OLI89

HUMAN HEALTH RISK ASSESSMENT OF POLYCYCLIC AROMATIC

HYDROCARBONS (PAHS) AND HEAVY METALS IN GROUNDWATER
FROM IJEGUN AND EJIGBO, LAGOS STATE, NIGERIA

BY
SHONUBI DORCAS
(190503011)

A RESEARCH PROJECT REPORT SUBMITTED TO THE

DEPARTMENT OF GEOLOGY AND MINERAL SCIENCES, COLLEGE
OF NATURAL AND APPLIED SCIENCES, CRAWFORD UNIVERSITY,
FAITH CITY, OGUN STATE.

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

AWARD OF BACHELOR OF SCIENCE (B.Sc.) DEGREE IN GEOLOGY
AND MINERAL SCIENCES

JUNE 2022

1
 ABSTRACT

This study was carried out to investigate the occurrence, distribution, source, composition and
health risk of Polycyclic Aromatic Hydrocarbons and Heavy Metals in groundwater in selected
oil polluted sites in Lagos. Twenty samples were collected in total: four from Ijegun, three from
Victoria Estate in Ejigbo, and the other three from Omilaye and Surprise Avenue from Ejigbo,
Lagos; and they were subjected to physicochemical analysis, elemental composition analysis
using AAS and PAH analysis using GC-FID.
Only ten samples out of the twenty were used for this study due to instrumental challenges. The
result from the physicochemical analysis showed the value of pH ranged from 3.54 to 6.6, TDS
between 0 to 0.448, and Turbidity between 2.5 to 35.7. Five heavy metals were analyzed for in
the samples; however Cadmium, Nickel and Chromium were identified to be below the detection
limit. Lead (Pb) ranges from 14.09 to 15.59 μg/l, and Iron (Fe) from 0.022 to 0.792 μg/l. 14 PAH
were identified in the water samples. The light fraction which include Fluorene and
Acenaphthene, were below the detection limit.
The estimated diagnostic ratio based on the formular BaA/(BaA+ ChR), showed that locations 1,
2, 4, 6, 9, and 10 were of petrogenic origin; location 7 was of fuel combustion, and locations 3
and 5 were of coal, grass and wood burning. The estimated non-carcinogenic risk showed that
the Hazard Quotients for NaP, PhE and Flou were below the USEPA maximum limit of 1, and
the Cancer Risk for the carcinogenic PAHs had 5 PAHs out of seven carcinogenic PAHs, which
are benzo(a)anthracene, benzo(b)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, and
indeno(1,2,3-cd)pyrene, exceed the threshold value of 1×10-1. Water from the study area was
observed not to be safe for drinking.

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 CERTIFICATION
I, undersigned hereby certify that this project “Human Health Risk Assessment of Polycyclic
Aromatic Hydrocarbons (PAHs) and Heavy Metals in Groundwater from Ijegun and
Ejigbo, Lagos State, Nigeria” was carried out by Shonubi Dorcas in the Department of Geology
and Mineral Sciences, of the College of Natural and Applied Sciences, , Crawford University,
Ogun State.

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 DEDICATION
This project is dedicated to God Almighty, and my beloved parents, Mr. and Mrs. Shonubi, who
have been supportive, encouraging, loving, and have prayerfully directed me in the right path.

iii
 ACKNOWLEDGEMENT

With a heart full of gratitude, I appreciate the God who made me and brought about the success
of this project work. I am grateful to Him for bountiful provisions and strength through time. He
has always come through even in difficulties, and has always made a way. I truly cannot express
my full gratitude to Him in words.

To my lovely parents, Mr. and Mrs. Shonubi, and my amazing siblings who have been my
greatest support and cheer leaders, I say a big thank you! You all have made me understand
myself better and have given me a reason to push to attain greatness. I cannot express my deep
and sincere love to you enough for all you mean to me.

I sincerely appreciate my supervisor, Mr. M.O Adeyemi, for his desire to see his students grow.
He made me appreciate knowledge and helped me learn, unlearn, and relearn. Indeed, his gesture
of kindness, passion and drive for excellence has instilled in me a mindset that strives for
excellence. I appreciate the commendations, rebuke and teachings he never ceased to give me. I
pray that God indeed rewards him amazingly. To my very wonderful and admirable Dean, Prof.
A.J Adeola, who played the role of a father, mentor, and lecturer, I indeed want to say thank you
Sir. You have indeed impacted me greatly and have given me a greater confidence as a Geologist
than I had before. Indeed I appreciate all your efforts Sir, and I pray God blesses you mightily.

Special gratitude goes to my distinguished lecturers Col. V.O Fagoyinbo (Rtd), Miss O.S
Olatunji, Miss V.A Dairo, and Mr R. Bello, for their undying efforts in exerting knowledge into
me, and also Mrs Oyeshikun for being so loving and kind. I am ever grateful to the wonderful
sisters God gave me in school, Monioluwa and Debby, and my indeed special course mates and
friends, Feranmi, Bolu, Daniel, Timi, Debola, Gbolahan, Esther, Chizoba, Ibukun, Grace,
Kelvin, Olumide and Kolatobi, for all the great time we spent together and your impact in my
life. May God bless you all In Jesus Mighty Name.

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 TABLE OF CONTENTS
CERTIFICATION...........................................................................................................................ii
DEDICATION...............................................................................................................................iii
ACKNOWLEDGEMENT..............................................................................................................iv
LIST OF FIGURES.......................................................................................................................vii
LIST OF TABLES.......................................................................................................................viii
CHAPTER ONE..............................................................................................................................1
1.1 INTRODUCTION.................................................................................................................1
1.2 GROUNDWATER IN LAGOS STATE...............................................................................2
1.3 PAHS AND PAHS IN DRINKING WATER.......................................................................3
1.3.1 PAH STRUCTURE........................................................................................................5
1.4 PAH AND HEALTH.............................................................................................................6
1.5 HEAVY METALS AND HEALTH......................................................................................7
1.6 AIM AND OBJECTIVES.....................................................................................................8
1.7 SCOPE OF THE STUDY......................................................................................................8
1.8 DESCRIPTION OF THE STUDY AREA............................................................................8
1.8.1 LOCATION AND ACCESSIBILITY OF THE STUDY AREA...................................8
1.8.2 RELIEF AND DRAINAGE.........................................................................................10
1.8.3 POPULATION AND POPULATION DENSITY.......................................................11
1.8.4 CLIMATE AND VEGETATION................................................................................11
1.9 PREVIOUS WORKDONE.................................................................................................11
CHAPTER TWO...........................................................................................................................13
2.1 REGIONAL GEOLOGY OF NIGERIA.............................................................................13
2.2 THE DAHOMEY BASIN...................................................................................................13
2.3 TECTONIC SETTING........................................................................................................15
2.4 LITHOSTRATIGRAPHY OF THE DAHOMEY BASIN..................................................17
2.4.1 ABEOKUTA GROUP..................................................................................................17
2.4.2 IMO GROUP................................................................................................................18
2.4.3 OSHOSUN FORMATION...........................................................................................18
2.4.4 ILARO FORMATION.................................................................................................19
2.4.5 BENIN FORMATION.................................................................................................19
CHAPTER THREE.......................................................................................................................20
3.1 RESEARCH METHODOLOGY........................................................................................20

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 3.2 FIELD METHODOLOGY..................................................................................................20
3.2.1 INSTRUMENTS AND MATERIALS USED FOR SAMPLE COLLECTION..........22
3.3 LABORATORY ANALYSIS.............................................................................................23
3.3.1 PHYSICOCHEMICAL TEST......................................................................................23
3.3.2 DETERMINATION OF PAHs.....................................................................................24
3.3.3 DETERMINATION OP PTEs.....................................................................................25
3.3.3 DIGESTION OF SAMPLES FOR PTEs.....................................................................25
3.4 HUMAN HEALTH RISK ASSESSMENT FOR HUMANS.............................................27
3.4.1 NON-CARCINOGENIC..............................................................................................28
3.4.2 CARCINOGENIC RISK..............................................................................................28
CHAPTER FOUR.........................................................................................................................30
RESULTS, INTERPRETATIONS AND DISCUSSIONS.......................................................30
4.1 RESULT PRESENTATION...............................................................................................30
4.2 PHYSICAL CHARACTERISTICS....................................................................................30
4.2.1 pH.................................................................................................................................30
4.2.2 TOTAL DISSOLVED SOLID (TDS)..........................................................................30
4.3 DETERMINATION OF THE HEAVY METALS.............................................................33
4.3.1 IRON.............................................................................................................................33
4.3.2 LEAD............................................................................................................................34
4.3.3 CHROMIUM (Cr)........................................................................................................35
4.3.4 CADMIUM (Cd)..........................................................................................................35
4.3.5 NICKEL (Ni)................................................................................................................35
4.4 PAHs RESULT....................................................................................................................37
4.5 DIAGNOSTIC RATIO REVEALING POSSIBLE SOURCES OF PAHs.........................44
CHAPTER FIVE...........................................................................................................................52
5.1 CONCLUSION....................................................................................................................52
5.2 RECOMMENDATIONS.....................................................................................................53
References......................................................................................................................................54

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 LIST OF FIGURES

Figure 1.1: Diagram Showing the 16 PAHs and their Ring Numbers............................................5
Figure 1.2: Study Area of Ijegun (a) and Ejigbo (b), Showing Sample Points...............................9
Figure 1.3: Study Area Map Extract Showing the Dendritic Drainage Pattern.............................10
Figure 2.1: Geologic Map of the Eastern Dahomey Basin............................................................14
Figure 3.1: Site Showing Water Tank Affected by the Presence of PAHs...................................21
Figure 3.2: Gas Chromatograph used in the lab............................................................................26
Figure 3.3: Fully Labeled Parts of the Gas Chromatograph..........................................................26
Figure 4.1: Box plot showing the physical parameters present in the samples.............................32
Figure 4.2: Pie Chat Showing Percentage Concentrations of PAHs present in L1-L4.................40
Figure 4.3: Pie Chat Showing Percentage Concentrations of PAHs present in L5-L8.................40
Figure 4.5: Pie Chat showing the Percentage Concentrations of PAHs in Locations 9 & 10.......42
Figure 4.6: Diagnostic Ratio Showing Sources of PAHs..............................................................45
Figure 4.7: Box Plot revealing the Carcinogenic and Non-carcinogenic PAHs............................49

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 LIST OF TABLES

Table 2.1: Stratigraphic Chart of the Southwestern Nigerian Basin 16

Table 3.1: Sampling Coordinates and Description........................................................................22
Table 3.2: Values used for the Calculation of Health Risk Assessment.......................................29
Table 3.4: Values used for the calculation of health risk assessment............................................29
Table 4.1: Physical Parameters of Ground Water at Ijegun and Ejigbo........................................31
Table 4.2: Concentrations of Heavy Metals Present in the Samples.............................................36
Table 4.3: PAHs Distribution and Concentration in Water Samples Analyzed............................39
Table 4.4: Table Showing the Mean and Range of the PAHs in the Samples..............................43
Table 4.5: Average Daily Dose by Dermal Absorption (ADDd) of both Non-carcinogenic and
Carcinogenic PAHs.......................................................................................................................30
Table 4.6: Hazard Quotient (HQ) of Dermal Absorption for nc-PAHs in each Location.............47
Table 4.7: Cancer Risk (CI) of Dermal Absorption for cPAHs in each Location.........................48
Table 4.8: Correlation Table showing Relationship between the Pollutants and Physicochemical
Parameters......................................................................................................................................51

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 CHAPTER ONE

1.1 INTRODUCTION

Water, being essential to life existence, makes up about 71% of the Earth’s surface, and just
about 2.5% is freshwater (Abioye & Perera, 2019). According to Graham et al., (2010), about
22-30% of freshwater is stored in underground aquifers, portraying the significance of
groundwater in the provision of good water quality. Groundwater is a very important resource
useful for drinking, domestic uses, irrigation as well as industrial purposes. The preference for
groundwater to surface water as a source for drinking is based on the fact that groundwater is
less susceptible to pollution because it is excluded from the atmosphere (Ayedun et al., 2015).
Groundwater is one of the vital resources that need adequate protection from anthropogenic
sources of pollution. Globally, the rate of anthropogenic activities as well as climate change has
impacted on the quality of both surface and groundwater resources (Akoteyon et al., 2018).
Groundwater can be influenced by lithology, water-rock interaction, and changes in space and
time (Todd and Larry, 2005; Bhattacharya and Bundschyh, 2015). Also, it is often of very good
natural quality, usually colourless, pathogen free, turbidity free and can be directly consumed
without artificial treatment (Jain et al., 1996). According to (Keith, 2015), groundwater
contamination is an undesirable change in groundwater quality which can result from human
activities. Urban growth, increased industrial activities, intensive farming, and overuse of
fertilizers in agricultural production have been identified as drivers responsible for these changes
(Patwardhan, 2003).

