INFLUENCE OF LANDUSE ON DISTRIBUTION

AND CONCENTRATION OF POLYCYCLIC

AROMATIC HYDROCARBONS (PAHs) IN

KELANTAN, MALAYSIA

AZLAN BIN AHMAD

MASTER OF SCIENCE

2016

Influence Of Landuse On Distribution And Concentration

Of Polycyclic Aromatic Hydrocarbons (PAHs) in

Kelantan, Malaysia

by

Azlan Bin Ahmad

A thesis submitted in fulfilment of the requirements for the degree of Master of Science

Faculty of Earth Science

UNIVERSITI MALAYSIA KELANTAN

2016

THESIS DECLARATION

I hereby certify that the work embodied in this thesis is the result of the original

research and has not been submitted for a higher degree to any other University or

Institution.

OPEN ACCESS I agree that my thesis is to be made immediately

available as hardcopy or on-line open access (full text).

EMBARGOES I agree that my thesis is to be made available as

hardcopy or on-line (full text) for a period approved by the Post Graduate Committee.

Dated from until

CONFIDENTIAL (Contains confidential information under the Official

Secret Act 1972) *

RESTRICTED (Contains restricted information as specified by the

organization where research was done)*

I acknowledge that University Malaysia Kelantan reserves the right as follows.

1. The thesis is the property of University Malaysia Kelantan.

2. The library of University Malaysia Kelantan has the right to make copies for

the purpose of research only.

3. The library has the right to make copies of the thesis for academic exchange.

SIGNATURE SIGNATURE OF SUPERVISOR

IC/PASSPORT NO. NAME OF SUPERVISOR

Date: Date:

i

ACKNOWLEDGEMENT

In the name of Allah, the Most Gracious and the Most Merciful Alhamdulillah, all praises to

Allah for the strengths and His blessing in completing this thesis. Special appreciation goes to

my co-supervisor, Associate Professor Dr. Aweng Eh Rak, Deputy Dean, Faculty of Earth

Science for his supervision and constant support. His valuable help of constructive comments

and suggestions throughout the experiment and thesis works have contributed to the success of

this research. For all I have learned from him and for his continuous help and support in all

stages of this thesis. I would also like to thank him for being an open person with ideas, and for

encouraging and helping me to shape my interest and ideas. Not forgotten, my appreciation to

my main supervisor Professor Dato’ Dr. Hj. Ibrahin Che Omar, Deputy Vice Chancellor

Research and Innovation/Director of UMK Jeli Campus for his support and knowledge

regarding this topic.

I would like to express my appreciation to the Dean, Faculty of Earth Science, Prof. Dr. Razak

Wahab, my late Director of Department of Environment, Kuala Lumpur Tuan Haji Hashin

Daud, Director, Department of Environment Kelantan, En. Khairuddin Idris, Environmental

Control Officer Kelantan, En. Mohammad Zamzani Ibrahim and GIS expert of EiMAS,

En.Maz Izuan Mohamad for their support and help towards my postgraduate affairs. My

greatest appreciation and friendship goes to my closest friend, En. Muhammad Che Isa, who

was always giving great support in all my struggles and my studies in UMK. My

acknowledgement also goes to all the technicians and office staffs of the Faculty of Earth

Science and Faculty of Agro-Based Industry for their co-operations especially En. Suhaimi

Omar, Pn Nur Izzati Salleh and En. Mohamad Rohanif Mohamed Ali. Sincere thanks to all my

friends, especially Sufian, Wan, Marina, Salmi, Wan Hee, Franklin and others for their

kindness and moral support during my study. Thanks for the friendship and memories.

Last but not least, my deepest gratitude goes to my beloved wives; Noorhaidah Arifin and

Rosnani Ahmad and also to my children, Amir, Ashraf, Akmal, Afwan, Alia, Afif, Hazirah and

Nabilah endless love, prayers and encouragement indirectly contributed to this research, your

kindness means a lot to me. Thank you very much.

