A

RESEARCH PROJECT

ON

PHYSICO-CHEMICAL ANALYSIS OF IKO RIVER IN EASTERN

OBOLO LOCAL GOVERNMENT AREA, AKWA IBOM STATE,
NIGERIA.

BY

ETUKUDO, UDUAK SUNDAY

AK18/BGS/MAB/018

SUPERVISED BY:
DR. (MRS) MARY P. EKANIM

SUBMITTED TO:

DEPARTMENT OF MARINE BIOLOGY

FACULTY OF BIOLOGICAL SCIENCES, AKWA IBOM

STATE UNIVERSITY.

IN PARTIAL FUFILMENT OF THE REQUIREMEMTS FOR THE

AWARD OF THE BACHELOR OF SCIENCE DEGREE (BSC) IN
MARINE BIOLOGY

APRIL, 2023

i
 Declaration

I, ETUKUDO, UDUAK SUNDAY declare that the research work titled

“PHYSICO-CHEMICAL ANALYSIS OF IKO RIVER IN EASTERN
OBOLO LOCAL GOVERNMENT AREA, AKWA IBOM STATE,”
submitted to the Department of Marine Biology, is a record of the original work
done by me under the supervision of Dr. (Mrs) Mary P. Ekanim and the Head of
Department, Dr Ini-Ibehe Nabuk Etim, and this project work is submitted in
partial fulfilment of the requirements for the award of the Bachelor of Science
Degree (B.Sc.) in Marine Biology. The results embodied in this thesis have not
been submitted to any other university or institute for the award of any degree
or diploma and the work presented in it are my own.

…………………………………....
ETUKUDO UDUAK SUNDAY
AK18/BGS/MAB/018

ii
 Certification

This is to certify that the project work entitled “PHYSICO-CHEMICAL

ANALYSIS OF IKO RIVER IN EASTERN OBOLO LOCAL
GOVERNMENT AREA, AKWA IBOM STATE,” is a piece of work done
by ETUKUDO, UDUAK SUNDAY from the Department of Marine Biology,
Akwa Ibom State University, with registration number AK18/BGS/MAB/018,
under the guidance and supervision of Dr. (Mrs) Mary P. Ekanim, during the
year 2022-2023 and is up to the expectation per the guideline governing the
award of Bachelor of Science (B.Sc.) Degree.

ETUKUDO, UDUAK SUNDAY ----------------------

Student Signature/Date

Dr. (Mrs) Mary P. Ekanim ----------------------

Supervisor Signature/Date

Dr. Ini-Ibehe Nabuk Etim --------------------

Head of Department Signature/Date

------------------------------- -----------------------
External Examiner Signature/Date

iii
 Dedication

This work is dedicated to the Almighty God for the strength, love, grace,
wisdom and His continuous mercy towards me. This work is also dedicated to
my parents, Engr. Mr. and Mrs. Ekerete Ukere, for their very profound support
and effort to ensure the acquisition of my first degree. And to all my family for
their prayers, advice and support.

iv
 Acknowledgement

I wish to acknowledge Dr, Ini-behe Nabuk Etim, the Head of Department, Dr.
(Mrs) Mary P. Ekanim, my supervisor for their discipline and encouragement
throughout the entire process of this work.

My gratitude is expressed to Engr. Mr. and Mrs. Ekerete Ukere, who have
made this dream a reality. I also acknowledge the staff of Marine Biology for
the assistance they provided in my analysis.

Special thanks to my best friends, Favour Bassey, Rose Akpan James and
Malachy Boniface Itakari for their love and good cheer. You guys have made
this B.Sc. journey worthwhile. And to my colleagues and friends who have in
one way or the other shown support throughout this work.

v
Abstract

vi
 TABLE OF CONTENTS

Title page: ………………………………………………………………………i

Declaration: ……………………………………………….................................ii

Certification: ………………………………………………...............................iii

Dedication: ……………………………………………………………………..iv

Acknowledgement: …………………………………………………………….v

Abstract: ……………………….…………………………………………….....vi

List of Table: .………………..………………………………………………..vii

List of Figures: …………………………………………………..…………...viii

Chapter 1: Introduction:………………………………………………………1

1.2 Significant of the Study:…………………………………………………2

1.3 Statement of Problem:……………………………………………………3

1.4 Justification:………………………………………………………………

1.5 Aim and Objectives:……………………………………………………...5

Chapter 2: literature Review:…………………………………………………..6

2.1 Physioco-chemical Parameter:…………………………………………...7

2.1.2 Physioco-chemical Characteristics:………………………………………8

2.1.3 Turbidity:…………………………………………………………………9

2.1.4 PH………………………………………………………………………..10
vii
2.1.5 Acidity:………………………………………………………………….11

2.1.6 Alkalinity:……………………………………………………………….12

2.1.7 Dissolved Oxygen:……………………………………………………...13

2.1.8 Biochemical Oxygen Demand:………………………………………….14

2.1.9 Total Dissolved Solids:………………………………………………….15

2.1.10 Total Suspended Solids:……………………………………………….16

2.1.11 Water Temperature:……………………………………….....................17

2.1.12 Conductivity:…………………………………………………………...18

2.1.13 Salinity:………………………………………………………………...19

Chapter 3: Materials and Method:……………………………………………20

3.1 Description of Study Area:……………………………………………..21

3.2 Sample Collection:…………………………………………...................22

3.3 Data Analysis:

………………………………………………...................23

3.4 Sample Analysis:……………………………………………………….24

3.4.1 Water Temperature:………………………………………….................25

3.4.2 Salinity:…………………………………………………………………26

3.4.3 Dissolved Oxygen:……………………………………………………..27

3.4.4 Conductivity:……………………………………………………………28

3.4.5 Biochemical Oxygen Demand:……………………………….................29

viii
3.4.6 Total Suspended Solids:……………………………………………..….30

3.4.7 Total Dissolved Solids :……………………………………………….31

3.5 Materials Used:………………………………………………………….32

3.5.1 Refractometer:…………………………………………………………..33

3.5.2 Mercury in Glass:………………………………………………………34

3.5.3 Secchi Disc:…………………………………………………………….35

3.5.4 Multimeter:……………………………………………………..………36

Chapter 4: Result and Discussion:……………………………………............37

Chapter 5: Conclusion and Discussion: ………………………….…………38

References

ix
 Chapter one

Introduction

1.0 Background of Study

Iko River had been an area of intense petroleum extraction activities

since 1973 by Shell Petroleum Development Company Nigeria Limited, in
what was referred to as the Utapete Operational Zone ( Ansa, 1998). Though,
the oil exploration activities had been discontinued communities and water
bodies within the area. One of the most negative activities in Iko is the
phenomenon of acid rain. The resulting high levels of acidity in the
environment manifest as severe corrosion of roof sheets on houses in Iko, skin
irritation , poor agricultural soils , destruction and reduction of fish life and
fisheries production of the waters, deterioration of the quality of surface and
ground waters ( Mobil, 1997 ; FIMSCO, 2002). Iko River in Eastern Obolo
Local Government Area, is located within the petroleum belt of the Niger Delta,
thus rivers in this area are exposed to additional risk of pollution from
petroleum and related sources.