Groundwater is trapped beneath the surface, thus it is more difficult to be monitored compared to
surface water, and it is being threatened by increased anthropogenic activities and unsustainable
practices (Nwankwoala, 2011). According to Ayedun et al., (2017), unsatisfactory supply of
water and unwholesome sanitary conditions can result in poor human health. The maintenance of
water quality therefore is an essential requirement for successful use of water resources. In order
to safeguard the long-term sustainability of the groundwater resources, the quality of the water
needs to be continuously monitored (Raihan and Alam, 2008). Water pollution by organic

1
compounds, which may be toxic or carcinogenic has caused a lot of concern worldwide (JSAC,
2004).
The release of crude liquid petroleum oil and other derived oils into the ecosystem is termed an
oil spill (Okoli et al., 2011). Oil spill can release both heavy metals and organic pollutants as
Polycyclic Aromatic Hydrocarbons (PAHs) and heavy metals into the environment, which is
capable of destroying the microorganisms which help in bio-degradation (Chowdhury et al.,
2016). Water pollution by (PAHs) and heavy metals is widespread in many countries
worldwide. Excessive human activities and inappropriate disposal of industrial wastes are some
of the reasons that lead to their detection in important water resources, including sea water, river
water and underground water, which directly affects the quality of drinking water and aquatic
organisms (Yan et al., 2018). The weathering and decomposition of some heavy metallic rocks
and ores can be a means through which heavy metals are transferred into groundwater
(Mohammadi et al., 2019). Heavy metals can be released into water in large quantities through
anthropogenic activities such as vehicle exhaust, poor waste disposal, fossil fuel combustion,
fertilizer and pesticide application, untreated water irrigation, and atmospheric precipitation, and
these can affect vegetation, food chain and water quality, thus influencing human health
(Mohammadi et al., 2019). Polycyclic Aromatic Hydrocarbons (PAHs), an important group of
organic pollutants, and also heavy metals, have received considerable attention because of their
documented carcinogenicity, thus, this study focuses on the presence of PAHs and heavy metals
in drinking water, their health impacts and also their environmental effects.

1.2 GROUNDWATER IN LAGOS STATE

For a long time in Lagos state, surface water was the major source of water for domestic and
industrial purposes, and a little supplement with hand-dug wells by individual concerns.
Increased awareness of the availability of underground water has led to the conception and
execution of development plans based on groundwater (Longe et al., 1987). In the city of Lagos,
potable water from the water supply boards are inadequate for the teeming population and fears
of contamination of the municipal drinking water supply is high since water treatment and
distribution is facing many problems (Yusuf, 2007). According to the (Int, 2019), only 39% of
people that live in cities have improved water sources, thus a large percentage of the population

2
depends on groundwater from their private wells or boreholes as the main source of drinking
water.

Groundwater is often considered pure and therefore can be served with little or no treatment; this
may be true for deep boreholes, but the problem of saline water intrusion and aquifer
contamination through anthropogenic activities may endanger the use of shallow groundwater in
Lagos (Awoyemi et al., 2014). The city of Lagos can be accessed through road, rail, air and
seaport. It experiences various degrees of saline incursion especially along the coastline as a
result of its sole reliance on the groundwater as the major source of portable water for domestic
and industrial purposes, so as to compensate for inadequate supply of piped water (M. A. Yusuf
& Abiye, 2019). According to JICA (1999), there are about 2000 industries in Lagos, the
majority of which discharge their effluents into Sasa and Odo Iya streams in the Ikeja suburb.
The water quality of the rivers therefore exceeds the standards of WHO and Federal
Environmental Protection Agency. Residents of the city depend on groundwater for regular
supply of portable water. Therefore, there is need for groundwater to be sustainably used,
monitored and protected (Keith, 2015).

1.3 PAHS AND PAHS IN DRINKING WATER

Drinking water is one of the oldest public health issues and is associated with a multitude of
health-related concerns. These concerns are derived into microbial and chemical pollutants,
which are comprehensively presented in the international guidelines for drinking water quality.
Chemical pollutants due to their adverse effects on human and the environment, chemical
pollutants, especially xenobiotic compounds, are of foremost importance. Polycyclic aromatic
hydrocarbons (PAHs) are a group of xenobiotic chemicals which are made up of carbon and
hydrogen (Karyab et al., 2013). PAHs are a group of hydrophobic organic compounds that are
widely distributed in the environment. The presence of PAHs in drinking water may be due to
surface water used as raw water sources, which can cause damage to human health. PAHs are
widely spread in the environment and can be found in food, air, soil and sediment, also in rural
runoffs, rain water, and street dusts. The major way PAH can reach water bodies is through dry
and wet deposition, road runoffs, industrial waste water, petroleum spills and fossil fuel
combustion (Simin Nasseri, 2013)..

3
The sources of PAHs are both natural and anthropogenic. Natural emissions occur in volcanic
eruptions, forest fires, or the biosynthesis of some plants. The anthropogenic sources could be
from incomplete burning of fossil fuels and organic material, emissions of motor vehicles,
industries and power generations, and from burning waste in particular (Niño et al., 2014). These
PAHs can also be transported over long distances, and finally be deposited in aquatic
environment, (Leidy, 2015). PAHs can be generated naturally through petrogenic processes or
through combustion mechanisms. The type and concentration of PAH compounds present in a
sample should be assessed in order to determine if the PAH origin is petrogenic or combustion
(Sarria-Villa et al., 2016). Petroleum derived or petrogenic PAH are formed from fossil organic
matter over millions of years at low temperature of about 150 oC (Mastran et al., 1994). This
petroleum derived PAH contain higher amount of the smaller molecular weight PAH such as the
naphthalene, acenaphthene and fluorine (Helfrich and Armstrong, 1986), and also alkylated PAH
such as methylnaphthalenes (Youngblood and Blumer, 1970). Combustion related PAHs result
from pyrolytic synthesis at high temperature (Helfrich and Armstrong, 1986). The lower
molecular PAHs may be rapidly lost from the water column due to volatilization and microbial
degradation, while the larger molecular weight PAHs are more susceptible to losses due to
photo-oxidation and may be removed as a result of sedimentation (Mastran et al., 1994).

Due to their long half-life, PAHs are categorized among persistent organic pollutants (POPs)
(Aygun & Bagcevan, 2019). Among a great number of PAHs present, sixteen are recommended
as priority pollutants by the United States Environmental Protection Agency (Sun et al., 2015).
The USEPA has categorized 16 of the PAHs as priority contaminants based on their possible for
human exposure, toxicity, frequency of occurrence at hazardous waste sites, and the extent of
information available (Mojiri et al., 2019). The 16 PAHs are: naphthalene (NAP),
acenaphthylene (ACY), acenaphthene (ACE), fluorene (FLO), phenanthrene (PHE), anthracene
(ANT), fluoranthene (FLA), pyrene (PYR), benz(a)anthracene (BaA), chrysene (CHR),
benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP),
dibenz(a,h)anthracene (DahA), indeno(l,2,3-cd)pyrene (IcdP), and benzo(g,h,i)perylene (BghiP).
The most commonly detected PAH in drinking water is fluoranthene, but under normal
conditions, its presence does not pose a threat to human health (Badawy & Embaby, 2010). The
permissible PAH content in water intended for human consumption is based on the sum of
benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(g,h,i)diperylene, and indeno(1,2,3-
4
cd)pyrene; it amounts to 0.1 _g/L, but must not exceed it due to the toxic, mutagenic and
carcinogenic properties of PAHs (Agata Rosinska, 2018).

1.3.1 PAH STRUCTURE

Figure 1.1: Diagram Showing the 16 PAHs and their Ring Numbers

5
1.4 PAH AND HEALTH

Organic compounds are used worldwide in high amounts, after which they are discharged into
water bodies where they can persist, thereby causing severe health and environmental problems
(Mojiri et al., 2019). Several Polycyclic aromatic hydrocarbons (PAHs) have been associated
with the development of a wide range of cancers (Wenzl et al., 2006). For this reason, many
countries have limits in their drinking water for a number of PAHs (Blokker et al., 2013). PAHs
are generally teratogenic, carcinogenic, and mutagenic and may induce lung, bladder, as well as
skin cancer. Exposure to high levels of PAH produces immunosuppressive effects and can cause
oxidative stress during its metabolism (Karyab et al., 2013). Under standards, adopted by the
European Union (EU) for drinking water, the limit of the maximum concentration is 200ng/l for
PAHs. The eight PAHs that are considered possible or probable carcinogens are:
benzo[a]alanthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene benzo[o]pyrene,
indeno [1,2,3,c-d]pyrene, i-henzo-[qh]anthracene and benzo[g,h,i]perylene (Santodonato, n.d.).

PAHs through drinking water can negatively affect not only human health but also some
sensitive species of organisms. A great amount of PAHs can accumulate in water bodies, bio-
accumulate or bio-magnify in food chains. The negative impacts of PAHs on human health and
the ecosystem due to the teratogenic, carcinogenic and mutagenic characteristics may be caused
by the accumulation of high levels of PAHs in environmental compartments, while the negative
impacts may be even greater in the aquatic environment (Sun et al., 2015). Increased incidence
of variety of cancers including stomach, oral, lung and bladder cancer, and other diseases such as
asthma and heart diseases in human is usually associated with high exposure to PAHs (Zhang et
al., 2019). PAHs are also able to suppress the immune system and are regarded as suspected
endocrine disrupting chemicals (EDCs) (Sun et al., 2015; Yu et al., 2018). Benzo[a]fluoranthene
(BaF), benzo[b]fluoranthene (BbF) and indeno[1, 2, 3-c,d]pyrene (InD) have been listed in the
class of possible carcinogenic substances that are harmful to human beings while benzo[g,h,
i]perylene (B[ghi]P) has not been classified as carcinogenic (Seker Fatma Aygun, 2020).

