suspension, absorption, precipitation and co-precipitation with other

elements in the form of oxides and hydroxides (Mohiuddin et al., 2010;

Awofolu et al., 2005) and also undergo complex formation reactions.

Heavy metals do not undergo biodegradation, and so can be concentrated

along the food chain. Therefore, their toxic effects in most cases are felt

or observed at points that are distances removed from the source of

pollution (Tilzer and Khondker, 1993). Human exposure to heavy metals

have been

associated with several diseased conditions in man, animals and plants,

more especially when they are present at high concentrations (Saha and

Hossain, 2011).

In order to properly monitor and restore the integrity of any water body,

there is the need to adequately protect the sediment quality of that

aquatic system. This will further help to preserve aquatic life, wild life and

2
human well-being (Issa et al., 2011). Sediment is known to be the final

sink for

pollutants in aquatic systems and also a very important part of aquatic

ecosystem. It serves as a habitat, food source, spawning ground and

rearing areas for many aquatic plants and animals (Issa et al., 2011).

This study was therefore carried out to examine the concentration of some

heavy metals in sediment in Andoni River, Rivers State, Niger Delta,

Nigeria.

conducted on sediments in river systems

1.2 Statement of Problem

Aquatic ecosystem is the ultimate recipient of almost everything including

heavy metals. Pollution of heavy metals in aquatic environment is a

growing problem worldwide and currently it has reached an alarming rate.

There are various sources of heavy metals, some originates from

anthropogenic activities like draining of sewerage, dumping of Hospital

wastes and recreational activities.

Conversely, metals also occur in small amounts naturally and may enter

into aquatic system through leaching of rocks, airborne dust, forest fires

and vegetation. As heavy metals cannot be degraded, they are

3
continuously being deposited and incorporated water, sediment and

aquatic organisms, thus causing heavy metal pollution in water bodies.

1.3 Aim and Objectives of the Study

The aim of this project research is to determine heavy metals in Unyeada,

Andoni River and its Sediments water and sediments.

The specific objectives are:

i. The determine the concentration of heavy metals in the sediment

sample

ii. To identify various heavy metals in the sediment and water samples.

iii. To compare the value obtained with the WHO regulatory standard.

1.4 Significance of the Study

The followings are the importance of the study:

i. This study will determine the water quality of Unyeada, Andoni

River and its Sediments water and sediments.

ii. This study will educate the inhabitants on the effects of heavy

metals on human consumption.

iii. This study will identify different heavy metals and their effect on

human health.

4
 iv. This study will add to the existing literature on the effect of heavy

metals on human health. Sources of materials used are cited as

references.

v. This study will investigate the sources of the water pollution and

provide solution to remediate them.

1.5 Scope of the Study

This study focuses on determination of heavy metals concentration in

Unyeada, Andoni River and its Sediments and sediments. This study will

also emphasize on the sources of heavy metals concentration in Unyeada,

Andoni River and its Sediments water and Sediments.

1.6 Definition of Terms

The followings are the scientific terms used in this study:

i. Heavy Metals: These are metals that are poisonous like Cu, Zn and

Al.

ii. Waste: Unwanted materials

iii. Pollutants: substance that are impure and has effect on both plants

and humans.

iv. Water Body: This refers to the rivers, stream and lack.

5
 CHAPTER TWO

LITERATURE REVIEW

Many studies in the field of checking river water quality in terms of heavy

metals have been reported. Odiyo et al., (2019) examined the

concentration of metals in Gamasyab River located in Hamedan province.

The results showed that the concentration of heavy metals of copper and

iron in the water of Gamasyab River had significant growth, possibly due

to the entrance and leakage of agricultural and urban wastewaters. In

addition, the results of studies conducted by Ahmad, J.U.; Goni, M.A.

(2014) evaluated the concentration of heavy metals in the water

resources and river of Borujerd City in 2008-2009.

Duruibe, J.O.; Ogwuegbu, M.O.C.; Egwurugwu, J.N. (2017) about the

evaluation of the superficial and internal contamination of the sediments

in the mouth of Kam River, and Hifung State in Vietnam indicated that

different sources such as industrial development with agricultural activities

in these regions, urban, and industrial wastewaters that enter into these

rivers have caused significant contamination with heavy metals. Karun

River is one of the largest rivers in Iran that is placed near agricultural

lands with large cities and several industries around itself, and the water

of the river is used for irrigation of areas of planted, urban green space,

6
and propagation, and growing aqua cultural. 87.33%, 6.44%, and 6.23%

of the Karun River's water are used for agriculture, aquaculture, and

drinking, respectively (Duruibe et al., 2017). However, unfortunately, due

to the rapid development of urbanization, industries, and technology

along with increased areas of cultivation, different contaminants in terms

of physical, chemical, and biological contaminants are entered in this river

annually. According to statistics, this river receives urban, agricultural, and

industrial wastewaters as much as 26, 48, and 23%, respectively.

