A STUDY ON METHODS FOR DETECTION IN CLANDESTINE METHAMPHETAMINE
LABORATORIES
LEE KHAI
UNIVERSITI SAINS MALAYSIA
2021
A STUDY ON METHODS FOR DETECTION IN CLANDESTINE METHAMPHETAMINE
LABORATORIES
by
LEE KHAI
Thesis submitted in fulfilment of the requirements for the degree of
Doctor of Philosophy
July 2021
ACKNOWLEDGEMENT
I would like to express my deepest gratitude to my supervisor, Associate Professor Dr Ahmad Fahmi Lim bin Abdullah, and co-supervisor, Dr Chang Kah Haw for the interesting and challenging research project. They had provided insight, suggestion, and encouragement that have showed me the correct path and mindset to have as a researcher. I would like to thank my field supervisor, Associate Professor Dr Warakorn Limbut from Division of Health and Applied Sciences, Faculty of Science, Prince of Songkhla University, Hat Yai, Songkhla for providing extensive knowledge and supervision in electrochemistry during my six-month research attachment in Department of Applied Science to complete one part of my research. Not to forget the help from “Subaru Group” in the analytical laboratory, especially Asmee, Kasrin, Jenjira, and Ping, for all exceptional assistance. I would like to thank the Dean of School of Health Sciences who has unconditionally supported my application. Also, I would like to specially acknowledge to the dedicated staff and laboratory technologists from Forensic Science Laboratory and Analytical Laboratory of School of Health Sciences, University Sains Malaysia, including Ms Hafizi, Mr Rosliza, Mr Baharuddin, Ms Hasnita, Mr Auzan, and Mr Sahnusi for their helps and guidance in the use of facilities.
I am also grateful to Universiti Sains Malaysia for providing the RU grant that have funded my research, and the Graduate Assistant Scheme that helped ease my financial burden throughout the course of my study. On a more personal note, I would like to express my gratitude to my research colleagues and all the friends that had directly or indirectly gave me support in my PhD study. Lastly, my family has been my strongest motivation and inspiration. As a sign of thankfulness, I dedicate this thesis and all my
TABLE OF CONTENTS
ACKNOWLEDGEMENT ... ii
TABLE OF CONTENTS ... iii
LIST OF TABLES ... x
LIST OF FIGURES ... xii
LIST OF EQUATIONS ... xviii
LIST OF SYMBOLS ... xix
LIST OF UNITS ... xx
LIST OF ABBREVIATIONS ... xxi
LIST OF APPENDICES ... xxv
ABSTRAK ... xxvi
ABSTRACT ... xxviii
CHAPTER 1 INTRODUCTION ... 1
1.1 Methamphetamine ... 1
1.2 Methamphetamine abuse and manufacture ... 3
1.2.1 Methamphetamine users in Malaysia ... 3
1.2.2 Manufactures of methamphetamine in Malaysia ... 5
1.2.3 Clandestine laboratories dismantled in Malaysia ... 6
1.2.4 Control and legislation of methamphetamine in Malaysia ... 7
1.3 Problem Statements ... 9
1.4 Scope of Study ... 12
1.5 Aim and Objectives ... 14
1.6 Significance of Study ... 14
CHAPTER 2 LITERATURE REVIEW ... 17
2.1 Overview ... 17
2.3 Manufactures of Illicit Methamphetamine ... 19
2.3.1 Introduction to methamphetamine synthesis ... 19
2.3.1(a) The Amalgam method ... 21
2.3.1(b) Red Phosphorus methods... 23
2.3.1(c) The Birch method ... 25
2.3.2 Drug manufacturing method preference across regions... 26
2.3.3 Current knowledge on clandestine methamphetamine synthesis ... 27
2.3.4 Classification of clandestine methamphetamine laboratories ... 31
2.3.5 Clandestine methamphetamine laboratory – Malaysia situations ... 34
2.3.6 Contamination at Clandestine Laboratories ... 37
2.3.6(a) Clandestine chemical hazards ... 39
2.3.6(b) Clandestine methamphetamine laboratory contamination – the degree and issues ... 41
2.3.7 Clandestine methamphetamine clean-up... 44
2.3.8 Detection strategies for illicit methamphetamine in clandestine laboratories ... 47
2.4 Colour test ... 48
2.4.1 Colour tests for methamphetamine ... 49
2.4.2 Simple Colourimetric-based Detection ... 50
2.5 Digital Image Analysis ... 52
2.5.1 Colourimetric-based detection using digital image analysis ... 53
2.5.2 Advantages of digital colour system ... 55
2.6 Ultraviolet-Visible Spectroscopy ... 57
2.6.1 Reagents for coloured-complex formation... 57
2.6.2 Colourimetric-based detection using ultraviolet-visible spectroscopy ... 59
2.7 Electrochemical detection ... 61
2.7.2 Three-electrode System ... 62
2.8 Gas Chromatographic Techniques ... 65
2.9 Surface Recovery of Methamphetamine ... 68
2.10 Summary ... 71
CHAPTER 3 METHODOLOGY ... 74
3.1 Overview ... 74
3.2 Materials and Equipment ... 76
3.2.1 Chemicals and Reagents ... 76
3.2.2 Chemical Standards ... 76
3.2.3 Apparatus and Equipment ... 77
3.3 Colour Spot Test ... 78
3.3.1 Preparation of methamphetamine standard solution ... 78
3.3.2 Preparation of colour reagents ... 78
3.3.3 Procedure for colour test ... 78
3.4 Colour Spot Test with Digital Image Analysis ... 79
3.5 Colour tests coupled with UV-Vis spectroscopy ... 80
3.5.1 Preparation of methamphetamine standard solution ... 80
3.5.2 Preparation of reagent-analyte solution ... 80
3.5.3 UV-Vis spectroscopic analysis ... 81
3.5.4 Behaviour of methamphetamine in colour reagents with various concentration levels ... 81
3.5.5 Detection limit ... 81
3.5.6 Behaviour of colour tests over time ... 82
3.6 Gas Chromatography ... 82
3.6.1 Preparation of standard and working solution ... 82
3.6.2 Preparation of internal standard solution ... 83
3.6.3 Trifluoroacetic acid anhydrous derivatisation ... 83
3.6.5 Gas chromatographic parameters ... 84
3.6.6 Method Verification ... 86
3.7 Surface Recovery of Methamphetamine ... 87
3.7.1 Deposition and wiping of sample from surfaces ... 87
3.7.2 Application of GC technique in analysis of filter paper extracts ... 88
3.7.3 Recovery percentage of methamphetamine from various surfaces ... 89
3.8 Electrochemical Detection ... 90
3.8.1 Preparation of Britton-Robinson buffer solution ... 90
3.8.2 Preparation of methamphetamine standard solution ... 91
3.8.3 Electrode modification ... 91
3.8.4 Voltammetric measurement ... 92
3.8.5 Optimisation of electrode modification parameters ... 94
3.8.6 Effect of pH condition of BRBS ... 95
3.8.7 Effect of scan rate... 95
3.8.8 Optimisation of voltammetric parameters ... 96
3.8.8(a) Selection of voltammetric technique ... 96
3.8.8(b) Optimisation of DPV parameters ... 96
3.8.8(c) Pre-condition parameters ... 96
3.8.9 Method validation ... 97
3.9 Summary ... 98
CHAPTER 4 RESULTS AND DISCUSSION ... 99
4.1 Overview ... 99
4.2 Colour Spot Test ... 99
4.2.1 Marquis test ... 100
4.2.1(a) Visual observation of Marquis test ... 100
4.2.1(b) Applicable range at trace levels for Marquis test ... 101
4.2.2(a) Visual observation of Simon’s test ... 102
4.2.2(b) Applicable range at trace levels for Simon’s test ... 104
4.2.3 Colour behaviour of methamphetmaine in Marquis and Simon’s reagents over time ... 105
4.2.3(a) Marquis test ... 105
4.2.3(b) Simon’s test ... 107
4.2.4 Advantages and challenges of colour spot tests ... 109
4.2.5 Summary ... 111
4.3 Colour Spot Test with Digital Image Analysis ... 112
