LEVELS AND RISK ASSESSMENT OF HEAVY METALS IN TRAFFIC IMPACTED SOILS

IN NKPOLU PORTHARCOURT

BY

OLAYINKA TAMARAU-PREYE JESUTOSIN

UG/19/1461

A RESEARCH WORK SUBMITTED TO THE DEPARTMENT OF CHEMICAL

SCIENCES,FACULTY OF SCIENCES

NIGER DELTA UNIVERSITY,WILBERFORCE ISLAND, BAYELSA STATE NIGERIA

APRIL.,2024

DECLARATION

I, OLAYINKA TAMARAU-PREYE JESUTOSIN (UG/19/1461), declare that the work In this

project is my original work and has not been previously submitted elsewhere or in this
university for the award of degree.

Signature _____________

Date __________________

CERTIFICATION
This project was carried out by Olayinka Tamarau-preye Jesutosin (Ug/19/1461), under the
supervision of Dr Leizou Kaywood, in the department of chemical sciences, faculty of
science, Niger Delta University. Wilberforce Island, Bayelsa state, and has met the partial
requirements for the award of Bachelor of science degree in Pure and Applied Chemistry.

STUDENT: Olayinka Tamarau-preye Jesutosin.

____________ ____________

Signature. Date

SUPERVISOR: Dr. Leizou kaywood

_____________ _____________

Signature Date

HOD: Dr. Jackson Godwin

____________ ____________

Signature Date

EXTERNAL SUPERVISOR: ________________

_______________ _____________

Signature Date

ACKNOWLEDGEMENT

My humble appreciation goes to my project supervisor Dr. Leizou Kaywood for his support,
correction and direction in accomplishing this work, the Head of Department, Lecturers, non-
academic staff and my course mate in the department of chemical sciences especially
Omegbu Obikonichi Lucy for her assistance.

My heartfelt appreciation goes to my parents Mr and Mrs Olawale-Phils olayinka, my siblings

- Ife-Jesu, Iyanu-Jesu, Ayanfe-Jesu and Ore-Jesu Olayinka for there immense financial
support moral encouragement, motivation and continuous prayers.

DEDICATION
This work is dedicated to the almighty God for his guidance, protection, provision and grace
all through my journey in the university. My father Mr Olawale-Phils olayinka, my mother Mrs
Tamarauarekefa Olawale-Phils olayinka , and my siblings.

TABLE OF CONTENT:

1. Introduction
2. Literature review
3. Materials and methods
4. Results
5. Discussion
6. Conclusion
7. Reference

LIST OF TABLES

LIST OF FIGURES

Abstract

This study assesses heavy metals’ levels in soil. it examines potential health risks
from consumption of the vegetables. The samples of soils, water were randomly
collected, processed, and analyzed for heavy metals using Atomic Absorption
Spectrophotometry. The heavy metals’ levels in soil were in the order of Zn > Cu >
Cr > Mn. Among the vegetables.This study recommends regular monitoring of heavy
metals in soils and foodstuffs to prevent excessive accrual in food chain.

INTRODUCTION

1.1 BACKGROUND OF STUDY

Heavy metals are naturally occurring elements that have a high density at least 5 times
greater than water and are toxic to living organism at high concentrations (Duffus, 2002).
They include elements such as Chromium (Cr), Manganese (Mn), Lead (Pb), Zinc (Zn), and
Cadmium (Cd). Although heavy metals play essential roles in biological processes at trace
levels, anthropogenic activities such as industrial processes, mining, agriculture, and
urbanization have significantly increased their presence in the environment. These activities
contribute to the contamination of soils and pose potential risks to ecological systems and
human health (fergusson et al., 1998).
Heavy metals (HMs) are defined as those elements having an atomic number greater
−3
than 20 and atomic density above 5 g cm and must exhibit the properties of metal.
The Heavy metals can be broadly classified into two categories: essential and
nonessential heavy metals. Essential Heavy metals are those required by living
organisms for carrying out the fundamental processes like growth, metabolism, and
development of different organs. There are numerous essential heavy metals like Cu,
Fe, Mn, Co, Zn, and Ni required by plants as they form cofactors that are structurally
and functionally vital for enzymes and other proteins [40]. Essential elements are
often required in trace amounts in the level of 10–15 ppm and are known as
micronutrients. Nonessential heavy metals like Cd, Pb, Hg, Cr, and Al are not
required by plants, even in trace amounts, for any of the metabolic processes.

Open drainages are essential components of urban infrastructure, designed to manage

storm-water runoff and prevent flooding. However they can become sinks for heavy metals
accumulation due to deposition of various pollutants carried by runoff from surrounding
areas (Kellis et al., 2013).

Heavy metals in effluents are poorly soluble in water, and cannot be degraded; they tend to
accumulate in soils and subsequently in plants (Orodu et al., 2018). Understanding the
sources of heavy metal pollution, the extent of ecological contamination, and the associated
health risks in soils of open drainages is crucial for effective environmental management and
public health protection.

