DEVELOPMENT OF AN EXPLOSIVE INFORMATION SYSTEM...
Transcript of DEVELOPMENT OF AN EXPLOSIVE INFORMATION SYSTEM...
UNIVERSITI TEKNOLOGI MALAYSIA
DEVELOPMENT OF AN EXPLOSIVE INFORMATION SYSTEM FOR THE
CHEMICAL COMPOSITION PROFILE OF EXPLOSIVES
MOHAMAD AFIQ BIN MOHAMED HURI
.
DEVELOPMENT OF AN EXPLOSIVE INFORMATION SYSTEM FOR THE
CHEMICAL COMPOSITION PROFILE OF EXPLOSIVES
MAY 2017
Faculty of Science
Universiti Teknologi Malaysia
A thesis submitted in fulfilment of the
requirements for the award of the degree of
Doctor of Philosophy (Chemistry)
MOHAMAD AFIQ BIN MOHAMED HURI
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In the name of Allah, the Most Beneficent and the Most Merciful.
I dedicate this work to:
My late father
Mohamed Huri Bin Zakaria
He was my hero
Stronger than a Superman
Used to be there when I needed him
The best father a son could have
My mother
Hamidah Binti Saidin
She is my heroine
More amazing than a Wonder Woman
Who love me more than anyone else
The best mother a son could have
My siblings
Shamsul Syamuri, Hana Huri, Hazairin Huri, Aishah Huri and Hanis Huri
Bonds that can never be broken
The best family that I could have
Alhamdulillahilladzi bi ni’matihi tatimmussolihaat.
DEDICATION
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Bismillahirrahmanirrahim,
Alhamdulillah, greatest thanks to Allah S.W.T for giving me strength, health
and goodness while preparing and completing this study. First of all, I would like to
express my deepest and warmest gratitude to my supervisor for this PhD project,
Assoc. Prof. Dr. Umi Kalthom binti Ahmad for her motivation, critical reviews and
enormous support and guidance in encouraging me to finish this project and writing
my thesis. Because of her patient guidance, I am able to complete this task
successfully. I have gained a lot of knowledge and experience during the course of this
research.
My sincere thanks to Science & Technology Research Institute for Defense
(STRIDE), Batu Arang, Selangor, especially to Brig. Gen. Mustafa Omar as my co-
supervisor. For my database development, I also would like to give my sincere thanks
to my another co-supervisor from Faculty of Computing UTM, Assoc. Prof. Dr
Roliana bt Ibrahim.
I am greatly indebted to all staffs in Chemistry Department, Faculty of Science
for their fruitful cooperation and helpful in completing this project. Last but not least,
I wish to thank my beloved family for their great support and valuable advice. I would
like to thank all my friends for their never ending support and willingness to give their
support and sharing knowledge about this research. Thank you very much.
ACKNOWLEDGEMENT
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ABSTRACT
ABSTRAK
ABSTRACT
Analysis of post-blast residues collected from a crime scene is of great importance
to forensic investigators in determining the nature of explosives used. The result of the
analysis can be used as ultimate evidence in court to link a suspect with the crime. The
traditional manual matching of explosive sample for case and control samples are often
laborious and inefficient. The scarcity of standard explosives further aggravates the
routine work of a forensic analyst. This study was therefore undertaken to develop a novel
forensic explosive database information system for rapid and efficient data retrieval and
matching. A total of 22 pre- and post-blast samples were collected including military
explosives, improvised explosive devices and pyrotechnic explosive samples. All samples
were subjected to spot test analysis prior to instrumental analysis. High performance liquid
chromatography with diode array detector (HPLC-DAD) and gas chromatography tandem
mass spectrometry (GC-MS/MS) were used for chemical profiling of high explosives with
limits of detection (LOD) in the range of 0.02-4.35 mg/L and 0.30-10.89 ng/L,
respectively. Ion chromatography (IC) was employed for chemical profiling of anionic
(LOD: 0.07-0.26 mg/L) and cationic (LOD: 0.08-0.28 mg/L) content of inorganic low
explosives. This study revealed that each sample displayed different chromatographic
profile that could discriminate from one to another. Nitroexplosive compounds of PETN
and tetryl were detected in GC-MS/MS analysis via the presence of degradation products
of 1,3-propanediol,2,2-dimethyl-,dinitrate and 2,4,6-trinitro-N-methyl-aniline,
respectively. Methods developed for IC, HPLC and GC-MS/MS were proposed as
standard methods for the generation of results to be incorporated in the explosive database.
A total of 52 data information was stored in the database using Microsoft SQL Server.
MyForensic Explosive Database (MyFED) graphical user interface was developed using
Microsoft Visual Studio. The database incorporated details of the explosives, results of
spot test analysis, retention factor and chromatographic profile of each analyte for data
searching, retrieval and matching with unknown explosive samples. The user interface
involved spot test analysis comparison, followed by chromatogram searching with
retention factor comparison. The administrator page allowed access only to the
administrator for viewing, inserting, editing and deleting information. The developed
MyFED information system supported easy matching of unknown explosive samples with
known samples stored in the database. Although the database contained a limited number
of explosives data, its capability of easily upgradable to handle more explosive
information renders MyFED an attractive and promising start of a Malaysian database
system available for use to forensic investigators in Malaysia as well as in the Asian
region.
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ABSTRAK
ABSTRAK
Analisis sisa pasca-letupan yang dikumpul daripada tempat kejadian jenayah
adalah sangat penting kepada penyiasat forensik dalam menentukan jenis bahan letupan
yang digunakan. Hasil analisis boleh digunakan di mahkamah sebagai bukti muktamad
untuk mengaitkan suspek dengan jenayah. Pemadanan tradisional secara manual sampel
bahan letupan bagi kes dan sampel kawalan sering payah dan tidak cekap. Kesukaran
mendapatkan bahan letupan piawai memburukkan lagi kerja rutin penganalisis forensik.