Iko River takes its rise from the Qua Iboe River catchment and drains directly
into the Atlantic Ocean at the Bight of Bonny. The devastation in the area is
also aggravated by the direct influence of seawater and the inward driving wind
from the Atlantic Ocean due to its closeness. There has been a reported case of
diurnal and seasonal changes in water temperature, Salinity, biochemical
oxygen demand, total dissolved solid, and conductivity of the water system in
Iko River (Ekpe et al, 1995).
x
 The river is of high economic and ecological importance, as it supports the
livelihood of a large number of artisanal fishermen. Iko River runs through both
mangrove and fresh water swamps with adjoining creeks and tributaries, with
communities settling all along the river. Therefore, whatever environmental
changes taking place in the river will affect the hydrology of the surrounding
creeks and tributaries (Imevbore, 1970; Egereonu et al, 2012).

In a study of the basic ecological features of the different sectors of the

mangrove and fresh water swamp forest of Nigeria, it was shown that the
ecological equilibrium is very delicate (Enyenihi et al, 1987). These effects are
bound to influence the overall high productivity of the environment (The World
Bank,1995).
There are reported cases of oil bunkering and establishment of local refineries in
Iko area, with indiscriminate dumping of petroleum residues, seepages and
spillages in Iko River. The deleterious effect of these activities in the ecosystem
is enormous and calls for concern. The need to protect the environment as a
prerequisite for preserving the quality of life has been emphasized in 1984 by a
report initiated by the South African Committee for Oceanographic Research
which established water quality criteria (WQI, 1991). The report defined, as “a
scientific yardsticks upon which a decision or judgment maybe made
concerning the ability of water of a given quality to support a designated
beneficial use”. Beneficial uses include preservation of ecosystem, direct
contact recreation, migration of aquatic life and mineral recovery. In the general
framework of the global environmental problems, and the large store of
background data about the deteriorating environment, this study is initiated to
monitor the spatial and seasonal distribution of petroleum hydrocarbon
pollutants and interactive effects on water quality parameters in the water and
sediments of Iko River. Therefore, the acquisition of accurate data on the
concentration and distribution of understanding the geochemical and
xi
biogeochemical cycles of the elements and deduce the extent to which the
equilibrium of the river ecosystem has been disturbed.

Most of the studies conducted on the monitoring and assessment of river and
estuarine water quality in the South-East Nigeria are within the lower and upper
Cross River Estuary (Lowenberg & Kunzel 1992; Ekwu & Sikoki 2006),
Calabar River (Asuquo 1999), and a few in the Bonny estuary (Dubbin-Green
1990), New Calabar River (Ekeh & Sikoki 2003) and Nkoro River (Abowei
2010) in the Niger Delta region. Other studies conducted include those of Lagos
Lagoon (Ayoola & Kuton 2009) and Tarkwa Bay (Edokpayi et al. 2010), in
western Nigeria. Eastern Obolo estuary is a unique aquatic environment in the
tropical belt with marked maritime influence due to riverine inflow, vertical
mixing, coastal nutrient enrichment, oil pollution and other anthropogenic
sources.

It is also one of the ecologically and economically rich marine ecosystems in

the Niger Delta region of Nigeria providing breeding grounds for a variety of
fish and shrimp species. Numerous activities such as oil exploitation and
exploration, laundry, fuel wood exploitation and capture fisheries take place
along the estuary/watershed. Small concentrations of anions and cations of
heavy metals are continuously present in the drinking water, which could
consequently pose health risk to the communities. This study seeks to provide
basic information and to enrich the scientific knowledge of the coastal
ecosystem of Nigeria with particular reference Eastern Obolo estuary and other
similar water bodies where little or no information is available for its effective
management and sustainability; and to prevent further degradation of the area.
The quality of aquatic bionetworks is vital for the productivity, survival and
support of aquatic organisms found in them. It is an index of health and well-
being of the ecosystem and has direct impact on human health. Physicochemical

xii
parameters of water provide nutritional balance and ultimately govern the biotic
relationships of organisms in an aquatic ecosystem; including ability to
withstand pollution load.

Industrialization, urbanization and modern agriculture practices directly impact

the water resources quantitatively and qualitatively. Many industries are sited
near these bodies of water presumably to facilitate easy discharge of effluents
and other pollutants into them. A typical example is the siting of several flow
stations on the territorial waters of the Eastern Obolo with its attendant and
often incessant oil spillages, gas flares which eventually lead to acid rains
(Udoessien, 2003) experienced in the area.

1.1 Significance of the Study

Over the years within this coastal region it has been established that the
hydrology of Iko River is affected by tides, although seasonal influences which
are related to the climatic regime, are evident. Iko River is directly influenced
by the processes in the Atlantic coastal waters (Ekpe et al, 1995). As such the
continuous study of the physico-chemical analysis of Iko River is of high
importance.

1.2 Aim and Objectives

The aim of this research work is to assess the physico-chemical parameters of

Iko River in Eastern Obolo L.G.A.

1.3 Objectives of the study

 To determine the physico-chemical parameters of Iko River in Eastern Obolo

Local Government Area, Akwa Ibom State, Nigeria.

xiii
 To compare the physico-chemical parameters in water samples with the
given standard.

 To determine if the levels of some physico-chemical variables in water

sample of Iko River in Eastern Obolo L.G.A are below or above the
permissible limits of the standards given.

 To suggest possible ways to maintaining balance in the altered parameters if

any.