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1.5 HEAVY METALS AND HEALTH

Heavy metals are metallic elements having relatively high density, and even at low
concentrations are poisonous (Cobbina et al., 2015). Heavy metals exist naturally in the earth’s
crust, but can cause serious problems for all living things (Fu & Xi, 2020). Heavy metals are
common pollutants in the environment, which are stable, non-biodegradable and accumulative,
making them a global problem (Mojiri et al., 2019). Both anthropogenic activities and natural
actions contribute to heavy metal abundance in the environment. Solid waste heaps; disposal of
metals; agricultural, municipal and industrial waste; animal and human excreta; geological
weathering; and leaching of metals from garbage are the main sources of environmental heavy
metals (Yan et al., 2018). Although some heavy metals are necessary for biosynthesis in human,
excessive amounts may be toxic, such as nickel (Ni), copper (Cu) and zinc (Zn). Some metals
have adverse effects on human even at very low concentrations, including lead (Pb) and
chromium (Cr). Due to their toxicity and non-biodegradability, the discharged heavy metals in
water seriously threaten aquatic organisms and human health via drinking water as well as food
chain pathways.
According to the Clean Air Amendment Act of 1980, 15 elements are considered as potentially
toxic and hazardous to human habitat and health (U.S. Statutes at large, 1990). These elements
are antimony (Sb)., arsenic (As)., beryllium (Be)., cadmium (Cd)., chlorine (Cl)., cobalt (Co).,
chromium (Cr)., manganese (Mn)., mercury (Hg)., molybdenum (Mo)., nickel (Ni).,
phosphorous (P)., selenium (Se)., uranium (U)., and thorium (Th). (Goodarzi & Mukhopadhyay
(Muki), 2000). A number of heavy metals can induce cancer (e.g., inorganic arsenic [As]) and/or
non-cancer (e.g., mercury [Hg]) risks in humans. Various epidemiological studies have shown
that heavy metals, namely Pb+2, Ni+2, Cd+2 and Cr+6, are carcinogenic and can cause diseases
related to lung, pulmonary, prostate, liver, renal, hematopoietic system, urinary bladder, stomach
and pancreas (Jalees et al., 2019). Natural and anthropogenic high concentrations of heavy
metals in water, is one of the major health problems. Poisoning by lead, copper, cadmium and
zinc have severe effects on the nervous system, kidneys and blood. Lead is involved in reducing
IQ, and can also delay learning, as well as the physical growth of children and adults. Chromium
can cause gastrointestinal tract and lung cancer (Peiravi et al., n.d.).

7
1.6 AIM AND OBJECTIVES

The major aim of this study is to assess the levels of Polycyclic Aromatic Hydrocarbon (PAHs)
and heavy metals contamination in selected oil spill sites within Lagos State, Nigeria.

Objectives include:

1. To assess the concentration of pollutants (PAHs and heavy metals) in groundwater

samples in the study area.
2. To determine the source of the pollutants
3. To investigate the distribution of the pollutants.
4. To carry out a health risk assessment of the pollutants

1.7 SCOPE OF THE STUDY

To achieve the above objectives, the scope of the study includes

1. Collection of ground water samples from the oil polluted sites in Lagos Nigeria.
2. Analysis of water samples using liquid-liquid extraction method.
3. Statistical analysis of data

1.8 DESCRIPTION OF THE STUDY AREA

1.8.1 LOCATION AND ACCESSIBILITY OF THE STUDY AREA

The study area is located within the Eastern Dahomey Basin of the Southwestern Nigeria. It is
located within longitudes 003o15'36.9" to 003o17'37.5" and latitudes 06o31'04.2" to 06o33'26.1",
Lagos State, Southwestern Nigeria. Major communities within the study area are Ijegun, Ejigbo
and Isheri. (Figure 1.1).

8
 a

Figure 1.2: Study Area of Ijegun (a) and Ejigbo (b), Showing Sample Points

9
1.8.2 RELIEF AND DRAINAGE
The topography of the area is undulating with some areas being lowland while some are
highlands. The drainage system is characterized by waterways and many small river channels.

Figure 1.3: Study Area Map Extract Showing the Dendritic Drainage Pattern

10
1.8.3 POPULATION AND POPULATION DENSITY

The study area is largely populated with an estimated number of about 2 million people. The
population density is about 14,812/km2, with an area of about 183.5 km2.

1.8.4 CLIMATE AND VEGETATION

The study areas have the same climatic conditions of partly tropical hot and humid weather. It
has an average daily temperature of only 31 degrees centigrade. There are two distinct climatic
seasons which are the dry season, lasting from November to March, and the wet season from
April to October. The air is very humid throughout the year, with monthly average temperatures
ranging from 28oC in July/August to 32oC in February/March. The vegetation cover is dominated
by swamp forest, wetlands and tropical swamp forest comprising of freshwaters and mangrove.
Vegetation in the study areas is sparse as compared to other areas.

1.9 PREVIOUS WORKDONE

Sarria-Villa et al., 2016, 2015 studied the human health risks due to the presence of PAHs in
drinking wate in the Columbian Cauca riverr, and the results showed likely carcinogenic effects
especially in children. A study by Okoli et al., 2011, examined the presence of polycyclic
aromatic hydrocarbons in groundwater sources of the coastal settlement in the Port Harcourt
refinery company, which revealed high concentration of PAHs which exceeded the WHO
maximum permissible limit for PAHs in drinking water. The study showed that Acenaphthene
had the highest concentration, while Acenaphthylene had the least maximum concentration. The
screening of PAHs in water samples was carried out by Pensado et al., 2004, and the strategic
sample composition technique was used. Results showed that the concentration levels spiked in
some cases were higher than allowed limits for drinking water, and in some other cases were just
in the limit or even down those limits. PAHs in drinking water constitute an important
environmental problem which was addressed in Zhejiang province, China, by Zhu et al., 2008,
and the sources were petroleum products. PAHs and benzene, toluene, ethylbenzene and xylenes
(BTEX) were identified in groundwater samples around gasoline stations in Rio de Janerio,

11
Brazil (Brindha & Elango, 2014). The carcinogenic and the non-carcinogenic risks due to PAHs
in drinking water were assessed by Fu & Xi, 2020.

A study carried out by the Central Pollution Control Board (CPCB) of India in some of the major
cities indicates the absence of PAHs in groundwater (Brindha & Elango, 2014). (Badawy &
Embaby, 2010), observed PAHs in water, sediments, soil and plants in Aojiang river, China,
which was due to the possible contribution from leather industries. Industrial wastewater and
municipal road runoff contributed to PAHs in surface waters, sediments and soils of Hangzhou,
China (Chen, 2007). (Brindha & Elango, 2014), carried out a research to identify the extent of
PAHs contamination in groundwater of Royapuram area, Chennai, India. (Karyab et al., 2013),
identified PAHs in agricultural soils due to the contribution from anthropogenic sources. In
Ghana, (Badr et al., 2011), Tay and Biney (2012), identified soils polluted by PAHs due to
incomplete combustion of petroleum products, especially from atmospheric fallout from
automobile exhausts.

12
 CHAPTER TWO

2.1 REGIONAL GEOLOGY OF NIGERIA

Nigeria lies between latitude 4oN and 15oN and longitude 3oE and 14oE within the Pan African
mobile belt in between the West African and Congo cratons. The geology of Nigeria as described
by Obaje (2019), comprises of three litho-petrological components which are: Basement
complex, the younger granites, and sedimentary basins. The basement complex which consists of
the Migmatite – Gneiss complex, the schist belts and the older Granites, is Pre Cambrian in age.
The younger granites, which are predominantly magmatic rings are Jurassic in age, while the
sedimentary Basins, which are made up of the Dahomey basin, the Sokoto Basin, the Chad basin,
the Benue trough, the Mid Niger Basin and the Niger Delta Basin comprises of sediment fill of
cretaceous to tertiary ages.

2.2 THE DAHOMEY BASIN

The Dahomey Basin is a combination of inland/coastal/offshore basin that stretches from

southeastern Ghana through Togo and the Republic of Benin to southwestern Nigeria (Okeke
O.C, 2019). The Nigerian sector of the Benin (Dahomey) Basin is located in the southwestern
Nigeria covering three different states, namely: Lagos, Ogun and Ondo (Abiahu, 2019). The
Eastern Dahomey Basin was initiated during the Mesozoic in response to the separation of the
African – South American land masses and the subsequent opening of the Atlantic ocean. The
Eastern Dahomey Basin is bounded on the west by faults and other tectonic structures. Its
Eastern limit is marked by the Benin hinge line, a major fault structure marking the western limit
of the Niger Delta basin. To the west of the Benin Hinge line is the Okitipupa Ridge (Adegoke,
1969). The tertiary sediments of the Dahomey Basin thin out and are partially cut off from the
sediments of the Niger Delta Basin against this ridge of basement rocks.

13
 Study Area (Ijegun & Ejigbo)

Figure 2.1: Geologic Map of the Eastern Dahomey Basin (Adegoke et al., 1981)

14
2.3 TECTONIC SETTING

The basin is a marginal pull – apart basin initiated during the early cretaceous separation of south
American and African plates thereby constituting part of a system of West Africa pre – cratonic
basins developed during the commencement of rifting, associated with the opening of the Gulf of
Guinea in the late Jurassic to early Cretaceous (Adegoke, 1980). The basin consists of cretaceous
– tertiary sequence, which outcrops in an arcuate belt roughly parallel to the ancient coastline.
The tertiary sediments thin out to the east and are partially out off from the sediments of Niger
Delta basin against the Okitipupa basement ridge. The Dahomey basin extends from southeastern
Ghana in the west, through southern Togo and southern Benin Republic to the southwest Nigeria.
The Lagos coast is made up of creeks and lagoons developed by barrier beaches associated with
sand deposition in the geologic past. The subsurface geology reveals two basic lithologies; clay
and sand deposits (M. A. Yusuf & Abiye, 2019). These deposits may be intercalated in places
with sandy clay or clayey sand and sometimes with vegetable remains and peat (K. A. Yusuf,
2007).

The geology is made up of sedimentary rock mostly of alluvial deposits. These are mainly
composed of loose and light grey sand mixed differently with varying proportion of vegetation
matter on the lowland; while the reddish and brown loamy soil exists in the upland (Olowofela et
al., 2012). The geology is underlain by inter-bedded sands, gravely sands, silts, and clays
(Akoteyon et al., 2011). The sub-surface is essentially composed of alternating sequence of sand
and clay (Akoteyon et al., 2011). The basin is bounded to the west by faults. Its eastern limit is
marked by the Benin hinge line, a major fault structure marking the western limit of the Niger
delta basin. The Dahomey basin was initiated during the Mesozoic in response to the separation
of the African-South American land masses (Gondwanaland) and the subsequent opening of the
Atlantic Ocean. Deposition was initiated in fault-controlled depressions developed in the
crystalline basement complex as a result of the rift-generated basement subsidence during the
Early Cretaceous (Neocomian). The subsidence gave rise to the deposition of a very thick
sequence of continental grits and pebbly sands over the entire basin (M. A. Yusuf & Abiye,
2019).