Oleh itu, kajian ini dilaksanakan untuk membangunkan satu sistem pangkalan data bahan
letupan forensik yang baharu untuk mendapatkan dan memadankan data secara cepat dan
cekap. Sebanyak 22 sampel pra- dan pasca-letupan telah dikumpul, termasuklah sampel
bahan letupan ketenteraan, peranti letupan improvisasi dan sampel bahan letupan
piroteknik. Semua sampel telah menjalani analisis ujian titik sebelum analisis
berinstrumen. Kromatografi cecair berprestasi tinggi dengan pengesan susunatur diod
(HPLC-DAD) dan kromatografi gas spektrometri jisim seiring (GC-MS/MS) telah
digunakan untuk pemprofilan kimia bahan letupan tahap tinggi dengan had pengesanan
(LOD) masing-masing dalam julat 0.02-4.35 mg/L dan 0.30-10.89 ng/L. Kromatografi ion
(IC) telah digunakan untuk pemprofilan kimia kandungan anion (LOD: 0.07-0.26 mg/L)
dan kation (LOD: 0.08-0.28 mg/L) bahan letupan tahap rendah tak organik. Kajian ini
mendedahkan bahawa setiap sampel letupan menunjukkan profil kromatografi berlainan
yang dapat mendiskriminasi daripada satu dengan yang lain. Sebatian bahan letupan nitro
PETN dan tetril masing-masing dikesan dalam analisis GC-MS/MS melalui kehadiran
produk degradasi 1,3-propandiol,2,2-dimetil-,dinitrat dan 2,4,6-trinitro-N-metil-anilina.
Kaedah yang dibangunkan untuk IC, HPLC dan GC-MS/MS dicadangkan sebagai kaedah
piawai bagi penghasilan keputusan yang perlu digabungkan ke dalam pangkalan data
bahan letupan. Sejumlah 52 maklumat data disimpan di dalam pangkalan data
menggunakan Microsoft SQL Server. Antaramuka laman grafik pengguna MyForensic
Explosive Database (MyFED) dibangunkan menggunakan Microsoft Visual Studio.
Pangkalan data ini menggabungkan butiran bahan letupan, keputusan analisis ujian titik,
faktor penahanan dan profil kromatografi bagi setiap analit untuk pencarian data, dapatan
semula dan pemadanan sampel bahan letupan yang tidak diketahui. Antara muka laman
pengguna melibatkan pemadanan analisis ujian titik, dan pemadanan kromatogram
dengan perbandingan faktor penahanan. Laman pentadbir hanya membenarkan hanya
pentadbir untuk melihat, memasukkan, menyunting dan memadam data. Sistem informasi
MyFED yang dibangunkan membantu memudahkan pemadanan sampel tidak diketahui
dengan sampel yang diketahui yang disimpan dalam pangkalan data. Walaupun sistem
mengandungi data bahan letupan yang terhad, keupayaannya yang mudah dinaiktaraf bagi
mengendalikan lebih banyak data bahan letupan manjadikan MyFED suatu permulaan
yang menarik dan menjanjikan bagi sistem pangkalan data Malaysia yang tersedia bagi
kegunaan penyiasat forensik di Malaysia mahupun di rantau Asia.
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TABLE OF CONTENTS
CHAPTER
TITLE PAGE
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES xiii
LIST OF FIGURES xvii
LIST OF ABBREVATIONS xxx
LIST OF APPENDICES xxxiii
1 INTRODUCTION 1
1.1 Background of Study 1
1.2 Statement of Problem 3
1.3 Objective of Study 3
1.4 Scope of Study 5
1.5 Significance of Study 5
1.6 Thesis Outline 6
2 LITERATURE REVIEW 7
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2.1 Introduction 7
2.2 Explosion 9
2.3 Chemical Explosives and its Classification 10
2.3.1 High Explosive 11
2.3.2 Low Explosives 13
2.4 Improvised Explosive Devices 17
2.5 Screening: On-Site Detection of Explosive Devices and
Explosive Residues 17
2.5.1 Non-optical Sensing Method 18
2.5.2 Optical Sensing Method 19
2.6 Sample Collection 21
2.6.1 Explosive Residue Distribution 21
2.6.2 Source of Evidence 22
2.6.3 Center of Blast 23
2.7 Sample Extraction 24
2.7.1 Swabbing Technique 25
2.7.2 Ultrasonication 25
2.7.3 Solid Phase Extraction 26
2.7.4 Solid Phase Microextraction 27
2.8 Instrumental Techniques 28
2.8.1 Gas Chromatography 29
2.8.2 High Performance Liquid Chromatography 30
2.8.3 Ion Chromatography 31
2.8.4 Capillary Electrophoresis 32
2.8.5 Other Techniques 33
2.8.6 Standard Method for Explosive Analysis 38
2.9 Database 40
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2.9.1 Database Management System 43
2.9.2 Microsoft SQL Server 43
2.9.3 Visual Basic Studio 44
2.9.4 Forensic Database 44
3 METHODOLOGY 47
3.1 Introduction 47
3.2 Flow Chart of Research Activities and Research Framework 47
3.3 Chemicals and Materials 49
3.4 Spot Test Analysis 50
3.4.1 Reagent A 50
3.4.2 Reagent B 51
3.4.3 Reagent C 51
3.4.4 Reagent D 51
3.4.5 Reagent E 52
3.4.6 Reagent F 52
3.5 Instrumentation 52
3.5.1 Ion Chromatography 53
3.5.2 High Performance Liquid Chromatography 54
3.5.3 Gas Chromatography Tandem Mass Spectrometry 54
3.5.4 Hardware and Software Specification for Database
Development 55
3.6 Sampling Exercise 55
3.6.1 Sampling Exercise I 55
3.6.2 Sampling Exercise II 59
3.7 Sample Preparation of Pre and Post-Blast Residues 62
3.8 Explosive Database System Design 63
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3.8.1 System User 64
3.8.2 Explosive Detail and Experimental Result 64
3.8.3 System Outline 66
4 DEVELOPMENT OF AN EXPLOSIVE SPOT TEST KIT 68
4.1 Introduction 68
4.2 Development of a Spot Test Kit 69
4.2.1 Reagent A 70
4.2.2 Reagent B 71
4.2.3 Reagent C 72
4.2.4 Reagent D 72
4.2.5 Reagent E 73
4.2.6 Reagent F 74
4.3 FOREHILEX Spot Test Kit 75
4.3.1 Contents of Spot Test Kit 75
4.3.2 Comparison of FOREHILEX with Other Spot Test Kit 77
5 EXPLOSIVE ANALYSIS OF INORGANIC IONS USING
ION CHROMATOGRAPHY 82
5.1 Preamble 82
5.2 Separation of Inorganic Anions and Cations 82
5.3 Calibration Graph and Detection Limits 84
5.4 Reproducibility and Repeatability 86
5.5 Development of Simultaneous Separation System for Ionic