4.3.1 Sample blank of Marquis and Simon’s tests ... 113
4.3.2 Digital image analysis of Marquis test ... 114
4.3.2(a) Calibration curve of Marquis test using Y-intensity ... 115
4.3.3 Digital image analysis of Simon’s test ... 118
4.3.3(a) Calibration curve of Simon’s test using C-intensity .... 119
4.3.4 Summary ... 122
4.4 Ultraviolet-Visible Spectroscopy ... 123
4.4.1 UV-Vis spectroscopy with Marquis test ... 126
4.4.1(a) Marquis reagent blank ... 126
4.4.1(b) UV-Vis behaviour of methamphetamine in Marquis reagent ... 127
4.4.2 UV-Vis spectroscopy with Simon’s test ... 130
4.4.2(a) Simon’s reagent blank ... 130
4.4.2(b) UV-Vis Behaviour of methamphetamine in Simon’s reagent ... 130
4.4.3 Behaviour of colour product over time ... 133
4.4.3(a) Behaviour of Marquis test with methamphetamine over time ... 134
4.4.3(b) Behaviour of Simon’s Test with methamphetamine over time ... 135
4.4.4 Summary ... 139
4.5 Gas Chromatographic Techniques ... 140
4.5.1 Optimisation of Gas Chromatographic methods ... 140
4.5.2 Peak identification ... 141
4.5.2(a) Underivatised methamphetamine ... 146
4.5.2(b) N-mono-trifluoroacetyl methamphetamine ... 148
4.5.3 Method Verification ... 150
4.5.3(a) Underivatised methamphetamine ... 150
4.5.3(b) N-mono-trifluoroacetyl methamphetamine ... 153
4.5.4 Summary ... 154
4.6 Surface Recovery of Methamphetamine ... 155
4.7 Electrochemical detection by Differential Pulse Voltammetry... 161
4.7.1 Electrode modification ... 161
4.7.1(a) Selection of electrode modification material ... 163
4.7.1(b) Optimisation of GO/GCE ... 166
4.7.2 Electrochemical behaviour of methamphetamine at GO/GCE .... 168
4.7.2(a) Effect of pH ... 168
4.7.2(b) Effect of scan rate on oxidation of methamphetamine 171 4.7.3 Development of electrochemical methodology for methamphetamine detection... 175
4.7.3(a) Selection of voltammetric technique ... 175
4.7.3(b) Optimisation of DPV parameters ... 177
4.7.3(c) Optimisation of pre-condition parameters ... 178
4.7.4 Method Validation ... 180
4.7.4(a) Linearity and detection limit ... 180
4.7.4(b) Repeatability and reproducibility ... 182
4.7.5 Summary ... 183
4.8 General discussion ... 183
CHAPTER 5 CONCLUSION AND FUTURE RECOMMENDATIONS .... 194
5.1 Conclusion ... 194
5.2 Limitations ... 196
5.3 Future recommendation ... 197
REFERENCES ... 199 APPENDICES
LIST OF TABLES
Page
Table 2.1: Trend in use of ATS in Malaysia, 2015–2019* ... 34
Table 2.2: Seizures of methamphetamine in Malaysia, 2015–2019 ... 35
Table 2.3: Number of illicit drug manufacturing facilities dismantled in Malaysia by drug type, 2015–2019 ... 36
Table 2.4: Chemicals used in a variety of methods to synthesise methamphetamine (HMWMD, 2003; Kozel et al., 2007; Abdullah and Miskelly, 2010c; MPCA, 2010). ... 40
Table 2.5: Colour test reagents for methamphetamine. ... 50
Table 2.6: Research gaps identified in literature review. ... 72
Table 3.1: Chemicals and reagents with their respective sources. ... 76
Table 3.2: Chemical standards with their respective sources. ... 77
Table 3.3: Apparatus and equipment with their respective company. ... 77
Table 3.4: Composition of acids and alkaline in BRBS for pH 7-12. ... 91
Table 3.5: The voltammetric parameters for CV, LSV, and DPV. ... 94
Table 3.6: Parameters for optimisation of electrode modification parameters ... 95
Table 3.7: Parameters for optimisation of DPV method. ... 96
Table 3.8: Parameters for optimisation of pre-condition step. ... 97
Table 4.1: Repeatability and reproducibility of GC-FID detection of underivatised methamphetamine. ... 151
Table 4.2: Mean recovery percentages for determination of underivatised methamphetamine. ... 152
Table 4.3: Repeatability and reproducibility for GC-FID detection of TFA- methamphetamine. ... 154
Table 4.4: Mean recovery percentages for GC-FID detection of TFA- methamphetamine. ... 154 Table 4.5: Recovery percentages of methamphetamine deposited on filter
papers. ... 159 Table 4.6: Recoveries of methamphetamine hydrochloride (0.5 µg/100 cm2)
deposited on various open surfaces. ... 159 Table 4.7: Optimised conditions for DPV detection of methamphetamine using
GCE/GO in BRBS at pH 10. ... 180 Table 4.8: Repeatability and reproducibility peak currents of
methamphetamine. ... 182 Table 4.9: Mean recovery percentage for methamphetamine detection. ... 183 Table 4.10: LOD of detection strategies in trace analysis of methamphetamine
with corresponding estimated surface concentration with positive result. ... 184 Table 4.11: The three scenarios, purposes and significance and forensic analysis,
as well as the detection strategies. ... 192
LIST OF FIGURES
Page Figure 1.1: Chemical structure of methamphetamine. ... 1 Figure 1.2: Trend of drug addicts based on type of drug used, 2014–2019
(NADA, 2020). ... 4 Figure 1.3: Number of cases for dismantled clandestine laboratories, 2011–
2019 (Hamdan et al., 2015; UNODC, 2015, 2020c; NADA, 2020). ... 6 Figure 1.4: Clandestine laboratory scenarios and key issues to be addressed in
this study. ... 12 Figure 2.1: Examples of methylenedioxyamphetamine type compounds (MDE:
N-ethyl-3,4-methylenedioxy amphetamine; N-OH MDA: N- hydroxy-3,4-methylenedioxy amphetamine; MMDA: 3-methoxy- 4,5-methylenedioxy amphetamine; MDMA: 3,4-methylenedioxy methamphetamine; MDA: 3,4-methylenedioxy amphetamine). ... 18 Figure 2.2: Examples of methylenedioxyamphetamine type compounds (DOB:
4-bromo-2,5-dimethoxy amphetamine; DMA: 2,5-dimethoxy amphetamine; DOET: 2,5-dimethoxy-4-ethyl amphetamine;
NNDA: N,N-dimethyl amphetamine; PMA: 4-methoxy amphetamine; DOM: 2,5-Dimethoxy-4-methyl amphetamine). ... 18 Figure 2.3: Chemical structure of (a) P2P and (b) ephedrine/pseudoephedrine. .. 20 Figure 2.4: Methamphetamine synthesis using Amalgam method. ... 21 Figure 2.5: Synthesis for d-methamphetamine and racemic methamphetamine
from ephedrine/pseudoephedrine and P2P respectively. ... 22 Figure 2.6: Diastereoisomeric structures of ephedrine and pseudoephedrine. ... 24 Figure 2.7: The production of iodine from methamphetamine synthesis. ... 25 Figure 2.8: Possible synthesis pathways from ephedrine/pseudoephedrine: (a)
Emde route, (b) Nagai route, (c) Nazi/Birch route, (d) Rosenmund
route, (e) Moscow route, and (f) Hypo route. Sourced from Onoka et al. (2020). ... 28 Figure 2.9: Emde method for methamphetamine synthesis. ... 30 Figure 2.10: Synthetic routes involving iodoephedrine/iodopseudoephedrine as
intermediate compound for methamphetamine synthesis. ... 31 Figure 3.1: Research flow of the present study. ... 75 Figure 3.2: Wiping pattern on an actual size of a 10 cm × 10 cm sampling area 88 Figure 3.3: The set-up of electrochemical cell for methamphetamine detection . 93 Figure 4.1: Immediate observation of Marquis test with (a) absence and (b)
presence of methamphetamine ... 100 Figure 4.2: Reaction mechanism of Marquis reagent with methamphetamine. . 101 Figure 4.3: Immediate observation of Marquis test with descending mass of
methamphetamine. (*LOD) ... 102 Figure 4.4: Simon’s test with the (a) presence and (b) absence of
