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CHAPTER ONE

1.0

INTRODUCTION TO THE STUDY.


The dramatic increase in public awareness and concern about the state of the global

and local environments which has occurred in recent decades has been accompanied and
partly prompted by an ever growing body of evidence on the extent to which pollution has
caused severe environmental degradation. The introduction of harmful substances into the
environment has been shown to have many adverse effects on human health, agricultural
productivity and natural ecosystems. (Garbarino et al.,1995).
Heavy metals is a general collective term which applies to the group of metals and metalloids
with atomic density greater than 4 g/cm3 or 5 times or more, greater than water (Nriagu and
Pacyna,1988; Hawkes, 1997). Their pollution of the environment, even at low levels and the
resulting long term cumulative health effects are among the leading health concerns all over
the world. (Huton and Symon, 1986; Mc. Cluggage, 1991).
Metals constitute the largest class of elements in the periodic table. As a group, metals share
some common physical, chemical and electrical properties (DAmore et al., 2005). Metals are
hard and strong, capable of being shaped mechanically (malleable and ductile), are good
conductors of heat and electricity and they have lustrous surfaces when clean. They tend to
lose electrons and form cations.
Metals, a major category of globally distributed pollutants, are natural elements that have
been extracted from the earth and harnessed for human use. Metals are notable for their wide
environmental dispersion from various activities; their tendency to accumulate in select
tissues of the human body; and their overall potential to be toxic even at relatively minor
levels of exposure.

Soils along highways typically contain high amount of heavy metals such as Fe, Mn, Zn, Pb,
and Cd, most commonly from vehicle exhaust and wear of vehicle parts. Since these heavy
metals do not degrade naturally, accumulation of high concentration in soils can be toxic to
organisms living in surrounding environment (Purves, 1985). Metals are natural parts of the
eco-system occurring in soil, rock, water, air and organism. A few metals including Cu, Mn,
and Zn are essential to plant metabolism in trace amounts. It is only when metals are present
at excessive levels in bioavailable forms, that they become potentially toxic.
Heavy metal contamination of roadside soil has been of major concern regarding their
toxicity, persistence and non-degradability in the environment. Heavy metal contamination of
roadside soil usually derives from anthropogenic sources such as emissions from automobile
exhaust, waste incineration, land disposal of wastes, use of agricultural inputs, emissions
from industrial processes, and wet and/or dry atmospheric deposits (Alloway, 1995).

1.1

AIMS AND OBJECTIVES.

1.1.1

General aims.
The aims of this study is to investigate the chemical fractionation and distribution of

heavy metals in roadside soil samples obtained within the Iwo area and to establish the heavy
metal concentration levels within the study area.
1.1.2 Specific objectives.
To determine total Mn, Fe, Cd, Zn and Pb in street dusts and roadside soils samples,
To identify and quantify different Mn, Fe, Cd, Zn and Pb species in the samples using
modified Tessiers nine stage sequential extraction method,

To establish the spatial distribution of heavy metals around major roads within Iwo area of
Osun State, Nigeria.

1.2

JUSTIFICATION OF THE STUDY.


The town of Iwo is on the rise, the increase in banking system, higher institutions, and

generally the influx of different tribes of people into the small town has caused a sharp
increase in the amount of vehicles that goes into the town on a daily basis and therefore
leading to increased amount of heavy metals that pollute the environment and since they do
not degrade naturally, high concentration in the soils can become harmful to living organisms
in the environment.
The modified Tessiers method was used to determine the chemical fractionations of heavy
metals in roadside soil (Tessier et al., 1979). It is the best known and most widely used
sequential extraction procedure, hence its popularity. The method provides comprehensive
information on the interaction between different species of the metal and environmental
media such as road side soil, in order to be able to predict their environmental impact. It is
most likely that the chemical properties of soil and sediment play an important role in heavy
metal retention or removal from road side soil. The impact of these properties may vary
according to the nature of the roads. There was, therefore, a need to investigate the behaviour
of the heavy metals distribution from roads with different characteristics.

1.3

SCOPE OF THE STUDY.


The present study was aimed at assessing the heavy metal fractions and distribution of

roadside soil of some selected roads in Iwo. Spatial distribution would only be investigated;
traffic counts, temporal study and physico-chemical analysis would be considered in further
study.