1.4 Scope of the study

To analyse the difference variables of physico-chemical parameters in Iko River

in Eastern Obolo L.G.A, such as temperature, salinity, total dissolved solid,
biochemical oxygen demand, total suspended solid and conductivity.

1.5 Justification

Iko River is used for artisanal fishing activities, transportation, domestic

purposes, as well as mining of silica and sand. The uncontrolled discharge of
domestic wastes has pollution implications, as they may change prevailing
conditions and alter the habitats of aquatic organisms and fishing activities are
major sources of livelihood, especially for artisanal fisher folks. Despite the
increasing anthropogenic influences occasioned by the rapid development of
Iko communities as one of the Niger Delta areas in Nigeria, no corresponding
update in scientific information regarding its limnology, most especially on
plankton and benthic macro-invertebrates of the river; hence, the need for this
study. This would provide additional information that could be utilized as a
platform for impact assessment, planning and proper management of Iko River.

xiv
1.5.1 Statement of the Problem

In a study of the basic physicochemical analysis of Iko River in Eastern Obolo

Local Government Area, it was shown that the physicochemical analysis is very
standardized. These effects are bound to influence the overall high productivity
of the environment (World Bank, 1995). Of recent,
there are reported cases of oil bunkering and establishment of local refineries in
Iko area, with indiscriminate dumping of petroleum residues, seepages and
spillages in Iko River. The deleterious effect of these activities in the ecosystem
is enormous and calls for concern. The need to protect the environment as a
prerequisite for preserving the quality of life has been emphasized in 1984 by a
report initiated by the South African Committee for Oceanographic Research
which established water quality criteria (WQI, 1991). The report defined these,
as “a scientific yardsticks upon which a decision or judgment maybe made
concerning the ability of water of a given quality to support a designated
beneficial use”. Beneficial uses include preservation of ecosystem, direct
contact recreation migration of aquatic life and mineral recovery. In the general
framework of the global environmental problems, and the large store of
background data about the deteriorating environment, this study is initiated to
monitor the spatial and seasonal distribution of petroleum hydrocarbon
pollutants and interactive effects on water quality parameters in the water and
sediments of Iko River. Therefore, the acquisition of accurate data on the
concentration and distribution of understanding the geochemical and
biogeochemical cycles of the elements and deduce the extent to which the
equilibrium of the river ecosystem has been disturbed.

xv
 Chapter two

Literature Review

2.0 Physicochemical Parameters

An understanding of the physicochemical variables of a water body is

importance when determining its productivity and other characteristics.
(Adebisi 1981), this affect the physical and chemical factors that must be
present at their optimum level to determine a good initial production (Jamu and
Ayinla, 2012).

The importance of physicochemical parameters in Iko River has been

recognized and attempts to relate certain limnological factors to inland water
productivity. These include the works of (Ovie 1995) the seasonal
physicochemical parameters in Iko river in Eastern Obolo LGA Akwa Ibom
State, Nigeria. The parameters measured included: Biochemical Oxygen
Demand (BOD), Dissolved Oxygen (DO), Temperature, Conductivity (C), Total
Dissolved Solids (TDS), and Total Suspended Solids (TSS). The mean values
of the measured parameters were compared with National Standard for Drinking
Water Quality (NSDWQ) and Environmental Protection Agency (EPA)
standards. (Usoro et al. 2013), reported on seasonal variation of physiochemical
parameters of water and sediments from Iko River in Eastern Obolo Local
Government Area Akwa Ibom State, Nigeria. Based on the physiochemical
parameters of the water, the pollution index determined for the wet season gave
a value of 0.97, which was less than a value 1 for an unpolluted surface water

xvi
body, but gave a pollution index of 1.34 during the dry season. This could be
attributed to reduction in water flow and surface water evaporation. The
variation of the dissolved oxygen was not significant in both seasons and was
higher than the 5.0mg/L WHO limit for surface waters, and indicated a highly
oxidized environment. The phosphate content of the sediment of the river was
lower in both seasons than average for soils, whereas, total nitrogen, total
organic carbon and sulphur content were higher than average for soils.

The principles of physicochemical analysis were established in the late 19th

century by Gibbs et al. The analytical method received its development in the
research of H. Le Châtelier, G. Tammann, H. Roozeboom, and, in particular, N.
S. Kurnakov and his school.

Physicochemical analysis is based on the phase rule and on the principles of

continuity and correspondence, which were introduced by N. S. Kurnakov. The
continuity principle holds that during continuous changes in the parameters of a
state the properties of a system also undergo continuous change (provided that
the number of phases in the system remains constant); when the number of
phases changes, certain properties change abruptly (continuity being broken).
According to the correspondence principle, each phase or group of phases of a
system corresponds to a certain geometric shape (point, line, surface, volume)
on the composition-properties diagram. Thus, the onset of phase crystallization
corresponds to the liquid curves (or surfaces), above which is located the region
of existence of one liquid phase (solution or melt); the end of crystallization
corresponds to the solidus lines (or surfaces), below which only solid phases
exist.

xvii
2.1 Physicochemical Parameters

Physicochemical parameters are considered as one of the most important

features that are capable of influencing the marine environment and have
showed wide temporal and spatial differences. All the physicochemical
parameters illustrate clear seasonal patterns, which are very typical to the
tropical marine environment (EPA, 2011).

It is very essential and important to test the water before it is used for drinking,
domestic, agricultural or industrial purpose. Water must be tested with different
physicochemical parameters. Selection of parameters for testing of water is
solely depends upon for what purpose we going to use that water and what
extent we need its quality and purity. Water does content different types of
floating, dissolved, suspended and microbiological as well as bacteriological
impurities. Some physical test should be performed for testing of its physical
appearance such as temperature, color, odour, pH, turbidity, TDS etc, while
chemical tests should be perform for its BOD, COD, dissolved oxygen,
alkalinity, hardness and other characters. For obtaining more and more quality
and purity water, it should be tested for its trace metal, heavy metal contents and
organic (Patil et al, 2013).

Physicochemical parameters in both surface waters and sediments are important

to understand riverine dynamics. Fluctuations in the input of natural processes
along the year such as rainfall, wind, solar radiation and water input as well as
geomorphology will affect the physicochemical parameters. The depth profile
of a river can change dramatically from its upper reaches to where it meets the
sea (Alexandre et al., 2016).

xviii
2.2 Physicochemical Characteristics

The most common physical contaminants of water are suspended sediments.