15
Table 1.1: Stratigraphic Chart of the Southwestern Nigerian Basin

16
2.4 LITHOSTRATIGRAPHY OF THE DAHOMEY BASIN

The stratigraphy and stratigraphic architecture have been well established by various workers
(Jones and Hockey, 1964; Omatsola and Adegoke 1981; Agagu, 1985; Enu, 1990, Nton, 2001;
Nton, et al 2006). However, Agagu (1985) placed together the stratigraphy of eastern Dahomey
basin from surface as well as subsurface data, deciphering that in most part of the basin, the
stratigraphy is dominated by monotony of sand and shale alternations with minor proportion of
limestone and clay. The stratigraphy of the cretaceous to tertiary sedimentary pile which
unconformably overlies the basement complex includes different lithostratigraphic units.

2.4.1 ABEOKUTA GROUP

Abeokuta group is the oldest group of sediment in the basins lying non-conformably in the
basement (Jones and Hockey, 1964). Omatsola and Adegoke (1981) on the lithostratigraphy of
Dahomey Basin recognized three formations belonging to the Abeokuta group based on
lithologic homogeneity and similarity of origin. This group is the thickest sedimentary unit
within the basin. The formations from oldest to youngest are Ise, Afowo and Araromi formation.

2.4.1.1 Ise Formation

Ise formation unconformable overlies the basement complex of southwestern Nigeria, consisting
of conglomerates and grits at the base which is in turn overlain by coarse to medium grained
sands with interbeded kaolinite. The conglomerates are imbricated and at some locations where
ironstone occur (Nton and Elueze, 2005). An age range of Neocomian – Albian is assigned to
this formation based on paleontological assemblages.

2.4.1.2 Afowo Formation

Afowo formation overlies the Ise formation, and is composed of coarse to medium grained
sandstone with variable but thick interbedded shale, siltstone and claystone. The sandy facies are
tar-bearing while shales are organic-rich (Enu, 1990). Using palynological assemblage, a
Turonian age is assigned to the lower part of this formation, while the upper par ranges into
Maastrichtian.

17
2.4.1.3 Araromi Formation

The youngest Cretaceous formation in the group is Araromi formation, which conformably
overlies the Afowo formation. It is composed of fine to medium grained sandstone as the base,
overlain by shales, silt and with interbedded limestones, marl and lignite. Omatsola and Adegoke
(1981) assigned a Maastrichtian to Paleocene age to this formation based on faunal content.

2.4.2 IMO GROUP

The Imo group overlies the Abeokuta group and chronologically consists of two
lithostratigraphic units which ranges from oldest to youngest are Ewekoro and Akinbo
formation.

2.4.2.1 Ewekoro Formation

Ewekoro formation overlies the Araromi formation in the basin and is described by Adegoke,
1977, to be a shaly limestone unit. This formation is an extensive limestone body, which is
traceable over a distance of about 320km from Ghana in the west, towards the eastern magin of
the basin in Nigeria (Jones and Hockey, 1964).

2.4.2.2 Akinbo Formation

Akimbo formation which is made up of shale and clay sequence overlies the Ewekoro formation
(Ogbe, 1972). The base of the formation is defined by the presence of glauconitic bands with
lenses of limestone (Ogbe, 1972).

2.4.3 OSHOSUN FORMATION

Oshosun formation overlies the Akinbo formation and consists of greenish grey or beige clay and
shale with interbeds of sandstones. The shale is thickly laminated and glauconitic. This
formation is phosphate – bearing (Jones and Hockey, 1964). An Eocene age is assigned to this
formation based on fossil content.

18
2.4.4 ILARO FORMATION

Conformably overlying the Oshosun formation is the Ilaro formation and consists of massive,
yellowish, poorly consolidated crodd-bedded sandstone. The formation shows rapid lateral facies
change.

2.4.5 BENIN FORMATION

The youngest stratigraphic sequence in the Eastern Dahomey basin is the Benin formation. It is
also known as the coastal plain sands (Jones and Hockey, 1964), and consists of poorly sorted
sands with lenses of clays. The sands are in part, cross-bedded and show transitional to
continental characteristics. The age is Oligocene to Recent.

19
 CHAPTER THREE

3.1 RESEARCH METHODOLOGY

The method employed basically involves the collection of water samples from suitable sites
where water has been affected, and the laboratory analysis carried out on the samples. It also
gives detailed explanations on the parameters being analyzed, and the locations where the
samples were taken. Multiple samples were taken and not just one, to enable a thorough research
work, thus providing more information. The samples were taken to the laboratory in less than 48
hours to prevent the breakdown of the water components and to also prevent chemical and
bacteriological changes, which would have affected the results being gotten.

3.2 FIELD METHODOLOGY

A total of 20 water samples were taken from various sites in Lagos including: Ejigbo, Victoria
Estate, Surprise Avenue, and Omilaye street (Table 3.2). The sampling points were gotten using
the Global Positioning System (GPS). The samples were collected in random locations of more
than 10m distance from each other, in not less than 200ml amber bottles, which were first
thoroughly cleaned with distilled water before the samples were being collected into them. The
samples were labeled with a paper tape and marker for easy identification and taken to the
research institute for marine oceanography lab not more than 48 hours after collection.

20
 Tank showing colour
which depicts PAH effect

Figure 3.1: Site showing water tank affected by the presence of PAH

21
3.2.1 INSTRUMENTS AND MATERIALS USED FOR SAMPLE COLLECTION

The following instruments were used to obtain samples from the study area. They include

1. Amber Bottles
2. Global Positioning System (GPS)
3. Paper Tape
4. Marker
5. Field Note

Table 3.1: Sampling Coordinates and Description

SAMPLE LOCATION LONGITUDE LATITUDE ELEVATION DESCRIPTION

ID (m)

IJ1 Ijegun 6.52117 3.2602 29.6 Borehole

IJ2 Ijegun 6.52125 3.2605 21.8 Borehole

IJ3 Ijegun 6.5218 3.2611 21.1 Borehole

IJ4 Ijegun 6.5221 3.2604 18.6 Borehole

VE5 Victoria Estate 6.5579 3.28997 33.1 Well

VE6 Victoria Estate 6.5587 3.2912 35.1 Borehole

VE7 Victoria Estate 6.5573 3.2882 39.0 Well

OML8 Omilaye 6.5567 3.2881 29.8 Well

SUP9 Surprise 6.5572 3.2901 30.2 Well

Avenue

SUP10 Surprise 6.5569 3.2904 24.7 Well

Avenue

22
3.3 LABORATORY ANALYSIS

3.3.1 PHYSICOCHEMICAL TEST

Physical parameter such as acidity (pH), Total dissolved solids (TDS), Electrical Conductivity,
turbidity, salinity and temperature ('C) were determined using the HORIBA multi parameter
tester (MPT).

PROCEDURE

1. Fill water sample in MPT to reach the marked point.

2. Put the Multi Parameter Tester on and read values.

3.3.1.1 PHYSICAL CHARACTERISTICS

pH
The pH is a measure of how acidic/basic water is. The range goes from 0-14, with 7 being
neutral. The U.S Environmental Protection Agency recommends that the pH level of water
sources should be at a pH measurement level within 6.5 to 8.5 on a scale that ranges from 0 to
14.
TDS
The Total dissolved solid (TDS) comprise inorganic salts, principally calcium, magnesium,
potassium, sodium, bicarbonates, chlorides, and sulfates and some small amounts of organic
matter that are dissolved in water. It is a measure of the combined content of all inorganic and
organic substances contained in a liquid in molecular, ionized or micro-granular suspended form.
TDS is measured in parts per million (ppm), and according to WHO, the palatability of water
with a total dissolved solids level of less than about 600mg/l is generally considered to be good;
drinking water becomes significantly and increasingly unpalatable at TDS levels greater than
about 1000mg/l

23
3.3.2 DETERMINATION OF PAHs
APPARATUS USED
1. Gas Chromatograph
2. Conical Flask
3. Pipette and Burette

3.3.2.1 EXTRACTION

This was carried out using the Gas Chromatography. A mixture of PAH standards, consisting of
the 16 USEPA priority PAHs (fluorene (Flur), pyrene (Pyr), fluoranthene (Fla),
benzo[k]fluoranthene (BkF), acenaphthylene (Acy), chrysene (Chr), phenanthrene, anthracene
(Ant), benzo[b]fluoranthene (BbF), dibenz[a,h]anthracene (DBahA), benzo[a]anthracene (BaA),
acenaphthene (Acp), indeno[1,2,3-cd]pyrene (Ind) and benzo[a]pyrene (BaP), naphthalene (Nap)
and benzo[g,h,i]perylene (BghiP)), was obtained. For PAHs analysis, a liquid-liquid extraction
system was used to extract PAHs from the water samples (1L each sample). After washing with
ethyl acetate (5 mL), 5 mL methanol and deionized water were used to condition the SPE
cartridges, respectively. Then, the samples flowed into the cartridges (1.2 mL/min) under
vacuum and eluted with ethyl acetate (3 mL). Anhydrous Na2SO4 was used to remove the water
from the extracts, which were reduced by N2 blow-down. Gas chromatographic type Flame
Ionization Detection (GC-FID) was used, with column HP5 (30m × 320um × 0.25um), with
highly purified Helium to analyze all samples. When the temperature was 270'C, aliquot sample
was injected under splitless mode. The temperature of the column was set initially at 60 'C for 1
min which gradually increased to 210'C for 12'C/min and then 320'C at 8'C/min, finally
maintained constant 320'C for 5 mins. The total run time was 32.25mins, and the detector
temperature was 325'C. All water samples were extracted without filtering to reflect exposure
levels of PAHs in the water samples. A separating funnel was used for the extraction of PAHs
from water samples: 250ml of separating funnel containing 25ml of water sample was extracted
twice with 25ml analytical grade Dichloro methane.

3.3.2.2 QUANTIFICATION
High performance liquid chromatographic flame ionization detection was used for the
quantification of PAHs in the water samples. The extracts were collected into 100ml beaker,

24
followed by evaporation to dryness. This extract was later reconstituted with 10ml n-hexane and
this was passed through an SPE column previously preconditioned with n-hexane and eluted
with 10ml n-hexane. The eluted sample was evaporated to dryness and later reconstituted with
1.5ml n-hexane and this was transferred to a vial bottle. The PAHs analysis was carried out using
GC-FID (Modified EPA Method 3510-C).

GC-FID
 Agilent GC-7820A
 Detector Type: FID
 Column: HP5 (30m x 250um x 0.25um)
 Flow Rate: 1.2mL/min
 Injection Volume: 1ul
 Inlet Temp: 270'C
 Inlet Mode: Splitless
 Carrier Gas: Helium Make-Up: Nitrogen
 Ignition Gases: Hydrogen and Compressed air

3.3.3 DETERMINATION OP PTEs

3.3.3.1 SAMPLE PREPARATION USING AAS
The collected samples were analyzed for five heavy metals including Pb, Ni, Zn, Cu, and Cr
using standard methods for the examination of water. Concentrations of the heavy metals in all
samples were measured using an inductively coupled plasma mass spectrometry (ICP-MS). The
limit of detection (LOD) of individual metal was in the range 0.5-5 ng/L for water samples.

3.3.3 DIGESTION OF SAMPLES FOR PTEs

A 25mls of liquid (aqueous) matrix was weighed into a beaker, then 25mls of Aqua Roga (i.e.,
3:1 of HCL: Nitric Acid) was added, and the beaker was placed on a hot plate and heated with
fume cupboard until content reduced to about 5mls. The sample was allowed to cool and then the
contents were filtered using filter paper. The collected sample was then made up to 50mls or
100mls with distilled water.