ii

TABLE OF CONTENTS

PAGE

THESIS DECLARATION i

ACKNOWLEDGMENTS ii

TABLE OF CONTENTS iii

LIST OF TABLES vi

LIST OF FIGURES vii

LIST OF ABBREIATIONS viii

ABSTRAK x

ABSTRACT xi

CHAPTER 1 INTRODUCTION

1.1 Overview 1

1.2 Problem Statement 5

1.3 Objectives of the Study 6

1.4 Significant of the Study 7

1.5 Scope of the Study 8

CHAPTER 2 LITERATURE REVIEW

2.1 General Information of Polycyclic Aromatic Hydrocarbon 9

2.2 Physical and Chemical Properties of PAHs 12

2.2.1 Napthalene 13

2.2.2 Acenaphthylene 14

2.2.3 Acenaphthene 15

2.2.4 Fluorene 16

2.2.5 Phenanthrene 17

2.2.6 Antracene 17

2.2.7 Fluoranthene 18

2.2.8 Pyrene 19

2.2.9 Benzo(a)antracene 20

2.2.10 Chrysene 20

iii

2.2.11 Benzo(b)fluoranthene 21

2.2.12 Benzo(k)fluoranthene 22

2.2.13 Benzo(a)pyrene 23

2.2.14 Dibenzo(a,h)anthracene 24

2.2.15 Indeno(1,2,3-c,d)pyrene 24

2.2.16 Benzo(g,h,i)perylene 25

2.3 Source of PAHs 26

2.4 PAHs In Soils 30

2.5 Importance of PAHs 33

2.6 Correlation between Soil Organic Matter (SOM), Total Organic Carbon

35 (TOC) and Polycyclic Aromatic Hydrocarbons (PAHs)

2.7 Concentration and Distribution of PAHs in Soils 39

CHAPTER 3 RESEARCH METHODOLOGY

3.1 Study Site and Sampling Stations 40

3.2 Soil Sampling Procedures 46

3.2.1 Sample Collection 46

3.2.3 Handling, preservation and storage 48

3.3 Sample Extraction and Analysis Procedure 49

3.3.1 Soil extraction : Mechanical Method 49

3.3.2 Determination of PAHs 51

3.3.3 Determination of soil organic matters content (SOM) 53

3.3.4 Determination of water content (WC) 54

3.3.5 Determination of total organic carbon (TOC) 55

3.3.6 Determination of soil particles 57

3.3.7 Quality control 60

3.3.8 Data analysis 60

CHAPTER 4 RESULTS AND DISCUSSION

4.1 PAHs Concentration 61

4.2 The Average Percentage TOC and Availability In The Study Area 67

4.3 The Average Percentage SOM and Availability In The Study Area 69

iv

4.4 The Average Percentage Clay+Silt and Availability In The Study Area 72

4.5 Correlation Between PAHs with TOC, SOM and Soil Textures 76

4.6 Correlation Between PAHs with Seasonal Variation 79

4.7 PAHs Distribution 81

CHAPTER 5 CONCLUSION AND FUTURE WORK

5.1 Conclusion 100

5.2 Future Work 101

REFERENCES 102

APPENDIX A 127

APPENDIX B 128

APPENDIX C 129

APPENDIX D 130

APPENDIX E 134

APPENDIX F 138

APPENDIX G 139

v

LIST OF TABLES

NO. PAGE

2.1 US EPA 16 priority PAHs 12

3.1 Sampling Location 42

4.1 Concentration of PAHs (mean concentration ± SE in µg/kg) 63

4.2 Comparison of PAHs Concentration in Kelantan Soils With Selected 66

Literatures

4.3 The Percentage of TOC (mean ± SE in %) 68

4.4 The Percentage of SOM (mean ± SE in %) 70

4.5 The Percentage of Clay+Silt (mean ± SE in %) 72

4.6 The Percentage of Sand (mean ± SE in %) 74

4.7 Composition in Percentage of Soil Texture (clay, silt, sand and 75

clay+silt)

4.8 The Pearson Correlations Analysis between landuses and TOC, 77

SOM, WC and ∑PAHs

4.9 Concentration of PAHs (mean ± standard error in µg/kg) and 78

percentage of TOC, SOM, Clay+Silt (mean ± SE in %) by landuses

4.10 Concentration of PAHs (mean ± Standard Error in µg/kg) and 80 percentage of TOC, SOM, Clay+Silt (mean ± SE in %) by season

4.11 Pearson Correlations Analysis Between Season Variation and TOC, 81

SOM, Clay+Silt, WC and ∑PAHs

4.12 Individual PAHs Concentration (µg/kg) Within Study Area 83

4.13 PAHs ratios and values for source diagnosis 92

4.14 Calculated ratios for source diagnosis 94

4.15 Mean ∑PAHs Concentration and TOC, SOM, Soil Textures 98 Percentage of different depth from selected landuses in Kelantan

