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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

iii

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

iv

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

v

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

x

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


6.3.1 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


7.4.1 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


8 DATABASE SYSTEM DEVELOPMENT 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


9 CONCLUSION AND RECOMMENDATIONS 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

xiii

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

xiv

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

xv

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

xvi

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

xvii

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

xviii

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

xix

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

xx

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


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


(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


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


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


explosive and (b) post-blast residues of Sample IED1. IC

xxi


2. NO3-, 2. SO4

2- 102



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



conditions as in Figure 5.1. 100x dilutions. Peak position

identities: 1. Cl-, 2. NO3-, 3. SO4

2- 104


(a) and post-blast residues (b) of Sample IED2. IC


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




identities: 1. Cl-, 2. NO3-, 2. SO4

2- 106


(a) and post-blast residues (b) of Sample IED3. IC


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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explosive and (b) post-blast residues of Sample C4. IC


2. NH4+, 3. Mg2+ 109


explosive and (b) post-blast residues of Sample CE. IC

conditions as in Figure 5.1. Peak position identities: 1. NO3-,

2. SO42-- 110


explosive and (b) post-blast residues of Sample CE. IC


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


2. NO3-, 3. SO4

2- 111


explosive and (b) post-blast residues of Sample DC. IC


2. NH4+, 3. K+, 4. Ca2+, 5. Mg2+ 112


explosive and (b) post-blast residues of Sample LSC. IC


2. NO3-, 3. SO4

2- 113


explosive and (b) post-blast residues of Sample LSC. IC


2. NH4+, 3. Mg2+ 113





























xxiii

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)


























xxiv

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


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


blast military explosive samples DC. HPLC conditions as

in Figure 6.4 (d) 134

Figure 6.15: Charge Lining Cutter (LSC) 135


blast military explosive samples LSC. HPLC conditions as

in Figure 6.4 (d) 136















xxv

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

xxvi

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


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


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


blast military explosive samples DC. GC-MS/MS











xxvii


military explosive sample LSC. GC-MS/MS conditions as

in Figure 7.3 158


blast military explosive samples LSC. GC-MS/MS


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 8.19: 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

xxix

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

xxxi

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

xxxii

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.

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