25
26
Figure 3.2: Gas Chromatograph used in the lab

Figure 3.3: Fully labeled parts of the Gas Chromatograph

27
3.4 HUMAN HEALTH RISK ASSESSMENT FOR HUMANS

In this study, human health risk was assessed by calculating the potential carcinogenic and non-
carcinogenic effects of exposure of a person to the PAHs over a certain period (US EPA, 2009;
Titilawo et al., 2018). The evaluation was done based on exposure by ingestion and dermal
contact since the borehole and well water is used for drinking, bathing, and washing. The two
pathways of water exposure considered in the present analysis were direct ingestion and dermal
absorption, which were calculated by Equations (1) and (2), respectively. These equations were
adopted from the USEPA, (2004).
For ingestion:
C × IR × EF × ED
ADDi= (eq 1)
( BW × AT ) ×CF

ADD is the Average daily intake through ingestion (mg/kg day); C is the concentration of PAH
in water (μg/L); IR is the ingestion rate (adult: 2 L/day; child: 1 L/day); EF is the exposure
frequency (350 days/yr. for both ingestion and dermal absorption); ED is the exposure duration
(adult: 60 yrs; child: 6 yrs); BW represents the average body weight (adult: 70 kg; child: 15 kg);
AT means the average time, i.e., ED × 365 days (adult: 10,950 days; child: 2190 days) and CF is
the conversion factor and is 10×-3 (US EPA, 1993; 2011; 2017).
For dermal adsorption:
C × SA Χ Kp Χ ET Χ EF Χ ED ×CF
ADDd= (eq 2)
BW Χ A T

ADD represents the average daily doses by dermal contact (mg/kg/ day); C (μg/L) is the
concentration of PAHs in water; SA (cm2) is the exposed skin area (adults: 18,000 cm2;
children: 6600 cm2); Kp (cm/h) is the dermal permeability coefficient 1.2; ET (h/day) is the
exposure time for shower and bathing (adults: 0.25 h/day; children: 0.33 h/day); EF is the
exposure frequency and 350 days/yr. for dermal absorption was used in the calculation; ED is the
exposure duration (adult: 60 yrs; child: 6 yrs); BW represents the average body weight (adult: 70
kg; child: 15 kg); AT means the average time, i.e., ED × 365 days (adult: 10,950 days; child:
2190 days), and CF is 10×-3 (US EPA, 1989; 1997; 2004 and 2011).

28
3.4.1 NON-CARCINOGENIC
Non-carcinogenic PAHs, hazard quotient (HQ) was calculated by dividing the ADDd by
reference dose (RfD) for individual contaminant as presented in Eq. (3). Hazard index (HI) and
the sum of HQs also were estimated for all PAHs congeners in the samples using Eq. (4). RfD,
which represents dermal reference dose for each PAH congener, was not available for other
priority compounds except for only six: i.e., naphthalene, fluorene, anthracene, phenanthrene,
fluoranthene, and benzo(g,h,i)perylene (Table 3.3).

ADDd
HQ= ( eq 3)
RfD

HI =Σ HQs (eq 4)

3.4.2 CARCINOGENIC RISK

Cancer risk (ILCR) and risk index (RI) were determined for carcinogenic PAHs (cPAHs) found
in the water samples using ADDi and ADDd (mg/kg/day), in which Eqs. (1) and (2) were used to
calculate the ADDd (by dermal contact) the same way as for ADD, only that AT = 25,550 was
used for the two age categories instead of the previous value. To calculate the Cancer Risk (CR)
and Risk Index (RI) in the water samples, Eqs. (5–7) were used according to USEPA guidelines
(US EPA, 1989; 2015; Jamhari et al., 2014).

For ingestion:
CRi=ADDi × CSF Eq(5)
For dermal adsorption:
CRd =ADDd × CSF (6)
RI =ΣCR (7)
CSF represents the cancer slope factor for each PAH congener. CSF for benzo(a)pyrene is 7.3
mg/kg/day (US EPA, 2015). Factors for other PAHs were afterward calculated from the values
for benzo(a)pyrene by taking a multiple of TEF for each compound and its respective CSF as
presented in Tables 4.3 (IARC 2006; Kumar et al., 2015; Wei et al., 2015; Adeniji et al., 2019).
RI is the risk index which is the sum of all the cancer risk values.

29
Table 3.2: Values used for the calculation of health risk assessment
Abrv. Parameter and Unit Value Reference
IR Water ingestion rate (mg/day) Children: 0.2 and Adult: 0.1 USEPA, 1993

EF Exposure frequency (day/y) 350 USEPA, 1993

ED Exposure duration (years) Children: 6 and Adult: 60 USEPA, 1993

BW Body weight (kg) Children: 15 and Adult: 70 USEPA, 1993
AT Average time (day) Children:2190 and Adult: 10,950; USEPA, 1993
SA Exposed surface area of skin (cm2) Children: 18000 and Adult: 6600 USEPA, 1993

CF Conversion factor (kg/mg) 10×-3 USEPA, 1993

ET Exposure time for shower and bathing h/day Children: 0.33 and Adult: 0.25 USEPA, 1993

Kp Dermal permeability coefficient (cm/h) NaP(6.9×10-3), PhE(2.7×10-1), Fluo (3.6×10-1), BghiP (-), Chry USEPA, 1993
(8.1×10 ), BaA (8.1×10 ), BbF(1.2), BaP(1.2), DahA (2.7),
-1 -1

BkF(-), AnT(-). IcdP (1.9)

RfDi Reference dose for ingestion pathway NaP(0.02), PhE(0.03), Fluo (0.04), BghiP (-), Romanus et al., 2019

RfDd Reference dose for dermal pathway NaP(0.02), PhE(0.04), Fluo (0.04), BghiP (-), Wei et al., 2015

CSF Cancer Slope Factor Chry (0.0073), BaA (0.73), BbF(0.73), BaP(7.3), DahA (7.3), Wang et al., 2009
BkF(-), IcdP(0.73)

30
 CHAPTER FOUR

RESULTS, INTERPRETATIONS AND DISCUSSIONS

4.1 RESULT PRESENTATION

The results for the analysis carried out to investigate the quality of groundwater in 10 locations
are shown in the various tables displayed and they are discussed appropriately.
The table 4.1 below shows the physical parameters tested in the water samples of the 10
locations.

4.2 PHYSICAL CHARACTERISTICS

4.2.1 pH
The average pH values of the Ijegun and Ejigbo range from 3.54 - 6.6 (Table 4.2), which slightly
indicates acidic water, with sample 5 having highest acidity (Table 4.1). This is due to the high
level of contamination of the groundwater in these locations. According to the W.H.O standard,
the water is not meet for human consumption.

4.2.2 TOTAL DISSOLVED SOLID (TDS)

The values in the samples are generally less than the maximum level.

31
Table 4.1: Physical parameters of ground water at Ijegun and Ejigbo

SAMPLE pH CONDUCTIVITY TURBIDITY TDS g/l

LOCATION mc/cm NTU
L1 4.79 0.127 2.5 0.083
L2 3.74 0.000 12.3 0.000

L3 5.03 0.064 3.0 0.041

L4 4.62 0.112 9.0 0.073

L5 3.54 0.172 14.2 0.112
L6 4.38 0.211 35.7 0.137
L7 4.11 0.000 3.9 0.000

L8 4.91 0.516 6.1 0.330

L9 4.99 0.147 5.1 0.095

L10 5.16 0.610 13.4 0.391

Mean 5.4225 0.27985 9.82 0.1804

min 3.54 0 2.5 0
max 6.6 0.7 35.7 0.448
Who limit 6.5-8.5 400μS/cm 5NTU 600ppm

32
Figure 4.1: Box plot showing the physical parameters present in the samples

33
4.3 DETERMINATION OF THE HEAVY METALS

The results of the heavy metal analysis on the water samples are presented in Table 4.3. Five
heavy metals were analyzed for in the groundwater samples collected in the study area.
However, Chromium (Cr), Cadmium (Cd), and Nickel (Ni) were identified to be below the
detection limit of 0.015 μg/l, 5.0 μg/l and 0.05 μg/l. Two out of five heavy metals determined
were frequently detected in all the sampling sites except that Iron (Fe) was not detected in
locations 3, 6,7 9, and 10. It is noteworthy that Chromium (Cr), and Cadmium (Cd) were below
detection limit in all the study sites. According to WHO, and US Environmental Protection
Agency guidelines, maximum allowable concentration of Lead in drinking water is 0.01 mg/l
and 0.015 mg/l respectively; while that of Iron is 0.3mg/l. the result is represented in Table 4.3

4.3.1 IRON
Iron the most abundant element by weight on earth (32.1%), and the fourth most abundant
element in earth's crust (Kumar and Puri, 2012) was detected in five out of the ten water samples
in the present investigation between 0.022 to 0.792 mg L-1, with a mean value of 0.3476 (Table
4.3). The observed experimental values were mostly below USEPA permissible limit of 0.3mg
L-1 which is considered safe for drinking in all the locations except L4 and L5 that had values of
0.626 mg L-1 and 0.792 mg L-1 respectively, indicating that the groundwater might not present
any serious aesthetic challenge. Values higher than 0.001mg L-1 are toxic to aquatic lives
(Fatoki et al., 2002; Daso and Osibanjo, 2012; Idoko et al., 2012).
Given its natural abundance in the earth, the concentrations recorded in this study could be due
to the interaction of rainwater with soils and rocks, releasing ferrous iron into the environmental
waters rather than any anthropogenic source (Idoko et al., 2012). This is because the metal of
interest is reportedly available in Nigeria soils, lagoons and aquatic lives in high quantity
(Asaolu and Olaofe, 2004; Nwajei and Gagophien, 2000). Other sources of iron in the study
sites, may include contributions from waste discharge, cookware, steel, cast and galvanized iron
pipes used for water supply in the capital city, as well as old roofing sheets that may be eroding
due to rainfall in the area (Roberts, 1999; Baby et al., 2010; Eletta, 2012; Godwin et al., 2015).

34
Moderate level of iron in water is desirable because it is an essential element in human nutrition,
and it is required for the synthesis of hemoglobin in the red blood corpuscles (Vetrimurugan et
al., 2017). It also supports growth and metabolic processes of both humans and animals (Tria et
al., 2007; WHO, 2008; Kumar and Puri, 2012; Edward et al., 2013). High concentration of iron
in water generally causes inky flavour, bitter, astringent and discolouring taste, plumbing fixtures
and scaling which encrusts pipes (Saeed and Shaker, 2008; Hassan, 2012). At toxic levels, iron
can bring about damage of the cells in the heart, liver, gastrointestinal tract, cardiovascular
system and kidneys, leading to cardiac arrest, depression, coma, convulsions and various
respiratory disorders (Roberts, 1999; Baby et al., 2010; Idoko et al., 2012).

