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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