CHAPTER TWO
2.0

LITERATURE REVIEW

2.1

ENVIRONMENTAL POLLUTION
Pollution is defined as the release of waste material or energy into land, water or air

that may cause detriment or lower the quality of life. Moreover, pollution can be defined as
the act of polluting or polluted state i.e. the state or condition of being polluted, meaning the
presence of pollutants in the environment (Encarta, 2009).
In the past, pollution used to be regarded as a local problem, close to where sources are
located. However, the industrialization of society, the explosion of the human population,
massive urbanization and the introduction and use of cars has caused growth in all spheres of
life. This growth has been coupled with an increase in waste by-products. Pollution has now
become a pandemic issue because pollutants can cross borders with the help of wind, water
and all other agents of pollution. Recently, results have shown that the harmful effects of
pollution only become apparent after long periods of exposure to it and so monitoring
pollution has suddenly become important as well as where it occurs (Alloway& Ayres, 1997).
Natural organic matter, that is, the remains of dead plants and animals are
biodegradable. These materials are broken down by microorganisms in water and soil. In this
way, nature takes care of its own waste. Synthetic organic products such as dichlorodiphenyltrichloroethane(DDT) are persistent and are not biodegradable due to their affinity for nonaqueous lipid tissues. Inorganic pollutants are usually man-made and are common in the areas
of domestic or industrial wastes.
Common forms of pollution that affect human life are air, water and soil pollutions.
Air pollution is a process that involves the release of gaseous chemicals and particulates into
5

the atmosphere. Common examples include carbon monoxide (CO), sulphur dioxide (SO 2),
chlorofluorocarbons (CFCs), nitrogen oxides (NOx) and heavy metals in form of particulates
produced by industry and motor vehicles. Water pollution affects oceans and inland water
bodies. Examples include organic and inorganic chemicals, heavy metals, petrochemicals and
microorganisms. Water pollution may also occur in the form of thermal pollution and the
depletion of dissolved oxygen. Soil contamination often occurs when chemicals are released
by spillages or underground storage tank leakage.
Environmental pollution can also result from natural disasters. For example, hurricanes often
cause water contamination from sewage and petrochemical leaks from ruptured storage tanks
contaminating ground water. Some sources of pollution, such as nuclear power plants or oil
tankers, can produce widespread and potentially hazardous releases when accidents occur.
2.1.1

SUGGESTIONS TO CONTROL ENVIRONMENTAL POLLUTION:


It is clear that fossil fuels are among the biggest sources of pollution. The need to find

alternative renewable sources of energy which can replace fossil fuels in the future has
become a major issue which has to addressed as soon as possible.
Building solar panels and using dry solar energy systems to meet at least part of home
electricity needs is another emerging opportunity for dry enthusiasts. This can really make a
positive difference to the environment and reduce current pollution levels.

2.2

HEAVY METALS
A heavy metal is a member of a loosely-defined subset of elements that exhibit

metallic properties. It mainly includes the transition metals, some metalloids, lanthanides, and
actinides.
Heavy metals constitute the largest class of elements in the periodic table. Heavy metals
occur naturally at levels that are not considered to have any toxic effects to plants, animals
and humans. Metals comprise 75% of the known elements and can form alloys with each
other and with non metals (Sparks, 2005). They have useful properties such as strength,
malleability and conductivity of heat and electricity. Some metals exhibit magnetic properties
and others are excellent conductors of electricity.
Heavy metals such as manganese, zinc, copper, chromium and iron are essential elements
when present in small amounts, heavy metals such as Pb and Hg are toxic at all levels.
The behaviour and toxicity of heavy metals or their compounds in the environment depends
largely on their concentrations and their chemical forms (Kot & Namiesnik, 2000; Tokalioglu
et al., 2003). For example, Cr (III) in food is an essential element, its stable; whereas Cr(VI)
is mobile and harmful. Also, the organic form of mercury is more toxic than its inorganic
derivative. While, the inorganic form of arsenic is more toxic than its organic form. Cases of
human poisoning by heavy metals have been reported. Cadmium (Cd) and its compounds are
extremely toxic at all levels but many metals are essential to life, although they occur only in
trace amounts in the body tissues.

2.3

HEALTH HAZARDS ASSOCIATED WITH HEAVY METALS.