Compound 88
5.6 Real Sample Analysis 93
5.6.1 Low Explosive Samples 93
5.6.2 Analysis of Improvised Explosive Device 101
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5.6.3 High Explosive Samples 107
5.7 Ion Chromatography Profile of Explosive Under Study 114
5.8 Summary of IC Chemical Profiling of Explosives 117
6 ANALYSIS OF ORGANIC EXPLOSIVES USING HIGH
PERFORMANCE LIQUID CHROMATOGRAPHY 119
6.1 Introduction 119
6.2 Optimization of HPLC Separation 119
6.2.1 Optimization of UV Wavelengths 120
6.2.2 Optimization of Mobile Phase 121
6.2.3 Calibration Graph and Detection Limits 126
6.2.4 Reproducibility Repeatability 127
6.3 Real Sample Analysis 130
6.3.1 HPLC Analysis of High Explosive 130
6.3.2 Analysis of Low Explosive and Improvised Explosive
Device Sample 136
6.3.3 Composition Profile of Pre-blast High Explosives
Samples 137
6.4 Chapter Summary 138
7 GAS CHROMATOGRAPHY TANDEM MASS
SPECTROMETRY FOR ANALYSIS OF ORGANIC
HIGH EXPLOSIVES 140
7.1 Overview 140
7.2 MRM Method Development Process 141
7.3 Calibration Graph and Detection Limit 146
7.4 Real Sample Analysis 148
7.4.1 GC-MS/MS Analysis of High Explosive C4 148
7.4.2 GC-MS/MS Analysis of High Explosive CE 152
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7.4.3 GC-MS/MS Analysis of High Explosive DC 155
7.4.4 GC-MS/MS Analysis of High Explosive LSC 158
7.5 Chapter Summary 160
8 DATABASE SYSTEM DEVELOPMENT 162
8.1 Introduction 162
8.2 Database Design 162
8.2.1 Conceptual Database Design 163
8.2.2 Logical Database Design 164
8.2.3 Physical Database Design 168
8.3 Database System Development 185
8.3.1 Interface Design 185
8.3.2 Module Design 212
8.3.3 System Testing 224
8.4 Evaluation of MyFED 234
8.5 Chapter Summary 235
9 CONCLUSION AND RECOMMENDATIONS 236
9.1 Introduction 236
9.2 Conclusions 236
9.2.1 Spot Test Kit 237
9.2.2 Low Explosive Analysis 237
9.2.3 High Explosive Analysis 238
9.2.4 Explosive Database System 240
9.3 Recommendations 241
REFERENCES 243
Appendices A-E 260-280
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LIST OF TABLES
TABLE NO.
TITLE PAGE
Table 2.1: Classification of fireworks based on United Nations
explosives shipping classification system (UN default
scheme for fireworks) 16
Table 2.2: Reference reagents for detection of explosive via
colorimetric reaction (Hoffman and Byall 1974; Royds et
al. 2005) 20
Table 2.3: Survey of explosive residue analysis according to
instruments used 35
Table 2.4: Explosive chemical compound analysis by using EPA
Method 8330 and EPA Method 8095 39
Table 2.5: Comparison between the different types of database
model 41
Table 2.6: List of available forensic databases 45
Table 3.1: Description of pyrotechnic pipe bomb samples used in this
study 56
Table 3.2: List of explosive material used for sampling exercise 59
Table 3.3: Attributes stored in database for explosive and
experimental results 65
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Table 4.1: Detection colour chart for FOREHILEX Test Kit 78
Table 4.2: Comparison of FOREHILEX with other commercial
available test kit 79
Table 5.1: Detection limit data of each analyte and comparison of
LOD obtained with other study 86
Table 5.2: Relative standard deviation of retention time for each
analyte within-day and day-to-day variation 88
Table 5.3: Similarities and differences between column
characteristic 89
Table 6.1: Limit of detection and correlation coefficient of explosive
analytes under study 128
Table 6.2: Percentage relative standard deviation of retention time
and peak area for explosive analyte for within-day and
day-to-day variation 129
Table 6.3: Amount of explosives detected in unexploded high
explosive samples 138
Table 7.1: Time fragment and precursor ion for each analyte 144
Table 7.2: Time fragment for each analyte and its precursor ion 144
Table 7.3: Selected product ion and its collision energy 145
Table 7.4: Limits of detection and correlation coefficient of
explosive analytes under study 147
Table 7.5: Qualifier ratio and accuracy of analytes detected in sample
C4 151
Table 7.6: Qualifier ratio and accuracy of analytes detected in sample
CE 154
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Table 7.7 : Qualifier ratio and accuracy of analytes detected in sample
DC 157
Table 7.8: Qualifier ratio and accuracy of each analytes for sample
LSC analysis 160
Table 8.1: The relational schema for explosive database under study 167
Table 8.2: Physical model for Explosive_Info 168
Table 8.3: Physical model for Spot_Test 169
Table 8.4: Physical model for SpotTestInfo 169
Table 8.5: Physical model for HPLC_Chrom 170
Table 8.6: Physical model for ICAnion_Chrom 171
Table 8.7: Physical model for ICCation_Chrom 171
Table 8.8: Physical model for GCMSMS_Chrom 172
Table 8.9: Physical model for Logon_History 172
Table 8.10 Tables and attributes description for the explosive
database 174
Table 8.11: Unknown sample matching 213
Table 8.12: Sub-module View 217
Table 8.13: Sub-module Insert 218
Table 8.14: Sub-module Edit 220
Tabl 8.15: Sub-module Delete 222
Tabl 8.16: System testing for unknown sample matching module 225
Tabl 8.17: System testing for sub-module view 228
Table 8.18: System testing for sub-module Insert 229
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Table 8.19: System testing for sub module edit 230
Table 8.20: System testing for sub-module Delete 231
Table 8.21: System testing for Help page 233
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LIST OF FIGURES
FIGURE NO.