4.3.2 LEAD
Lead is a metal which occurs naturally, and is used in many industrial activities (Ibeto et al.,
2012). It is a very soft metal and was principally used in pipes, drains, soldering materials,
batteries, cable coverings, plumbing, fuel additives, PVC plastics, x-ray shielding, crystal glass
production, pesticides and as paint pigments (Baby et al., 2010). Lead was detected in all the
water samples examined in this study. It ranged from 14.098μg/l to 15.594μg/l, with a mean
value of 15.0289μg/l. Lead showed the highest concentration in groundwater present in L7, and
had the least concentration in L9. Maximum allowable concentration of Lead in drinking water
according to WHO and USEPA is 0.01 mg/l and 0.015 mg/l respectively, and the water samples
showed values above the permissible limit, making it unsafe for drinking.
Lead is a carcinogenic PTE that is very toxic even in trace levels to aquatic organisms as well as
humans (Idoko et al., 2012). Exposure to Lead, even in low concentrations could result in many
negative health effects, affecting body organs and systems including the bones, brain, blood,
kidneys, gastrointestinal tract, thyroid gland and reproductive system (Baby et al., 2010; Ibeto et
al., 2012; Edward et al., 2013; Jeje and Oladepo, 2014; Vetrimurugan et al., 2017).

35
4.3.3 CHROMIUM (Cr)
Chromium is mostly used in the manufacture of some products such as pigments for paints,
metal alloys, cement, rubber and paper (Jalees et al., 2019). Other sources of Cr in the
environment include plastics, dyes, printing ink, cutting oils, photographic materials detergents,
wood preservatives, erosion of rocks, power plants, liquid fuels, brown and hard coal, industrial
and municipal wastes, laundry chemicals, road run off due to tire wear, corrosion of bushings,
brake wires and radiators. In the study, concentration of chromium was not detected in any of the
sampling site (Table 2). Also, its non-detection does not really mean it was actually absent in the
groundwater but that it was obtainable in extremely trace concentrations below the detection
limit of the analytical instrument.

4.3.4 CADMIUM (Cd)

Cadmium is a naturally occurring metallic element, which is used in many industrial processes
including electroplating and galvanization; production of pigments, and manufacturing of
batteries, plastics, metal containers, and fertilizers. Cadmium has been recognized to be a highly
toxic element, in which exposure to it can result in damage to the blood – brain barrier and
nervous systems, kidney damage (proteinuria) and respiratory effects, e.g., reduction in forced
vital capacity and reduction in peak expiratory flow rate. Cadmium was not detected in any of
the water samples, but might still be present in trace concentrations.

4.3.5 NICKEL (Ni)

Nickel belongs to the transition metals and is hard and ductile. Pure Nickel is found in Earth’s
crust only in tiny amounts, usually in ultramafic rocks. Nickel is slowly oxidized by air at room
temperature and is considered corrosion-resistant. Historically, it has been used for plating iron
and brass, coating chemistry equipment, and manufacturing certain alloy that retain a high
silvery polish, such as German silver. The major source of Nickel exposure is oral consumption,
as Nickel is essential to plants. Humans may absorb Nickel directly from tobacco smaoke and
skin contact with jewelry, shampoos, detergents, and coins.
Nickel compounds are classified as human carcinogens based on increased respiratory cancer
risks observed in epidemiological studies of sulfidic ore refinery workers. Nickel allergies

36
affecting pierced ears are often marked by itchy, red skin. Nickel was however not detected in
any of the
LOCATION LEAD NICKEL IRON (Fe) CADMIUM CHROMI
(Pb) (Ni) (mg/l) (Cd) UM (Cr)

IJ1 14.908 ND 0.165 ND ND

IJ2 15.060 ND 0.022 ND ND

IJ3 14.937 ND ND ND ND

IJ4 14.784 ND 0.626 ND ND

VIC5 14.556 ND 0.792 ND ND

VIC6 15.565 ND ND ND ND

VIC7 15.594 ND ND ND ND

OML8 15.441 ND 0.133 ND ND

SUP9 14.098 ND ND ND ND

SUP10 15.346 ND ND ND ND

MIN 14.098 ND 0.022 ND ND

MAX 15.594 ND 0.792 ND ND

MEAN 15.0289 ND 0.3476 ND ND

groundwater samples.
Table 4.2: Concentrations of Heavy Metals present in the Samples

37
4.4 PAHs RESULT

Results represented in Table 4.4.1 showed that 14 PAHs Naphthalene (NaP), acenaphthylene
(AcY), Phenanthrene (PhE), Anthracene (AnT), Fluoranthene (FlA), Pyrene (PyR),
Benz(a)anthracene (BaA), Chrysene (ChR), Benzo(b)fluoranthene (BbF), Benzo(k)fluoranthene
(BkF), Benzo(a)pyrene (BaP), Dibenz(a,h)anthracene (DahA), Indeno(l,2,3-cd)pyrene (IcdP),
and Benzo(g,h,i)perylene (BghiP) were identified in the water samples collected from Ijegun and
Ejigbo, Lagos State confirming the ubiquitous nature of the pollutants (Wang & Campiglia,
2008). However, Naphthalene (NaP), and acenaphthylene (AcY), were only present in samples
IJ1 and VIC6 respectively, while Fluorine (FLO) and Acenaphthene (ACE) were not detected in
any sample during the period of study. The total concentration of detected PAHs in the first four
samples gotten from Ijegun was 47.66, while that of VIC which is samples 5 to 7 was 48.66, and
the samples from SUP and OML totaled 27.45. The locations present in VIC are identified to
have the highest concentration of PAHs compared to the other locations (Table 4.3). From the
mean, it is shown that Benzo(g,h,i)perylene has the greatest concentration of PAHs present in the
groundwater samples in the 10 locations, and is revealed to be 34% (Figure 4.5), followed by
Indeno(1,2,3-cd)pyrene (13%), and then Chrysene (12%).
As stipulated by WHO (2017), the maximum permissible limits for total PAHs in drinking water
is 0.2 μg/L. Water samples from this study area have seven PAHs with concentration higher than
the standard set by WHO, indicating a public health concern because PAHs have been confirmed
to be carcinogenic, and man stands the greatest risk of bioaccumulation.. The seven PAHs with
total concentration higher than the set standards are Phenanthrene (PhE), Fluoranthene (Fluo),
Pyrene (PyR), Benz(a)anthracene (BaA), Benzo(b)fluoranthene (BbF), Benzo(a)pyrene (BaP),
Dibenz(a,h)anthracene (DahA), and Benzo(g,h,i)perylene (BghiP); while those below the limit
are Anthracene (AnT), Benzo(k)fluoranthene, Naphthalene (NaP), acenaphthylene (AcY),
Indeno(l,2,3-cd)pyrene (IcdP), and Chrysene (Chr).
The petroleum-derived PAH assemblages contain high amounts of the low molecular weight
(LMW) PAHs such as naphthalene, acenaphthalene and fluorine. Combustion-derived PAH
results from pyrolytical synthesis at high temperature. These PAH assemblages tend to contain
more of higher molecular weight PAHs (HMW PAHs) such as phenanthrene, fluoranthene,

38
pyrene, BaP, It was detected that low molecular weight (LMW), medium molecular weight
(MMW), and high molecular weight (HMW) PAHs were present in the samples (Table 4.3).
Naphthalene is one of petrogenic PAHs with low molecular weight that originates from oil spills
and coal incineration (Sun et al., 2015). Concentrations of LMW PAHs in the area, indicate
naturally occurring PAHs (petrogenic and biogenic origins), while PAHs from combustion
processes (pyrolytic origin) suggest elevated concentrations of HMW. In this study, it is
observed that LMW PAHs occurred in a ratio lower than the MMW and HMW PAHs (4:10),
suggesting that PAHs in the water samples were generally of both petrogenic and combustion
origin, but more of petrogenic origin. The presence of LMW PAHs in water can be attributed to
their high vapor pressure and water solubility, also due to their persistence in the environment
and more PAHs could have accumulated within years, while the high concentration of HMW
PAHs can be attributed to their lower water solubility, inability to decompose quickly and great
tendency to adsorb onto solid phases.

39
Table 4.3: PAH Distribution and Concentration in Water Samples Analyzed

MMW
LMW HMW

I(1,2,3- Ben(g,h, TPAH

LOC NaP Anth AcE PhE Fluo Pyr B(a)A Chr. B(k)F B(b)F B(a)P. D(a,h)A
cd)P i)p s
0.26
IJ1 0.177 0.109 0 0.114 0.189 0.141 0.963 0.714 0.336 0.422 0.552 0.228 0.393
6 4.604
IJ2 0 0.884 0 0.269 0.287 0.42 0 0.106 1.17 0.35 0.747 0.896 2.79 6.5 14.419
13.477
IJ3 0 0.933 0 0.69 0.203 0.57 0.817 1.22886 0.841 0.218 0.529 0.646 2.22595 4.57607
88
0.34 15.155
IJ4 0 0.748 0 0.127 0.195 0.201 0.901 0.973 4.445 0.564 0.747 0.454 5.45268
8 68
MEA 0.044 0.40 0.79971 1.42448 4.23043 47.656
0.6685 0 0.3 0.2185 0.28975 0.9245 1.33725 0.5655 0.71025
N 25 1 5 75 8 56
0.33 20.525
VIC5 0 5.4527 0 0 0.252 0.524 0.649 1.11439 0.277 0.743 0.94 3.58168 6.65445
7 22
0.96 19.317
VIC6 0 0.332 0.136 0.524 0.16 0.977 8.6297 2.31918 0.461 0.282 0.483 0.756 3.28969
8 57
8.8176
VIC7 0 0.559 0 0.222 0.314 0 0.246 0.514 0.85 0.365 0.324 0 1.62593 3.79775
8
MEA 2.11456 0.04533 0.91533 0.43 0.58233 3.26423 1.42785 0.36766 0.44966 0.47433 48.660
0 0.242 1.98787 4.58063
N 667 333 333 5 333 333 667 667 667 333 47
OMI 0.34 10.410
0 0.501 0 0.31 0.139 1.02613 0.425 1.22696 0.332 0.375 0.681 0.691 4.35864
8 5 73
SUR 8.7975
0 0.524 0 0 0.236 0 0 0.422 0.643 0 0.333 0.553 2.01393 4.07258
9 1
SUR 8.2433
0 0.463 0 0 0.409 0 0 0.437 0.588 0 0.324 0 1.86277 4.15957
10 4
MEA 0.10333 0.26133 0.11 0.34204 0.11066 0.41133 1.52256 27.451
0 0.496 0 0.428 0.81932 0.344 4.19693
N 333 333 5 333 667 333 667 58
RIN
2 3 3 3 4 4 4 4 5 5 5 5 6 6
GS

40
 NaP
IJ2 PhE
IJ1
AcE Anth
PhE Fluo
Anth Pyr
Fluo 2% 6% 2
4% 2% Benz(a)ant
2% %
5% Pyr
4% Chr.
9% Benz(a)ant 23
6% 7% %% Ben(b)Flu
3% Chr.
12% 42%
8% Benzo(k)Flu
Ben(b)Flu
9% 21% Benzo(k)Flu Benzo(a)py.
5
16% Benzo(a)py. Dib(a,h)ant
18% 6%
Dib(a,h)ant % Ind(1,2,3-
7% cd)py
Ind(1,2,3-
cd)py Ben(g,h,i)pe
Ben(g,h,i)pe r
r