Humans are always exposed to the natural levels of trace elements. Under normal

circumstances, the body is able to control some of these amounts. Increased exposure may
occur through inhalation of airborne particles or through ingestion of contaminated soil by
children or by absorption through the skin.
Metals can cross the placenta and harm an unborn child in pregnant women. Children are the
most susceptible to health problems caused by heavy metals, because their bodies are smaller
and still developing (Thomson, 2007). High levels of toxic metals deposited in body tissues
and subsequently in the brain may cause significant developmental and neurological damage,
including depression, increased irritability, anxiety, insomnia, hallucinations, memory loss,
aggression and many other disorders. Chronic effects of prolonged low level exposure to
arsenic poisoning causes skin pigmentation, keratoses, skin cancers and death if exposed to
high levels. Mercury poisoning symptoms include blindness, deafness, brain damage,
digestive problems, kidney damage, lack of coordination and mental retardation. Cadmium
poisoning causes softening of the bones and kidney failures and was responsible for the itaiitai disease (a name derived from the painful screams in Japanese language) due to the
severe pain in the joints and the spine (Wikipedia, 2007). Cadmium was released in the rivers
by mining companies in the mountains in Japan in the late 1940s. The disease arose from
increased uptake of cadmium in locally consumed rice grown in paddy fields irrigated with
cadmium-contaminated river water.

2.4

HEAVY METALS IN THE ENVIRONMENT.


The main source for metal input to plants and soils is atmospheric deposition. Volatile

metalloids such as As, Hg, Se, and Sb can be transported over long distances in gaseous
forms or enriched in particles, while trace metals such as Cu, Pb, and Zn are transported in
particulate phases (Adriano, 2001; Adriano et al. 2005). Microorganisms can transform
metals such as Hg, Se, Sn, As, and Cr by means of oxidation reduction and methylation (the
process of replacing an atom, usually a H atom, with a methyl group) and dimethylation
reactions. These processes affect transport or mobility and solubility or toxicity of metals
(Adriano 2001; Sparks 2005). Methylation is favoured in environments characterized by low
oxygen levels, low pH, and high soil organic matter (SOM) contents.
Heavy metal contamination of soils is a far more serious problem than air or water pollution
because heavy metals are usually tightly bound by the organic components in the surface
layers of the soil. Heavy metals can also be very quickly translocated through the
environment by erosion of the soil particles to which they are adsorbed or bound and redeposited elsewhere. The transport, cycling, fate, bioavailability and toxicity of heavy metals
are markedly influenced by their physico-chemical forms in water, sediments and soils.
Whenever a heavy metal or its compound is introduced into an aquatic environment, it is
subjected to a wide variety of physical, chemical and biological processes. These include
hydrolysis, chelation, complexation, redox, biomethylation, precipitation and adsorption
reactions.
2.4.1

ANTHROPOGENIC SOURCES OF HEAVY METALS;


Anthropogenic sources of heavy metals include agriculture (fertilizers, animal

manures and pesticides), metallurgy (mining, smelting and metal finishing), sewage sludge,

scrap disposal and energy production (power plants, leaded and unleaded petrol). (Adriano
2001).
2.5

METAL ADDITIVE IN PETROL.


Petrol in high compression internal combustion engines, has a tendency to ignite

early, causing a damaging engine knocking noise (Wikipedia, 2006). To obtain the
maximum energy from the petrol, the compressed fuel-air mixture inside the combustion
chamber needs to burn evenly, propagating out from the spark plug until all the fuel is
consumed (Hamilton, 1995). Knocking occurs when these reactions form products that can
auto ignite before the flame front arrives.
Lead and recently manganese are commonly used as metallic additives in petrol. They are
added as petrol soluble chemicals that can produce the desired effect at the parts-per-million
concentration range. These additives prevent premature knocking, protect engine valves
against wear and increase the efficiency and power of engines (Chevron, 2002).

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CHAPTER THREE
3.0

MATERIALS AND METHODS

3.1

STUDY AREA
The study was conducted within the town of Iwo, the second largest town in Osun

State. The samples were collected with a cutlass and put into a air-tight polythene bag. The
samples were taken at 0cm 5cm into the soil.
3.1.1

SAMPLING SITES
The sampling sites were at the following road junctions: Odo Ori Roundabout; Ibadan

Express Road; Bowen Road; Ejigbo Road; Hospital Road; Adeeke Road; Osogbo Road;
Agbowo Estate, Waterworks Road.
3.1.2