TITLE PAGE
Figure 2.1: Distribution of journal publication on low explosive and
high explosive based on SCOPUS database journal
publication from year 1995-2015 8
Figure 2.2: Distribution of terrorism method used by terrorist (2000-
2010) 8
Figure 2.3: Classification of chemical explosives 11
Figure 2.4: Distribution of journal publication on the selected
instrumentation based on SCOPUS database journal
publication from year 2000-2015 28
Figure 3.1: Flow chart of research activities 48
Figure 3.2: Flow chart of research framework 48
Figure 3.3: Photograph of home-made bomb container (a) and
dimensions of the PVC pipe (b) used for the preparation of
pipe bomb 56
Figure 3.4: Photographs showing (a) Arrangement of pipe bomb
surrounded by sandbags, (b) Sand bag and aluminium sheet
used to cover the pipe bomb, (c) Scene immediately after
explosion, and (d) Debris from seat of explosion ready to be
collected 57
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Figure 3.5: Sketch of the sampling location 58
Figure 3.6: (a) Photograph of pepper bottle container, (b) Dimensions
of the bottle used for the bomb container 60
Figure 3.7: Photograph showing (a) Arrangement of pipe bomb
surrounded by sandbags, (b) Sandbag used to cover the pipe
bomb, (c) Scene immediately after the explosion, (d) Debris
from the seat of explosion ready to be collected 60
Figure 3.8: Sketch of the sampling location 61
Figure 3.9: Flow chart of database framework 67
Figure 4.1: Photographs of FOREHILEX Test Kit showing. (a) Front
view, and (b) inner view of the FOREHILEX spot test kit 76
Figure 5.1: Separation of standard anions (3 mg/L) on Metrosep A
Supp 4 column. Eluent: 1.8 mmol/L Na2CO3 and 1.7
mmol/L NaHCO3; flow rate: 1.0 mL/min; suppressed
conductivity detection; injection volume: 20 µL;
temperature: 30oC; eluting sequence: 1. F- (3.9 min), 2. Cl-
(5.4 min), 3. NO2- (6.2 min), 4. ClO3
- (7.5 min), 5. NO3
- (8.5
min), 6. PO43-
(12.8 min), 7. SO42-
(14.9 min), 8. ClO4- (43.1
min). Separation of perchlorate ion shown as a broad peak
(inset as enlarged peak) 83
Figure 5.2: Separation of standard cations (3 mg/L) on Metrosep C4
column. Eluent: 2.5 mmol/L 5-sulfosalicylic acid dehydrate
and 2% acetonitrile; flow rate: 1.0 mL/min; conductivity
detection; injection volume: 20 µL; eluting sequence: 1. Li+
(4.98 min), 2. Na+ (5.78 min), 3. NH4+ (6.23 min), 4. K+
(7.55 min), 5. Ca2+ (12.12 min), and 6. Mg2+ (14.58 min) 84
Figure 5.3: Calibration graph of nine anions plot using 1 to 5 mg/L
concentration of standard solutions 85
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Figure 5.4: Calibration graph of six standard cations plot using 0.2 to 2
mg/L concentration of standard solutions 85
Figure 5.5: Separation of standard cation (3 mg/L) on Metrosep C4
250/4.0 column. Eluent (a) 2.0 mmol/L, (b) 2.5 mmol/L, (c),
3.0 mmol/L 5-sulfosalicylic acid dehydrate + 2%
acetonitrile; flow rate: 1.0 mL/min. Other IC conditions as
in Figure 5.2 90
Figure 5.6: Separation of standard cation (3 mg/L) on Metrosep C4
250/4.0 column. Eluent (a) 6.0 mmol/L, (b) 4.0 mmol/L, (c),
2.0 mmol/L phtalic acid + 2% acetonitrile; flow rate: 1.0
mL/min 91
Figure 5.7: Separation of standard anions (5 mg/L) on Metrosep A
Supp 4. Eluent (a) 2.5 mmol/L 5-sulfosalicylic acid
dehydrate + 2% acetonitrile, (b) 6.0 mmol/L phtalic acid +
2% acetonitrile, (c) 1.8 mmol/L Na2CO3 + 1.7 mmol/L
NaHCO3; flow rate: 1.0 mL/min 92
Figure 5.8: Packaging of Happy bomb pyrotechnic samples 94
Figure 5.9: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample HB. IC
conditions as in Figure 5.1. Peak position identities: 1. Cl-,
2. NO2-, 3. NO3
-, 4. SO4
2-, 5. ClO4
- 94
Figure 5.10: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast of Sample HB. IC conditions
as in Figure 5.2. Peak position identities: 1. Na+, 2. NH4+, 3.
K+, 4. Ca2+, 5. Mg2+ 95
Figure 5.11: Packaging of Monster bomb pyrotechnic sample 96
Figure 5.12: IC chromatogram of target anions in unexploded explosive
(a) and post-blast residues (b) of Sample MS. IC conditions
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as in Figure 5.1. Peak position identities 1. Cl-, 2. NO2-, 3.