methamphetamine. ... 103 Figure 4.5: Chemical reaction of Simon’s reagent with methamphetamine. ... 104 Figure 4.6: Simon’s test with descending mass of methamphetamine. (*LOD) 105 Figure 4.7: The colour of freshly prepared Marquis reagent (left) and that of
prepared over three months (right)... 106 Figure 4.8: Immediate observation of Marquis test in the presence of
methamphetamine (left) and the colour change after 60 minutes (right). ... 107 Figure 4.9: Immediate observation of Simon’s reagent blank (left) and the
colour change after 60 minutes (right). ... 108 Figure 4.10: Immediate observation of Simon’s reagent in the presence of
methamphetamine (left) and the colour change after 60 minutes (right). ... 109 Figure 4.11: Conversion of RGB image into C, M, and Y images. ... 113
Figure 4.12: CMY-images of Marquis tests on (a) negative control, (b) positive control (50 µg) and (c) at trace level (5 µg). ... 115 Figure 4.13: A curve of Y-intensity against mass of methamphetamine for
Marquis test with potential linear range. ... 116 Figure 4.14: Calibration curve of Y-intensity in Marquis reagent against mass of
methamphetamine. ... 117 Figure 4.15: Y-images with 1µg and 0.5µg of methamphetamine for Marquis
test. ... 118 Figure 4.16: CMY-images of Simon’s tests on (a) negative control, and (b)
positive control (50 µg). ... 119 Figure 4.17: A curve of C-intensity against mass of methamphetamine for
Simon’s test. ... 120 Figure 4.18: Calibration curve of C-intensity in Simon’s reagent against mass of
methamphetamine. ... 121 Figure 4.19: C-images with 10 µg and 5 µg of methamphetamine for Simon’s
test. ... 122 Figure 4.20: UV-Vis spectrum of methanolic methamphetamine solution with
concentration of 50 µg/mL... 124 Figure 4.21: Calibration curve of methamphetamine in methanol using UV-Vis
spectroscopy. ... 125 Figure 4.22: UV-Vis spectrum of Marquis reagent blank. ... 126 Figure 4.23: UV-Vis spectrum of methamphetamine in Marquis reagent with
concentration of 25 µg/mL... 127 Figure 4.24: UV-Vis spectra of reagent-analyte solution of Marquis test with
methamphetamine concentration ranged 1–250 µg/mL. ... 128 Figure 4.25: Calibration curve of absorbance at 469 nm against concentration of
methamphetamine in reagent-analyte solution for Marquis test. ... 129 Figure 4.26: UV-Vis spectrum of Simon’s reagent blank. ... 130
Figure 4.27: UV-Vis spectrum of methamphetamine in Simon’s reagent with concentration of 25 µg/mL... 131 Figure 4.28: UV-Vis spectra of reagent-analyte solution of Simon’s test with
methamphetamine concentration from 2.5 to 250 µg/mL. ... 132 Figure 4.29: Calibration curve of the absorbance at 580 nm against concentration
of methamphetamine in reagent-analyte solution for Simon’s test. 133 Figure 4.30: UV-Vis spectra of reagent-analyte solution of Marquis test with 25
µg/mL of methamphetamine and the corresponding λmax (table) at reaction time from 0 to 120 min. ... 135 Figure 4.31: UV-Vis spectra of Simon’s reagent blank in at 0 to 60 min of
reaction time. ... 136 Figure 4.32: Formation of coloured product after mixing of Simon’s reagent. ... 137 Figure 4.33: UV-Vis spectra of reagent-analyte solution of Simon’s test with 25
µg/mL of methamphetamine after baseline correction with the corresponding λmax (table) at reaction time from 0 to 120 min. ... 138 Figure 4.34: Representative gas chromatogram of methamphetamine with IS. ... 141 Figure 4.35: Representative gas chromatograms of TFA-methamphetamine with
IS. ... 143 Figure 4.36: GC responses of underivatised methamphetamine at concentration
of 100 µg/mL ... 144 Figure 4.37: GC responses of TFA-methamphetamine at concentration of 100
µg/mL. ... 144 Figure 4.38: GC responses of methamphetamine at concentration of 100 µg/mL
after derivatisation using BSTFA. ... 145 Figure 4.39: Mass Spectrum of underivatised methamphetamine. ... 146 Figure 4.40: Fragmentation pathway of ionised methamphetamine in formation
of ions with m/z 58, m/z 91, m/z 134 and m/z 148 from the parent molecule with m/z 149. ... 147 Figure 4.41: Mass spectrum of TFA-methamphetamine. ... 148
Figure 4.42: Fragmentation of ionised TFA-methamphetamine in formation of ions with m/z 154, m/z 118, m/z 110 and m/z 91 from the parent molecule with m/z 245. ... 149 Figure 4.43: Calibration curve for GC-FID analysis of underivatised
methamphetamine. ... 151 Figure 4.44: Calibration curve for GC-FID analysis of TFA-methamphetamine.153 Figure 4.45: Cyclic voltammogram of BRBS at pH 10 using unmodified GCE;
scan rate=50 mV/s ... 162 Figure 4.46: SEM images of (a) Graphene nanoplatelet (GrNPs), (b) Graphene
oxide nanoplatelet (GONPs), (c) Graphene ink (GI), and (d) Glassy carbon sphere (GCS). ... 163 Figure 4.47: Cyclic voltammograms of all unmodified and modified electrode
with 14.92 µg/mL of methamphetamine in BRBS pH 10 ... 164 Figure 4.48: Peak current and peak potential for voltammetric signal of 14.92
µg/mL of methamphetamine in BRBS pH 10, using (a) GCE (unmodified), (b) GpI/GCE, (c) GI/GCE, (d) GCS/GCE, (e) GNP/GCE, and (f) GO/GCE. ... 165 Figure 4.49: The peak current and sensitivity of GCE with different amount of
GO. ... 167 Figure 4.50: Cyclic voltammograms of BRBS pH 10 at GCE without (a) and with
(b) 100 µM methamphetamine; and that at GO/GCE without (c) and with (d) 100 µM methamphetamine. ... 168 Figure 4.51: Cyclic voltammograms of 14.92 µg/mL of methamphetamine at
GO/GCE in BRBS within pH range of 7-12. ... 169 Figure 4.52: The peak current and peak potential of voltammetric signals of
14.92 µg/mL of methamphetamine at GO/GCE in BRBS within pH range of 7-12. ... 169 Figure 4.53: Negative linear relationship of peak potential against pH values of
BRBS. ... 170
Figure 4.54: Cyclic voltammograms of 14.92 µg/mL of methamphetamine in BRBS pH 10 with the scan rate ranged 10-100 mV/s... 172 Figure 4.55: The plot of (a) Ip against V, (b) Ip against V1/2, (c) log Ip against log
V, and (d) Ep against ln V for the oxidation of methamphetamine at the surface of GO/GCE. ... 173 Figure 4.56: A possible mechanism of electrochemical oxidation of
methamphetamine on the surface of GO/GCE, as suggested by Švorc et al. (2014). ... 175 Figure 4.57: Comparison of DPV and LSV in detection of methamphetamine in
BRBS pH 10 at concentration range of 1.49–7.46 µg/mL. ... 177 Figure 4.58: Voltammograms from DPV of methamphetamine in BRBS at pH
10 with (a) step potential range: 0.008–0.020 V, (b) pulse potential range: 0.025–0.250 V, and (c) pulse time range: 100–1000 ms (Note: The bold lines represent the optimum conditions)... 178 Figure 4.59: Graph of peak current obtained from DPV of methamphetamine
after pre-conditioning step with (a) pre-condition potential range: - 0.2–0.4 V, and (b) pre-condition time range: 15–150 s. ... 179 Figure 4.60: Voltammograms from DPV of concentration of methamphetamine
ranged 0.15–17.91 µg/mL in BRBS at pH 10 on GO/GCE at optimised parameters. ... 181 Figure 4.61: The calibration curve of peak current against concentration of