Disposal of waste and proper management of open drainages are crucial aspects of
maintaining a clean and healthy environment. This is because improper disposal of waste
and management of open drainages can lead to accumulation of certain toxic materials
which are very harmful to the human health.

The connection between waste disposals and open drainage system can never be over-
emphasized. This is because both solid, semi-solid and liquid waste are found in our present
open drainage system. This waste when not properly managed and treated or disposed of,
leave an indelible mark of toxicity in it’s wake.

As such for purpose of this study, electronic waste, municipal waste, industrial and Bio-
medical waste are of major concerns.

The need to checkmate this is paramount as these open drainages most often, are
channelled into larger water bodies. Also these heavy metals tend to be accumulated by
plants, which is a primary source in the food chain. So you see one way or the other
Humans will definitely be on the receiving Heavy metals are a group of metals and
metalloids that have relatively high density and are toxic even at ppb levels [16].
Examples include Pb, As, Hg, Cd, Zn, Ag, Cu, Fe, Cr, Ni, Pd, and Pt. These metals are
released into the environment by both natural and anthropogenic sources such as
industrial discharge, automobiles exhaust, and mining. Unlike organic pollutants,
heavy metals are nonbiodegradable and have tendency to accumulate in living
beings. In fact, most of them are known to be potential carcinogens. Various adverse
health hazards are known due to long term and continuous exposure to heavy metals.
Since they are nondegradable and tend to bioaccumulate, suitable methods need to
be established for their efficient removal from the environment. Guideline values for
some of the heavy metals are listed in Table 1.
Table 1.1. Guideline values of heavy metals (according to World Health
Organization)

Heavy Metal Guideline Value (mg L

−1
)

Antimony (Sb) 0.02

Arsenic (As) 0.01

Barium (Ba) 0.7

Cadmium (Cd) 0.003

Copper (Cu) 2

Chromium (Cr) 0.05

Lead (Pb) 0.01

Manganese (Mn) 0.4

Mercury (Hg) 0.006

Molybdenum (Mo) 0.07

Nickel (Ni) 0.07

Selenium (Se) 0.01

Uranium (U) 0.015

1.2 Aim and objective of the study

The primary aim and objective of this study are

1. To identify and quantify the concentrations of (Cr, Cu, Mn, Zn,) in soils of selected soil
samples located in nkpolu, port harcourt Riverstate.

2. To determine the potential sources of heavy metal in soil within Port harcourt through
source apportionment technique.

3. To access the ecological contamination level of heavy metals in soils within Nkpolu port
harcourt using standard environmental quality indices.

4. To evaluate the health risk posed by heavy metal exposure to residents consuming
vegetables contaminated.

CHAPTER TWO

LITERATURE REVIEW

2.1 Heavy metal in soils

Heavy metals are common pollutants in our environment. This statement was certified
correct when a research conducted on the assessment of harmful heavy metals in
contaminated soil in Liaoning province, China, showed heavy metals to be major pollutants
of the soil environment, rendering the area unsafe for agricultural purposes. (Haodong et al.,
2022)

Leizou et al (2018) conducted a research on heavy metals in water, sediments and Clam
and found traces of heavy metals in them although at a moderate state. Also research
conducted on penington river also showed traces of heavy metals at a moderate state
(Leizou et al., 2015).

Considering the fact that toxicity builds up with time, it is very important to not ignore the
monitoring of this heavy metal in our environs. Using the research on the auto mechanic
village as a case study, the research work showed that the heavy element researched at that
moment was relatively balanced and did not pose a treat to humans (Orodu et al., 2017).

All the above research except that of Liaoning province, when put together shows the
presence of heavy metals which did not pose any threat to humans.

Open drainages which serve as Urban channels for both waste and run-off water have
channels linked to our major rivers and creeks which houses most important aquatic food
chain. If there is danger of heavy metal toxicity in our open drainage system, then our rivers
and agricultural soils are not safe either. This itself becomes a threat not just for those living
in Port harcourt alone.
Soils may become contaminated by the accumulation of heavy metals and metalloids
through emissions from the rapidly expanding industrial areas, mine tailings, disposal of high
metal wastes, leaded gasoline and paints, land applica- tion of fertilizers, animal manures,
sewage sludge, pesticides, wastewater irrigation, coal combustion residues, spillage of
petrochemicals, and atmospheric deposition. Heavy metals constitute an ill-defined group of
inorganic chemical hazards, and those most commonly found at contaminated sites are lead
(Pb), chromium (Cr), arsenic (As), zinc (Zn), cadmium (Cd), copper (Cu), mercury (Hg), and
nickel (Ni) . Soils are the major sink for heavy metals released into the environment by
aforementioned anthropogenic activities and unlike organic contaminants which are oxidized
to carbon (IV) oxide by microbial action, most metals do not undergo microbial or chemical
degradation, and their total concentration in soils persists for a long time after their
introduction. Changes in their chemical forms (speciation) and bioavailability are, however,
possible. The presence of toxic metals in soil can severely inhibit the biodegradation of
organic contaminants . Heavy metal contamination of soil may pose risks and hazards to
humans and the ecosystem through: direct ingestion or contact with contaminated soil, the
food chain (soil-plant-human or soil-plant-animal- human), drinking of contaminated ground
water, reduction in food quality (safety and marketability) via phytotoxicity, reduction in land
usability for agricultural production causing food insecurity, and land tenure problems.