4.16 Pearson Correlation Analysis Between Depth and Mean ∑PAHs, 99 TOC, SOM, Clay, Silt and Sand

vi

LIST OF FIGURES

NO. PAGE

3.1 Location Map of Sampling Site in Kelantan 44

3.2 Study Area and Sampling Stations 45

3.3 Soils Sampling Bored Hole 46

3.4 Soil Wrapped into Aluminum Foils 47

3.5 Soil Extraction for PAHs Analysis 50

3.6 Determination of SOM content in soil samples 54

3.7 Determination of WC content in soil samples 55

3.8 Determination of TOC content in soil samples 57

4.1 Mean soil texture results as a function of landuse 76

4.2 Distribution of 2-Aromatic Rings PAHs (µg/kg), Kota Bharu District 84

4.3 Distribution of 3-Aromtic Rings PAHs (µg/kg , Kota Bharu District 85

4.4 Distribution of 4-Aromatic Rings PAHs (µg/kg , Kota Bharu District 86

4.5 Distribution of 5-Aromatic Rings PAHs (µg/kg), Kota Bharu District 87

4.6 Distribution of 6-Aromatic Rings PAHs (µg/kg), Kota Bharu District 88

4.7 Distribution of 2-Aromatic Rings PAHs (µg/kg, Jeli District 89

4.8 Distribution of 3-Aromatic Rings PAHs (µg/kg), Jeli District 89

vii

LIST OF ABBREVIATIONS

ASE

-

Accelerated Solvent Extraction

ATSDR - Agency for Toxic Substances and Disease Registry

DDT - Dichlorodiphenyltrichloroethane

DNA - Deoxyribonucleic Acid

ECHA - European Chemicals Agency

EU - European Union

GIS - Geographic Information System

GPS - Global Positioning System

HCH - Hexachlorocyclohexane

HMW - High Molecular Weight

HOCs - Hydrophobic Organic Compounds

HPLC - High Performance Liquid Chromatography

HSGs - Hydrologic Soil Groups

IARC - International Agency for Research on Cancer

IPCSCEC - International Programme on Chemical Safety, Commission of the European Communities

IR - Infrared Detection Cell

ITER - International Toxicity Estimates for Risk

LMW - Low Molecular Weight

MAE - Microwave-Assisted Extraction

NMHCs - Non-Methane Hydrocarbons 3-

NO - Nitrate

NPI - National Pollutant Inventory

OERS - Office of Emergency and Remedial Response

OH - Hydroxyl

OSHA - Occupational Safety and Health Administration

PAHs - Polycyclic Aromatic Hydrocarbons

PEL - Permissible Exposure Limit

viii

PL - Vapor Pressures

POP - Persistent Organic Pollutants

PTFE - Polytetrafluoroethylene

QC - Quality Control

SFE - Supercritical Fluid Extraction

SOM - Soil Organic Matter

SVHC - Substances of Very High Concern

TOC - Total Organic Carbon

UMK - Universiti Malaysia Kelantan

UNEP - United Nations Environment Program

USDA - United State Department of Agriculture

USEPA - US Environmental Protection Agency

USHHS - US Department of Health and Human Services

WC - Water Content

ix

Taburan Dan Kepekatan Polycyclic Aromatic Hydrocarbons (PAHs) Dalam

Pelbagai Jenis Kegunaan Tanah Di Negeri Kelantan, Malaysia

ABSTRAK

Satu kajian mengenai pencemaran Polycyclic Aromatic Hydrocarbon (PAHs)

di dalam kandungan tanah telah dijalankan iaitu ke atas 291 sampel tanah dari Jajahan

Kota Bharu dan 54 sampel tanah dari kawasan UMK, Jajahan Jeli. Keputusan telah

menunjukkan bahawa purata jumlah pencemaran PAHs yang direkodkan di Negeri

Kelantan adalah rendah (Σ16 USEPA PAHs=7.97±0.75µg/kg) bagi kegunaan tanah di

kawasan bandar, kawasan lebuhraya, kawasan pertanian dan kawasan perindustrian.