NO3-, 4. SO4
2-, 5. ClO4
- 96
Figure 5.13: IC chromatogram of target cations in unexploded explosive
(a) and post-blast (b) of Sample MS. IC conditions as in
Figure 5.2. Peak position identities: 1. Na+, 2. NH4+, 3. K+,
4. Ca2+, 5. Mg2+ 97
Figure 5.14: Physical shape of Mercun ketupat firecracker 98
Figure 5.15: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample MK. IC
conditions as in Figure 5.1. Peak position identities: 1. F-,
2. Cl-, 3. NO3-, 4. SO4
2-, 5. ClO4
- 98
Figure 5.16: IC chromatogram of target cations in unexploded explosive
(a) and post-blast (b) of Sample MK. IC conditions as in
Figure 5.2. Peak position identities: 1. Na+, 2. NH4+, 3. K+,
4. Ca2+, 5. Mg2+ 99
Figure 5.17: Appearance of Mercun bola firecracker 99
Figure 5.18: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample MB. IC
conditions as in Figure 5.1. Peak position identities: 1. F-,
2. Cl-, 3. NO3-, 4. SO4
2- 100
Figure 5.19: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast of Sample MB. IC conditions
as in Figure 5.2. Peak position identities: 1. Na+, 2. NH4+, 3.
K+, 4. Ca2+, 5. Mg2+ 100
Figure 5.20: Emulex explosive 102
Figure 5.21: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample IED1. IC
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conditions as in Figure 5.1. Peak position identities: 1. Cl-,
2. NO3-, 2. SO4
2- 102
Figure 5.22: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast residues of Sample IED1. IC
conditions as in Figure 5.2. Peak position identities: 1. Na+,
2. NH4+, 3. K+, 4. Ca2+, 5. Mg2+ 103
Figure 5.23: IED2 explosive material contained in a plastic pepper
container 104
Figure 5.24: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample IED2. IC
conditions as in Figure 5.1. 100x dilutions. Peak position
identities: 1. Cl-, 2. NO3-, 3. SO4
2- 104
Figure 5.25: IC chromatogram of target cations in unexploded explosive
(a) and post-blast residues (b) of Sample IED2. IC
conditions as in Figure 5.2. 100x dilutions. Peak position
identities: 1. Na+, 2. NH4+, 3. K+, 4. Ca2+, 5. Mg2+ 105
Figure 5.26: Components of IED3 explosive placed on a weighing scale 106
Figure 5.27: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample IED3. IC
conditions as in Figure 5.1. 100x dilutions. Peak position
identities: 1. Cl-, 2. NO3-, 2. SO4
2- 106
Figure 5.28: IC chromatogram of target cations in unexploded explosive
(a) and post-blast residues (b) of Sample IED3. IC
conditions as in Figure 5.2. 100x dilutions. Peak position
identities: 1. Na+, 2. NH4+, 3. K+, 4. Ca2+, 5. Mg2+ 107
Figure 5.29: IC chromatogram of target anions in unexploded explosive
(a) and post-blast residues (b) of Sample C4. IC conditions
as in Figure 5.1. Peak position identities: 1. NO3-, 2. SO4
2- 108
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Figure 5.30: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast residues of Sample C4. IC
conditions as in Figure 5.2. Peak position identities: 1. Na+,
2. NH4+, 3. Mg2+ 109
Figure 5.31: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample CE. IC
conditions as in Figure 5.1. Peak position identities: 1. NO3-,
2. SO42-- 110
Figure 5.32: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast residues of Sample CE. IC
conditions as in Figure 5.2. Peak position identities: 1. Na+,
2. NH4+, 3. K+, 4. Ca2+, 5. Mg2+ 110
Figure 5.33: IC chromatogram of target anions in explosive (a)
unexploded and (b) post-blast residues of Sample DC. IC
conditions as in Figure 5.1. Peak position identities: 1. Cl-,
2. NO3-, 3. SO4
2- 111
Figure 5.34: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast residues of Sample DC. IC
conditions as in Figure 5.2. Peak position identities: 1. Na+,
2. NH4+, 3. K+, 4. Ca2+, 5. Mg2+ 112
Figure 5.35: IC chromatogram of target anions in (a) unexploded
explosive and (b) post-blast residues of Sample LSC. IC
conditions as in Figure 5.1. Peak position identities: 1. Cl-,
2. NO3-, 3. SO4
2- 113
Figure 5.36: IC chromatogram of target cations in (a) unexploded
explosive and (b) post-blast residues of Sample LSC. IC
conditions as in Figure 5.2. Peak position identities: 1. Na+,
2. NH4+, 3. Mg2+ 113
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Figure 5.37: Composition profile of anion and cation separation of
pyrotechnic explosive under study 116
Figure 5.38: Composition profile of anion and cation separation of
improvised explosive device explosive under study 117
Figure 6.1: Graph of UV wavelength comparison of each target
analytes 120
Figure 6.2: HPLC-DAD separation of standard mixture on Supelco
Ascentis C18 (4.6 x 250 mm, 3.5 µm) column, Eluent:
acetonitrile-water (65:35), flow rate: 1.0 mL/min; injection
volume: 20 µL detection at 220 nm; eluting sequence: 1.
HMX, 2. 4-nitrobenzonitrite, 3. RDX, 4. nitroglycerin,
TNT, 2,6-DNT, 2,4-DNT, 5. PETN, 6. 2-
nitrodiphenylamine, 7. N-nitrosodiphenylamine, 8. 4-
nitrodiphenylamine, 9. diphenylamine, and 10. ethyl
centralite 121
Figure 6.3: HPLC-DAD separation of standard explosive mixture on
Supelco Ascentis C18 (4.6 x 250 mm, 3.5 µm) column,
Eluent: methanol-water (65:35), flow rate: 1.0 mL/min;
injection volume: 20 µL detection at 220 nm; eluting
sequence: 1. HMX, 2. 4-nitrobenzonitrite, 3. RDX, 4.
nitroglycerin, 5. TNT, 6. 2,6 DNT, 7. 2,4 DNT, 8. PETN, 9.