Obviously, this over-contamination has hampered self-purification abilities

of the river (Duruibe et al., 2017), Aquatic ecosystem is the ultimate

recipient of almost everything including heavy metals. Pollution of heavy

metals in aquatic environment is a growing problem worldwide and

currently it has reached an alarming rate. There are various sources of

heavy metals; some originates from anthropogenic activities like draining

of sewerage, dumping of Hospital wastes and recreational activities.

Conversely, metals also occur in small amounts naturally and may enter

into aquatic system through leaching of rocks, airborne dust, forest fires

and vegetation. As heavy metals cannot be degraded, they are

continuously being deposited and incorporated in water, sediment and

aquatic organisms, thus causing heavy metal pollution in water bodies.

7
A study by Song et al., (2019) suggested that, concentrations of metallic

pollutants are greatest near towns, indicating their urban industrial

origins. Within the lake basin, extensive mining occurs mainly in Tanzania

where small-scale miners use water to remove mud and impurities and

mercury to collect gold Vergas, (Migliavacca, et al., 2018). The

wastewater from such processes is usually disposed off into nearby

streams with ultimate destination into Lake Victoria basin. Other possible

sources of pollution include; domestic effluents, urban storm water runoff,

landfill leachate, atmospheric sources and boating activities.

Earlier studies on sediment, water and biota of Lake Victoria reflected no

significant heavy metal pollution (Vergas, 2018). However, subsequent

studies have shown increased levels of especially lead (Vergas, 2018).

This was attributed to increased shipping traffic, car washing and

discharge from local industries.

In a review by Edokpayi (2019) concluded that generally lower

concentration of heavy metals occur in African aquatic ecosystems

compared to other areas of the world. However, due to increases in

urbanization and socioeconomic activities, the threat of pollution was

bound to increase within our aquatic systems.

8
Varol, M.; Sen, B. (2019) described that rapid development of industries

such as chemical industries along with the discharge of a variety of

industrial and urban wastewaters into the environment over the past few

decades has caused the contamination of surface and groundwater

resources and the emergence of several environmental problems. Among

the most important portable and consumed water resources in cities and

villages, rivers play an important role in providing human and

environmental health. However, unfortunately over the past few years, in

response to various human activities, the quality of water of these

important resources has changed, and the harmful effects of water

contamination have gradually been unearthed. Among the contaminants

exist in wastewater industries, mines and urban and agricultural runoffs

entered aquatic ecosystems; heavy metals are noteworthy.

Unlike organic contaminants, decomposition in the environment requires

a long time and due to their toxicity, persistence, and non-degradability

in the environment.

In addition, bioaccumulation potential in many aquatic species is one of

the most important environmental hazards. Since some of these metals

have biomagnifications properties after accumulation in the tissues of

living organisms, they move toward higher levels of the food web, and

9
finally, are transferred into the human body, which is on the top of the

food web, sometimes threaten the human health. Therefore, the

determination of the levels of heavy metals in aquatic ecosystems can

play an important role in the health of living organisms, especially human.

The study of river water quality in terms of heavy metals due to their very

low concentrations, and thus, the low measurement accuracy in water, is

difficult, whereas the concentration of the metals is far higher in

sediments.

Jadia and Fulekar (2019) postulates that Heavy metals appear in marine

sediments in low concentrations, ranging from µg kg-1 to mg kg-1 (Szefer,

2002). Stoeppler (1991) provided a comprehensive review of the most

frequently used techniques for quantitative analysis of metallic trace

elements. Instrumental determination of heavy metals in the acidic

solution obtained is carried out depending on the instrument and

manufacturer's specifications. In most cases, i.e., in most marine

sediments, Cd and Pb can be determined by GFAAS (Graphite Furnace

Atomic Absorption), while Cu, Zn, Cr, Ni, Mn, Al, and Fe can also be

determined by the less sensitive flame atomization.

Earlier studies on sediment, water and biota of Lake Victoria reflected no

significant heavy metal pollution (Edokpayi, 2019). However, subsequent

10
studies have shown increased levels of especially lead (Samarghandi et

al., 2018). This was attributed to increased shipping traffic, car washing

and discharge from local industries.

In a review by Samarghandi et al. (2018) it was concluded that generally

lower concentration of heavy metals occur in African aquatic ecosystems

compared to other areas of the world. However, due to increases in

urbanization and socioeconomic activities, the threat of pollution was

bound to increase within our aquatic systems. Similar conclusion was

made following a study on 3000 lakes with the Nordic region in which the

sparsely populated Northern region was found to much less polluted

compared to the south with heavy anthropogenic activities (Samarghandi

et al., 2018).

