v
CONTENTS
CHAPTER
1
TITLE
PAGE
AUTHOR’S DECLARATION
ii
DEDICATION
iii
ACKNOWLEDGEMENT
iv
CONTENTS
v
ABSTRACT
viii
ABSTRAK
ix
ABBREVIATION
x
LIST OF TABLE
xii
LIST OF FIGURE
xiv
INTRODUCTION
1.1 Introduction
1
1.2 Problem Statement
4
1.3 Objective of Study
5
1.4 Hypothesis of Study
5
1.5 Scope of Study
6
vi
2
LITERATURE REVIEW
2.1 Pesticide
2.1.1 Routes of Pesticide
10
2.1.2 Distribution of Pesticide
11
2.1.3 Pesticides in Peninsular Malaysia Rivers
12
2.1.4 Aldrin, Dieldrin and Endrin
13
2.2 Suspended Solid
16
2.3 River
17
2.3.1 Rivers in Johor
2.4 Sample Extraction
3
7
18
19
2.4.1 Ultrasonic Solvent Extraction
20
2.4.2 Theory of Ultrasonic
22
2.5 Gas Chromatography
24
2.6 Liquid Chromatography
27
METHODOLOGY
3.1 Chemical, Material and Apparatus
29
3.2 Sampling and Storage
30
3.3 Extraction of Raw River Water Sample
31
3.4 Qualitative Analysis
32
3.5 Preparation of Standard and Calibration Curve
32
3.6 Optimization of Ultrasonic Extraction
34
3.7 Chromatographic Analysis
3.7.1
Gas Chromatography Mass Selective
Detector
35
vii
4
3.7.2
Liquid Chromatography Mass
Spectrometry
35
3.7.3
Gas Chromatography Electron Capture
Detector
36
RESULT AND DISCUSSION
4.1 Introduction
37
4.2 Qualitative Study
38
4.3 Quantitative Study
41
4.4 Optimization of Extraction
4.4.1 Effect of Organic Solvent Selection
45
4.4.2 Effect of Extraction Time
47
4.5 Application on Sample
5
REFERENCES
49
CONCLUSION
5.1 Conclusion
51
5.2 Recommendation
52
53
x
ABBREVIATION
APCI
-
Atmospheric Pressure Chemical Ionization
ASE
-
Accelerated Solvent Extraction
BHC
-
Benzenehexachloride
DDD
-
Dichlorodiphenyldichloroethane
DDE
-
Dichlorodiphenylchloroethane
DDT
-
Dichlorodiphenyltrichloroethane
DOC
-
Dissolved Organic Carbon
DOM
-
Dissolved Organic Matter
ECD
-
Electron Capture Detection
EPA
-
Environmental Protection Agency
EU
-
European Union
FELDA
-
Federal Land Development Agency
FIFRA
-
Federal Insecticide, Fungicide, and Rodenticide Act
GC
-
Gas Chromatography
GC-ECD
-
Gas Chromatography-Electron Capture Detector
GC-MSD
-
Gas Chromatography-Mass Selective Detector
xi
HCH
-
Hexachlorocyclohexane
KOW
-
Octanol-Water Partition Coefficient
LOD
-
Limit of Detection
LOQ
-
Limit of Quantitation
MAE
-
Microwave Assisted Extraction
MS
-
Mass Spectrometry
OCPs
-
Organochlorine Pesticides
PAHs
-
Polycyclic Aromatic Hydrocarbons
PCB
-
Polychlorinated Biphenyls
PLE
-
Pressurized Liquid Extraction
RSDs
-
Relative Standard Deviations
SFE
-
Supercritical Fluid Extraction
SIM
-
Selected Ion Monitoring
U.S
-
United States
USE
-
Ultrasonic Solvent Extraction
xii
LIST OF TABLE
TABLE
TITLE
PAGE
NO.
1.1
Physiochemical properties of the analytes
3
2.1
The major classes of pesticides and its target
8
pest group [8,9]
2.2
Physical properties and structure of aldrin,
15
dieldrin and endrin [25,27]
3.1
Concentration used in the standard addition
33
calibration method
4.1
Comparison of limit of detection and limit of
45
quantification
4.2
Recovery of pesticide (%) and repeatability
46
(%RSD)
(n = 3) obtained by USE with various solvent
and analysis using GC-ECD
4.3
Recovery of pesticide (%) and repeatabilities
(%RSD)
(n = 3) obtained by USE with various time of
extraction and analysis using GC-ECD
48
xiii
4.4
Percentage recovery for OCPs from spiked
sample (50 µg/L) of Sungai Skudai using GCECD.
50
xiv
LIST OF FIGURES
FIGURE
TITLE
PAGE
NO.
2.1
Trends in the agrochemical market in Malaysia
[6].
9
2.2
Fate and transport processes for contaminants in
11
the agricultural soil environment [15].
3.1
Location of sampling point: SAJ Water Treatment
30
Plants of Sungai Skudai.
3.2
Flow chart of methodology used in this study.
31
4.1
Chromatogram of GC-MSD of Sungai Skudai
39
after
extraction
by
using
dichloromethane:
methanol (1:1).
Column: DB-35ms Ultra Inert, 30 m × 0.25 mm ×
0.25 μm. Temperature programming: 120˚C, hold
for 1 min, and increased at a rate of 20˚C min-1 to
200˚C and held for 1 min, 220˚C for 1 min to
290˚C at 10°C min− 1 and hold at 290˚C for 2 min.
4.2
Chromatogram of LC-MS-MS after extraction by
using dichloromethane: methanol (1:1) of Sungai
Skudai.
Column: C18 reversed phase, Acclaim PA column
40
xv
(1 mm × 5 mm, 3 μm). Gradient programming:
10% of B at 0 min and 80% of B at 30 min with a
flow rate of 0.2 mL/min and the mobile phase used
were water with 0.1% formic acid (A) and
methanol (B).
4.3
Separation of OCPs standard mixture of 25 µg/L
42
by using GC-ECD: (1) Aldrin, (2) Dieldrin, (3)
Endrin.
Condition: Column: DB-5 capillary column, 30 m
× 0.25 mm × 0.25 µm. Temperature programming:
80°C for 1 min, 30°C min–1 to 180°C, at 10°C
min–1 to 200°C, and at 15°C min–1 to 260°C, hold
6 min.
4.4
Calibration curve of: (a) aldrin, (b) dieldrin, (c)
endrin.
Condition: Column: DB-5 capillary column, 30 m
× 0.25 mm × 0.25 µm. Temperature programming:
80°C for 1 min, 30°C min–1 to 180°C, at 10°C
min–1 to 200°C, and at 15°C min–1 to 260°C, hold
6 min.
43