2-nitrodiphenylamine, 10. N-nitrosodiphenylamine, 11. 4-
nitrodiphenylamine, 12. diphenylamine, and 13. ethyl
centralite 122
Figure 6.4: HPLC-DAD separation of explosive standard mixture on
Supelco Ascentis C18 (4.6 x 250 mm, 3.5 µm) column, flow
rate: 1.0 mL/min; injection volumn: 20 µL analyte detection
at 220nm, Eluent: methanol-acetonitrile-water; at various
mobile phase composition of (a) 40:20:40, (b) 30:30:40, (c)
40:10:50, (d) 50:10:40. Analyte detection at 220 nm. Peak
identity: (1) HMX, (2) 4-nitrobenzonitrite, (3) RDX, (4)
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nitroglycerin, (5) TNT, (6) 2,6 DNT, (7) 2,4 DNT, (8)
PETN, (9) 2-nitrodiphenylamine, (10) N-
nitrosodiphenylamine, (11) 4-nitrodiphenylamine, (12)
diphenylamine, and (13) ethyl centralite 124
Figure 6.5: Chemical structure of 2,4-dinitrotoluene, 2,6-dinitrotoluene
and trinitrotoluene 125
Figure 6.6: HPLC-DAD calibration graph of thirteen organic explosive
compound 126
Figure 6.7: Plastic Explosive PP01 (C4) 131
Figure 6.8: HPLC-DAD chromatograms of (i) post-blast and (ii) pre-
blast military explosive samples C4. HPLC conditions as in
Figure 6.4 (d) 131
Figure 6.9: Chemical structure of PETN and RDX 131
Figure 6.10: Appearance of CE Primer (CE) as cylindrical block 132
Figure 6.11: HPLC-DAD chromatograms of (i) post-blast and (ii) pre-
blast military explosive samples CE. HPLC conditions as in
Figure 6.4 (d) 133
Figure 6.12: Chemical structure of tetryl 133
Figure 6.13: Detonating Cord (DC) 134
Figure 6.14: HPLC-DAD chromatograms of (i) post-blast and (ii) pre-
blast military explosive samples DC. HPLC conditions as
in Figure 6.4 (d) 134
Figure 6.15: Charge Lining Cutter (LSC) 135
Figure 6.16: HPLC-DAD chromatograms of (i) post-blast and (ii) pre-
blast military explosive samples LSC. HPLC conditions as
in Figure 6.4 (d) 136
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Figure 6.17: HPLC-DAD chromatograms of (i) 100 ppm KNO3 (ii) pre-
blast explosive samples IED1 (ii) post-blast explosive
samples IED1. HPLC conditions as in Figure 6.4 (d) 137
Figure 7.1: Triple quadrupole mass spectrometry detection system 141
Figure 7.2: Workflow for MRM method development process (Agilent,
2009) 142
Figure 7.3: Total ion scan separation of explosive standard mixture on
HP5-MS (30 m x 0.25 mm x 0.25 μm) column. A
temperature program was employed using an initial oven
temperature of 100oC for 3 min, then ramped to 280oC at
15oC/min and finally held at 280oC for 1 min. Injector
temperature was set at 230oC and detector temperature at
300oC. Carrier gas was helium at a flow rate of 1 mL/min.
Peak identity: (1) 4-nitrobenzonitrite, (2) 2,6-DNT, (3) 2,4-
DNT, (4) diphenylamine, (5) TNT, (6) ethyl centralite, (7)
2-nitrodiphenylamine, and (8) 4-nitrodiphenylamine 142
Figure 7.4: A schematic diagram of MRM development process on a
triple quadrupole instrument. The precursor ion is selected
in Q1, fragmentation occurs in Q2, and the product ion is
selected by Q3 (Agilent, 2009) 143
Figure 7.5: Mass spectrum for 4-nitrobenzonitrile (4-NBN) 143
Figure 7.6: MRM GC-MS/MS separation of explosive standard
mixture. Peak identity: (1) 4-nitrobenzonitrite, (2) 2,6-
DNT, (3) 2,4-DNT, (4) diphenylamine, (5) TNT, (6) ethyl
centralite, (7) 2-nitrodiphenylamine, and (8) 4-
nitrodiphenylamine. GC-MS/MS conditions as in Figure
7.3 146
Figure 7.7: GC-MS/MS calibration graph of eight organic explosive
compound 147
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Figure 7.8: TIC chromatograms of (i) pre-blast and (ii) post-blast
military explosive sample C4. GC-MS/MS conditions as in
Figure 7.3 149
Figure 7.9: Mass spectrum of 1,3-propanediol, 2,2-dimethyl-, dinitrate 149
Figure 7.10: Possible fragmentation of PETN to yield 1,3-propanediol,
2,2-dimethyl-, dinitrate 150
Figure 7.11: MRM chromatograms of (i) pre-blast and (ii) pre-blast
military explosive samples C4. GC-MS/MS conditions as
in Figure 7.3 151
Figure 7.12: TIC chromatograms of (i) pre-blast and (ii) post-blast
military explosive sample CE. GC-MS/MS conditions as in
Figure 7.3 152
Figure 7.13: Mass spectra of 2,4,6-trinitro-N-methyl-aniline .153
Figure 7.14: Possible degradation of tetryl to yield 2,4,6-trinitro-N-
methyl-aniline (Tamiri and Zitrin, 1986) 153
Figure 7.15: GC-MS/MS chromatograms of (i) pre-blast and (ii) post-
blast military explosive samples CE. GC-MS/MS
conditions as in Figure 7.3 154
Figure 7.16: TIC chromatograms of (i) pre-blast and (ii) post-blast
military explosive sample DC. GC-MS/MS conditions as in
Figure 7.3 155
Figure 7.17: Mass spectra of di-n-octyl phthalate 156
Figure 7.18: GC-MS/MS chromatograms of (i) pre-blast and (ii) post-
blast military explosive samples DC. GC-MS/MS
conditions as in Figure 7.3 157
xxvii
Figure 7.19: TIC chromatograms of (i) pre-blast and (ii) post-blast
military explosive sample LSC. GC-MS/MS conditions as
in Figure 7.3 158
Figure 7.20: GC-MS/MS chromatograms of (i) pre-blast and (ii) post-
blast military explosive samples LSC. GC-MS/MS
conditions as in Figure 7.3 159
Figure 8.1: ERD of Conceptual model explosive database 163