The adequate protection and restoration of soil ecosystems contaminated by heavy metals
require their characterization and remediation. Contemporary legislation respecting
environmental protection and public health, at both national and international levels, are
based on data that characterize chemical properties of environmental phenomena,
especially those that reside in our food chain. While soil characterization would provide an
insight into heavy metal speciation and bioavailability, attempt at remediation of heavy metal
contaminated soils would entail knowledge of the source of contamination, basic chemistry,
and environmental and associated health effects (risks) of these heavy metals. Risk
assessment is an effective scientific tool which enables decision makers to manage sites so
contaminated in a cost effective manner while preserving public and ecosystem health.

Immobilization, soil washing, and phytoremediation techniques are frequently listed among
the best demonstrated available technologies (BDATs) for remediation of heavy metal
contaminated sites.

In spite of their cost- effectiveness and environment friendliness, field applications of these
technologies have only been reported in developed countries. In most developing countries,
these are yet to become commercially available technologies possibly due to the inadequate
awareness of their inherent advantages and principles of operation. With greater awareness
by the governments and the public of the implications of contaminated soils on human and
animal health, there has been increasing interest amongst the scientific community in the
development of technologies to remediate contaminated sites. In developing countries with
great population density and scarce funds available for environmental restoration, low cost
and ecologically sustainable remedial options are required to restore contaminated lands so
as to reduce the associated risks, make the land resource available for agri- cultural
production, enhance food security, and scale down land tenure problems.

In this paper, scattered literature is utilized to review the possible sources of contamination,
basic chemistry, and the associated environmental and health risks of priority heavy metals
(Cr, Zn,Mn,Cu,) which can provide insight into heavy metal speciation, bioavailability, and
hence selection of appropriate remedial options.

2.2 Sources of heavy metals in soil.

Heavy metals occur naturally in the soil environment from the pedogenetic processes of weathering of
parent materials at levels that are regarded as trace (<1000mgkg−1) and rarely toxic. Due to the
disturbance and acceleration of nature’s slowly occurring geochemical cycle of metals by man, most
soils of rural and urban environments may accumulate one or more of the heavy metals above defined
background values high enough to cause risks to human health, plants, animals, ecosystems, or other
media.The heavy metals essentially become contaminants in the soil environments because (i) their
rates of generation via manmade cycles are more rapid relative to natural ones.

(ii) they become transferred from mines to random environmental locations where higher
potentials of direct exposure occur.

(iii) the concentrations of the metals in discarded products are relatively high compared to
those in the receiving environment.

(iv) the chemical form (species) in which a metal is found in the receiving environmental
system may render it more bioavailable.

A simple mass balance of the heavy metals in the soil can be expressed as follows:

Mtotal = Mp +Ma +Mf +Mag +Mow +Mip −(Mcr +Ml),

(1)

where “M” is the heavy metal, “p” is the parent material, “a” is the atmospheric deposition, “ f
” is the fertilizer sources, “ag” are the agrochemical sources, “ow” are the organic waste
sources, “ip” are other inorganic pollutants, “cr” is crop re- moval, and “l” is the losses by
leaching, volatilization, and so forth.

It is projected that the anthropogenic emission into the atmosphere, for several heavy
metals, is one-to-three orders of magnitude higher than natural fluxes [17]. Heavy metals in
the soil from anthropogenic sources tend to be more mobile, hence bioavailable than
pedogenic, or lithogenic ones [18, 19]. Metal-bearing solids at contaminated sites can
originate from a wide variety of anthropogenic sources in the form of metal mine tailings,
disposal of high metal wastes in improperly protected landfills, leaded gasoline and lead-
based paints, land application of fertilizer, animal manures, biosolids (sewage sludge),
compost, pesticides, coal combus- tion residues, petrochemicals, and atmospheric
deposition.

Heavy metals in the soil are derived from the soil parent (Lithogenic source) and various
anthropogenic sources, most of which involves several metals (Brian, 2018).

Soil serves as a major reservoir of contaminants as it can bind to various chemicals

(Maryam et al., 2015). Various anthropogenic activities including, industrial processes,
agricultural practices and urbanization are major sources of heavy metal pollution in the
environment. Reported sources of heavy metals in the environment include, geogenic,
industrial, agricultural, pharmaceutical, domestic effulents, and atmospheric sources (He et
al., 2005).