Kandungan PAHs di dalam tanah telah ditentukan dengan menggunakan High

Performance Liquid Chromatography dengan Photodiode Array Detector (HPLC-

PDA). Taburan purata Jumlah PAHs bagi Negeri Kelantan telah ditafsirkan secara plot

pemetaan kontor dengan menggunakan Aplikasi GIS. Taburan PAHs didapati

berkaitan rapat dengan punca pencemaran dan jenis kegunaan tanah. Kepekatan purata

PAHs tertinggi di Jajahan Kota Bharu adalah daripada sampel tanah berhampiran jalan

raya dengan jumlah PAHs sebanyak 5.08μg/kg, diikuti dengan Pengkalan Chepa

4.29μg/kg dan Banggu sekitar 3.28μg/kg. Di kawasan UMK , Jajahan Jeli purata

jumlah PAHs direkodkan adalah sebanyak 27.44μg/kg. Hasil kajian juga mendapati

trend kepekatan PAHs secara individu adalah Acenaphthylene>Fluorene>Naftalena di

kawasan industri, Acenaphthylene>Fluorene>Acenaphthene di berhampiran jalanraya

dan Acenaphthylene>Fluorene>Acenaphthene di kawasan perumahan dan pertanian.

Hasil kajian menunjukkan Acenaphthylene, Fluorene dan Acenaphthene adalah

merupakan individu PAHs yang paling kerap ditemui. Nisbah PAHs seperti

Phenanthrene dan Anthracene ([R1=Ant/(Ant+Phe)], Fluoroanthene dan Pyrene

[R2=Fla/(Fla+Pyr)], serta Benzo(a)anthracene dan Chryene [R3=Baa/(Baa+Chy)],

digunakan untuk menentukan sumber kehadiran PAHs di dalam tanah. Nisbah R1 di

dalam sampel di antara julat 0.06 hingga 0.87, julat nisbah R2 antara 0.33 hingga 0.93

dan julat nisbah R3 antara 0.06 hingga 0.32. Nisbah ini menunjukkan tanah yang dikaji

telah tercemar dengan PAHs yang terhasil daripada pembakaran engine kenderaan.

Kajian ini juga mengesahkan bahawa PAHs berkait rapat dengan TOC, SOM dan

tekstur tanah mengikut musim dan kedalaman tanah di Kelantan.

x

Influence Of Landuse On Distribution And Concentration Of Polycyclic

Aromatic Hydrocarbons (PAHs) in Kelantan, Malaysia

ABSTRACT

An extensive soil survey was carried out to study the polycyclic aromatic

hydrocarbon (PAHs) contaminations in 291 soil samples collected throughout Kota

Bharu District and 54 soil samples was from UMK Jeli area. Results demonstrated that

there was low levels of average Total PAHs contaminations in Kelantan ( ∑16 US

EPA PAHs = 7.97±0.75 µg/kg dw) for all land uses (urban area, highway area,

agricultural area, and industrial area). The content and type of polycyclic aromatic

hydrocarbons (PAHs) in soils from Kota Bharu District and upland areas in UMK Jeli

were determined using High Performance Liquid Chromatograph to Photodiode Array

Detector (HPLC-PDA). The distribution map of total PAHs of Kelantan were obtained

as a contour plot using a geographical information system. The overall distribution of

PAHs was found to be closely related to the pollution sources and the type of land

uses. The mean highest concentrations in Kota Bharu District were found in soils

sampled near road site in Kota Bharu with total PAHs 5.08µg/kg, followed by

Pengkalan Chepa 4.29µg/kg and Banggu at 3.28µg/kg. The area in UMK, Jeli District

was the highest mean of total PAHs 27.44µg/kg. The trends of the concentration of the

major PAHs found in present study were Acenaphthylene>Fluorene>Naphthalene at

industrial site, Acenaphthylene>Fluorene>Acenaphthene at roadside and

Acenaphthylene>Fluorene>Acenaphthene at residential and agricultural sites. In all the

sites Acenaphthylene, Fluorene and Acenaphthene were the predominant compounds.