PRE-TREATMENT
All the glass wears, were washed with non-ionic detergents, rinsed with tap water

then with distilled water and soaked in 10% Nitric acid for 48 hours to avoid trace metals
contamination.
3.2 METHODS.
3.2.1 SELECTIVE SEQUENTIAL EXTRACTION.
The modified procedure of Tessier et al (1979, 1985) was used for this study except
for the introduction of two important fractions (water soluble and plant available). In this
scheme, heavy metals were separated into nine operationally defined fractions: water soluble
(S1), exchangeable (S2), bound to carbonate (S3), plant available (S4), bound to Mn oxide (S5),
bound to amorphous Fe oxide (S6), bound to crystalline Fe oxide (S7), bound to organic
matter (S8), and residual fraction (S9).
11

Principle: Sequential extraction to fractionate metals or other elements in solid


materials (soils, sediments, sludge, solid waste, etc.) into several groups of different
leachability is widely employed to determine the distribution of metals in different phases.
Although the procedures used are generally tedious and time consuming, the results furnish
detailed information about the origin, mode of occurrence, bioavailability, potential mobility,
and transport of the metals in natural environments. The technique is therefore, widely used
as a tool for the study of the origin and fate of metals in the environment.
The fundamental principle underlying this scheme is based on a careful selection of
reagents and detailed operating conditions to give satisfactory results for the targeted phases
or fractions of the metals. Since heavy metals exist in different forms and are bound to
different sites and components in the soil, appropriate solvents or reagents are equilibrated at
specific pH, concentration and temperatures to ensure timely dissolution of these metals in
solution. The metals are released into solution on solubility basis, exchange reactions
between exchange sites in the clay and organic matter matrix, reducing conditions which
favour the release of the metals held in the occluded fractions and also oxidizing conditions
of the organic, sulphide and all oxidizable matter in the soil. The metals are determined using
the appropriate spectrophotometric techniques. It is important to emphasise that this
operationally defined extraction procedure provides knowledge on metal affinity to soil
components and the strength with which they are bound to the matrix (Narwal et al., 1999).
Procedure: One gram of each soil sample was weighed and extractions were made
through steps (S) by centrifugation and filtration at 10,000 rpm placing the sample in
polyethylene centrifuge tubes. Distilled/deionised water was used to wash the residues
following subsequent extractions in order to ensure selective dissolution and avoid possible
inter-phase mixing between the extractants. All samples were run in duplicates.

12

S1 Water soluble metals: Water-soluble metals were extracted with a solution of 50ml
distilled deionised water at pH 7.0 and at 280C for 2 hours.
S2

Exchangeable metals: The residue from (a) was extracted with 25ml of 1.0M

NH4COOCH3 (pH = 7.0). The suspension was shaken for 30 min at 280C.
S3 Metals bound to carbonate: The residue from (b) was extracted with 1M sodium
acetate (CH3COONa) adjusted to pH 5.0 with acetic acid (CH3COOH). The suspension was
shaken for 5 hours.
S4 Plant Available Metals: The residue from (c) was extracted by shaking with a
solution mixture of 50ml of 0.025M HCl + 0.05M H2SO4 for 30 mins at 280C.
S5 Bound to Mn-Oxide: The residue from (d) was shaken for 30 minutes at 28 0C with
a solution of 25ml 0.1M NH2OH.HCl in 25% CH3COOH (pH 2 3).
S6 Bound to Amorphous Fe-oxide: The residue from (e) was extracted with 25ml of
0.2M (NH4)2C2O4 (pH 3.0) for 30 minutes at 500C using a water bath with occasional stirring.
S7 Bound to Crystalline Fe-oxide: The residue from (f) was extracted using 25ml of
0.04M NH2OH.HCl in 25% acetic acid (pH 2) and heated in a water bath with occasional
stirring at 1000C for 6 hours.
S8 Bound to organic matter: The residue from (g) was extracted with 10ml of 0.02M
HNO3 and 15ml of 30% H2O2 (adjusted to pH 2 with HNO 3). The mixture was then heated to
850C for 5 hours with occasional agitation. A second 15ml liquot of 30% (pH 2 with HNO 3)
was added and the mixture heated again to 85 0C for 3 hours with intermittent agitation. After
cooling, 5ml of 3.2M NH4COOCH3 in 20% (v/v) HNO3 was added and the samples diluted to
20ml and agitated continuously for 30 min.

13

S9 Residual metals: The residue from (h) was digested with a mixture of concentrated
HNO3 and HClO4 for 8 hours.
The metal content of all the extracts in the centrifuged solutions were determined by atomic
absorption spectrophotometer (Unicam Solar 1969 Series). Standard solutions for the metals
were prepared for each extraction step in a background solution of the extracting reagents.
The following metals were determined , Pb, Cd, Cr, Ni, Cu, Zn, Mn, Fe, and V. All the
analysis were done in duplicates.