Previous studies have investigated the contribution of different activities to the release of
heavy metals into the soil and their subsequent transport into open drainages.
Understanding these sources is crucial for effective pollution control and management
strategies.
Table 1.0 shows various heavy metals and their source;

Heavy metals Common source

Copper (Cu) Fertilizers, tanning and photovoltaic cells

Chromium (Cr) Leather industry, tanning and chrome

plating industries

Zinc (Zn) Soldering, cosmetics and pigments

Manganese (Mn) Batteries, steel, electrode materials,

2.3 Health risk assessment

The most common heavy metals found at contaminated sites, in order of abundance are
[Cu, Cr, Zn, Mn]. Those metals are important since they are capable of decreasing crop
production due to the risk of bioaccumulation and biomagnification in the food chain. There’s
also the risk of superficial and groundwater contamination. Knowledge of the basic
chemistry, environmental, and associated health effects of these heavy metals is necessary
in understanding their speciation, bioavailability, and remedial options. The fate and
transport of a heavy metal in soil depends significantly on the chemical form and speciation
of the metal. Once in the soil, heavy metals are adsorbed by initial fast reactions (minutes,
hours), followed by slow adsorption reactions (days, years) and are, therefore, redistributed
into different chemical forms with varying bioavailability, mobility, and toxicity. This
distribution is believed to be controlled by reactions of heavy metals in soils such as;

(i) mineral precipitation and dissolution.

(ii) ion exchange, adsorption, and desorption.

(iii) aqueous complexation.

(iv) biological immobilization and mobilization.

(v) plant uptake

2.3.1 Chromium (Cr):Chromium is a first-row d-block transition metal of group VIB in the periodic
table with the follow- ing properties: atomic number 24, atomic mass 52, den- sity 7.19 g cm−3 ,
melting point 1875◦ C, and boiling point 2665◦C. It is one of the less common elements and does not
occur naturally in elemental form, but only in compounds. Chromium is mined as a primary ore
product in the form of the mineral chromite, FeCr2 O4 . Major sources of Cr- contamination include
releases from electroplating processes and the disposal of Cr containing wastes. Chromium(VI) is the
form of Cr commonly found at contaminated sites. Chromium can also occur in the +III oxidation
state, depending on pH and redox conditions. Chromium(VI) is the dominant form of Cr in shallow
aquifers where aerobic conditions exist. Chromium(VI) can be reduced to Cr(III) by soil organic
matter, S2− and Fe2+ ions under anaerobic conditions often encountered in deeper groundwater.
Major Cr(VI) species include chromate (CrO42−) and dichromate (Cr2 O7 2− ) which precipitate
readily in the presence of metal cations (especially Ba2+, Pb2+, and Ag+). Chromate and di-
chromate also adsorb on soil surfaces, especially iron and aluminum oxides. Chromium(III) is the
dominant form of Cr at low pH (<4). Cr3+ forms solution complexes with NH3, OH−, Cl−, F−, CN−,
SO42−, and soluble organic ligands. Chromium(VI) is the more toxic form of chromium and is also
more mobile. Chromium(III) mobility is decreased by adsorption to clays and oxide minerals below
pH 5 and low solubility above pH 5 due to the formation of Cr(OH)3(s) [50]. Chromium mobility
depends on sorption characteristics of the soil, including clay content, iron oxide content, and the
amount of organic matter present. Chromium can be transported by surface runoff to surface waters in
its soluble or precipitated form. Soluble and un-adsorbed chromium complexes can leach from soil
into groundwater. The leachability of Cr(VI) increases as soil pH increases. Most of Cr released into
natural waters is particle associated, however, and is ultimately deposited into the sediment [39].
Chromium is associated with allergic dermatitis in humans.

2.3.2 Manganese (Mn):

Manganese as a cofactor of multiple enzymes, exhibits great significance to the human

body, plants and animals. It is also a critical raw material and alloying element. However it’s
extensive use for industrial purposes leads to it’s excessive emission into the environment,
turning it into a significant threat to the ecosystem and public health (Rongrong et al., 2022).
Mn has been widely used in the production of non-ferrous metallurgy, steel, batteries,
electrodes materials and catalyst (Sihaib et al., 2017). The stacking of electrolytic
manganese residue (EMR) leads to the infiltration of leachate and has become the largest
source of Mn contamination in the soil (Zhang et al., 2018). Manganese (Mn) is an essential
plant mineral nutrient, playing a key role in several physiological processes, particularly
photosynthesis.

2.3.3 ZINC (Zn):

Zinc is a transition metal with the following characteristics: period 4, group IIB, atomic number 30,
atomic mass 65.4, density 7.14 g cm−3 , melting point 419.5◦ C, and boiling point 906◦C. Zinc occurs
naturally in soil (about 70 mg kg−1 in crustal rocks), but Zn concentrations are rising unnaturally, due
to anthropogenic addition. Most Zn is added during industrial activities, such as mining, coal, and
waste combustion and steel processing. Many foodstuffs contain certain concentrations of Zn.