Special PAHs compound ratios, such as Phenanthrene and Anthracene

[R1=Ant/(Ant+Phe)], Fluoroanthene and Pyrene [R2=Fla/(Fla+Pyr)], and

Benzo(a)anthracene and Chryene [R3=Baa/(Baa+Chy)] were calculated to evaluate the

PAHs origin. The R1 ratios in Kelantan samples ranged from 0.06 to 0.87, R2 ratios

from 0.33 to 0.93 and R3 ratios ranged from 0.06 to 0.32. It can be seen that there was

a strong combustion sources from traffic emission influence on soil PAHs in all soils

sample in Kelantan. The study also confirm that PAHs was significantly correlated

with TOC, SOM and Soil Textures with seasonal variation and different soil depth

interval in Kelantan.

xi

CHAPTER 1

INTRODUCTION

1.1 Overview

Polycyclic aromatic hydrocarbons (PAHs) are a class of ubiquitous and

persistent organic pollutants (POPs) in the environment, and produced mainly from

incomplete combustion of fossil fuels, biomass and pyro synthesis of organic materials

(Wang et al., 2007a). It is believed that combustion processes, including thermal

combustion conditions, fuel/stove types and even burning stages, are responsible for

the abundance and profiles of PAHs that enter the environment (Chen et al., 2005). In

combustion-derived PAHs, low molecular weight (LMW) (three rings) species are

abundantly produced at low to moderate temperatures, such as wood and coal

combustion. On the contrary, high molecular weight (HMW) (four and more rings)

PAHs are generated at high temperatures, such as vehicle emission (Mastral & Callen,

2000). Once PAHs are released into the atmosphere, they are subject to sink into the

soil via dry and wet deposition. Because of their persistence, low vapor pressures (PL)

and high octanol/air partition coefficients (KOA), PAHs can strongly adsorb to soil

organic matter (SOM), and are likely to be retained for a long time (Wilcke, 2000).

Consequently, soil is one of the main reservoirs for PAHs in the environment. Previous

studies implied that POPs measured in soils correlate with those in the atmosphere, and

1

therefore, soil PAH concentrations are usually considered as good indicators of the

surrounding pollution (Wild & Jones, 1995).

Polycyclic aromatic hydrocarbons (PAHs), a group of stable chemicals, are

constantly existence organic contaminants in environments, such as sediments and

soils (Baumard et al., 1998; Hoffman et al., 1984; Jones, 1991; Ribes et al., 2003;

Wild & Jones, 1993). They have been listed as priority pollutants by both the US

Environmental Protection Agency (EPA) and the European Union (EU). While PAHs

can occur naturally, but mostly they are originated from anthropogenic processes, such

as burning of fossil fuels and other organic substances (Simoneit, 1977; Wakeham et

al., 1980a, 1980b). PAHs containing two or more rings usually have high stability in

the environments. Due to the high hydrophobicity and stable chemical structure, PAHs

are not very soluble and can be adsorbed rapidly onto soil particles, particularly on soil

organic matter (Means et al., 1980). PAHs in soils can be dispersed by surface runoff

and dust production; soils can therefore be considered as one of the pollution sources

for PAHs contamination in the air and sediments (Mai et al., 2003). Soil types and

properties such as organic carbon play the most important role in the absorption of

PAHs in soils (Jonker & Smedes, 2000; McGroddy & Farrington, 1995).

It has been well established that PAHs has carcinogenic, mutagenic and

teratogenic effects on animals (Grimmer et al., 1983; D. Hoffman & Wynder, 1971;

Perera, 1997). This has led to intensive research into their chemical and biological

properties in the environments, and the mechanisms by which these physiological

effects are produced. For the assessment of environmental risks associated with soil

contamination with PAHs, it is important to evaluate the spatial distribution and

2

pathways (sources) of PAHs in soils. Molecular indices based on individual compound

concentrations were developed to assess the various origins of these compounds (Sicre

et al., 1987). As anthropogenic activities are the main sources of PAHs, the levels of

PAHs in soils in urban areas are approximately a factor of 2–10 higher than those in

rural areas (Lodovici et al., 1994; Wagrowski & Hites, 1997).

Pollution of the urban area by carbon compound had received considerable

attention over the last decades, mainly because of the public health risk associated with

fine particles and carcinogenic and mutagenic effects of PAHs (Menzie et al., 1992).

Polycyclic aromatic hydrocarbons (PAHs) consist of two or more fused benzene rings.