methamphetamine ranged 0.15–17.91 µg/mL in BRBS at pH 10 on GO/GCE at optimised parameters... 181
LIST OF EQUATIONS
Page Equation 2.1: AX = - log(lX-l𝐵)
(l𝑊-l𝐵)= - log(lX)C
(l𝑊) C
= - log RX ... 55
Equation 3.1: RSD = SD
mean × 100% ... 86 Equation 3.2: %Recovery=measured value
expected value×100%... 87 Equation 3.3: %Recovery=pAfilter paper
pAbase ×100% ... 90 Equation 3.4: %Recovery= pAsurface
pAfilter paper×100% ... 90 Equation 3.5: LOD=3×SDblank
Slinear ... 97 Equation 3.6: LOQ=10×SDblank
Slinear ... 97 Equation 4.1: Slope = RT
2naF ... 174
LIST OF SYMBOLS
AX Absorbance
a Charge transfer constant
C Concentration
Ep Peak potential F Faraday constant IX Intensity
Ip Peak current
n Number of electrons
pA Peak area
pKa Acid dissociation constant R Ideal gas constant
RX Reflectance R2 Linear coefficient
S Slope
T Temperature
V Scan rate
λ Wavelength
LIST OF UNITS
% percent
°C degree Celcius
µA microampere
µg microgram
µL microliter
µm micrometre
µm micrometre
cm centimetre
cm2 square centimetre
g gram
m meter
m3 cubic metre
mg milligram
min minute
mL millilitre mm millimetre
mol mole
ms millisecond
ng nanogram
nm nanometre
s second
V volt
LIST OF ABBREVIATIONS
%Recovery Percentage of recovery Ad-Tip Adsorption tip
AOAC Association of Official Analytical Chemists
ATS Amphetamine-type stimulant
AuNP Gold nanoparticle
BDD Boron-doped diamond
BRBS Britton Robinson buffer solution BSTFA Bis(trimethylsilyl)-trifluoroacetamide
C-14 n-Tetradecane
CAS Chemical Abstracts Service
CCH Caring Community House
CCSC Cure & Care Service Centre
CMV Capillary microextraction of volatiles
CMY Cyan-Magenta-Yellow
CV Cyclic voltammetry
DAINAP Drug Abuse Information Network for Asia and the Pacific
DCE Dichloroethane
DCM Dichloromethane
DDA Dangerous Drugs Act
DMA 2,5-dimethoxy amphetamine
DMF N,N-dimethylformamide
DMMA Dimethoxymethamphetamine
DOB 4-bromo-2,5-dimethoxy amphetamine
DOC Department of Chemistry
DOET 2,5-dimethoxy-4-ethyl amphetamine DOM 2,5-Dimethoxy-4-methyl amphetamine DPV Differential pulse voltammetry
EA Ethyl amphetamine
ESR Zealand Institute for Environmental Science and Research FFT-SWV Fast Fourier transform square wave voltammetry
FID Flame ionisation detector
FTIR Fourier transform infrared spectroscopy
GC Gas chromatography
GCE Glassy carbon electrode
GC-FID Gas chromatography-flame ionisation detector GC-MS Gas chromatography-mass spectrometry
GCS Glassy carbon sphere
GI Graphene ink
GIMP GNU Image Manipulation Program GLP Good laboratory practice
GNP Graphene nanoplatelet
GO Graphene oxide
GpI Graphite ink
HFBA Heptafluorobutyric anhydride
HMWMD Hazardous Materials and Waste Management Division HP-5 (5%-Phenyl)-methylpolysiloxane
HPLC High performance liquid chromatography i.d. Internal diameter
ICP-MS Inductive coupled plasma-mass spectrometry idPAD Paper analytical device for illicit drugs
INCSR International Narcotics Control Strategy Report
IR Infrared
IRD Infrared detection
ISCC-NBS Inter-Society Colour Council and the National Bureau of Standards
IUPAC International Union of Pure and Applied Chemistry
LC liquid chromatography
LOD Limit of detection
LOQ Limit of Quantification
LSV Linear sweep voltammetry
m/v Mass/volume ratio
MBDB Methylbenzodioxolylbutanamine MBTFA N-methyl-bis-trifluoroacetamide MDA 3,4-methylenedioxy amphetamine
MDE N-ethyl-3,4-methylenedioxy amphetamine
MIP Molecularly imprinted polymers
MMDA 3-methoxy-4,5-methylenedioxy amphetamine MOHA Ministry of Home Affairs
MPCA Minnesota Pollution Control Agency
MS Mass spectrometry
MTBSTFA N-methyl-N-t-butyldimethylsilyl trifluoroacetamide MWCNT Multi-walled carbon nanotube
NADA National Anti-Drug Agency
NCID Narcotic Crime Investigation Department NIDA National Institute of Drug Abuse
NIST National Institute of Standards and Technology NNDA N,N-dimethyl amphetamine
N-OH MDA N-hydroxy-3,4-methylenedioxy amphetamine NPD Nitrogen phosphorus detector
NQS 1,2-naphthoquinone-4-sulphonate ODS Octadecylsilyl-silica
P2P Phenyl-2-propanol
PDMS Polydimethylsiloxane PDRM Royal Malaysian Police
PFBCF o-Pentafluorobenzyl chloroformate PGE Pencil graphite electrode
PMA 4-methoxy amphetamine
PMMA Paramethoxymethamphetamine
Pt Platinum wire
QC Quality control
RAL Reichs-Ausschuß für Lieferbedingungen und Gütesicherung
RfD Reference dose
RGB Red-Green-Blue
RMP Royal Malaysia Police
RRFIA Reagent regeneration flow injection anlysis RSD Relative standard deviation
SCE Saturated calomel electrode
SD Standard deviation
SMART Synthetics Monitoring: Analyses, Reporting and Trends
SN1 First order nucleophilic substitution SN2 Second order nucleophilic substitution
SWGDRUG Scientific Working Group of the Analysis of Seized Drugs
SWV Square wave voltammetry
TBPE Tetrabromophenolphthalein ethyl ester
TFA Trifluoroacetyl
TFAA Trifluoroacetic acid anhydrous TLC Thin layer chromatography
TMS Trimethylsilyl
UNODC United Nations Office on Drugs and Crime
UV Ultraviolet
UV-Vis Ultraviolet-visible
v/v Volume/volume ratio
VUV Vacuum ultraviolet detection
LIST OF APPENDICES
Appendix A Properties of Chemicals Associated with Methamphetamine Appendix B Colour Spot Test (Marquis Test)
Appendix C Colour Spot Test (Simon’s Test)
Appendix D Colour Test with Digital Image Analysis Appendix E Colour Test with UV-Vis Spectroscopy
Appendix F Gas Chromatography-Flame Ionisation Detector Appendix G Recovery Study
Appendix H Differential Pulse Voltammetry
KAJIAN ATAS KAEDAH-KAEDAH PENGESANAN DALAM MAKMAL HARAM METAMFETAMIN
ABSTRAK
Masalah metamfetamin telah mengancam secara global, dan lebih dari sepertiga daripada jumlah anggaran pengguna global telah tercatat dalam Asia Timur dan Tenggara. Hal ini merupakan isu keselamatan dan kesihatan yang serius dan potensi bahaya yang terhasil daripada makmal-makmal haram metamfetamin dengan mengambil kira banyak makmal sedemikian yang tidak dapat dikesan. Daripada perspektif sains forensik, penentuan produk haram dan aktiviti-activiti yang berkaitan secara pantas dalam suatu makmal haram terkesan adalah penting. Daripada sudut pandangan orang awam, sesuatu struktur kediaman perlu ditentukan sama ada ia selamat daripada pendedahan sisa-sisa metamfetamin selepas proses penghapusan dan pemulihan. Justeru, kajian ini bertujuan untuk membangunkan satu siri strategi bagi pengesanan metamfetamin yang berpotensi untuk diguna pakai dalam pelbagai penetapan pada situasi makmal haram. Dalam kajian ini, ujian warna, analisis imej digital, spektroskopi ultraungu-nampak (UV-Vis), teknik gas kromatografi, dan pengesanan elektrokimia telah disiasat. Seterusnya, peratusan pemulihan semula bagi sisa metamfetamin pada permukaan daripada permukaan isi rumah lazim telah ditentukan. Keputusan telah menunjukkan bahawa sebagai ujian saringan, ujian Marquis dan Simon masing-masing membenarkan pengesanan metamfetamin sehingga 5 µg dan 10 µg. Dengan bantuan analysis imej digital, intensiti warna Kuning dan Sian telah berjaya diaplikasikan untuk mentaksir keputusan ujian Marquis dan ujian Simon secara objektif dengan membenarkan pengesanan masing-masing pada 1 µg dan 10 µg.