Drinking water also contains certain amounts of Zn, which may be higher when it is stored in
metal tanks. Industrial sources or toxic waste sites may cause the concentrations of Zn in
drinking water to reach levels that can cause health problems. Zinc is a trace element that is
essential for human health. Zinc shortages can cause birth defects. The world’s Zn
production is still on the rise which means that more and more Zn ends up in the
environment.

Water is polluted with Zn, due to the presence of large quantities present in the wastewater
of industrial plants. A consequence is that Zn polluted sludge is continually being deposited
by rivers on their banks. Zinc may also increase the acidity of waters. Some fish can
accumulate Zn in their bodies, when they live in Zn contaminated waterways. When Zn
enters the bodies of these fish, it is able to biomagnify up the food chain. Water soluble zinc
that is located in soils can contaminate groundwater.

Plants often have a Zn uptake that their systems cannot handle, due to the accumulation of
Zn in soils. Finally, Zn can interrupt the activity in soils, as it negatively influences the activity
of microorganisms and earthworms, thus retarding the breakdown of organic matter.

2.3.4 Copper (Cu):

Copper is a transition metal which belongs to period 4 and group IB of the periodic table with atomic
number 29, atomic weight 63.5, density 8.96 g cm−3 , melting point 1083◦ C and boiling point 2595◦
C. The metal’s average density and concentrations in crustal rocks are 8.1 × 103 kg m−3 and 55 mg
kg−1 , respectively.

Copper is the third most used metal in the world. Copper is an essential micronutrient
required in the growth of both plants and animals. In humans, it helps in the production of
blood haemoglobin. In plants, Cu is especially important in seed production, disease
resistance, and regulation of water. Copper is indeed essential, but in high doses it can
cause anaemia, liver and kidney damage, and stomach and intestinal irritation. Copper
normally occurs in drinking water from pipes, as well as from additives designed to control
algal growth. While Cu’s interaction with the environment is complex, research shows that
most Cu introduced into the environment is, or rapidly becomes, stable and results in a form
which does not pose a risk to the environment. In fact, unlike some manmade materials, Cu
is not magnified in the body or bioaccumulated in the food chain.

In the soil, Cu strongly complexes to the organic implying that only a small fraction of copper
will be found in solution as ionic copper, Cu(II).

The solubility of Cu is drastically increased at pH 5.5, which is rather close to the ideal
farmland pH of 6.0–6.5 [57].

Copper and Zn are two important essential elements for plants, microorganisms, animals,
and humans. The connection between soil and water contamination and metal uptake by
plants is determined by many chemical and physical soil factors as well as the physiological
properties of the crops. Soils contaminated with trace metals may pose both direct and
indirect threats: direct, through negative effects of metals on crop growth and yield, and
indirect, by entering the human food chain with a potentially negative impact on human
health. Even a reduction of crop yield by a few percent could lead to a significant long-term
loss in production and income. Some food importers are now specifying acceptable
maximum contents of metals in food, which might limit the possibility for the farmers to
export their contaminated crops.

3.1 Remediation of Heavy Metal-Contaminated Soils:

The overall objective of any soil remediation approach is to create a final solution that is
protective of human health and the environment [66]. Remediation is generally subject to an
array of regulatory requirements and can also be based on assessments of human health
and ecological risks where no legislated standards exist or where standards are advisory.
The regulatory authorities will normally accept remediation strategies that centre on reducing
metal bioavailability only if reduced bioavailability is equated with reduced risk, and if the
bioavailability reductions are demonstrated to be long term.
For heavy metal-contaminated soils, the physical and chemical form of the heavy metal
contaminant in soil strongly influences the selection of the appropriate remediation treatment
approach. Information about the physical

Table 1: Soil concentration ranges and regulatory guidelines for some heavy metals.

Metal

Pb Cd Cr Hg Zn

Soil concentration range† (mg kg−1 ) 1.00–69 000 0.10–345

0.05–3 950 <0.01–1 800 150–5 000

Regulatory limits‡ (mg kg−1 ) 600

100

100

270

1 500

† [64]; ‡ Nonresidential direct contact soil clean-up criteria [65].

Table 2: Target and intervention values for some metals for a stan-

dard soil [60]. Metal

Target value (mg kg−1) 140.00 0.30

Intervention value (mg kg−1) 720.00 10.00

Ni

Cu

Zn — —

Cd 100.00

Pb 35.00

As 200 625 Cr 20 240 Hg 85 530

characteristics of the site and the type and level of contamination at the site must be
obtained to enable accurate assessment of site contamination and remedial alternatives.
The contamination in the soil should be characterized to establish the type, amount, and
distribution of heavy metals in the soil. Once the site has been characterized, the desired
level of each metal in soil must be determined. This is done by comparison of observed
heavy metal concentrations with soil quality standards for a particular regulatory domain, or
by performance of a site-specific risk assessment. Remediation goals for heavy metals may
be set as total metal concentration or as leachable metal in soil, or as some combination of
these.
Several technologies exist for the remediation of metal- contaminated soil. [Gupta et al.]
have classified remediation technologies of contaminated soils into three categories of
hazard alleviating measures:

(i) gentle in situ remediation.