These substances are produced by maturation of organic matter, hence the relative

abundance of an extremely complex mixture of these compounds in ancient organic-

rich sediments and petroleum. Incomplete combustion or pyrolysis is also a known

source of PAHs in the environment (Douben, 2003). Natural source of PAHs includes

volcanic eruptions, natural vegetation fires and digenetic processes. However, in urban

areas, their occurrences are normally associated with anthropogenic activities such as

domestic waste and fossil fuels burning. Other sources are from oil spillage and waste

discharge from domestic or industrial activities. In certain studies, they also correlate

formation of PAHs with a biological orientation in soils (Gocht et al., 2001).

Soils are one of the known sink of PAHs, whereby they are deposited either in

gaseous state or associated with particulate matter in the air. Therefore, it is a good

indicator of pollution and environmental risk as it is continuously subjected to

pollution due to its open system nature and capability to accumulate various pollutants.

Previous research showed that there was a significant level of PAHs found in soils all

3

over the earth including remote areas which originated from forest fires or airborne

pollution (Tam et al., 2001). Soils from an urban industrial area usually consist of the

high concentration of PAHs, sometimes, be 10 to 100 times higher than those in less

populated and undeveloped areas. Similarly, the urban area is also reported to have a

higher soil concentration of PAHs than forest or agricultural soils, mainly because of

direct exposure to vehicular emissions (Chung et al., 2007). A few studies have been

carried out in Malaysia (Omar et al., 2002; Tahir et al., 2005), but none has been

reported for the PAHs level in soils at various land uses in Kelantan.

Polycyclic aromatic hydrocarbons (PAHs) are a group of organic compounds

composed of fused aromatic rings. Some higher molecular weight (greater than four

fused rings, HMW) PAHs is considered to be carcinogenic, mutagenic and teratogenic

even at low concentrations (IARC, 1983). Because of their hydrophobic nature and low

solubility, PAHs are resistant to biodegradation and can bioaccumulate in the

environment through the food chain (Yu et al., 2006). Therefore, PAHs in the

environment represents a long-term threat to human health and have received more and

more environmental concern (Yu et al., 2006). In China, extensive investigations on

PAH concentration and distribution in the atmosphere (Lee et al., 2001), water (Zhou

& Maskaoui, 2003), sediment (Wu et al., 2003), soil (Tao et al., 2004) and dust (Wu et

al., 2005) have been carried out. Most PAHs are released from anthropogenic sources,

such as wastewater irrigation (Wang et al., 2004b), vehicle exhausts (Chen et al., 2005;

Ma et al., 2005a), hydrocarbon spillage (Ou et al., 2004), residential coal combustion

(Chen et al., 2004), use of organic waste as compost and fertilizer (Smith

et al., 2001), industrial activities including coke ovens, gasworks, petroleum refineries,

4

wood conservation plants, power plants and blast furnaces (Stalikas et al., 1997; Van

Brummelen et al., 1996).

In India, few studies have reported ambient PAH concentration in Ahmedabad

(Raiyani & Shah, 1993), Mumbai (Sahu et al., 2001), Delhi (Kannan & Kapoor, 2004).

To our knowledge, there has been a shortage of soil PAH studies. Since PAHs is one of

the most serious pollutants because of their carcinogenicity and mutagenicity (IARC,

1987; Massei & Ollivon, 2004; Yang et al., 1991), it is important to determine the

amounts of PAHs in soil as their concentration in soil (Massei & Ollivon, 2004; Nam

et al., 2003; Vogt et al., 1987) and is a good indicator of the surrounding sources.

1.2 Problem Statement

PAHs in the environment released by various anthropogenic sources, mainly

from vehicle combustion are widespread and typically concentrated in the urban

centers. The distribution of PAHs in Kuala Lumpur shows that vehicular emission is

the dominant source of PAHs in atmospheric particles (Omar et al., 2002). Human

exposure to PAHs has been widely associated with elevated levels of DNA adducts

and mutations and also with reproductive defects (Gaspari et al., 2003). As pollutants,

they are of concern because some compounds have been identified as carcinogenic,

mutagenic and teratogenic (Omar et al., 2002). PAHs are transboundary and settle on

soil and food as the ultimate sink, increasing the exposure pathways as a result.

Breathing of contaminated air and ingestion of contaminated soils and food is

5

considered to be an important exposure pathway in humans (Finley and Paustenbach,

1994; Staneck et al., 1995).

PAHs in soils may further accumulate in vegetables and other biota via food

chains (Kipopoulou et al., 1999; Li et al., 2008). This accumulation leads to direct or

indirect exposure in humans. Moreover, leaching of PAHs from soils are possible

sources of groundwater contamination (Bispo et al., 1999; Cousins et al., 1999).