These are properties which are often apparent to the eyes such as colour, odour,
taste and turbidity. Chemicals are the major sources of water contamination.
Some chemicals are introduced during movement through geological materials
or when disposed directly into water bodies.

2.3 Turbidity

Turbidity is the cloudiness of water. It is a measure of the ability of light to pass

through water. It is caused by suspended material such as clay, silt, organic
material, plankton, and other particulate materials in water. The impact of
turbidity can be summarized in the following points:

 It can increase the cost of water treatment for various uses.

 The particulates can provide hiding places for harmful microorganisms and
thereby shield them from the disinfection process.
 Suspended materials can clog or damage fish gills, decreasing its resistance
to diseases, reducing its growth rates, affecting egg and larval maturing, and
affecting the efficiency of fish catching method.
 Suspended particles provide adsorption media for heavy metals such as
mercury, chromium, lead, cadmium, and many hazardous organic pollutants
such as polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons
(PAHs), and many pesticides.

xix
2.4 Potential Hydrogen (pH)

pH is one of the most important parameters of water quality. It is defined as the

negative logarithm of the hydrogen ion concentration. It is a dimensionless
number indicating the strength of an acidic or a basic solution. Actually, pH of
water is a measure of how acidic/basic water is. Acidic water contains extra
hydrogen ions (H+) and basic water contains extra hydroxyl (OH −) ions. It
depends on the release of carbon dioxide from the atmosphere, the balance of
respiratory and photosynthetic metabolism, as well as the origin of waters, the
geological nature of the crossing environment and discharges of sewage.

Pollution can modify the pH of water, which can damage animals and plants
that live in the water (APHA, 2005).

The effects of pH on animals and plants can be summarized as follows:

 Most aquatic animals and plants have adapted to life in water with a specific
pH and may suffer from even a slight change.
 Even moderately acidic water (low pH) can decrease the number of hatched
fish eggs, irritate fish and aquatic insect gills, and damage membranes.
 Water with very low or high pH is fatal. A pH below 4 or above 10 will kill
most fish, and very few animals can endure water with a pH below 3 or
above.
 Amphibians are extremely endangered by low pH because their skin is very
sensitive to contaminants. Some scientists believe that the current decrease
in amphibian population throughout the globe may be due to low pH levels
induced by acid rain.

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2.5 Acidity

Acidity is the measure of acids in a solution. The acidity of water is its

quantitative capacity to neutralize a strong base to a selected pH level. Acidity
in water is usually due to carbon dioxide, mineral acids, and hydrolyzed salts
such as ferric and aluminum sulfates. Acids can influence many processes such
as corrosion, chemical reactions and biological activities. Carbon dioxide from
the atmosphere or from the respiration of aquatic organisms causes acidity when
dissolved in water by forming carbonic acid (H 2CO3). The level of acidity is
determined by titration with standard sodium hydroxide (0.02N) using
phenolphthalein as an indicator.

2.5.1 Total Alkalinity

The alkalinity of water is its acid-neutralizing capacity comprised of the total of

all titratable bases (APHA, 2005). The measurement of alkalinity of water is
necessary to determine the amount of lime and soda needed for water softening
(e.g., for corrosion control in conditioning the boiler feed water). Alkalini3ty of
water is mainly caused by the presence of hydroxide ions (OH −), bicarbonate
ions (HCO3−), and carbonate ions (CO32−), or a mixture of two of these ions in
water. As stated in the following equation, the possibility of OH − and HCO3−
ions together are not possible because they react together to produce CO 32− ions:

OH− + HCO3− → CO32− + H2O

Alkalinity is determined by titration with a standard acid solution (H 2SO4 of

0.02N) using selective indicators (methyl orange or phenolphthalein). The high
levels of either acidity or alkalinity in water may be an indication of industrial
or chemical pollution. Alkalinity or acidity can also occur from natural sources
such as volcanoes. The acidity and alkalinity in natural waters provide a
buffering action that protects fish and other aquatic organisms from sudden
xxi
changes in pH. For instance, if an acidic chemical has somehow contaminated a
lake that had natural alkalinity, a neutralization reaction occurs between the acid
and alkaline substances; the pH of the lake water remains unchanged. For the
protection of aquatic life, the buffering capacity should be at least 20mg/L as
calcium carbonate. (Tchobanoglous et al., 2003)

2.5.2 Dissolved Oxygen

Dissolved oxygen (DO) is considered to be one of the most important

parameters of water quality in streams, rivers, and lakes. It is a key test of water
pollution. The higher the concentration of dissolved oxygen, the better the water
quality. Oxygen is slightly soluble in water and very sensitive to temperature.
For example, the saturation concentration at 20°C is about 9mg/L and at 0°C is
14.6mg/L. The actual amount of dissolved oxygen varies depending on
pressure, temperature, and salinity of the water. Dissolved oxygen has no direct
effect on public health, but drinking water with very little or no oxygen tastes
unpalatable to some people. There are three main methods used for measuring
dissolved oxygen concentrations: the colorimetric method quick and
inexpensive, the Winkler titration method traditional method, and the
electrometric method

2.5.3 Biochemical oxygen demand (BOD)

Bacteria and other microorganisms use organic substances for food. As they
metabolize organic material, they consume oxygen. The organics are broken
down into simpler compounds, such as CO 2 and H2O, and the microbes use the
energy released for growth and reproduction (Tchobanoglous, 2003). When this
process occurs in water, the oxygen consumed is the Dissolve Oxygen in the
water. If oxygen is not continuously replaced by natural or artificial means in
the water, the Dissolve Oxygen concentration will reduce as the microbes

xxii
decompose the organic materials. This need for oxygen is called the
biochemical oxygen demand (BOD). The more organic material there is in the
water, the higher the Biochemical Oxygen Demand used by the microbes will
be. Biochemical Oxygen Demand (BOD) is used as a measure of the power of
sewage; strong sewage has a high BOD and weak sewage has low BOD. The
complete decomposition of organic material by microorganisms takes time,
usually 20 d or more under ordinary circumstances. The quantity of oxygen
used in a specified volume of water to fully decompose or stabilize all
biodegradable organic substances is called the ultimate Biochemical Oxygen
Demand. Biological Oxygen Demand (BOD) is a function of time. At time = 0,
no oxygen will have been consumed and the BOD = 0. As each day goes by,
oxygen is used by the microbes and the BOD increases. Ultimately, the BODL
is reached and the organic materials are completely decomposed.