14

CHAPTER FOUR.
4.0

RESULTS AND DISCUSSION.


The following tables represent the concentrations of heavy metals of the roadside soil

samples that were extracted with the selective sequential extraction methods.
Tables 4.1 to 4.9 presents the results of the selective sequential extraction methods which
showed that Fe is more predominant in the roadside soils in Iwo with the highest average
mean value of 21.243.74g/g (Table 4.5) and Cd is the lowest occurring heavy metal in the
soils with an average mean value of 0.040.01g/g (Table 4.3) which is well expected
because it has been reported that iron (Fe) occurs at high concentration in Nigeria soil
(Asaolu et al., 1997; Asaolu and Olaofe, 2004; Nwajei and Gagophien, 2000), and it will seen
that in all the roadside soils in Iwo, Fe is the most occurring heavy metal.

TABLE 4.1: Concentration of water soluble metals of roadside soil in Iwo (g/g).
Fraction 1
Adeke

Mn
8.03

0. 06

Fe

Zn

Pb

Cd

13.03020

5.110.15

0.090.00

0.040.01

Agbowo

10.100.25

19.930.10

6.090.15

0.100.00

0.050.00

Bowen

11.200.24

20.030.07

5.170.28

0.100.00

0.050.00

Ejigbo

10.100.12

16.100.16

4.870.19

0.110.00

0.060.00

Exp

9.810.08

17.080.33

4.000.04

0.100.00

0.050.00

Hosp

10.400.09

17.430.14

5.120.16

0.090.01

0.030.00

Odoori

10.560.14

21.060.11

4.310.10

0.100.00

0.050.00

Osogbo

12.250.20

19.020.33

5.140.10

0.120.00

0.050.00

Waterworks

11.00.21

21.040.42

6.620.13

0.090.00

0.040.00

MeanSD

10.361.12

18.302.58

5.160.79

0.100.01

0.050.01

15

TABLE 4.2:

Concentration of exchangeable metals of roadside soil in Iwo (g/g).

Fraction 2

Mn

Fe

Zn

Pb

Cd

Adeke

11.870.19

20.090.32

5.950.09

0.090.00

0.040.00

Agbowo

11.350.19

21.290.51

5.650.19

0.090.00

0.050.01

Bowen

9.930.26

20.950.15

6.320.15

0.110.00

0.040.00

Ejigbo

8.680.52

17.320.16

6.890.16

0.110.01

0.050.00

Exp

11.100.16

23.070.07

8.040.08

0.120.00

0.040.01

Hosp

13.080.14

21.060.17

6.320.10

0.090.00

0.040.00

Odoori

10.480.14

20.060.11

4.490.10

0.100.00

0.050.00

Osogbo

11.010.04

18.070.11

6.080.12

0.100.00

0.050.00

Waterworks

10.440.13

19.690.45

4.990.02

0.110.00

0.040.01

MeanSD

10.711.36

19.622.36

6.250.82

0.110.01

0.040.01

TABLE 4.3:

Concentration of metals bound to carbonate of roadside soil in Iwo (g/g).

Fraction 3

Mn

Fe

Zn

Pb

Cd

Adeke

13.000.16

21.980.10

6.330.15

0.080.00

0.040.00

Agbowo

12.010.05

17.140.25

4.990.02

0.100.00

0.050.00

Bowen

7.050.10

15.190.27

4.680.16

0.100.00

0.050.01

Ejigbo

9.440.13

18.150.24

5.220.19

0.090.00

0.040.00

Exp

10.100.30

17.030.12

4.940.11

0.090.00

0.050.00

Hosp

12.090.14

19.502.48

6.090.13

0.080.00

0.030.00

Odoori

14.090.15

22.970.15

6.210.16

0.110.00

0.050.00

Osogbo

8.900.25

16.020.07

5.260.09

0.100.00

0.040.00

Waterworks

13.100.15

20.890.20

5.720.15

0.090.00

0.040.00

MeanSD

11.092.26

18.772.71

5.500.60

0.100.01

0.040.01

16

TABLE 4.4:

Concentration of plant available metals of roadside soil in Iwo (g/g).