ujian Marquis dan 580 nm untuk ujian Simon dengan had pengesanan masing-masing pada 1.0 µg/mL dan 2.5 µg/mL. Seterusnya, analisis gas kromatografi terhadap metamfetamin terbitan asid trifluoroasetik telah mempertingkatkan kepekaan yang membolehkan pengesanan positif pada julat linear dari 19.53 ng/mL ke 2.5 µg/mL dan mencapai had pengesanan pada 2.44 µg/mL. Tahap sisa metamfetamin pada 0.5 µg/100 cm2 telah berjaya dikesan pada empat permukaan. Pemulihan semula yang baik telah dicapai pada permukaan kaca (62.49%), plastik (69.47%) dan keluli tahan karat (72.66%), manakala pemulihan semula yang lebih rendah secara relatif telah dilaporkan daripada permukaan kayu tanpa varnis (33.78%). Teknik pengesanan elektrokimia yang menggunakan elektrod karbon kekaca terubahsuai dengan grafena oksida berupaya mengesan metamfetamin pada kepekatan serendah 0.041 µg/mL. Kesimpulannya, kerangka bagi kaedah-kaedah pengesanan metamfetamin telah berjaya dibangunkan dan sedia diaplikasikan dalam senario makmal haram metamfetamin yang berbeza, berdasarkan kepekaan masing-masing serta adanya dan jenis sampel yang akan dipulih semula. Suatu pengesanan elektrokimia yang baharu selepas pengubahsuaian elektrod juga dibangunkan dan ditubuhkan. Kajian ini akan bermanfaat untuk membantu dalam penyiasatan forensik dan memastikan keselamatan penghuni, dengan itu menggalakkan kesejahteraan sosial yang lebih baik.
A STUDY ON METHODS FOR DETECTION IN CLANDESTINE METHAMPHETAMINE LABORATORIES
ABSTRACT
Methamphetamine-related problems appear to threaten globally, and over one third of the estimated global number of users was recorded in East and South-East Asia.
This is a serious security and health issue, as well as the potential hazards arisen from clandestine methamphetamine laboratories, considering many of such laboratories which are not detected. From forensic science perspective, quick determination of illicit products and related activities in a discovered clandestine laboratory is crucial. From the public’s perspective, a structure, particular residential structure, must be determined whether it is safe from exposure of methamphetamine residues after dismantlement and remediation. Therefore, this study was aimed to establish a series of strategies for methamphetamine detection potentially applicable in the varying settings of clandestine laboratory situations. In this study, colour tests, digital image analysis, ultraviolet- visible (UV-Vis) spectrometry, gas chromatographic techniques, and electrochemical detection were investigated. Subsequently, the percentage recoveries of residual surface methamphetamine from the common household surfaces were determined. The results show that Marquis and Simon’s test allowed detection down to 5 µg and 10 µg of methamphetamine, respectively. Aiding by digital image analysis, the Yellow and Cyan intensities were successfully applied to objectively interpret the Marquis and Simon’s test, allowing detection at 1 µg and 10 µg, respectively. UV-Vis spectroscopy detected methamphetamine at wavelength of 469 nm for Marquis test and 580 nm for Simon’s test with respective detection limits at 1.0 µg/mL and 2.5 µg/mL. Subsequently, gas
methamphetamine had increased the sensitivity, enabling positive detection in a linear range from 19.53 ng/mL to 2.5 µg/mL and achieving detection limit of 2.44 ng/mL.
Residual methamphetamine level at 0.5 µg/100 cm2 were successfully detected on four different surfaces, where good recoveries were achieved on glass (62.49%), plastic (69.47%) and stainless-steel surfaces (72.66%), while relatively lower recovery was reported on unvarnished woof surfaces (33.78%). Electrochemical detection technique using glassy carbon electrode modified with graphene oxide was able to detect methamphetamine as low as 0.041 µg/mL. To conclude, a framework of methamphetamine detection strategies was established and readily applied to different scenarios of clandestine methamphetamine laboratories based on their respective sensitivities as well as the availability and type of samples to be recovered. A novel electrochemical detection upon electrode modification was also developed and established. This study would be beneficial to assist forensic investigation and to ensure the safety of occupants, thus promoting a better societal well-being.
CHAPTER 1 INTRODUCTION
1.1 Methamphetamine
Methamphetamine (Figure 1.1) is the principal member in a group of drugs, known as amphetamine-type stimulants (ATS). It is a highly additive stimulant that acts on the central nervous system by stimulating the excess secretion of dopamine in brain.
Note that dopamine plays role in movement, motivation, and reinforcement of rewarding behaviours (NIDA, 2019). Methamphetamine usually appears as usually a white, bitter-tasting powder, or pills with various colours, or crystal with glass fragments or shiny bluish-white rocks (NIDA, 2019). People can take methamphetamine by injecting, ingesting, snorting, and smoking the drug to give the long-lasting effects. Consuming methamphetamine allows users to experience “highs”
for hours (NIDA, 2019).
Figure 1.1: Chemical structure of methamphetamine.
Methamphetamine was first synthesised by a German Chemist in 1887.
Subsequently, it was synthesised from ephedrine by a Japanese pharmacologist in 1893 (Suwaki et al., 1997). The first medical use of this drug was in 1932 as a nasal spray for the treatment of asthma. It was also reported to provide relief from narcolepsy, reduce activity in hyperactive children, suppress appetite, as well as enable individuals to stay
conditions and disorders, namely schizophrenia, morphine addiction, tobacco smoking, low blood pressure, radiation sickness, and persistent hiccups (Julien, 2013). In fact, Methamphetamine was not widely used until World War II when the drug was provided to the military personnel to increase endurance and performance, and to the military support industries to improve productivity of civilian factory workers. After the war, widespread abuse of the drug occurred when methamphetamine from surplus army stocks had occupied the market. Although law restriction had introduced, the abuse of methamphetamine continued to spread among construction workers, truck drivers, and other blue-collar workers, as well as students, housewives, and office workers during that era (Anglin et al., 2000).
Since 1970, the United States (US) government intensified the restriction and made methamphetamine use in most circumstances (Anglin et al., 2000). Black market which illegally supplied mainly from pharmaceutical companies, distributors, and physicians, as well as American motorcycle gang, known as Bay Area motorcycle gangs took over majority of the manufacture and distribution of methamphetamine, and subsequently spread its use along the Pacific Coast (Miller, 1997). In the 1990s, while large laboratories were set up by Mexican drug trafficking organisation in California (Morgan and Beck, 1997), smaller “stove top” laboratories were also appeared. From there, it spread across the United States and into Europe through the Czech Republic.