IJ3
PhE IJ4
PhE
Anth Anth
7
% Fluo Fluo
2 1% 7% 2
5% % Pyr Pyr
4
% 3
Benz(a)ant Benz(a)ant
% %
2
6 Chr. Chr.
34% 8% %
% Ben(b)Flu 4 Ben(b)Flu
49%
9% %
Benzo(k)Flu Benzo(k)Flu
9%
17% 2 Benzo(a)py. Benzo(a)py.
%
6 Dib(a,h)ant 5 Dib(a,h)ant
5% 4 % 7 %
% Ind(1,2,3- 4% Ind(1,2,3-
cd)py %
cd)py
Ben(g,h,i)per Ben(g,h,i)per

Figure 4.2: Pie Chart Showing Percentage Concentrations of PAHs present in L1-L4

41
 NaP
VIC5 AcE
PhE
VIC6 AcE

Anth PhE
Fluo Anth
Pyr Fluo
Benz(a)ant 4 1% 3% 2% 1% Pyr
1%Chr. % 5
32% 27% % 5 Benz(a)ant
2%Ben(b)Flu 3 17% %
% Chr.
Benzo(k)Fl
3%u Ben(b)Flu
1
17% 3%Benzo(a)py % 12% 45% Benzo(k)Flu
.
1% Dib(a,h)ant 2 Benzo(a)py.
5% 4% 5% Ind(1,2,3- % Dib(a,h)ant
cd)py
Ind(1,2,3-cd)py
Ben(g,h,i)p
er Ben(g,h,i)per

VIC7 PhE OMI8

PhE
Anth Anth
4 Fluo
% Fluo

3% 6% 3 Pyr 3% 5% 1 Pyr
% Benz(a)ant % Benz(a)ant
6 3
Chr. % Chr.
% 10%
43% Ben(b)Flu 42% 4 Ben(b)Flu
4
% %
10% Benzo(k)Flu Benzo(k)Flu
3
12%
Benzo(a)py. % Benzo(a)py.
18% 4 Dib(a,h)ant Dib(a,h)ant
%
Ind(1,2,3-
7% 7% 4 Ind(1,2,3-cd)py
%
cd)py
Ben(g,h,i)per
Ben(g,h,i)per

Figure 4.3: Pie chart showing the Percentage Concentrations of PAHs in L5-L8.
NOTE: Locations 5 to 8 are found closer to the pipeline than locations 1 to 4.

42
 SUR9
Anth
SUR10 Anth
Fluo
Fluo
Pyr
5 Pyr
%3 Benz(a)ant
6%% Benz(a)ant
5
7 Chr. 6%
% 5
% %7 Chr.
4 Ben(b)Flu
% Ben(b)Flu
46% %
6 Benzo(k)Flu 4 Benzo(k)Flu
50% %
23% %
Benzo(a)py. Benzo(a)py.
23%
Dib(a,h)ant Dib(a,h)ant

Ind(1,2,3- Ind(1,2,3-
cd)py
cd)py
Ben(g,h,i)per
Ben(g,h,i)per

Figure 4.4: Pie chart showing the Percentage Concentrations of PAHs in Locations 9 & 10

Mean AcE
PhE
1%
3% Anth
8%
2% Fluo
4% Pyr
34%
4% Benz(a)ant
Chr.
12% Ben(b)Flu
Benzo(k)Flu
3% Benzo(a)py.
13% 8% Dib(a,h)ant
5% 4% Ind(1,2,3-cd)py
Ben(g,h,i)per

Figure 4.5: Pie chart showing Average Concentrations of PAHs in all the Locations

43
Table 4.4: Table showing the mean and range of the PAHs in the samples

NAME MINIMUM MAXIMUM MEA REMARK

(min) (max) N

Napthalene (NaP) NaP was only found in

1.77E-01 1.77E-01 1.77E-01 IJ1

Acenaphthene (AcE) AcE was only found in

1.36E-01 1.36E-01 1.36E-01 VIC6

Phenanthren (PhE) IJ1 had the min. conc.,

1.14E-01 6.90E-01 3.22E-01 while IJ3 had max

Anthracene (AnT) 1.09E-01 5.45E+00 1.05E+00 IJ1 - min, VIC5 - max

Fluoranthene (FlA) OML8 min, SUR10

1.39E-01 4.09E-01 2.39E-01 max

Pyrene (PyR) 2.66E-01 9.68E-01 4.65E-01 IJ1 - min, VIC6 - max

Benzo(a)anthracene IJ1 - min, OML8 –

(BaA) 1.41E-01 1.03E+00 5.62E-01 max

Chrysene (ChR), SUR9 - min, max is

4.22E-01 8.63E+00 1.52E+00 VIC6

Benzo(b)fluoranthene IJ3 - min, VIC6 - max

(BbF) 2.18E-01 4.61E-01 3.48E-01

Benzo(k)fluoranthene Min- SUR10, max

(BkF) 5.88E-01 2.32E+00 1.04E+00 VIC6

Benzo(a)pyrene (BaP) VIC had min, IJ2 had

2.82E-01 7.47E-01 4.64E-01 max

Dibenz(a,h)anthracene VIC6 - min, VIC5 –

(DahA) 4.83E-01 9.40E-01 6.87E-01 max

Indeno(l,2,3-cd)pyrene Min – IJ1, max – VIC5

(IcdP) 2.28E-01 3.58E+00 1.62E+00

Benzo(g,h,i)perylene Min – IJ1, max – VIC5

(BghiP) 3.93E-01 6.65E+00 4.33E+00

44
4.5 DIAGNOSTIC RATIO REVEALING POSSIBLE SOURCES OF PAHs

The diagnostic ratios or molecular ratios of some selected PAHs were widely used to identify the
respective sources of contamination (Cardoso et al., 2008; Ma et al., 2008). The primary sources
of PAHs contamination can be categorized as petrogenic, pyrogenic, and diagenetic sources.
Generally, the PAHs concentration ratios, such as BaA/(BaA + Chry), and IcdP/ (IcdP + BgP)
are used as distinct chemical tracers for identifying possible sources of PAHs in environmental
samples (Chowdhury et al., 2016; Wang & Campiglia, 2008). In this study, the ratios of BaA/
(BaA + Chry) versus IcdP/ (IcdP + BgP) were compared. For water samples, If the ratio of BaA/
(BaA + Chry) < 0.2, > 0.35, and ranged from 0.2 to 0.35, this showed a petrogenic origin, fuel
combustion, and coal, grass, wood-burning. The ratios of IcdP/(IcdP + BgP) < 0.2, > 0.5, and
from 0.2 to 0.5 showed a petrogenic origin, coal, grass, wood-burning, and fuel combustion,
respectively (Sarria-Villa et al., 2016). From the diagnostic ratios, 60% ratios of BaA/(BaA +
Chry) were < 0.2, which showed the dominance of petrogenic sources. 10% showed the fuel
combustion source and about 30% showed sources of coal, grass, and wood burning. The scatter
plots for drinking water samples were used to identify the sources of PAHs (Fig. 4.6). Based on
the molecular ratios, the PAHs sources are petrogenic, fuel combustion and coal, grass, and
wood burning. The molecular ratios were used to assess the sources of contamination of PAHs in
drinking water samples, and the predicted sources were petrogenic source, fuel combustion and
coal, grass, and wood burning.

45
Figure 4.6: Diagnostic Ratio Showing Sources of PAHs

46
4.6 HEALTH RISK ASSESSMENT OF PAHs IN GROUNDWATER

Table 4.5: Average Daily Dose by Dermal Absorption (ADDd) of both non-carcinogenic and carcinogenic PAHs
NON-CARCINOGENIC CARCINOGENIC
LO NaP NaP PhE PhE Flou Flou BaA BaA IcdP IcdP BbF BbF ChR ChR BaP BaP DahA DahA
C. adult child adult child adult child adult child adult child adult child adult child adult child adult child
0.001 0.010 0.003 0.000 0.000 0.000 0.0060 0.001 0.2295 0.0518 0.0213 0.004 0.0412 0.0093 0.026 0.006 0.0789 0.0178
IJ1 506 035 795 368 839 947 46 366 98 58 46 821 96 27 809 055 04 22
0.008 0.000 0.001 0.001 0.2806 0.0633 0.0222 0.005 0.0454 0.0102 0.047 0.010 0.1280 0.0289
IJ2 0 0 954 868 274 439 0 0 41 87 35 022 55 67 456 719 75 28
0.022 0.002 0.000 0.001 0.0350 0.007 0.2243 0.0506 0.0138 0.003 0.0527 0.0119 0.033 0.007 0.0923 0.0208
IJ3 0 0 968 228 901 018 35 913 12 65 49 128 45 13 607 591 4 57
0.004 0.000 0.000 0.000 0.0086 0.001 0.0456 0.0103 0.0282 0.006 0.0386 0.0087 0.035 0.008 0.1067 0.0241
IJ4 0 0 228 41 865 977 19 947 67 15 71 385 37 27 831 093 77 17
VIC 0.001 0.001 0.0224 0.005 0.3601 0.0813 0.0175 0.003 0.0278 0.0062 0.047 0.010 0.1343 0.0303
5 0 0 0 0 118 263 7 075 06 36 98 975 31 86 202 661 65 49
VIC 0.017 0.001 0.000 0.000 0.0418 0.009 0.0760 0.0171 0.1473 0.033 0.3700 0.0835 0.017 0.004 0.0690 0.0155
6 0 0 443 692 71 802 96 463 45 76 88 29 75 88 915 046 41 94
OM 0.007 0.000 0.001 0.001 0.0105 0.002 0.1639 0.0370 0.0231 0.005 0.0220 0.0049 0.020 0.004
L7 0 0 39 717 394 574 49 383 59 33 88 237 42 78 584 649 0 0
OM 0.010 0.001 0.000 0.000 0.0441 0.009 0.0695 0.0156 0.0210 0.004 0.0182 0.0041 0.023 0.005 0.0973 0.0219
L8 0 0 319 001 617 697 69 976 06 99 92 764 25 16 824 381 43 87
SU 0.001 0.001 0.2021 0.0456 0.0180 0.0040 0.021 0.004 0.0790 0.0178
P9 0 0 0 0 047 183 0 0 82 66 0 0 96 87 155 778 46 54
SU 0.001 0.002 0.1870 0.0422 0.0187 0.0042 0.020 0.004
P10 0 0 0 0 815 05 0 0 94 58 0 0 4 33 584 649 0 0

Table 4.6: Hazard Quotient (HQ) of Dermal Absorption for nc-PAHs in Each Location

47
 Flou
NaP PhE
ADUL CHILD
LOCATION ADUL CHIL ADUL
T
S T D T CHILD
0.02097 0.02368
0.07529 0.5017 0.00920
1 4
IJ1 7 6 0.09487 1
0.03184 0.03596
0.02171
5 4
IJ2 0 0 0.22386 2
0.02252 0.02543
0.57421 0.05569
5 8
IJ3 0 0 2 3
0.02163 0.02443
0.10568 0.01025
7 5
IJ4 0 0 8 1
0.02796 0.03157
2 8
VIC5 0 0 0 0
0.01775
0.43606 0.04229
3 0.02005
VIC6 0 0 9 4
0.03484 0.03934
0.18474 0.01791
1 7
VIC7 0 0 7 9
0.01542 0.01741
0.25797 0.02502
3 8
OML8 0 0 9 1
0.02618 0.02957
6 3
SUPA9 0 0 0 0