Fraction 4

Mn

Fe

Zn

Pb

Cd

Adeke

15.150.25

24.870.20

6.990.03

0.090.00

0.040.00

Agbowo

11.370.20

24.010.48

6.450.10

0.100.01

0.040.00

Bowen

14.070.17

21.940.10

6.290.15

0.100.01

0.040.00

Ejigbo

10.010.18

20.090.16

6.000.03

0.100.00

0.050.00

Exp

9.540.26

15.960.33

5.200.09

0.090.00

0.040.00

Hosp

11.030.08

22.220.21

6.080.13

0.090.00

0.040.00

Odoori

8.060.11

12.950.13

4.430.08

0.080.00

0.040.00

Osogbo

13.090.14

21.240.54

7.030.18

0.110.00

0.050.00

Waterworks

9.930.27

20.990.02

6.320.02

0.100.00

0.050.00

MeanSD

11.362.25

20.483.68

6.090.81

0.100.01

0.040.01

TABLE 4.5:

Concentration of metals bound to manganese oxide of roadside soil in Iwo (g/g).

Fraction 5

Mn

Fe

Zn

Pb

Cd

Adeke

19.00.18

24.520.28

5.990.02

0.100.00

0.040.00

Agbowo

15.440.12

24.150.25

5.890.20

0.110.01

0.050.00

Bowen

10.930.17

21.070.13

5.960.25

0.110.01

0.040.00

Ejigbo

21.070.13

27.990.23

6.980.04

0.100.01

0.050.00

Exp

7.880.21

16.040.09

5.000.01

0.100.00

0.040.00

Hosp

17.130.27

21.770.30

5.870.20

0.090.00

0.040.00

Odoori

8.440.09

16.970.24

5.250.07

0.100.00

0.040.00

Osogbo

13.030.08

19.840.39

4.280.12

0.100.00

0.040.00

Waterworks

10.890.22

18.800.41

4.010.01

0.100.00

0.050.00

MeanSD

13.764.53

21.243.74

5.470.91

0.100.01

0.040.01

17

TABLE 4.6:

Concentration of metals bound to amorphous iron oxide of roadside soil in Iwo (g/g).

Fraction 6

Mn

Fe

Zn

Pb

Cd

Adeke

12.290.13

20.050.09

5.830.15

0.090.00

0.040.00

Agbowo

9.910.19

17.960.14

5.160.13

0.090.00

0.040.00

Bowen

15.590.55

24.040.21

6.250.16

0.100.01

0.050.00

Ejigbo

13.880.20

16.870.20

4.990.05

0.090.00

0.040.00

Exp

7.490.15

13.400.15

4.270.16

0.110.01

0.050.00

Hosp

10.960.19

21.990.01

5.330.20

0.110.01

0.050.00

Odoori

10.020.05

17.070.17

4.930.27

0.100.01

0.050.00

Osogbo

14.160.24

21.970.16

6.080.13

0.100.01

0.050.00

Waterworks

9.940.13

17.160.25

5.410.11

0.110.00

0.050.00

MeanSD

11.582.52

18.953.23

5.360.61

0.100.01

0.050.01

TABLE 4.7:

Concentration of metals bound to crystalline iron oxide of roadside soil in Iwo (g/g).

Fraction 7

Mn

Fe

Zn

Pb

Cd

Adeke

17.430.15

22.660.12

6.010.03

0.090.00

0.040.00

Agbowo

9.120.19

16.150.54

5.220.14

0.100.00

0.050.00

Bowen

10.060.27

14.070.21

5.880.20

0.110.01

0.050.00

Ejigbo

8.370.54

12.900.15

5.440.17

0.090.00

0.030.00

Exp

15.030.14

29.670.16

6.830.17

0.100.00

0.050.00

Hosp

10.820.33

12.5211.92

6.260.09

0.090.00

0.040.00

Odoori

11.410.15

21.130.37

6.000.03

0.110.01

0.050.00

Osogbo

14.970.34

21.990.03

5.990.12

0.080.01

0.040.00

Waterworks

14.490.16

20.000.02

5.000.19

0.090.00

0.050.00

MeanSD

12.413.06

18.906.15

5.850.55

0.100.01

0.050.01

18

TABLE 4.8:

Concentration of metals bound to organic matter of roadside soil in Iwo (g/g).