Today, manufacture of methamphetamine continues to dominate and the global methamphetamine market is expanding but remains mainly concentrated in North America, as well as East and South-East Asia (UNODC, 2020a).
1.2 Methamphetamine abuse and manufacture
Despite harsh penalties imposed on drug users as well as drug smugglers or distributors, methamphetamine-related problems appear to record an increasing trend.
According to the World Drug Report (UNODC, 2020b), signs of increasing in the usage of methamphetamine is seen in the United States, Europe countries, Australia, and New Zealand. In East and South-East Asia, specifically, the abuse of methamphetamine and its threat remains prevalent. These regions consist of more than one third of the estimated global number of users of amphetamine-type substances (ATS), referring to amphetamine, methamphetamine, and pharmaceutical stimulants (UNODC, 2020b).
Global seizure of methamphetamine, particularly, had increased sevenfold in the past two decades (UNODC, 2020a). However, the domestic methamphetamine manufactures, mainly in the United States, China, and Islamic Republic of Iran, had dropped sharply in recent years. Such situation was also reflected in the decreased number of dismantled laboratories (UNODC, 2020a). On the other hand, seizures of methamphetamine were highly reported and signs of marked expansions of methamphetamine trafficking in the region were noticed in Mexico, as well as East and South East Asia (UNODC, 2020a). It was evident that the methamphetamine market had been shifted from the “traditional” countries in North America to East and Southeast Asia. In context of Malaysia, methamphetamine seizures in 2018 had contributed to approximately 8% (nearly 7,000 kg) of the seizures in East and South East Asia (UNODC, 2020a). A three-folds was marked as compared with the previous year (NADA, 2020).
1.2.1 Methamphetamine users in Malaysia
In global setting, the use of methamphetamine tablets is more common than the
of people seeking drug treatment were users of crystalline methamphetamine (NADA, 2020; UNODC, 2020b). In 2019, 16,154 methamphetamine users were recorded among a total of 27,811 drug addicts (NADA, 2020). Figure 1.2 illustrates the trend of drug addicts based on types of drugs used in six years period (2014–2019).
Figure 1.2: Trend of drug addicts based on type of drug used, 2014–2019 (NADA, 2020).
As reported by the National Anti-Drug Agency (NADA, 2020), methamphetamine (crystalline and tablet) had surpassed opiates since 2017, and became the most widely used illegal drugs in Malaysia (Figure 1.2). The number of users has drastically increased from 11,485 (42.86%) in 2017 hiking up to 16,384 (61.12%) in 2018, and 16,154 (58.08%) last year. In addition, the reported price of crystalline methamphetamine had dropped at approximately 30% in 2018 from RM 70,000 to RM 50,000 (NADA, 2020). The trend had also indirectly reflected the demands of synthetic drugs by the increased number of drug users, particularly methamphetamine in illicit drug market and regional supply. Subsequently, the illicit
22,355 27,479
31,764
26,791 26,449 27,811
0 5,000 10,000 15,000 20,000 25,000 30,000 35,000
2014 2015 2016 2017 2018 2019
Number of cases
Year
ATS (Ecstacy &
Amphetamine) Cannabis
Methamphetamine (Crystalline & Tablet) Opiates (Heroin &
Morphine) Others
manufacturing and trafficking activities of methamphetamine had been triggered (Hamdan et al., 2015; UNODC, 2020a).
1.2.2 Manufactures of methamphetamine in Malaysia
To date, methamphetamine is known to be the most commonly manufactured ATS and well established in the illicit drug markets worldwide (UNODC, 2019). Over the period between 2014 – 2018, the majority of clandestine laboratories (95%) dismantled worldwide synthesised illicit methamphetamine (UNODC, 2020a). Unlike heroin or cocaine, methamphetamine manufacturing does not require the extraction of active compounds from plants that have to be cultivated under certain growth conditions in a period. Due to this simplicity, such drug can be manufactured in either small scale using simple “ingredients” in any closed apartments for local consumption; or produced in large scale with sophisticated manufacturing equipment in clandestine laboratories, utilising a range of precursor chemicals and synthetic routes (UNODC, 2016). Such relatively simple procedure had resulted in creations of manufacturing sites in a variety of premises and structures (Granholm and Olszewski, 2007; Owens, 2017; UNODC, 2019), deserving forensic investigation.
Quantity of amphetamine-type stimulant seized at the global level has quadrupled over the past two decades (UNODC, 2020a). However, it is difficult to estimate the global production of methamphetamine based on seizures and dismantled laboratories (UNODC, 2019), as the amount of illicit drugs that successfully enter the black market remains unknown. Furthermore, limited data and information that available from the world drug markets on the trend of abuse in addition to the appearance of new psychoactive drugs had restrict the accurate interpretation on the current drug status, particularly the illicit methamphetamine (UNODC, 2019). Also,
operate the clandestine laboratories due to the security issues and high rate of violence crime, had caused the uneven records of cases across countries (UNODC, 2020a).
1.2.3 Clandestine laboratories dismantled in Malaysia
Methamphetamine seized in Malaysia is thought to be manufactured within the national boundaries (INCSR, 2014; Reych, 2016), based on simple synthesise pathway (Frank, 1983; Burgess and Chandler, 2003; Christian, 2004; Abdullah et al., 2014;
INCSR, 2014). In Malaysia, a seizure of 23 clandestine laboratories was reported in 2019, bringing up the number of such laboratories to 261 within ten years period, 2011 – 2019 (Figure 1.3) (Hamdan et al., 2015; UNODC, 2015, 2020c; NADA, 2020).
Figure 1.3: Number of cases for dismantled clandestine laboratories, 2011–2019 (Hamdan et al., 2015; UNODC, 2015, 2020c; NADA, 2020).
A decrease in number of cases for clandestine laboratory discoveries from 35 in 2018 to 23 in 2019 by approximately 34.28% had indirectly showed that the success of law enforcement in Malaysia in deterring the manufacture activities (NADA, 2020).
30 32 34
26
39
24
19
35
22
0 5 10 15 20 25 30 35 40 45
2011 2012 2013 2014 2015 2016 2017 2018 2019
Number of cases
Year
However, the data could be underestimated. As reported by the Royal Malaysian Police (RMP) recently (Ismail, 2020; Omar, 2020; Hamid, 2020; Ramli, 2020), the manufacturing sites were found in remote areas, rental room, and underground of a house which are not easily identified if the activities are concealed well. With that, there might be other clandestine methamphetamine laboratories that have been operated in areas that are yet to be noticed by the authorities and law enforcement agencies.
1.2.4 Control and legislation of methamphetamine in Malaysia
As efforts to respond to the expanding illegal methamphetamine supply, methamphetamine is listed in Dangerous Drugs Act (DDA) 1952 under the First Schedule (Dangerous Drugs Act, 1952). Poison Act 1952 meanwhile monitors the marketing, as well as the trafficking of related precursors and other essential chemicals (Poison Act, 1952). DDA 1952 is the main regulation against the drug-related offences, including trafficking, importation, manufacturing, selling, possessing, exporting and self-administration of all types of drugs. It also provides the punishment for various drugs offences under the Act. For methamphetamine, specifically, the punishments are subjected as follows:
a) Any person who found with possession of less than 5 g in weight of methamphetamine will be liable to a fine not exceeding RM 5,000 or to imprisonment up to 2 years or both.
b) Any person who found with possession of 5 g or more but less than 30 g in weight of methamphetamine will be punished with imprisonment for 2-5 years and whipping of 3-9 strokes.
c) Any person who found with possession of more than 30 g in weight of methamphetamine will be subjected to more than 5 years or lifetime imprisonment, as well as with whipping of more than 10 strokes.
d) Any person who has involved in trafficking, or preparatory for the purpose of trafficking of methamphetamine will be convicted with death penalty.