This study focuses on four different types of land use such as township

(urbanization), agricultural area, industrial area and highway area. The use of different

land use in this study is much simpler and cheaper and the findings of this study can

also lead to incorporate in solving environmental pollution problems in local planning

and development. It is important to study the relationship between the distribution of

PAHs in soil and the degree of PAHs pollution in the environment by different land

use for future development and to restore the environment.

Although polycyclic aromatic hydrocarbons (PAHs) are not among the ‘dirty

dozen’ of the Stockholm convention on Persistent Organic Pollutants, they were

included in the Convention on Long Range Transboundary Air Pollution Protocol on

Persistent Organic Pollutants by United Nations Economic Commission for Europe

and their toxic effects on both human and ecosystem health are well documented.

PAHs released from many types of pollution source floats in the air for some

times, but the organic matter will later be removed from the atmosphere both in vapour

– phase and condensed form, absorbed and deposited on water, soil and plant foliage

(Nicola et al., 2008). In general, lighter, less hydrophobic particulates are dispersed in

the environment at greater distance than heavier, more hydrophobic particulates. As for

6

PAHs, the most important property is their lipophilicity: they may accumulate in fat

tissue of vertebrates and invertebrates, also in lipophilic parts of plants, accumulation

can take place (Keymulen et al., 1995).

1.3 Objectives of the Study

This study aims to determine the concentrations of pollutant compounds in

soils at the various land uses in Kelantan as well as distribution by producing map

using GIS and also to assess the possible some of their compounds.

The objectives of the study are:

i. To determine the concentrations of 16 PAHs that are listed by the United

States Environmental Protection Agency as priority pollutants in the

surface soil samples from different type of land use of Kelantan,

Malaysia; and

ii. To determine the correlation between PAHs with seasonal variation,

depth, TOC, SOM and soil textures.

1.4 Significance of the study

Soil is the primary environmental reservoir for PAHs. Due to their high

hydrophobicity and stable chemical structure, PAHs are not very soluble in water and

can be adsorbed rapidly onto soil particles, particularly on soil organic matter (Means

et al., 1980; Xing, 2001). Polycyclic aromatic hydrocarbons are ubiquitously

7

distributed in both air and soil matrices which deserve some attention because they are

highly stable and toxic and can produce carcinogenic and mutagenic effects. They

cannot be easily remedied and therefore will persist over long periods, resulting in their

accumulation and long term risk of transport to other environmental matrices such as

groundwater (Wild and Jones, 1995). This might therefore contribute to groundwater

contamination in areas with high levels of PAHs.

From literature not many studies has been conducted to address the

accumulation and distribution of PAHs in the surface soils in Kelantan. The results of

this study will provide valuable information for the Ministry of Natural Resources and

Environment and state government or other environmental policy makers to develop

environmental soil quality guidelines for Kelantan. It will also provide baseline

information on the concentration and distribution of PAHs in the soil samples in

Kelantan.

1.5 Scope of the Study

Different locations in urban area (Kota Bharu township), industrial area

(Pengkalan Chepa), agricultural area (Banggu) and highway area (Jeli) with different

profile of pollution were selected as sampling sites. The study was concentrated on the

same 27 locations in Kelantan and visited during different seasons for a year.

A few parameters were established to achieve the objectives of the study; total

organic carbon (TOC), soil organic matter (SOM), soil textures and variable of

8

different seasons, and different depth. All parameters were correlated with found

PAHs.

Out of hundreds of different PAHs, Sixteen PAHs are considered priority

pollutants: naphthalene, acenaphthylene, acenaphtene, fluorene, phenanthrene,

anthracene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene,

benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenz(a,h)anthracene

and benzo(g,h,i)perylene are the main focus in this study.