(ii) in situ harsh soil restrictive measures.

(iii) in situ or ex situ harsh soil destructive measures.

The goal of the last two harsh alleviating measures is to avert hazards either to man, plant,
or animal while the main goal of gentle in situ remediation is to restore the malfunctionality of
soil (soil fertility), which allows a safe use of the soil.

At present, a variety of approaches have been suggested for remediating contaminated

soils. USEPA has broadly classified remediation technologies for contaminated soils into

(i) source control

(ii) containment remedies.

(i) Source control: involves in situ and ex situ treatment technologies for sources of
contamination. In situ or in place means that the contaminated soil is treated in its original
place; unmoved, unexcavated; remaining at the site or in the subsurface.In situ treatment
technologies treats or removes the contaminants from the soil without excavation or removal
of the soil.

Ex situ means that the contaminated soil is moved, excavated, or removed from the site or
subsurface. Implementation of ex situ remedies requires excavation or removal of the
contam- inated soil. Containment remedies involve the from soil without excavation or
removal of the soil. Ex situ means that the contaminated soil is moved, excavated, or
removed from the site or subsurface. Implementation of ex situ remedies requires excavation
or removal of the contaminated soil.

Containment remedies involve the construction of vertical engineered barriers (VEB), caps,
and liners used to prevent the migration of contaminants.

Another classification places remediation technologies for heavy metal contaminated soils
under five categories of general approaches to remediation: isolation, immobilization, toxicity
reduction, physical separation, and extraction. The key factors that may influence the
applicability and selection of any of the available remediation technologies are: (i) cost, (ii)
long-term effective- ness/permanence, (iii) commercial availability, (iv) general acceptance,
(v) applicability to high metal concentrations, (vi) applicability to mixed wastes (heavy metals
and organ- ics), (vii) toxicity reduction, (viii) mobility reduction, and (ix) volume reduction.
The present paper focuses on soil washing, phytoremediation, and immobilization
techniques since they are among the best demonstrated available technologies (BDATs) for
heavy metal-contaminated sites.

CHAPTER 3

MATERIALS AND METHODS

MATERIALS:

Apparatus: 250ml conical flask,250ml beaker,100ml beaker, 100ml volumetric flask,

electronic weighing balance, fume cupboard, hand gloves, whatman 125 mm filter
paper,nose mask.

Reagents: Aqua ragia (3:1 v/v of Nitric acid(HNO3) and Hydrochloric acid (Hcl), and Distilled
water(H2O).

3.1 STUDY AREA

3.2 SAMPLE COLLECTION

3.3 SAMPLE PREPARATION

1. soil samples was collected from soils of the three different locations and put into three
different sample bottles.

2. The sample was mixed to achieve homogenity and then air dryed them by spreading them
on a tray and leaving them out in the open.

3. When dry, the samples was sieved through a sieve to remove large debris and stones.

1. About 5g of each sample was weighed into the dry digesting tube. 5ml of conc. Aqua
regia was added in the ratio and stirred. The digestion tube is placed on the water
bath set at 100֯ C to boil for 2 hours. To avoid caking, the sample was shaken
vigorously and the resulting solution is referred to as the stock solution. The stock
solution is filtered and make up to 100ml with distilled water. The stock solution was
used directly to determine the elements.
2. The samples was then bottled, labelled and sent for further analysis.

CHAPTER FOUR

RESULTS AND DISCUSSION

4.1 Chemical characteristics of Soil:

The environmental data are important to determine the degree of pollution and to interpret the

geochemical data. Table 4.1- 4.4 shows the heavy metal distribution values by station, while

Fig 4.1-4.4 shows the the graphically representation. The average abundance of metals

(mg/kg) was in the following order: Zn> Cu>Mn>Cr. The highest occurring heavy metal was

Cu found in all stations. Comparison of metal concentrations in the sewage sluge with

background values showed that the the studied heavy metals were within permissible limits.

These results are concomitant to those reported by Leizou et al., 20215.

 Table 4.1 descriptive statistic of heavy metals in soils, MSS

N Range Minimum Maximum Mean Std. Deviation Variance

Statistic Statistic Statistic Statistic Statistic Std. Error Statistic Statistic

HEAVY METALS 3 .22 3.03 3.25 3.1100 .07024 .12166 .015

MANGANESE 3 .02 .04 .06 .0500 .00577 .01000 .000
COPPER 3 1.12 2.15 3.27 2.5533 .35927 .62228 .387
CHROMIUM 2 .12 .42 .54 .4800 .06000 .08485 .007
Valid N (listwise) 2