Fraction 8

Mn

Fe

Zn

Pb

Cd

Adeke

14.430.15

23.070.33

7.920.14

0.100.00

0.050.00

Agbowo

19.570.62

29.160.27

7.140.22

0.090.00

0.040.00

Bowen

8.930.39

14.880.21

5.950.25

0.120.01

0.050.00

Ejigbo

9.400.12

18.080.17

6.030.06

0.100.00

0.040.00

Exp

10.450.09

20.970.26

6.140.09

0.110.01

0.050.00

Hosp

10.110.17

20.970.17

6.870.20

0.090.00

0.040.00

Odoori

8.040.13

13.080.15

5.000.02

0.100.01

0.050.00

Osogbo

20.990.14

25.050.38

7.090.14

0.100.00

0.050.00

Waterworks

17.030.41

22.720.18

6.660.20

0.110.01

0.050.00

MeanSD

13.224.78

20.894.84

6.530.84

0.100.01

0.050.01

TABLE 4.9:

Concentration of residual metals of road sidesoil in Iwo (g/g).

Fraction 9

Mn

Fe

Zn

Pb

Cd

Adeke

11.060.13

22.940.30

5.980.03

0.080.00

0.040.00

Agbowo

8.590.22

16.960.23

5.260.09

0.090.00

0.040.00

Bowen

8.060.11

14.040.42

4.870.16

0.090.00

0.040.00

Ejigbo

8.840.47

14.080.34

5.360.09

0.100.00

0.050.00

Exp

10.430.13

19.250.38

5.430.15

0.100.00

0.040.00

Hosp

9.460.09

19.930.12

5.630.15

0.090.00

0.040.00

Odoori

15.870.21

22.600.58

6.060.18

0.100.00

0.040.00

Osogbo

9.420.14

21.120.56

6.200.09

0.130.01

0.050.00

Waterworks

7.840.25

16.110.30

4.990.02

0.110.01

0.050.00

MeanSD

9.952.38

18.563.33

5.530.46

0.100.01

0.040.01

19

The highest concentration of heavy metal recorded was Fe with mean value 29.670.16g/g
(Table 4.7) on the Express Road and the lowest was Cd with mean value 0.030.00g/g
(Table 4.1) on the Hospital Road which might be due to the fact that higher number of
vehicles travel on the Express Road than on the Hospital Road which is a residential area.
This assumption will be backed by Eitminaviius L., Matuseviius K., Antanaitis A., (2001)
who stated that soils along highways tend to be polluted with Fe and other heavy metals such
as Zn, Cd, Pb etc.
On the average, the concentration of iron, manganese, zinc, and all other heavy metals
extracted vary from one location to another. This could be attributed to geological distribution
of minerals that vary from one location to the other. Similar variations were reported in
roadside soils of highways in Egypt (Adriano et al., 2007).
The overall order Fe > Mn > Zn > Pb > Cd will support the values below and can be seen in
Fig 4.1. The overall total mean values are Fe (175.7132.62g/g), Mn (104.4424.26g/g),
Zn (51.746.39g/g), Pb (0.910.09g/g), Cd (0.400.09g/g).

Total mean values


180
160
140
120
100

Total mean values

80
60
40
20
0
Mn

Fe

Zn

Pb

Cd

Fig 4.1: Total Mean Values of Mn, Fe, Zn, Pb, Cd

20

The total concentration of heavy metals were found out and Fe was discovered to be
predominant in the roadside soils that were selected from the nine sampling points, it is very
clear that Fe have the highest leading value due to some factors which may include, wear and
tear of tyres on the road, vehicle exhaust and corrosion of metals because in all these nine
sampling locations there is possibility of the mentioned factors to occur frequently or
sparingly, sources of Zn could be associated with human activities such as the use of
chemicals or zinc based fertilizers by farmers (Egila and Nimyel, 2002). Concerning Pb, one
of the heavy metals in the result above showed that its level is lowest, this is simply so
because Pbs major source arises mainly from refineries, TEL(tetra ethyl lead) in vehicle
gasoline which is not in use in this country, industries e.t.c which is very rare in above
mentioned areas while the remaining heavy metals which include Mn, Cd, are referred to as
the trace elements, and in small quantities, the above heavy metals are nutritionally essential
for a healthy life.

21

4.1

HEAVY METAL FRACTIONS.