2.5.4 Total Suspended Solids (TSS)

Total Suspended Solids (TSS) is the dry-weight of suspended particles that are
not dissolved in a sample of water that can be trapped by a filter that is analyzed
using a filtration apparatus. It is a water quality parameter used to assess the
quality of a specimen of any type of water or water body, ocean water for
example, or wastewater after treatment in a wastewater treatment plant. TSS
values are expressed in (mg/l) (Michaud et al., 1994). The physicochemical
properties of water decide the quality of water and its biological diversity. The
changes in the physicochemical parameters tend to change those living
conditions, especially in the number, diversity and distribution of the biota of
that ecosystem. Fluctuations in physicochemical factor adversely affect the
organisms, limiting their production and interfering in the physiological
processes which reduce their ability to compete with other population within
the environment. The physicochemical analysis is the prime consideration to

xxiii
assess the quality of water for its best utilization like drinking, irrigation,
fisheries and industrial purposes and is helpful in understating the complex
processes and interactions between climatic and biological processes in the
water.

2.5.5 Water temperature

The natural water temperature plays a key role in the distribution of the species
also by its extreme levels and its diurnal or seasonal variations. It is an
important factor in the life of a river estuary. The normal elevation of this
setting is due to a direct input of heat from industries using water as refrigerant.

Temperature affects the body metabolic activities of any living organism

(Murhekar, 2011). It also plays a vital role in the control of the solubility of
gases in water (Nirmala et al., 2012).

Effluents contamination in water increases temperature and reduces the

dissolved oxygen in water (Murhekar, 2011). It is measure in Celsius (oC).

We must remember that the three factors that control aquatic environments in
general are on the one hand, the illumination, on the other hand temperature and
depth. Indeed, if the illumination conditions in the first place the plant and
animal life, the temperature adjusts the diffusion of gases (O 2 and CO2) in water
and subsequently influences the process of photosynthesis. Therefore, this
parameter must be known accurately for all samples studied.

2.5.7 Conductivity

Conductivity is a measure of water’s capability to pass electrical flow. This

ability is directly related to the concentration of ions in the water (Wetzel, R. G.
2001). The conductivity of water is an indicator of changes in the composition

xxiv
of materials and their overall concentrations. It is proportional to the quality of
dissolved ionizable salts.

These anion and cations in water also depends on mobility of the ions at a
particular temperature (Nirmalaet al., 2012). It is a measure of salinity that
greatly affects the taste of water and it shows the presence of dissolved ions.
High electrical conductivity is caused by higher ionizable salts in water (Jain &
Agarwal, 2012). It is measured in (ms cm-1).

2.5.6 Salinity

Salinity is the amount of salt dissolved in water or the concentration of

dissolved mineral salts present in water. This is the percentage of chloride in
water. Which distinguish normal seawater salinity of 35g/l of chlorides and
fresh waters that contain up to 5g/l. The salinity factor controls the distribution
of fauna, flora and minerals. The normal salinity water shelters stenohaline
forms (Brachiopods, crustaceans and lamellibranches). Brackish waters shelter
to some euryhaline organisms and freshwater shelters to freshwater organisms.
Perisalins environments where chlorides are very high, which makes them toxic
and therefore are not shelter any form of life.

Chlorides exist in all waters at concentrations very variables whose origin may
be a percolation through dirty areas, infiltration of seawater into groundwater
aquifers or deep, of human waste (urine), extractive industries (petroleum
industries, coal etc.) and especially the industries of salt (saline), of soda and
potash. Chlorides levels founded in brackish waters are generally 10 to 20mg/l
chloride ions but can reach a few grams per liter in contact with certain
geological formations. It is measured in parts per thousand (o/oo).

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2.6 Heavy metals

Heavy metals are natural elements characterized by their rather high atomic
mass and their high density. Although typically occurring in rather low
concentration, they can be found all through the crust of our planet. Some heavy
like copper, selenium or zinc are essential trace elements, with functions
indispensable for various biological processes also driving the entire human
metabolism. Physical and chemical characterization of heavy metals needs to be
treated with caution, as the metals involved are not always consistently defined.
As well as being relatively dense, heavy metals tend to be less reactive than
lighter metals and have far fewer soluble sulfides and hydroxides. While it is
relatively easy to distinguish a heavy metal such as tungsten from a lighter
metal such as sodium, a few heavy metals, such as zinc, mercury, and lead, have
some of the characteristics of lighter metals, and, lighter metals such as
beryllium, scandium, and titanium, have some of the characteristics of heavier
metals. (Baldwin and Marshall 2000).

2.7 Sources of Heavy Metals

 Natural Sources of Heavy Metals

Their natural sources in the environment include weathering of metal-

containing rocks and volcanic eruptions, while principal anthropogenic sources
include industrial emissions, mining, smelting, and agricultural activities like
application of pesticides and phosphate fertilizers. Combustion of fossil fuels
also contributes to the release of heavy metals such as cadmium (Cd) to the
environment (Spiegel, 2002). Heavy metals are persistent in the environment,
contaminate the food chains, and cause different health problems due to their
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toxicity. Chronic exposure to heavy metals in the environment is a real threat to
living organisms (Wieczorek-Dąbrowska, et al., 2013).

 Anthropogenic Sources

Heavy metals mainly enter aquatic environments as a result of a variety of

human activities (e.g., agriculture, combustion, corroded underground pipes,
industrial plants, sewage, smelting, and vehicles) (Rajeshkumar, 2018). The
anthropogenic sources of heavy metals in the environment include mining and
industrial and agricultural activities. These metals (heavy metals) are released
during mining and extraction of different elements from their respective ores.
Heavy metals released to the atmosphere during mining, smelting, and other
industrial processes return to the land through dry and wet deposition.
Discharge of wastewaters such as industrial effluents and domestic sewage add
heavy metals to the environment. Exposure to heavy metals has been linked to
various negative health effects, including cancer, behavioral problems,
impaired intelligence, developmental problems, kidney damage, and
miscarriage or stillbirth (Alomary and Belhadj, 2007). Heavy metals are not
readily degraded in the environment, and those that enter a water body can
remain there for some time. They are usually found in low concentrations in
aquatic systems, (Guo and He, 2013) and high concentrations of heavy metals
in sediments can indicate anthropogenic rather than natural sources. (Tylmann,
et al., 2011).