Table 4.2 descriptive statistic of heavy metals in soils, MWS

N Range Minimum Maximum Mean Std. Deviation Variance

Statistic Statistic Statistic Statistic Statistic Std. Error Statistic Statistic

HEAVY METALS 3 1.30 2.25 3.55 2.9100 .37541 .65023 .423

MANGANESE 3 .69 .06 .75 .3800 .20075 .34771 .121
COPPER 3 .82 2.75 3.57 3.0533 .25964 .44970 .202
CHROMIUM 3 .32 .32 .64 .4867 .09262 .16042 .026
Valid N (listwise) 3

Table 4.3 descriptive statistic of heavy metals in soils, VFS

N Range Minimum Maximum Mean Std. Deviation Variance

Statistic Statistic Statistic Statistic Statistic Std. Error Statistic Statistic

HEAVY METALS 3 .92 2.73 3.65 3.0767 .28875 .50013 .250

MANGANESE 3 .04 .62 .66 .6433 .01202 .02082 .000
COPPER 3 .92 2.85 3.77 3.1867 .29282 .50718 .257
CHROMIUM 2 .08 .44 .52 .4800 .04000 .05657 .003
Valid N (listwise) 2

Heavy metals MSS MWS VFS

ZINC 3.11±0.12 2.91±0.65 3.08±0.50
MANGANESE 0.05±0.01 0.38±0.34 0.64±0.02
COPPER 2.55±0.02 3.05±0.44 3.19±0.50
CHROMIUM 0.48±0.0.08 0.48±0.16 0.48±0.05

Table 4.4. Concentrations of heavy metal (mg/kg) in soil

 s

Fig. 4.1 The distribution of heavy metals mg/kg in soils

Fig. 4.2 The distribution of heavy metals mg/kg in soils

 Fig. 4.3 The distribution of heavy metals mg/kg in soils

Fig. 4.4 The distribution of heavy metals mg/kg in soils

4.2 Assessment of metal contamination

In this study, single pollution induces such as, contamination factor (CF), pollution load

index (PLI) and Geo-accumulation Index (Igeo), were employed to assess heavy metal

contamination in sediments of Kolo creek.. Comparison of metal concentration is a quick and

practical method for detecting heavy metal contamination and ecological risk. In comparison
to documented studies, it was observed that the levels of heavy metals in the Kolo creek

were lower.

4.2.1 Contamination Factor (Cf)

Table 4.5: Contamination factor(Cf) of soils

HM MSS MWS VFS

ZN A 0.063509 0.061413 0.057221
B 0.06812 0.04716 0.059736
C 0.063928 0.074408 0.076504
MN A 4.71E-05 0.000388 0.000729
B 5.88E-05 0.000882 0.000765
C 7.06E-05 7.06E-05 0.000776
CU A 0.121813 0.155807 0.161473
B 0.185269 0.202266 0.213598
C 0.126912 0.160907 0.166572
CR A 0.008312 0.006333 0.010291
B 0.010687 0.012666 0.008708
C 0.00851 0.009895 0.011874

CF value is the index used to evaluate the metal source and is listed in descending order as

follows: Zn> Cu> Mn> Cr. According to the CF values, the elements Zn Cu, Mn and Cr

showed low contamination

4.2.2 The Geo-accumulation index (Igeo

The Geo-accumulation index (Igeo), introduced by Muller (1979) for determining the extent

of metal accumulation in sediments, and has been used byvarious workers in their studies

(Sagheer, 2013; Leizou et al., 2015) etc.

Where, Cn is the concentration of element ‘n’

Bn is the geochemical background value of the metal (n).

1.5 is the background matrix correction factor due to lithogenic effects.

The geoaccumulation index (Igeo) scale consists of seven grades (0-6) ranging from

practically to extremely contaminated. The contamination state of the soil was determined by

the Geo-accumulation index "Igeo ( Müller (1981) All of these metals remained as

background levels in the sediment of the study area.

Table 4.6 The Igeo values of heavy metals in soils

HM MSS MWS VFS

ZN A 0.012744 0.012323 0.011482
B 0.013669 0.009463 0.011987
C 0.012828 0.014931 0.015352
MN A 9.44E-06 7.79E-05 0.000146
B 1.18E-05 0.000177 0.000153
C 1.42E-05 1.42E-05 0.000156
CU A 0.024444 0.031265 0.032402
B 0.037177 0.040588 0.042862
C 0.025467 0.032289 0.033425
CR A 0.001668 0.001271 0.002065
B 0.002144 0.002542 0.001747
C 0.001708 0.001986 0.002383