48
 0.04538 0.05125
2 2
SUPA10 0 0 0 0
0.26452 0.29873
0.07529 0.5017 1.87742 0.18209
6 8
HI( Σ HQs ¿ 7 6 5 1

49
Table 4.7: Cancer Risk (CI) of Dermal Absorption for cPAHs in each location

LOCATION BaA BaP BbF ChR DahA IcdP

ADULT CHILD ADULT CHILD ADULT CHILD ADULT CHILD ADULT CHILD ADULT CHILD
0.00441 0.04420 0.57599 0.16760
4 0.000997 0.195709 4 0.015582 0.00352 0.003015 0.000681 6 0.130098 6 0.037857
IJ1
0.07824 0.00366 0.20486
0 0 0.346432 7 0.016232 6 0.003318 0.000749 0.93495 0.211174 8 0.046273
IJ2
0.02557 0.05541 0.00228 0.67408 0.16374
5 0.005777 0.245332 2 0.01011 4 0.00385 0.00087 2 0.152253 8 0.036985
IJ3
0.00629 0.05907 0.00466 0.77947 0.03333
2 0.001421 0.261563 8 0.020638 1 0.002821 0.000637 3 0.176057 7 0.00753
IJ4
0.01640 0.07782 0.00290 0.98086 0.26287
3 0.003705 0.344577 8 0.012846 2 0.002032 0.000459 2 0.221544 7 0.059375
VIC5
0.03058 0.02953 0.02430 0.50399 0.05551
4 0.006908 0.130782 9 0.107593 2 0.027015 0.006102 6 0.113836 3 0.012538
VIC6
0.00770 0.03393 0.00382
1 0.001739 0.15026 9 0.016927 3 0.001609 0.000363 0 0 0.11969 0.027034
VIC7
0.03224 0.03928 0.00347 0.71060
3 0.007283 0.173912 1 0.015397 8 0.00133 0.0003 3 0.160502 0.05074 0.01146
OML8
0.03488 0.57703 0.14759
0 0 0.154434 1 0 0 0.001321 0.000298 9 0.130334 3 0.033336
SUPA9
0.03393 0.13657
0 0 0.15026 9 0 0 0.001368 0.000309 0 0 9 0.030849
SUPA10

50
 0.12321 0.04863 5.73700
3 0.02783 2.15326 0.48635 0.215326 5 0.047679 0.010769 1 1.295797 1.34255 0.303237
RI =ΣCR

51
Figure 4.7: Box Plot revealing the Carcinogenic and Non-carcinogenic PAHs

52
Bio-concentration and bio-accumulation of PAHs occur in organisms through ingestion and
dermal contact route(s) (Mohammadi et al., 2019). The health risk in groundwater in the areas of
study was assessed via dermal absorption pathway. The estimated hazard quotients of PAHs in
the borehole water by dermal absorption ranged from 0.020971 to 0.145 in adults and from
0.0085 to 0.211in children and adults, respectively (Table 4.6). The results indicate that HQs for
both age categories in the water column were below the US EPA maximum limit of 1. Hence,
the chance of humans contracting any non-carcinogenic disease or other health-related issues by
using the water for domestic purposes is very unlikely. Also, the dermal incremental lifetime
cancer risk values calculated were high. CRd varied between 0.0479 and 5.737 for adults, with
chrysene and dibenz(a,h)a, recording the lowest and highest values in that order (Table 4.7), and
from 0.010769 to 1.29579 for children, respectively, with chrysene and benzo(a)pyrene
recording the lowest and highest values in that order. The highest values for hazard index for the
non-carcinogenic PAHs for both adult and children are 1.8774 and 0.50176, with PhE having the
highest value for adult, and NaP having the highest for children.
In particular, 5 of the 7 cPAHs, which are benzo(a)anthracene, benzo(b)fluoranthene,
benzo(a)pyrene, dibenzo(a,h)anthracene, and indeno(1,2,3-cd)pyrene exceeded the threshold
value of 1 ×10-1 (Wang & Campiglia, 2008). No Kp value was available for BkF; hence, ADDd
and CRd were not computed for it. It therefore, could be inferred that the groundwater in those
areas is unfit for bathing because there is a chance that 1 in every 500 adults and 300 children
who bath with these waters are exposed to the risk of having cancer, respectively. The
carcinogenic risk calculated for both adults and children was higher than the USEPA acceptable
cancer risk, but much higher in adult, indicating that adults may be prone to cancer through
dermal absorption. Hence, necessary caution should be taken by everyone using borehole and
well water close to pipeline areas.

53
Table 4.8: Correlation Table showing Relationship between the Pollutants and Physicochemical Parameters

Bghi
NAP ACY PHE ANT FLA PYR BaA CHR BbF BkF BaP DahA IcdP P Ph EC Turb TDS Pb Fe
-
NAP 1.00 -0.11 -0.17 -0.65 -0.21 0.07 -0.22 -0.08 -0.07 -0.19 -0.09 0.00 0.16 -0.23 0.16 -0.12 -0.29 -0.12 -0.09 -0.01
ACY -0.11 1.00 0.45 -0.34 -0.34 0.76 0.50 0.99 0.97 -0.54 -0.37 -0.07 -0.38 -0.43 -0.09 0.03 0.90 0.03 0.39 -0.21
PHE -0.17 0.45 1.00 0.26 -0.46 0.74 0.70 0.51 0.49 -0.05 -0.07 0.10 -0.27 -0.25 0.11 -0.23 0.22 -0.23 0.43 -0.40
ANT -0.65 -0.34 0.26 1.00 0.14 0.07 0.01 -0.29 -0.30 0.55 0.67 0.42 0.26 0.68 -0.31 -0.35 -0.17 -0.35 -0.22 0.22
-
FLA -0.21 -0.34 -0.46 0.14 1.00 0.61 -0.66 -0.37 -0.43 -0.16 0.01 -0.56 0.39 0.13 -0.09 0.16 -0.09 0.16 0.09 -0.17
PYR -0.07 0.76 0.74 0.07 -0.61 1.00 0.70 0.81 0.81 -0.07 0.14 0.44 -0.21 0.00 -0.19 -0.16 0.67 -0.16 0.27 0.02
BaA -0.22 0.50 0.70 0.01 -0.66 0.70 1.00 0.50 0.54 0.11 -0.14 0.21 -0.34 -0.21 0.05 0.19 0.35 0.19 0.39 0.02
CHR -0.08 0.99 0.51 -0.29 -0.37 0.81 0.50 1.00 0.98 -0.52 -0.30 -0.02 -0.35 -0.39 -0.11 -0.04 0.88 -0.04 0.38 -0.20
BbF -0.07 0.97 0.49 -0.30 -0.43 0.81 0.54 0.98 1.00 -0.40 -0.27 0.01 -0.42 -0.35 -0.20 -0.08 0.86 -0.07 0.45 -0.11
-
BkF -0.19 -0.54 -0.05 0.55 -0.16 0.07 0.11 -0.52 -0.40 1.00 0.70 0.60 0.21 0.74 -0.45 -0.11 -0.37 -0.11 -0.06 0.45
BaP -0.09 -0.37 -0.07 0.67 0.01 0.14 -0.14 -0.30 -0.27 0.70 1.00 0.76 0.60 0.96 -0.64 -0.41 -0.11 -0.41 -0.38 0.59
DahA 0.00 -0.07 0.10 0.42 -0.56 0.44 0.21 -0.02 0.01 0.60 0.76 1.00 0.28 0.71 -0.39 -0.31 0.03 -0.31 -0.50 0.54
-
IcdP 0.16 -0.38 -0.27 0.26 0.39 0.21 -0.34 -0.35 -0.42 0.21 0.60 0.28 1.00 0.56 -0.47 -0.29 -0.20 -0.29 -0.44 0.18
Bghi
P -0.23 -0.43 -0.25 0.68 0.13 0.00 -0.21 -0.39 -0.35 0.74 0.96 0.71 0.56 1.00 -0.64 -0.25 -0.10 -0.25 -0.39 0.64
-
Ph 0.16 -0.09 0.11 -0.31 -0.09 0.19 0.05 -0.11 -0.20 -0.45 -0.64 -0.39 -0.47 -0.64 1.00 0.50 -0.29 0.50 -0.02 -0.44
-
EC -0.12 0.03 -0.23 -0.35 0.16 0.16 0.19 -0.04 -0.08 -0.11 -0.41 -0.31 -0.29 -0.25 0.50 1.00 0.16 1.00 0.28 -0.08
Turb -0.29 0.90 0.22 -0.17 -0.09 0.67 0.35 0.88 0.86 -0.37 -0.11 0.03 -0.20 -0.10 -0.29 0.16 1.00 0.16 0.34 0.00
Pb -0.09 0.39 0.43 -0.22 0.09 0.27 0.39 0.38 0.45 -0.06 -0.38 -0.50 -0.44 -0.39 -0.02 0.28 0.34 0.28 1.00 -0.39
Fe -0.01 -0.21 -0.40 0.22 -0.17 0.02 0.02 -0.20 -0.11 0.45 0.59 0.54 0.18 0.64 -0.44 -0.08 0.00 -0.08 -0.39 1.00

54
 CHAPTER FIVE

5.1 CONCLUSION

The levels of PAHs and PTEs were investigated in ten groundwater samples of the area of
Ejigbo and Ijegun, Lagos State, and these areas showed some levels of contamination.
Analysis of the physicochemical parameters measured for all the ten samples show slight
acidity in all the samples, with location 5 having the highest acidity. For the metals analyzed
which were Lead, Iron, Cadmium, and Chromium, only two were detected; Iron (Fe), and
Lead (Pb), while the other two were undetected. Results showed that the concentration of
Lead was more than the WHO permissible limit for drinking water, thus efforts should be
made to ensure they are kept below the acceptable limit. Evidence of PAHs pollution in the
studied area was confirmed, and the sources were identified to be petrogenic, fuel
combustion, and wood, coal and grass burning. The profile showed that low, medium and
high molecular weight PAHs were present in the samples. The 2 and 3- rings PAHs, which
are the low molecular weight PAHs are of more concern because they are water soluble and
can be transported in groundwater over long distances.
Result of the human health risk assessment indicated that the probability of non-carcinogenic
effect arising from individual exposure to PAHs through dermal absorption is less likely. The
health risk due to 7 carcinogenic PAHs and 3 non-carcinogenic PAHs were calculated based
on dermal absorption, and the cancer risk showed that adults are at a greater risk compared to
children. The result also showed that the carcinogenic risks calculated for 7 PAHs due to
dermal absorption had 5 PAHs above the permissible limit, thus the water is not suitable for
drinking or bathing and must be treated to make it free from contaminants.

55
5.2 RECOMMENDATIONS

Based on results gotten from this study, appropriate measures should be taken to address the
issue of pollutants infiltrating into the groundwater through pipeline leakage, vandalization
and other anthropogenic activities such as:

1. Measures and laws should be adopted to ensure full protection of water sources,
including use of good pipes, and replacement of old pipes to prevent leakage.
2. Strict security should be ensured to prevent vandalization of petroleum.
3. Removal of PAHs and PTEs from the groundwater and water sources by advanced
water treatment technologies.
4. Indiscriminate disposal of wastes into water bodies should be addressed.
5. Policies should be adopted and campaigns carried out to educate the public on the
need to protect them.
6. Pollutant monitoring should be mandatory for protection of humans and the
environment.

56
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