2.8 Basic Parameters for Heavy Metals Are:

 Lead (Pb)
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Lead is a metal belonging to a group IV and period 6 of the periodic table with
atomic number 82, atomic mass 207.2, density 11.4gcm -3, melting point
327.40C, and boiling point 17250C. Lead is also harmful in environmental
pollutant which has high toxic effects to many body organs. Even though lead
can be absorbed from the skin, it is mostly absorbed from respiratory and
digestive systems. Lead exposure can induce neurological, respiratory, urinary,
and cardiovascular disorders due to immune-modulation, oxidative, and
inflammatory mechanisms. Furthermore, lead (Pb) could disturb the balance of
the oxidant–antioxidant system and induce inflammatory responses in various
organs. Exposure to lead can produce alteration in physiological functions of the
body and is associated with many diseases (Joseph et al., 2005; Jacobs et al.,
2009; Kianoush et al., 2012). Lead is highly toxic which has adverse effects on
the neurological, biological, and cognitive functions in the bodies. The
international level-of-concern for lead poisoning is 10 μg/dl in the blood (Burki,
2012; Kianoush et al., 2013). Adulteration of opium with lead has been
considered as a threat to human health in recent years (Kianoush et al., 2015).

 Mercury (Hg)

Mercury (Hg) is found in air, water, and soil and exists in three forms:
elemental or metallic mercury (Hg0), inorganic mercury (Hg+, Hg2+), and
organic mercury (commonly methyl or ethyl mercury) (Li R. et al., 2017).
Elemental mercury is liquid at room temperature and can be readily evaporated
to produce vapor. Mercury vapor is more hazardous than the liquid form.
Container breakage causes Hg0 spills and inhaling large amounts of Hg vapor
can be fatal. Organic mercury compounds such as methyl mercury (Me-Hg) or
ethyl mercury (Et-Hg) are more toxic than the inorganic compounds. The order
of increasing toxicity related to different forms of mercury is defined as Hg 0 <
Hg2+, Hg+ < CH3-Hg (Kungolos et al., 1999). Mercury compounds have many
xxviii
applications in mining for example extraction of gold and some industrial
processes. In lamp producing factories, Hg is used in the production of
fluorescent light bulbs. Me-Hg and Et-Hg have been used as fungicides to
protect plants against infections. Moreover, mercury has had medicinal uses in
the past, but such drugs have been replaced by safer pharmaceutical medicines.

 Arsenic

Arsenic is a metalloid in group VA and period 4 of the periodic table that occurs
in a wide variety of minerals, mainly as A S2O3 and can be recovered from
processing of ores containing mostly Cu, Pb, Zn, Ag and Au. It is also present
in ashes from coal combustion. Arsenic has the following properties: atomic
number 33, atomic mass 75, density 5.72gcm -3 melting point 8170C and boiling
point 6130C, and exhibits fairly complex chemistry and can be present in
several oxidation states (-III, 0, III, V) (Smith, and Means, 1995). In aerobic
environments, As (V) is dominant, usually in the form of arsenate (AsO4 3-) in
various protonation states: H3AsO4 , H3AsO4- , HAsO42- and AsO4. Arsenate and
other anionic forms of arsenic behave as chelates and can precipitate when
metal cations are present. Many as compounds adsorb strongly to soils and are
therefore transported only short distances in groundwater and surface water.
Arsenic is Associated with skin damage, increased risk of cancer, and problems
with circulatory system (scragg, 2001) .

 Iron

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Iron is an abundant element in marine sedimentary system, it exist in two forms
soluble ferrous iron and insoluble ferric particulate iron. In most aquaculture
system, there will be a high oxygen concentration, and all iron present in the
water will be in the form of insoluble ferric fe 3+. Ferric iron as a chemical non -
toxic, however this doesn’t mean to say that it does not exert a pathological
response.

 Nickel

Nickel, a known heavy metal is found at very low levels in the environment.
Nickel is available in all soil types and meteorites and also erupts from volcanic
emissions. In the environment, nickel is principally bound with oxygen or sulfur
and forms oxides or sulfides in earth crust. The vast industrial use of nickel
during its production, recycling and disposal has led to widespread
environmental pollution. Nickel is discharged into the atmosphere either by
nickel mining or by various industrial processes, such as power plants or
incinerators, rubber and plastic industries, nickel-cadmium battery industries
and electroplating industries. The extensive use of nickel in various industries or
its occupational exposure is definitely a matter of serious impact on human
health. Heavy metals like nickel can produce free radicals from diatomic
molecule through the double step process and generate superoxide anion.
Further, these superoxide anions come together with protons and facilitate
disputations to form hydrogen peroxide, which is the most important reason
behind the nickel-induced pathophysiological changes in living system (Kusal,
et al., 2018).

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 Vanadium

Vanadium is a chemical element with the symbol V and atomic number 23. It is
a hard, silvery-grey, malleable transition metal. The elemental metal is rarely
found in nature, but once isolated artificially, the formation of an oxide layer
(passivation) somewhat stabilizes the free metal against further oxidation.
Vanadium is an average-hard, ductile, steel-blue metal. It is electrically
conductive and thermally insulating. Some sources describe vanadium as "soft",
perhaps because it is ductile, malleable, and not brittle. Vanadium is harder than
most metals and steels. It has good resistance to corrosion and it is stable
against alkalis and sulfuric and hydrochloric acids. It is oxidized in air at about
933 K (660 °C, 1220 °F), although an oxide passivation layer forms even at
room temperature.