The diagrams below (Fig. 4.2 - 4.6) represent the distribution of heavy metals in the

roadside soils of Iwo. The distribution shows the level of the percentage each heavy metal
occur in each fractions that is in water soluble metals, exchangeable metals, metals bound to
carbonate, plant available metals, metals bound to mn-oxide, metals bound to amorphous feoxide, metals bound to crystalline fe-oxide, metals bound to organic matter and residual
metals.
MANGANESE: in manganese, it was noted that metals bound to Mn-oxide and metals
bound to organic matter has highest percentage with 13% respectively with residual metals as
lowest in Fig 4.2 and this conclusion is in agreement with the research work of Shadung John
Moja, (2007) who worked on manganese in roadside soils extensively in Tshwane, South
Africa.
IRON: in iron, it was noted that plant available metals, metals bound to Mn-oxide and metals
bound to organic matter are highest with 12% respectively and water soluble metals and
residual metals are lowest with 10% respectively in Fig 4.3.
ZINC: in zinc, metals bound to organic matter was highest with 13% and water soluble
metals, metals bound to Mn-oxide, metals bound to amorphous Fe-oxide are lowest with 10%
respectively in Fig 4.4.
LEAD: in lead, exchangeable metals was highest with 12% and the rest had 11% each in Fig
4.5.
CADMIUM: in cadmium, it was noted that only metals bound to organic matter was highest
with 12% and the remaining fractions have 11% respectively in Fig 4.6.

22

Mn
Water soluble metal

Exchangeable metals

Metal bound to carbonate

Plant available metals

Metals bound to Mn-oxide

Metal bound to armorphous Fe-oxide

Metals bound to crystalline Fe-oxide

Organic matter

Residual metal

10% 10%
13%
10%
11%
12%
11%

11%
13%

Fig. 4.2: Distribution of Mn in Roadside Soils of Iwo

Fe
Water soluble metal

Exchangeable metals

Metal bound to carbonate

Plant available metals

Metals bound to Mn-oxide

Metal bound to armorphous Fe-oxide

Metals bound to crystalline Fe-oxide

Organic matter

Residual metal

11% 10%
12%
11%
11%
11%
12%
11%
12%

Fig. 4.3: Distribution of Fe in Roadside Soils of Iwo


23

Zn
Water soluble metal

Exchangeable metals

Metal bound to carbonate

Plant available metals

Metals bound to Mn-oxide

Metal bound to armorphous Fe-oxide

Metals bound to crystalline Fe-oxide

Organic matter

Residual metal

11% 10%
12%
13%
11%

11%
12%

10%
11%

Fig. 4.4: Distribution of Zn in Roadside Soils of Iwo

Pb
Water soluble metal

Exchangeable metals

Metal bound to carbonate

Plant available metals

Metals bound to Mn-oxide

Metal bound to armorphous Fe-oxide

Metals bound to crystalline Fe-oxide

Organic matter

Residual metal

11% 11%
11%
12%
11%
11%

11%
11%

11%

Fig. 4.5: Distribution of Pb in Roadside Soils of Iwo


24

Cd
Water soluble metal

Exchangeable metals

Metal bound to carbonate

Plant available metals

Metals bound to Mn-oxide

Metal bound to armorphous Fe-oxide

Metals bound to crystalline Fe-oxide

Organic matter

Residual metal

11% 11%
12%

11%
11%

11%
11%

11%

11%

Fig. 4.6: Distribution of Cd in Roadside Soils of Iwo

25

CHAPTER FIVE.
CONCLUSION.
The aim of this research was to determine the fractions and levels of heavy metals in
Iwo and to determine their relevance to the environment.
In summarizing the obtained results, it has emerged that in the total amounts of the heavy
metals (Mn, Fe, Zn, Pb, Cd), Fe is predominant. The results presented indicate that the
roadside soil samples collected from the Iwo area contained high level of Fe, 50% followed
by manganese, 35% followed by zinc, 13% and then trace amounts of lead and cadmium with
concentrations not more than 1% respectively. The sequential extraction analysis indicated
that Fe is more concentrated in the roadside soils of Iwo than any other heavy metal because
it has been reported that iron (Fe) occurs at high concentration in Nigeria soil (Asaolu et al.,
1997; Asaolu and Olaofe, 2004; Nwajei and Gagophien, 2000).
In conclusion, small quantities of certain heavy metals are nutritionally essential for a healthy
life. They become toxic when they are not metabolized by the body and accumulate in soft
tissues. It is therefore very important that we take protective measures against excessive
exposure to some of these heavy metals that occur naturally.

RECOMMENDATION.
In further studies, traffic counts, temporal studies, physico-chemical analysis should
be carried out extensively to be able to ascertain heavy metals pollution in soils.
These heavy metals (Mn, Fe, Zn, Pb, Cd) are essential for a healthy life in small
quantities, they become toxic when they are not metabolized by the body and accumulate in

26

soft tissues. It is therefore very important that we take protective measures against excessive
exposure to some of these heavy metals that occur naturally.

27

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