Narcotic Crime Investigation Department (NCID), Royal Malaysian Police enforces Dangerous Drug Act (Special Preventive Measures) 1985 against drug traffickers or liable individuals that had involved in illegal drugs activities (MOHA, 2019). It implements the right of Royal Malaysian Police to detain any suspected individuals for not more than 60 days. This is followed by detention under Home Ministry involving the movement restriction and monitored by electronic monitoring device for up to two years (Dangerous Drugs (Special Preventive Measures) Act, 1985).
Dangerous Drugs Act (Forfeiture of Property) 1988 is also enforced to provide authorities the powers to trace, freeze and forfeit the assets of drug traffickers, including vehicles and questioned properties (Dangerous Drugs (Forfeiture of Property) Act, 1988).
Lastly, Drug Dependents Act (Treatment and Rehabilitation) 1983 is specialised for drug addicts with treatment and rehabilitation (Drug Dependants (Treatment and Rehabilitation) Act, 1983). All the drug dependents’ cases are now investigated under the NADA of Ministry of Home Affairs to relieve the burden on the police department.
Instead of compulsory drug rehabilitation including arrests, court orders and legal implication, NADA has adopted paradigm shift in transforming the Act into more accessible and voluntary-based services in government clinics. This application had proved to be effective in Malaysia. According to the statistics compiled by NADA
(2020), the number of drug addicts that received treatment and rehabilitation in the community centres such as Cure & Care Service Centre (CCSC) and Caring Community House (CCH) had increased about 24.86% in 2019 (NADA, 2020).
1.3 Problem Statements
In operational level during the investigation of dismantled methamphetamine manufacturing and packaging sites, an investigative officer is required to determine the identity of the illicit drug. On the other hand, they are requested to detect the possible presence of residual methamphetamine, especially when dealing with an inactive laboratory (Martyny et al., 2007). Additionally, complex scenes with large number of items also make forensic investigation difficult to trace the manufacturing, trafficking, packaging, distribution, and sale of such illicit drugs. Available colour tests that currently used as routine procedures (i.e. Marquis and Simon’s test) can be applied for detection of trace amount of surface methamphetamine but the sensitivity is in questioned (Harper et al., 2017). In such situations, subjective interpretation of conventional colour screening tests shall carry advantages to assist the investigation. A more objective screening strategy is crucial to allows on-the-spot screening on identity of illicit drugs, as well as the presence of residual drug on the contaminated surfaces.
Current methods of detection and quantitation of residual methamphetamine at the suspected clandestine laboratories and illicit samples recovered from dismantled laboratories rely heavily on instrumental analyses. The methods included gas chromatography (GC) coupled with mass spectrometry (MS) or flame ionisation detector (FID) for the confirmation and quantitation by forensic analysts. Although
Seized Drugs (SWGDRUG, 2013), not all of these methods may be suitable for on-the- spot setting. Recoveries of methamphetamine from common surfaces in clandestine laboratory had been established by Abdullah and Miskelly (2010b), but its applicability and suitability in Malaysian settings shall be tested and investigated.
In overseas, analysis is conducted merely to establish whether methamphetamine is present in the structure. Note that the colour tests might not be a good choice in such scenario where they should not be directly tested on some surfaces due to corrosiveness nature of reagents, such as sulphuric acid in Marquis reagent. If a testing is requested, GC-MS is undoubtable the gold standard as described in the EPA Method 8270 (EPA, 2013). However, when a potential tenant or buyer wishes to have a quick safety check on possible methamphetamine contamination in a room, to make them feel comfortable and secured, random surface sampling was carried out, resulting in large number wipe samplings to be analysed, to establish the safety of the questioned property. Although GC-MS possesses the required sensitivity level, it can be costly and timely. Therefore, a relatively more portable, rapid and cost-effective detection method, which is able to provide complementary results to GC analyses, is necessary for public health and safety purposes.
Owing to the relatively simple synthesis method, manufacture of methamphetamine could take place in any space using common household materials.
The activities of illicit drug production and packaging could have contaminated the surfaces of a structure. Either in active or inactive state, contaminated sites or properties that involved “cooking” of methamphetamine may possess physical, chemical, and environmental hazards to the successive tenants (Martyny et al., 2007; Abdullah and Miskelly, 2010c; Kuhn et al., 2019). Forensic investigators who visited a scene require
the knowledge on the appropriate sampling and testing strategies to maximise the investigative information. As a general public, a thorough screening and confirmatory procedure for safety check on all possible methamphetamine contamination surfaces followed by remediation of the whole room or property (if necessarily) is particular important to ensure the security and comfortable of the occupants (Owens, 2017).
With that, the varying scenarios of clandestine laboratories possess different purposes of analysis, leading to different significance and outcome of the analytical results. This study hence aims to address the key issues in forensic analysis of illicit methamphetamine. Figure 1.4 illustrates the three main scenarios arisen from the clandestine laboratories and the relevant key issues. Based on the different settings of clandestine laboratories, it was noted that the questions addressed are different and shall be responded through different strategies. In other words, appropriate detection methods and strategies shall be applied on the case-by-case basis, aiding to save the cost and time, as well as to properly plan the sampling and evidence collection for benefit of forensic science communities and the societies.
Scenarios Perspective Key issues Dismantled
Clandestine Laboratories
→ Forensic
Investigation →
What is the illicit drug found in an active dismantled clandestine laboratory?
Former/Suspected Clandestine Laboratories
→ Forensic
Investigation →
Is a site encountered by the law enforcement team a former clandestine laboratory?
What is the forensic evidence to be collected for analysis of trace methamphetamine?
→ Health and safety issue →
Is a clean-up procedure necessary on a confirmed former clandestine laboratory?
Is the cleaning-up procedure carried out adequately effective to remove the residual methamphetamine?
Suspicious Clandestine Laboratories
→ Health and safety issue →
Is a structure or property previously used for any illegal drug related activities?
Figure 1.4: Clandestine laboratory scenarios and key issues to be addressed in this study.
1.4 Scope of Study
Most guidelines used the surrogate approach to monitor the level of methamphetamine contamination as a marker for decision making (EPA, 2013;
enHealth, 2017; WA Health, 2020). It is assumed that cleaning methamphetamine to a particular level is also simultaneously cleaning other chemicals, immediate products or co-products potentially appeared on any surface in the setting of clandestine laboratories, given that the cleaning procedure is adequately effective. Hence, the present study focuses on the detection of methamphetamine to confirm the presence of
methamphetamine-related activities in simulation of clandestine laboratories, as well as to determine the necessary of remediation and its effectiveness.
The detection methods that were selected in the study included the common routine procedures in forensic investigation, namely colour tests (Marquis and Simon’s tests for methamphetamine) and GC techniques. Digital image analysis and UV-Vis spectroscopy were applied to achieve objective colour determination of Marquis and Simon’s test. Chemical derivatisation was conducted prior to increase sensitivity of GC techniques.
In a simple clandestine laboratory setting, glass surfaces were usually found on various lab apparatus; trays or common containers for storage or transportation were often found with stainless steel or plastic surfaces; while wood surfaces were commonly seen on benches or working tables where synthesis processes may take place. Therefore, four household surfaces, namely glass, stainless steel, plastic, and unvarnished wood surfaces were selected for recovery study.
Electrochemical detection had gained popularity in rapid and cost-effective detection of methamphetamine sample in various matrices (Švorc et al., 2014; Oghli et al., 2015; Akhoundian et al., 2019; Haghighi et al., 2020). Hence, a novel electrochemical detection based on glassy carbon electrode was developed for methamphetamine detection. Carbon materials were chosen for electrode modification due to its good electrical conductivity and lower price.