Figure 8.2: ERD of Logical model for the explosive database 165
Figure 8.3: Multiplicity constraints for 6 entities in explosive database 166
Figure 8.4: Tables and attributes for explosive database 173
Figure 8.5: Table description in Microsoft SQL Server database
management system 179
Figure 8.6: Explosive_Info table design 179
Figure 8.7: Detail view for explosive information 180
Figure 8.8: Spot_Test table design 181
Figure 8.9: SpotTestInfo table design 181
Figure 8.10: Detail view for Spot_Test table 182
Figure 8.11: Detail view for SpotTestInfo table 182
Figure 8.12: HPLC_Chrom table design 183
Figure 8.13: Detail view for HPLC_Chrom table 184
Figure 8.14: Chart detail of GUI for MyForensic Explosive Database 186
Figure 8.15: Welcome page for MyForensic Explosive Database 187
Figure 8.16: User guide page 1 188
xxviii
Figure 8.17: User guide page 2 188
Figure 8.18: User guide page 3 189
Figure 8.19: Log in page 190
Figure 8.20: Spot test match page 190
Figure 8.21: Spot test guide page 191
Figure 8.22: Chromatogram matching page 192
Figure 8.23: IC Match page 192
Figure 8.24: HPLC Match Page 194
Figure 8.25: HPLC Match Page: Open image chromatogram 194
Figure 8.26: HPLC Match Page: Open print info 195
Figure 8.27: HPLC Match Page: Sample match confirmation 195
Figure 8.28: Admin Login page 197
Figure 8.29: Administrator page 197
Figure 8.30: View page 198
Figure 8.31: View: View Sample 198
Figure 8.32: View: HPLC Chromatogram 199
Figure 8.33: View: Spot Test 199
Figure 8.34: View: Log History 200
Figure 8.35: Insert page 201
Figure 8.36: Insert: Insert New Sample 202
Figure 8.37: Sample Code Info page 202
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Figure 8.38: Insert: Insert New Spot Test 203
Figure 8.39: Insert: Insert New Chromatogram (HPLC) 203
Figure 8.40: Edit page 204
Figure 8.41: Edit: Explosive Info 205
Figure 8.42: Edit: Spot Test Info 206
Figure 8.43: Edit: HPLC Edit page 206
Figure 8.44: Delete page 207
Figure 8.45: Delete: Explosive Delete page 208
Figure 8.46: Delete: Spot Test Delete page 208
Figure 8.47: Delete: HPLC Delete page 209
Figure 8.48: Help page 210
Figure 8.49: Help: System Requirement 210
Figure 8.50: Help: K Calculator 211
Figure 8.51: Help: Contact Developer 211
xxx
LIST OF ABBREVIATIONS
HPLC - High Performance Liquid Chromatography
DAD - Diode Array Detector
IC - Ion Chromatography
GC - Gas Chromatography
MS - Mass Spectrometry
MS/MS - Tandem Mass Spectrometry
ECD - Electron Capture Detector
DDW - Double Distilled Deionized Water
IED - Improvised Explosive Device
ND - Not Detected
RSD - Relative Standard Deviation
RMP - Royal Malaysia Police
STRIDE - Science Technology Research Institute for Defense
PDRM - Polis Diraja Malaysia
SPE - Solid Phase Extraction
SPME - Solid Phase Microextraction
MyFED - MyForensic Explosive Database
FOREHILEX - Forensic Reagent for Low and High Explosive
GTD - Global Terrorism Database
HMX - Cyclotetramethylenetetranitramine
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4-NBN - 4-nitrobenzonitirle
RDX - Cyclotrimethylenetrinitramine
NG - Nitroglycerin
TNT - 2,4,6-trinitrotoluene
2,6-DNT - 2,6-dinitrotoluene
2,4-DNT - 2,4-dinitrotoluene
PETN - Pentaerythritoltetranitrate
N-NDP - N-nitrosodiphenylamine
4-NDP - 4-nitrodiphenylamine
DP - Diphenylamine
2-NDP - 2-nitrodiphenylamine
EC - Ethyl centralite
EGDN - Ethyleneglycoldinitrate
ANFO - Ammonium Nitrate Fuel Oil
UN - United Nations
TLC - Thin Layer Chromatography
VBIED - Vehicle-Borne Improvised Explosive Device
EPA - Environmental Protection Agency
UV - Ultraviolet
MEKC - Micellar Electrokinetic Chromatography
PDMS/DVB - Polydimethylsiloxane/divinylbenzene
CAR/PDMS - CarboxenTM/ polydimethylsiloxane
TEA - Thermal Energy Analyzer
PCI - Positive Chemical Ionization
XRD - X-ray Powder Diffraction
XF - X-ray fluorescence
IMS - Ion Mobility Spectrometry
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ESI - Electrospray Ionization
DBMS - Database Management System
SQL - Structured Query Language
RDBMS - Rational Database Management System
VB - Visual Basic
GUI - Graphic User Interface
IDE - integrated development environment
IR - Infrared
IBIS - Integrated Ballistic Identification System
PDQ - Paint Data Query
k - Capacity Factor/Retention Factor
IAFIS - Integrated Automated Fingerprint Identification
System
xxxiii
LIST OF APPENDICES
APPENDIX
TITLE PAGE
A FOREHILEX User’s Manual 261
B IED1 and IED2 HPLC Chromatogram 264
C Explosive Database Table Contents 265
D Evaluation Form of MyFED 277
E Abstract of Attended Conferences and Publications 280
INTRODUCTION
1.1 Background of Study
An explosion may result from a criminal act and can also occur by accident,
for example from an ignition's spark of a leak of domestic gas. In recent years, terrorists
have used improvised explosives devices (IED) for the purpose of increasing damage
of explosion. Growing number of cases involving improvised explosives devices in
local and international media have raised the awareness of forensic researchers and
law enforcers to study explosives components in details (Ahmad et al., 2011).