4.3 Human Health Risk Assessment: noncarcinogenic heavy metal risk

The health risk of Zn, Cu, Mn, and Cr to induce non-carcinogenic diseases via ingestion,
inhalation, and dermal contact was calculated for adults (Table 4.7-4.9).
 Table 4.7: Non-narcinogenic risk Assessment of Heavy metals in sewage sluge, MSS
Heavy metals location ADIingestion ADIinhalation ADIdermal HQ
Zn MSSA 4.33 6.36X10-10 2.86X10-8 9.33X10-8
MSS B 4.64 6.83X10-10 3.06X10-8 1.02X10-7
MSS C 4.36 6.41X10-10 2.87X10-8 9.57X10-8
Mn MSSA 0.06 8.40X10-12 3.77X10-10 2.64X10-7
MSSB 0.07 1.05X10-11 4.71X10-10 3.29X10-7
MSSC 0.08 1.26X10-11 5.66X10-10 3.96X10-7
Cu MSSA 3.07 4.52X10-10 2.02X10-8 5.05X10-7
MSSB 4.67 6.87X10-10 3.08X10-8 7.7X10-7
MSSC 3.2 4.70X10-10 2.11X10-8 5.28X10-7
Cr MSSA 0.6 8.82X10-11 3.96X10-9 1.05X10-4
MSSB 0.77 1.13X10-10 5.09X10-9 2.11X10-4
MSSC 0.61 9.03X10-11 4.05X10-9 1.65X10-4

Table 4.8: Non-narcinogenic risk Assessment of Heavy metals in sewage sluge, MWS
Heavy metals location ADIingestion ADIinhalation ADIdermal HQ
Zn MWSA 4.18 6.15X10-10 2.76X10-8 9.2X10-8
MWS B 3.21 4.73X10-10 2.12X10-8 7.07X10-8
MWS C 5.07 7.46X10-10 3.35X10-8 1.12X10-7
Mn MWSA 0.47 6.93X10-11 3.11X10-9 2.17X10-6
MWSB 1.07 1.57X10-10 7.07X10-9 4.94X10-6
MWSC 0.08 1.26X10-11 5.66X10-10 3.96X10-7
Cu MWSA 3.93 5.78X10-10 2.59X10-8 6.47X10-7
MWSB 5.1 7.5X10-10 3.37X10-8 8.42X10-7
MWSC 4.06 5.97X10-10 2.68X10-8 6.7X10-7
Cr MWSA 0.46 6.72X10-11 3.02X10-9 1.05X10-4
MWSB 0.91 1.34X10-10 6.03X10-9 2.11X10-4
MWSC 0.71 1.05X10-10 4.71X10-9 1.65X10-4

Table 4.9: Non-narcinogenic risk Assessment of Heavy metals in sewage sluge, VFS

Heavy metals location ADIingestion ADIinhalation ADIdermal HQ

Zn VFS A 3.9 5.73X10-10 2.57X10-8 8.57X10-8
VFS B 4.07 5.99X10-10 2.69X10-8 8.97X10-8
VFS C 5.21 7.67X10-10 3.44X10-8 1.15X10-7
Mn VFS A 0.89 1.30X10-10 5.84X10-9 4.08X10-6
 VFS B 0.93 1.36X10-10 6.13X10-9 4.29X10-6
VFS C 0.94 1.39X10-10 S6.22X10-9 4.35X10-6
Cu VFS A 4.07 5.99X10-10 2.69X10-8 6.72X10-7
VFS B 5.38 7.92X10-10 3.55X10-8 8.87X10-7
VFS C 4.2 6.18X10-10 2.77X10-8 6.92X10-7
Cr VFS A 0.74 1.09X10-10 4.90X10-9 1.71X10-4
VFS B 0.63 9.24X10-11 4.15X10-9 1.45X10-4
VFS C 0.86 1.26X10-10 5.66X10-9 1.98X10-4

The HQ values of the study in the pathways was maximum at the range of 4.07 x 10-7 to 7.61

x 10-4 for all metals. HQ MSS range from 2.88 x 10 -7 to 4.93 x 10-4, HQ MWS range from 2

.12 x 10-7 to 1.52 x 10-4 and HQ VFS (a range from 74.07 x 10 -7 to 7.51 x 10-4 respectively.

This result implies that the non-carcinogenic risk of diseases caused by the ingestion of all

heavy metals from the riverine sediment of the Kolo creek is much more low. These

observations are analogous to the findings of the studies conducted by (Varol, 2020; Ustaoğlu

& Islam, 2020). The HQ ranking of metals demonstrated the descending order of Zn > Cu>

Mn > Cr for the three exposure pathways (Varol, 2020; Ustaoğlu & Islam, 2020)..

References

Ustaoğlu, F., & Islam, M. S. (2020). Potential toxic elements in sediment of some rivers at
Giresun, Northeast Turkey: A preliminary assessment for ecotoxicological status and health
risk.
Ecol. Ind. 113, 106237

Varol, M. (2020). Environmental, ecological and health risks of trace metals in sediments of a
large reservoir on the Euphrates River (Turkey). Environ. Res. 187, 109664

CONCLUSION

This study has investigated the health risk of chromium (Cr), Manganese (Mn), Zinc (Zn) and

Copper (Cu) In contaminated soils from Nkpolu community, Riverstate Nigeria. The
concentration of Cr, Mn, Zn, Cu in this study were within the permissible limits of

WHO,FAO, USEPA.

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