The presence of heavy metals in the water may have a profound effect

on the microalgae which constitute the main food source for bivalve

mollusks in all their growth stages, zooplankton (rotifers, copepods, and

brine shrimps) and for larval stages of some crustacean and fish species.

Moreover, bio-concentration and magnification could lead to high toxicity

of these metals in organisms, even when the exposure level is low. Under

such conditions, the toxicity of a moderately toxic metal could be

enhanced by synergism and fish population may decline.

11
Apart from destabilizing the ecosystem, the accumulation of these toxic

metals in aquatic food web is a threat to public health and thus their

potential long term impact on ecosystem integrity cannot be ignored. The

present study was therefore undertaken to assess the levels of heavy

metals in water and sediment from Lake Victoria and how this relates to

bioaccumulation of the pollutants in microalgae.

The study also aimed at determining how the level of heavy metal

pollution varies with dry, short rain and long rain seasons.

Heavy metals concentration was determined from water, sediment and

microalgae samples. The results clearly indicate that concentration were

highest in the sediment samples from both gulfs compared to water and

microalgae.

In general, metal content in sediments is indicative of the degree of

pollution and serves as a source of solubilization into water depending on

the physico-chemical circumstances (pH, temperature etc) and the uptake

by benthic organisms. At Winam Gulf for instance, Zn, Hg and Cr were

more concentrated in sediment samples, the same trend was also noted

in Mwanza samples. Hg is the only metal known to be liquid at room

temperature and with low solubility in water. Dissolved Hg is distributed

among several chemical forms including elemental Hg, that is volatile but

12
relatively uncreative, a number of mercuric species Hg(II) and organic-

Hg such as methyl, dimethyl and ethyl mercury. In general, the levels of

total Hg and MeHg are higher near the sediments (Samarghandi et al.,

2018). This could possibly account for the results of our study that

indicated higher levels of Hg in sediments compared to either water or

microalgae samples. The same explanation could apply for the other

metallic elements, being no biodegradable in nature (Duruibe et al.,

2017). Metals are commonly found adsorbed in sediments. The presence

of higher concentration of heavy metal in sediments from this study is in

agreement with other related studies.

A study on heavy metal pollution in Lake Victoria sediments from samples

collected from seventeen different locations around the lake town of

Mwanza, representing three zones of activities. The results showed that

sediments samples collected from southern part, which is the industrial

area, had the highest concentrations of V, Cu, Zn, As and Pb but the same

were generally low in the northern part which is least in anthropogenic

activities. Another study on the shores of Lake Victoria, within the urban

area of Mwanza showed elevated levels of heavy metal, notably Pb

(54.6±11.1 ppm) and Zn (83.7±21.5 ppm) in sediment samples (Duruibe

et al., 2017). The link between anthropogenic activity and heavy metal

13
pollution in lake Victoria was further supported by a study on the level of

contamination in wetland soils and plants in lake basin around Kampala

city.

Furthermore, a study by Tole and Shitsama (2019) suggested that,

concentrations of metallic pollutants are greatest near towns, indicating

their urban industrial origins. Within the lake basin, extensive mining

occurs mainly in Tanzania where small-scale miners use water to remove

mud and impurities and mercury to collect gold (Duruibe et al., 2017).

The wastewater from such processes is usually disposed off into nearby

streams with ultimate destination into Lake Victoria basin. Other possible

sources of pollution include; domestic effluents, urban storm water runoff,

landfill leachate, atmospheric sources and boating activities (Ahmad and

Goni, 2014).

CHAPTER THREE

MATERIALS AND METHODS

14
3.1 Materials

The followings are the materials used for the analysis:

i. Water sample

ii. Sediment samples

iii. Test tube

iv. iv. Detergent

v. Ice boxes

vi. Polyethylene bottles

vii. Eckman grabber

viii. Mortar and pestle

ix. Wide mouthed plastic containers

Reagent

10% HNO3

HCL (ag)

3.1.1 Study Area

15
The study was carried out in Unyeada, Andoni River and its Sediments

water and sediments. These sites were chosen due to their proximity to

catchments with activities that potentially contribute to pollution of the

river.

3.2 Method (Procedures)

3.2.1 Collection of Water Sample

Water samples were collected in polyethylene bottles. The water samples

were then taken to the Department of Science Laboratory Technology,

Kenule Beeson Saro-Wiwa Polytechnic, Bori for analysis. Each sample was

collected by submerging the sample container into the river at about 50-

30mm below the surface with an open end facing against the current flow

direction.

3.2.2 Preparation of Water Sample

500-mL. polyethylene sample containers were cleaned using livid

detergent, followed by rinsing with tap water until they were free of

detergent. In the field, the containers were rinsed three times with water

at the sampling point before collection.

The sample was double-distilled with 2ml trioxonitrate (iv) HNO3. Water

samples were acidified with 10% HNO3, brought to the Department of

16
Science Laboratory Technology, Kenule Beeson Saro-Wiwa Polytechnic,

Bori and kept refrigerated until analyzed.