 Phosphate

Phosphate rock is a source of heavy metal pollution of air, soil, water, food
chain etc, therefore requires removal of heavy metals from the rock prior to its
use. Phosphate rock belongs mainly to sedimentary, slightly too igneous, and
negligibly to metamorphic rocks. It is used for the production of phosphorous
based fertilizers, acids, detergents and many products of common use. The rock
is mainly composed of phosphorous and minutely of many other elements. As a
non-renewable resource, phosphorus (P) is the second most important
macronutrient for plant growth and nutrition. Demand of phosphorus
application in the agricultural production is increasing fast throughout the globe.
(Chandra and Kulshreshtha 2004). The bioavailability of phosphorus is
distinctively low due to its slow diffusion and high fixation in soils which make
phosphorus a key limiting factor for crop production. Applications of
xxxi
phosphorus-based fertilizers improve the soil fertility and agriculture yield but
at the same time concerns over a number of factors that lead to environmental
damage need to be addressed properly. Phosphate rock mining leads to
reallocation and exposure of several heavy metals and radionuclides in crop
fields and water bodies throughout the world. Proper management of
phosphorus along with its fertilizers is required that may help the maximum
utilization by plants and minimum run-off and wastage (Ferner, 2010)

 Silicate

Silicate, or silicic acid (H4SiO4), is a very important nutrient in the ocean. Unlike
the other major nutrients such as phosphate, nitrate, or ammonium, which are
needed by almost all marine plankton, silicate is an essential chemical
requirement only for certain biota such as diatoms, radiolaria, silicoflagellates,
and siliceous sponges. The dissolved silicate in the ocean is converted by these
various plants and animals into particulate silica (SiO 2), which serves primarily
as structural material (i.e., the biota’s hard parts). The reason silicate cycling has
received significant scientific attention is that some researchers believe that
diatoms (one of the silica-secreting biota) are one of the dominant
phytoplankton responsible for export production from the surface ocean.

xxxii
 Nitrate

Nitrate is often regarded mainly as a water pollutant and its presence in the diet
of man is seen as an unfortunate consequence of the use of nitrogen fertilizers in
agriculture. Increasingly stringent regulations to limit nitrate intake suggest that
nitrate has wholly undesirable effects including formation of N-nitrosamines,
infantile methemoglobinemia, carcinogenesis, and possibly teratogenesis.
Nitrates are a set of compounds that involve nitrogen and oxygen molecules.
While they are often associated with cured meats, green, leafy vegetables are
actually much richer in nitrates. The nitrate content in waters is usually low but
can rise to appreciable levels in farming wastewater as a result of soil
fertilization. (McKnight et al., 2007).

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 CHAPTER THREE

3.0 MATERIALS AND METHOD

Iko River is located at Eastern Obolo Local Government Area Akwa Ibom
State, Nigeria. The area lies within latitude 4 0 33N and 40, 50’N 70 45’E - 70
55’E. About 650m sea level in the tropical mangrove forest belt east of the
Niger Delta between the lower Imo and Qua Iboe river estuaries. The tidal range
in the area is about 0.8m at neap tides and 2.0m during spring tide with little
fresh water input join by numerous tributaries as there empty into the Atlantic
Ocean (NEDECO 1961). The climate of the area is tropical with distinct rainy
(April to October) and dry seasons (October to May) with a high annual rainfall
averaging about 2500mm (AKUTEC Report 2006; Gibo 1998). The area is
characterized by an extensive mangrove swamp with inter-tidal mud flats
influenced by the semi diurnal tidal regime of the estuary. Fishing and farming
are the main economic activities in this study area. Oil palm (Elaesis guineen)
and coconut palm (Cocoa nueifera) are also widely distributed in the
surrounding villages.

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Figure 1: Map of Eastern Obolo estuary showing sampling stations

(Inset: Location of site in southeast Nigeria; Source: Google Earth)

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3.1 Description of Study Site

Coastal Water of Eastern Obolo drains into Altantic Ocean and is connected to
Qua Iboe River Estuary at the East and Imo River Estuary at the West. It is
located at 40 33’N-4050;N; 70 45’E-7 055;E and about 650m above the sea level
in the tropical mangrove forest belt east of the Niger Delta, The tidal regime
here in semidiurnal and has a range of about 0.8m at neap tides and 2.20m
during spring tides with little fresh water input joined by numerous tributaries
(NEDECO 1961). Eastern Obolo is an area blessed with many communities
with diver socio-economic activities such as artisanal fishing, timbering and
boat transport. The water is fringed with diversity of flora such as Avicennia
Africana and Nypa fruticans that is normally found during wet season. Oil palm
and coconut palm are also widely distributed in the villages. The area is also an
oil-producing area with several oil exploration wells but there is no oil
exploration going on, and many fisheries. Nypa fruticans and red mangrove are
the dominant species of flora. The area is characterized by a lot of creeks and
with and extensive mudflat at Iko creek and others dotted all over the
environment. (May to October) and wet (April to October) with an annual
rainfall averaging about 2500mm (AKUTEC Report, 2006).

3.2 Sample Collection

The water samples will be collected from Iko River in Eastern Obolo, at three
different stations. The sampling stations are: Station 1: Upstream (IKO),
Station 2: Midstream (UTI IKO), Station 3: Downstream (BELLA). Using
three plastic bottles for the sample collection. The sampling plastic bottles will
be washed using distilled water to avoid any contaminant. The plastic bottle will
be covered properly to prevent air entering. The water sample will be labelled
xxxvi
accordingly and transported immediately after collection from the site to the
laboratory for analysis.

3.3 LABORATORY PREPARATION:

3.4 SAMPLE ANALYSIS

The samples will be analyzed with in-situ to record the Total Suspended Solid
(TSS), Biochemical Oxygen Demand (BOD), Turbidity, Dissolved Oxygen
(DO), pH, Total Alkalinity, Silicate, Nitrate, Phosphate, Salinity and water
temperature using thermometer, refractometer and Multimeter .The method
source is from American Society for testing and material (ASTM, 2010),
American public health Association(APHA,1998) and world health
organization (WHO,1978).

3.4 Data Analysis

Data analyses will be done using descriptive statistics. Two-tailed correlation

coefficient (r) was used to determine the relationships existing between the
physico-chemical parameters of the water and plankton and benthic macro-
invertebrates’ abundance. Spatial variations in physico-chemical parameters,
plankton and benthic macro-invertebrates’ abundance were determined using
the one way Analysis of Variance (ANOVA). Seasonal variations were
determined using student’s t-test significance. Shannon-Wierner diversity index
and evenness were determined using PAST software (Hammer and Harper,
2005). The factor analysis procedures, using principal components analysis
(PCA) extraction method for data reduction was used to remove redundant
(highly correlated) physicochemical variables from the data file and replacing
the entire file with a smaller number of uncorrelated variables (factor), and to
further examine the underlying (or latent) relationships between the variables.
xxxvii
The magnitudes of the reign values and 75% (0.75) rules for variance
contribution were used for factor selection (Manly,1986).The cluster analysis
(CA) was used to explore and reveal natural groupings (or clusters) within the
plankton assemblages that would otherwise not be apparent.