1.5 Aim and Objectives
The present study aims to study the detection of illicit methamphetamine using a series of detection strategies in clandestine laboratory settings. To achieve the aim, the specific objectives were set as follows:
i. To explore the detection of illicit methamphetamine using Marquis and Simon’s tests with naked-eye observation and digital image analysis.
ii. To explore the detection of illicit methamphetamine using Marquis and Simon’s tests followed by ultraviolet-visible (UV-Vis) spectroscopy.
iii. To determine underivatised and derivatised illicit methamphetamine using gas chromatography-flame ionisation detector (GC-FID) and gas chromatography- mass spectrometry (GC-MS).
iv. To investigate the recovery of illicit methamphetamine from common household surfaces using gas chromatography-flame ionisation detector (GC-FID).
v. To investigate the electrochemical detection of illicit methamphetamine with differential pulse voltammetry (DPV).
vi. To compare the applicability of established detection strategies in different scenarios of clandestine laboratories.
1.6 Significance of Study
This study would benefit the law enforcement agencies in both forensic intelligence and public health and safety perspective. The novelty of this study would be the proposal on the different strategies for the detection of methamphetamine and its residues based on the various types of clandestine laboratory scenario. It was important
to note the appropriate detection strategies shall be selected in a clandestine laboratory scenario as the conditions of these structure would not be the same. For example, detection strategies for preliminary investigation on the confirmed or suspected site, the availability of seized illicit drug, as well as appropriate sampling methods at the crime scene shall be taken into consideration during forensic investigation.
No two crime scenes are exactly the same and forensic investigator must always prepare for the worst scenario. To maximise the chance of true positive detection and to enhance the percent recovery of residual methamphetamine, an investigative team must be able to carry out the most appropriate strategies, adjusted for the conditions of dismantled or suspected clandestine laboratories. Rapid and relatively sensitive detection strategy could play important role in the detection of both bulk and residual methamphetamine at the scene of clandestine laboratories. The continuously dismantlement of clandestine laboratories also justifies the need for cost effective approach to perform field testing before the routine instrumental analyses.
From the perspective of public, there are instances where the owners or tenants of properties are suspicious regarding the activities that had been carried out in these properties. A readily available and established screening and testing procedure shall be carried out to determine the presence of residual illicit methamphetamine, the necessary of remediation, as well as the suitability of a property to be occupied. This is important for security check by the owners to manage their properties and ensure the safety of their tenants from health hazards. Besides, the findings could serve for both intelligence and evidential purposes to link the sources of seizures. It could also help to disclose the distribution network in the illegal drug market by elucidating the possible sites of
manufacturing, packaging, and storing illicit methamphetamine along with the route of drug trafficking in Malaysia.
The current study investigates a series of detection strategies for on-the-spot testing of surface methamphetamine, including colorimetric-based detection with both digital image analysis and UV-Vis spectroscopy, as well as the electrochemical detection with a simple electrode sensor. Digital image analysis and UV-Vis spectroscopy aids in objective determination of colour tests to prevent false results, as well as to minimise inter-rater variation. Development of a novel electrochemical detection based on commercial electrode modified with low-cost materials would assist the detection of residual methamphetamine. Adequate sensitivity achieved by electrochemical detection also demonstrates the potential in providing testing outcomes that complement with GC analyses.
In addition to the sensitivity, the potential to be modified into portable devices for convenience field testing based on the outcome of this research study shall assist the investigative procedure. It requires low amount of reagent and the sample analyte that could effectively save cost and time. With that, the suggested methods could serve as an alternative to the conventional screening tests which are subjective in nature. They could also help to reduce the workload of investigators at the scene, and to minimise the backlog of samples prior to analytical analyses in the forensic laboratories.
CHAPTER 2 LITERATURE REVIEW
2.1 Overview
The literature review describes the properties of methamphetamine, including both physical and chemical aspects. The situations of clandestine laboratories, their contamination as well as the remediation strategies and standards are reviewed. In addition, various analytical methods of illicit methamphetamine detection, covering the colorimetric detection, UV-Vis spectroscopy, electrochemistry, as well as gas chromatographic methods, are also critically discussed. Lastly, the sampling method of surface methamphetamine is also covered.
2.2 Physical and chemical properties of methamphetamine
ATS are phenethylamines that consists of the principal members, namely amphetamine, methamphetamine and other ring-substituted, carbon-substituted, or nitrogen-substituted compounds. The compounds resemble the chemical structure of amphetamine (UNODC, 2009b; NIDA, 2019). This group of illicit substances can also be categorised into another two groups, i.e. methylenedioxyamphetamine type compound (Figure 2.1) and amphetamine type compound (Figure 2.2), depending on the site of substitution occurs (UNODC, 2006; UNODC, 2009b).
MDE R1=C2H5; R2=H N-OH MDA R1=OH; R2=H MMDA R1=H; R2=OCH3
MDMA R1=CH3; R2=H MDA R1=H; R2=H
Figure 2.1: Examples of methylenedioxyamphetamine type compounds (MDE: N- ethyl-3,4-methylenedioxy amphetamine; N-OH MDA: N-hydroxy-3,4- methylenedioxy amphetamine; MMDA: 3-methoxy-4,5-methylenedioxy amphetamine; MDMA: 3,4-methylenedioxy methamphetamine; MDA: 3,4- methylenedioxy amphetamine).
DOB R1,R2=H; R3,R5=OCH3; R4=Br DMA R1,R2,R4=H; R3,R5=OCH3
DOET R1,R2=H; R3,R5=OCH3; R4= C2H5
NNDA R1,R2=CH3; R3,R4,R5=H PMA R1,R2,R3,R5=H; R4= OCH3
DOM R1,R2=H; R3,R5=OCH3; R4=CH3
Figure 2.2: Examples of methylenedioxyamphetamine type compounds (DOB: 4- bromo-2,5-dimethoxy amphetamine; DMA: 2,5-dimethoxy amphetamine;
DOET: 2,5-dimethoxy-4-ethyl amphetamine; NNDA: N,N-dimethyl amphetamine; PMA: 4-methoxy amphetamine; DOM: 2,5-Dimethoxy-4- methyl amphetamine).
Methamphetamine, with an IUPAC name of (2S)-N-methyl-1-phenylpropan-2- amine, is a base with chemical formula of C10H15N and molecular mass of 149.23 g/mol. It can be sticky waxy base (McKetin et al., 2005) or colourless volatile oil (EMCDDA, 2013). However, methamphetamine seizures is usually encountered in solid form either as powder, crystals, or tablets (McKetin et al., 2005). The hydrochloride salts are the commonly encountered as salt form, which appear heavier (molecular mass = 185.69 g/mol), less volatile (melting point = 170–175 °C), and typically encountered as racemic mixture, i.e. d,l-methamphetamine (UNODC, 2006).
The proportion of these two optical isomers is closely related to the chemical precursors
and synthetic pathway (Stojanovska et al., 2013; Kunalan, 2014; Hamdan et al., 2015;
Onoka et al., 2020). Use of hydrochloric acid (HCl) as the conjugate of methamphetamine base could be due to the performance of HCl-protonated amine group in terms of oxidation stability and water solubility (Thomas and Rubino, 1996;
Park et al., 2019). Its relatively better recrystallisation favours the production during manufacture of methamphetamine (Park et al., 2019).
In term of solubility, methamphetamine base is slightly soluble in water but miscible with diethyl ether. Methamphetamine hydrochloride salt, meanwhile, practically insoluble in diethyl ether but dissolves well in water. Both forms of methamphetamine are soluble in methanol, dichloromethane (DCM) and chloroform (UNODC, 2006). Therefore, methanol, DCM and chloroform are commonly used as solvents for sample extraction and instrumental analysis of methamphetamine.
2.3 Manufactures of Illicit Methamphetamine
2.3.1 Introduction to methamphetamine synthesis
Methamphetamine is normally illegally synthesised in clandestine laboratories for domestic use as well as illegal drug trade (Scott and Dedel, 2006). Generally, 1- phenyl-2-propanol (P2P) and ephedrine/pseudoephedrine (Figure 2.3) are the two main precursors used in the manufacture of methamphetamine (Allen and Cantrell, 1989;
Stojanovska et al., 2013; Onoka et al., 2020). Different pathways can be implemented to produce the end product of illicit methamphetamine utilising these two precursors.