3.2.3 Collection of Sediment Samples

Sediment samples were collected using Eckman grabber and put into wide

mouthed plastic containers, kept in ice boxes containing wet ice and

stored at -80°C until analysis.

3.2.4 Preparation of Sediment Samples

The sediment samples were sub-sampled for dry weight determination at

105°C. The samples were freeze-dried, finely crushed and homogenized

using mortar and pestle.

3.2.5 Determination of Heavy Metals in Water Samples

100ml of water samples were measured and poured in a test tube, 10ml

of HNO, and 1 ml of HCL were added in the culture test tube, and then

incubated at 80°C in a water bath, after total digestion and subsequent

cooling; the solution was diluted to 50ml and analyzed for heavy metals

concentration using Atomic Absorption Spectrophotometer (AAS).

3.2.6 Determination of Heavy Metals in Sediment Samples

17
The sediment samples were freeze-dried, finely crushed and homogenized

using mortar and pestle. About 0.5g of the homogenized sample was

digested in 10 ml of HNO3 and HCl in the ratio of 3:1. 1 ml of HCL was

poured in a culture test tube and incubated at 80% in a water bath, after

then it was digested and allowed to cool. The solution was then diluted to

50ml and analyzed for heavy metals in a closed system using Atomic

Absorption Spectrophotometry.

3.3 Data Analysis

The results obtained shall be analyzed using the spread sheet package

(excel software). Data shall be presented in form of graph, bar chart etc.

to show the heavy metals concentration in Unyeada Andoni Rivers State.

CHAPTER FOUR

18
 RESULTS AND DISCUSSION

4.1 Result

In this section the results of the experiment shall be presented to show

the mean concentration of heavy metals in Unyeada Andoni Rivers State

and Sediments.

Results shall be presented in form of table and bar chart.

Table 4.1: Mean concentration of heavy metal concentration in Unyeada

Adoni River and its sediments.

S/N PARAMETERS WATER SEDIMENTS W.H.O LIMITS

1 Chromium, Cr (mg/l) 0.181 0.241 0.05

2 Zinc. Zn (mg/l) 0.06 1.020 3.00

3 Mercury, Hg (mg/l) 0.001 0.009 0.05

4 Lead Pb (mg/l) 0.023 0.341 0.01

5 Cadmium, Cd (mg/l) 0.009 0.025 0.003

1.2

19
1

0.8

0.6 WATER

0.4 SEDIMENTS

0.2

Figure 4.1: Mean Concentration of Heavy Metals in Unyeada Andoni River

3.5

2.5

1.5

1 WATER

0.5 SEDIMENTS

0 W.H.O LIMITS

Cr (mg/l) Zn(mg/l) Hg(mg/l) Pb(mg/l) Cd(mg/l)

Figure 4.2: Shows the mean concentration of heavy metals in Unyeada,

Andoni River and its Sediments with their WHO permissible limits.

4.2 Discussion

20
This study was conducted to investigate the mean concentration of heavy

metals in Unyeada, Andoni River and Sediments. The result of the analysis

indicated that the concentration of heavy metals were less than toxicity

threshold unit in Unyeada, Andoni River and sediments.

The high level of Chromium in water (0.181) and sediments (0.241) which

was above the WHO permissible limit.

Chromium is very toxic by inhalation and dermal route and causes lungs

cancer, nasal irritation, nasal ulcer and hypersensitivity reactions like

contact dermatitis and asthma. Chromium affects various components of

the immune system and may results in immunostimulation or

immunosuppression.

CHAPTER FIVE

CONCLUSION AND RECOMMENDATIONS

21
5.1 Conclusion

The concentration of trace metals from two different samples ie, water

and sediments of Unyeada, Andoni River were determined. Our results

indicate that there were differences in trace metal concentration in water

and sediment samples. In the river, heavy metal concentrations were

highest in the sediment samples than the water samples. There are

various sources of heavy metals; some originates from anthropogenic

activities like draining of sewerage, dumping of Hospital wastes and

recreational activities. Conversely, metals also occur in small amounts

naturally and may enter into aquatic system through leaching of rocks,

airborne dust, forest fires and vegetation. As heavy metals cannot be

degraded, they are continuously being deposited and incorporated in

water, sediment and aquatic organisms, thus causing heavy metal

pollution in water bodies.

5.2 Recommendations

The followings are the recommendations to the study:

i. Water should be analyzed before consumption

ii. Government should enact a law that prohibit indiscriminate

dumping of refuge or waste in the water bodies

22
iii. Water bodies should be maintained and monitored to prevent

contamination.

iv. An agency should be created by the government to monitor the

water bodies to prevent water pollution.

v. There should be an enlightenment campaign to educate the

masses on the effect of heavy metals contamination on human

health.

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