Bombing activities that occurred in the past few years such as the Bali bombing in
2002, the Altantuyaa murder in October 2006 and the Jakarta bombing in July 2009
have all involved improvised explosives devices that were made from both low and
high explosive materials (Oam and Royds, 2013).
According to Malaysian Corrosive and Explosive Substances and Offensive
Weapons Act 1958, the term "explosive substance" include “materials for making any
explosive substance and any bomb, grenade, apparatus, machine, implement, or
material used or intended to be used or adapted for causing or aiding in causing any
explosion in or with any explosive substance and any part of such bomb, grenade,
apparatus, machine or implement”. Explosives can exist in the form of solid, liquid or
gases. It is made of either mixtures or pure compounds (Akhavan, 2011). Pure
2
explosive compounds be can further divided into organic and inorganic explosives.
Furthermore, explosive can also be classified as low explosive and high explosive
based on their impact of bombardment. Improvised explosives devices are usually
made from low explosive materials since the materials are commonly used and easily
obtained in the local market. It arises as a potential menace to public safety as
pyrotechnics such as crackers and fireworks can be conveniently purchased either
legally or illegally from local market (Yoong, 2013).
In a case of Boston marathon bombing in 2013, an improvised explosive device
with pressure cooker as the container was detonated close to the marathon finish line
(Sara and Ellen, 2015). The perpetrator used low explosive materials believed to be
from firework and increased the explosion damage by adding shrapnel in their
explosive device (Dezenski, 2013; Singh et al., 2014). However, the criminals at
international level often used high explosive material in their explosive device because
of its capability to increase the damage tremendously. In the Bali bombing of 2002,
high explosive material identified as trinitrotoluene (TNT), had been used as the main
charge for all three explosions that were detonated almost at the same time (Royds et
al., 2005).
Determining the nature of an explosion can be a significant challenge to the
forensic investigator. High level of contamination, small amount of device fragment
or minimal amount of post-blast residue found at the crime scene are among the
challenges that need to be faced by each forensic investigator. Proper investigation and
analysis must be carried out because from the evidence collected at crime scene, the
researcher can determine the type of explosive after the sample has been analysed and
can be used as evidence in court to link the suspect with the crime (Ahmad and Heng,
2007; Ladham et al., 2005; Sharma et al., 2010; Varga and Ulbrich, 2004).
3
1.2 Statement of Problem
The expanding threat, unlawful behaviour and illicit activities utilising
energetic explosive materials for criminal and terrorism activities have urged the need
for a reliable, rapid but also an accurate investigation technique for analysing crucial
puzzles left at the scene of the crime. Analysis of explosive residues become more
difficult since the residues of origin material from post-blast samples usually trapped
and fused into surrounding. To identify unknown explosive samples, it demanding a
competency technique to determine an extensive number of organic and inorganic
explosive material. It is a great importance for the analysis of explosive and their post-
blast residues analysis to assist forensic scientist in determining the origin of explosive
material used in the bombing and eventually help the law enforcement in narrowing
down the investigation.
However, the lack of an explosive database has caused great difficulties for the
law enforcement when investigating explosion cases in connecting the explosives to
their source of origin. Thus, a research to develop an explosive database is important
in order to assist the bombing investigators. This research is therefore undertaken to
answer the following questions; what are the techniques suitable to analyse explosive
residues? What database information system can be used to facilitate in finding a link
of post-blast residues to the source of origin and ultimately to the perpetrator of crime?
1.3 Objective of Study
The objectives of this study are divided into two phases which are experimental
and computational part.
4
Phase 1
In the experimental part, the objectives are focused on the chemical reaction
and instrument optimization.
i. To develop a portable explosive spot test kit as a screening technique for
the field detection of organic high explosive and inorganic low explosives.
ii. To analyse inorganic low explosives by using ion chromatography.
iii. To determine organic high explosives by using high performance liquid
chromatography
iv. To apply gas chromatography tandem mass spectrometry for analysis of
high explosive.
v. To propose suitable chromatographic methods for analysis of low and high
explosives.
Phase 2
In the second phase, the objectives are focused on computational work aim to
develop an information system for explosives by using the experimental data from the
first phase. The novelty of this research lies in the building a database information
system. The database information system is focused on recognition system and the
user may use the program to identify the profiling of the real sample with data that has
been stored in the database. Two more objectives are listed as follows:
vi. To develop an explosive database information system for the profiling of
explosives.
vii. To apply the developed explosive database information system for the
comparison of unknown samples of explosive with database of known
sample.
5
1.4 Scope of Study
The scope of this study involved the analysis of both high and low explosives.
Colour spot tests were employed to screen for target analytes that were recovered
onsite. The samples were analysed using ion chromatography, high performance liquid
chromatography, and gas chromatography tandem mass spectrometry. Standards and
post-blast residues were collected with the collaboration of Royal Malaysia Police
(RMP), and Science Technology Research Institute for Defense (STRIDE). A database
information system of the chemical composition profile of explosives named as
MYForensic Explosive Database was developed by using Microsoft SQL server and
Microsoft visual studio. This database was intended to serve a great support in order
to determine the source or types of explosive of unknown samples with known samples
stored in the database. The flexibility of database system also allowed administrator
the capability of viewing, inserting, editing and deleting data from the database.
1.5 Significance of Study
Results of this study will be particularly useful to forensic investigators
especially those working at Jabatan Kimia Malaysia in handling such evidence of
explosion cases to determine the nature of the explosive and to profile its origin.
Identification of the nature of the explosives may lead to the perpetrator of the crime.
Therefore, this study will be able to assist other institutions like Royal Malaysia Police
or any private agencies to further their investigation in establishing links to the
suspects once the nature of the explosives used is positively identified.
6
1.6 Thesis Outline
This thesis is divided into nine chapters. Chapter 2 presence the literature
review. Chapter 3 describes the general experimental work and chapter 4 describes the
development of a spot test kit. Analysis of explosives using IC, HPLC and GC-MS/MS
are described in chapter 5, 6 and 7 respectively. Chapter 8 deals with the development
of explosive database system. The final chapter 9 concludes the experimental results
and opens up the world of future research in explosives.