Sampling was conducted during pre-monsoon (August-September 2010),

monsoon (November-December 2010) and dry season (Mac-April 2011)

9

CHAPTER 2

LITERATURE REVIEW

2.1 General Information of Polycyclic Aromatic Hydrocarbon

One of the most notorious and ubiquitous pollutants is polycyclic aromatic

hydrocarbons (PAHs) (Chung et al., 2007). It is also one of the Persistent Toxic

Substances (PTS). PTS typically share the major characteristics of 12 Persistent

Organic Pollutants (POPs) in the Stockholm Convention (United Nations Environment

Programme 2005). They are characterized by their exceptional toxicities towards many

living organisms, reluctance in degradations and high lipophilicity, making them a

class of very dangerous compounds (Chung et al., 2007). Some PAHs were found to

be very toxic and 16 of them have been identified by US EPA as being toxic, partially

mutagenic and carcinogenic ‘‘priority pollutants’’ (Chung et al., 2007). They represent

most of the adverse effects that are caused primarily as a result of anthropogenic

activities (Keith & Telliard, 1979).

Polycyclic aromatic hydrocarbons (PAHs) are chemicals containing two or

more fused benzene rings in a linear, angular or cluster arrangement. PAH contain only

carbon and hydrogen (Masih & Taneja, 2006). They are usually generated under

inefficient combustion conditions, such as insufficient oxygen (Nam et al., 2003;

Sorensen, 1994) by primary natural sources which are forest fires and volcanic activity,

but most of the PAHs released into the environment arise from anthropogenic

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sources such as burning of fossil fuels, petroleum refinery, industrial processes, as a

constituent of coal tar and motor vehicle exhaust. The lighter PAH (2–3 rings),

generally not carcinogenic, are mostly found in the gas phase while the heavier ones

are mainly associated with airborne particles. Heavier PAH (with more than three

rings) is rapidly attached to existing particles, usually soot particles, by adsorption or

condensation upon cooling of fuel gas (Kamens et al., 1995). The environmental

occurrence of PAHs has been associated with adverse effects on public health

(Grimmer et al., 1983; Rost & Loibner, 2002; Yang et al., 1991). Persistent organic

pollutants (POPs) are transported in the atmosphere at over short and long distances in

both gaseous and particulate forms. Although some POPs are released slowly into the

atmosphere (Harner et al., 1995), these omnipresent compounds are subject to

redistribution and transformation processes (Massei & Ollivon, 2004; Reilley et al.,

1996). Atmospheric deposition constitutes the main input of semi-volatile organic

compounds to soil (Tremolada et al., 1996). Once entered in the soil they accumulate

in horizons rich in organic matter where they are likely to be retained for many years

due to their persistence and hydrophobicity (Krauss et al., 2000). Consequently, soils

are an important reservoir for these compounds (Ockenden et al., 2003) and exchanges

between soils and the atmosphere is a widely studied process (Bidleman & McConnell,

1995; Wania & Mackay, 1996). With the increase in fossil fuel combustion, resulting

from the industrial expansion, traffic and population growth, over last few decades, the

atmospheric concentrations of PAH in Asian countries are expected to be high. Thus, it

is important to acquire information about this environmental compartment and its role

in the micro pollutant cycle.

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Polycyclic aromatic hydrocarbons (PAHs) are a very large number of naturally

occurring and man-made chemicals characterized by two or more fused aromatic rings.

In pure form they are as white or yellowish crystalline solids. However, they are not

usually found in this pure form, they are commonly found as environmental pollutants

that belong to the hydrophobic organic compounds (HOCs) group based on their

properties. The fate of PAHs in nature is becoming a pollutant of great environmental

and human health concerns due to their widespread occurrence, strong persistence,

long-range transportation potential carcinogenic, mutagenic and teratogenic properties

as well as their high concentration and frequently found in the environment. Table 2.1

shows the 16 priority PAHs as listed by the United States Environmental Protection

Agency (USEPA).

Naphthalene, the first member of the PAH group, is a common micropollutant

in potable water. The toxicity of naphthalene has been well documented and

cataractogenic activity has been reported in laboratory animals (Goldman et al., 2001;

Mastrangela et al., 1997). Naphthalene binds covalently to molecules in liver, kidney

and lung tissues, thereby enhancing its toxicity; it is also an inhibitor of mitochondrial

respiration (Falahatpisheh et al., 2001). Acute naphthalene poisoning in humans can

lead to hemolytic anemia and nephrotoxicity. In addition, dermal and ophthalmological

changes have been observed in workers occupationally exposed to naphthalene.

Phenanthrene is known to be a photosensitizer of human skin, a mild allergen and

mutagenic to bacterial systems under specific conditions (Mastrangela et al., 1997).

Little information is available for other PAHs such as acenaphthene, fluranthene and

flourene with respect to their toxicity in mammals. However, the toxicity of

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