CHAPTER FOUR

4.0 RESULTS

Table 4.1: shows the data gotten from the physico-chemical analysis taken at

the six sampling stations in Eastern Obolo

Atm Water
H TDS Turbidity DO Salinity
Sample P Temp Temp
(ppm) (NTU) (ppm) (ppm)
(oC) (oC)
Upstream
(SW1) 7.8 860 8.7 16.2 29 32 32,000
Midstream
(SW2) 7.8 860 9.2 15.9 29 33 31,000
Downstream
(SW3) 8.2 910 9.2 16 30 34 31,500

PH
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Figure 4.1 Column chart showing the PH level of salt water sample collected at

three different locations in Eastern Obolo.

Figure 4.2 Column chart showing the Turbidity level of salt water sample

collected at three different locations in Eastern Obolo.

xxxix
Figure 4.3 Column chart showing the TDS of salt water sample collected at

three different locations in Eastern Obolo

Figure 4.4 Column chart showing the Salinity level of salt water sample
collected at three different locations in Eastern Obolo

xl
 Figure 4.5 Column chart showing the Dissolved Oxygen level in the water
sample collected at three different locations in Eastern Obolo

Table 4.2: Concentration of heavy metals in upstream, midstream and

downstream in the water sample collected in Eastern Obolo
Sample As Fe Pb Hg Cd

Upstream
(SW1) 0.001 0.812 0.015 0.001 0 1.6 0.8 0.01

Midstream
(SW2) 0.001 0.68 0.021 0.001 0 1.4 0.6 0.01

Downstream
SW3 0.001 0.724 0.032 0.001 0 1.2 0.4 0.002

As – Arsenic; Fe – Iron; Pb – Lead; Hg – Mercury; Cd – Cadmium; -

Phosphate;

- Nitrate; – Silicate

xli
Table 4.3: World Health Organization (WHO), 2003: Maximum permissible
limits (mg/l)
Nickel 0.07
Mercury 1.0
Lead 0.05
Cadmium 0.006
Arsenic 0.01
Iron 100-300

xlii
 Figure 4.6 Column chart showing the concentration of heavy metals in
upstream, midstream and downstream in the water sample collected in Eastern
Obolo

Table 4.4: Summary of result

Grou Averag Scaled_Av Varianc STD
ps Count Sum e g e SD error

As 3 0.0030 0.0010 0.0007 0.0000 0.0000 0.0000

Fe 3 2.2160 0.7387 0.5276 0.0045 0.0672 0.0224

Pb 3 0.0680 0.0227 0.0162 0.0001 0.0086 0.0029

Hg 3 0.0030 0.0010 0.0007 0.0000 0.0000 0.0000

Cd 3 0.2340 0.0780 0.0557 0.0000 0.0040 0.0013

PO4 3 4.2000 1.4000 1.0000 0.0400 0.2000 0.0667

NO2 3 1.8000 0.6000 0.4286 0.0400 0.2000 0.0667

SiO3 3 0.0220 0.0073 0.0052 0.0000 0.0046 0.0015

Table 4.5: ANOVA - Single factor

Source of
Variation SS df MS F P-value F crit
Between
Groups 5.574 7.000 0.796 75.270 0.0000000000473 2.657
xliii
Within
Groups 0.169 16.000 0.011

Total 5.743 23
SS – Sum of squares; df – degree of freedom; MS – Mean squared; fcrit –
Fcritical

xliv
 DISCUSSION
The analysis suggests that there are differences in the levels of heavy metal
concentration in different location of the stream (upstream, midstream and
downstream) and this may be influenced by various factors such as human
activities, land use, or natural processes.

The concentrations of heavy metals in the water samples as shown in table 4.1,
were analyzed and measured in parts per million (ppm) or milligrams per liter
(mg/L). The table shows that the concentration of lead in the downstream
sample (SW3) is above the World Health Organization (WHO) recommended
limit of 0.01 mg/L for safe drinking water. Long-term exposure to lead can
cause serious health problems such as kidney damage, nervous system damage,
and developmental delays in children.

The concentration of arsenic, mercury, and cadmium in all three samples was
below the recommended limits for safe drinking water. However, it is worth
noting that exposure to even low levels of these heavy metals over a long period
of time can have adverse health effects, including damage to the central nervous
system, liver, and kidneys. The concentration of iron in all three samples was
above the recommended limit of 0.3 mg/L for safe drinking water according to
WHO. This is not unexpected, given that iron is a common mineral in the
geology of the area. While high levels of iron in drinking water are not
generally considered a health risk, they can cause aesthetic problems such as
discoloration and staining of clothing and fixtures.

The levels of phosphate and nitrate in all three samples were above the
recommended limits for safe drinking water set by the World Health
Organization (WHO). Excessive levels of these chemicals in drinking water can
cause health problems such as gastrointestinal illness, and can also lead to
environmental problems such as eutrophication of water bodies. The presence
xlv
of high levels of phosphate and nitrate in the water samples suggests that human
activities such as agriculture and domestic waste are contributing to pollution in
the river.

The results of the ANOVA (Analysis of Variance) in table 4.6, indicates that
there are significant differences in the mean concentrations of the analyzed
parameters between the three sampling locations in Iko River (upstream,
midstream, and downstream). The F-value for the between-groups variation is
75.27, which is much greater than the F-critical value of 2.657 at the 0.05
significance level. This indicates that there is a statistically significant
difference between the mean values of the analyzed parameters in the different
sampling locations. The P-value in this analysis is very small, which means that
the probability of obtaining such a large F-value by chance is very low. This
confirms that the differences in mean values between the sampling locations are
not due to random variation, but rather, are likely to be caused by differences in
environmental conditions or human activities in the different locations. Table
4.6 also shows that the largest source of variation in the data is between groups,
as indicated by the higher value of the sum of squares (SS) for between-groups
compared to within-groups. This suggests that the differences in mean values
between the sampling locations account for most of the variation in the data.

In conclusion, the results obtained in table 4.6 supports the conclusion that the
physico-chemical parameters analyzed in the Iko River vary significantly
between the different sampling locations, likely due to differences in
environmental conditions and human activities. The identification of such
differences in water quality is an important step towards developing effective
strategies to protect and improve the quality of water resources in the area.

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REFERENCES

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