Development of Analysis Methods to Detect the Use of Explosives and Chemical Warfare Agents

107 Pages·2017·10.31 MB·English

by  Viivi Jokk

TALLINN UNIVERSITY OF TECHNOLOGY
DOCTORAL THESIS
45/2018
Development of Analysis Methods
to Detect the Use of Explosives
and Chemical Warfare Agents
HEIDI LEES
TALLINN UNIVERSITY OF TECHNOLOGY
School of Science
Department of Chemistry and Biotechnology
The dissertation was accepted for the defense of the degree of Doctor of Philosophy in
Chemistry on 21st of June, 2018.
Supervisors: Senior Researcher Merike Vaher
Department of Chemistry and Biotechnology
Tallinn University of Technology
Tallinn, Estonia
Emeritus Professor Mihkel Kaljurand
Department of Chemistry and Biotechnology
Tallinn University of Technology
Tallinn, Estonia
Opponents: Professor Bogusław Buszewski
Department of Environmental Chemistry and
Bioanalytics
Nicolaus Copernicus University
Toruń, Poland
Professor Miguel de la Guardia
Department of Analytical Chemistry
University of Valencia
Valencia, Spain
Defense of the thesis: 24th of August, 2018, Tallinn
Declaration:
Hereby I declare that this doctoral thesis, my original investigation and achievement,
submitted for the doctoral degree at Tallinn University of Technology has not been submitted
for doctoral or equivalent academic degree before.
Heidi Lees
Signature
Copyright: Heidi Lees, 2018
ISSN 2585-6898 (publication)
ISBN 978-9949-83-295-8 (publication)
ISSN 2585-6901 (PDF)
ISBN 978-9949-83-296-5 (PDF)
TALLINNA TEHNIKAÜLIKOOL
DOKTORITÖÖ
45/2018

Analüüsimetoodikate arendamine
keemiarelva- ja lõhkeainete
kasutamise tuvastamiseks
HEIDI LEES

CONTENTS
LIST OF PUBLICATIONS ...................................................................................................... 7
THE AUTHOR’S CONTRIBUTION ........................................................................................ 8
ABBREVIATIONS ................................................................................................................ 9
INTRODUCTION ............................................................................................................... 11
1 LITERATURE OVERVIEW ............................................................................................... 13
1.1 Sea-dumped chemical weapons ............................................................................... 13
1.1.1 Sulfur mustard and its degradation products ........................................................ 14
1.1.2 Analysis methods for sulfur mustard degradation products ................................. 16
1.2 Explosives .................................................................................................................. 17
1.2.1 Terrorism and the need for trace explosive detectors .......................................... 18
1.2.2 Analysis of explosives ............................................................................................. 18
1.2.3 Fingerprint analysis ................................................................................................ 19
1.3 General aspects of the separation techniques used for method development ....... 19
1.3.1 Capillary electrophoresis ........................................................................................ 19
1.3.2 High performance liquid chromatography ............................................................. 20
1.3.3 Detection ................................................................................................................ 21
1.4 Spectral imaging ........................................................................................................ 22
1.4.1 Multispectral imaging ............................................................................................ 23
1.5 Data analysis ............................................................................................................. 25
1.5.1 Principal component analysis ................................................................................. 25
1.5.2 Analysis of variance ................................................................................................ 25
2 AIMS OF THE STUDY ..................................................................................................... 27
3 EXPERIMENTAL ............................................................................................................. 28
3.1 Reagents and samples ............................................................................................... 28
3.1.1 Reagents ................................................................................................................. 28
3.1.2 Seawater and pore water samples for method development ............................... 30
3.1.3 Explosive samples .................................................................................................. 30
3.1.4 Sample preparation and fingerprint collection ...................................................... 31
3.2 Instrumentation ........................................................................................................ 32
3.2.1 Capillary electrophoresis ........................................................................................ 32
3.2.2 High performance liquid chromatography ............................................................. 32
3.3 Validation .................................................................................................................. 32
3.4 Multispectral imaging ............................................................................................... 33
4 RESULTS AND DISCUSSION ........................................................................................... 34
4.1 Development of CE and HPLC methods for the analysis of sulfur mustard
degradation products ...................................................................................................... 34
4.1.1 Optimization of the sample derivatization ............................................................ 34
4.1.2 Optimization of the developed methods ............................................................... 35
4.1.3 Validation and comparison of the CE and HPLC methods for quantitative analysis
of HD degradation products ............................................................................................ 38
4.2 Fingerprinting of post-blast explosive residues ........................................................ 41
4.3 Transfer of explosive residues in consecutive fingerprints ....................................... 42
4.3.1 Transfer of PETN residues in consecutive fingerprints by different persons ......... 42
4.3.2 Transfer of residues of explosives to different surfaces in successive fingerprints...... 43
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5 CONCLUSIONS .............................................................................................................. 46
REFERENCES .................................................................................................................... 48
APPENDIX ........................................................................................................................ 57
Publication I .................................................................................................................... 57
Publication II ................................................................................................................... 65
Publication III .................................................................................................................. 75
Publication IV .................................................................................................................. 85
ACKNOWLEDGEMENTS ................................................................................................... 96
ABSTRACT ........................................................................................................................ 97
KOKKUVÕTE .................................................................................................................... 99
LIST OF ORIGINAL PUBLICATIONS ................................................................................. 101
CURRICULUM VITAE ...................................................................................................... 103
ELULOOKIRJELDUS ........................................................................................................ 105

6
LIST OF PUBLICATIONS

The thesis is based on the following publications, which are referred to by Roman
numerals within the text:

I P. Jõul, H. Lees, M. Vaher, E.-G. Kobrin, M. Kaljurand, M. Kuhtinskaja, Development
of a capillary electrophoresis method with direct UV detection for the analysis of
thiodiglycol and its oxidation products, Electrophoresis. 36 (2015) 1202–1207.
II H. Lees, M. Vaher, M. Kaljurand, Development and comparison of HPLC and MEKC
methods for the analysis of cyclic sulfur mustard degradation products,
Electrophoresis. 38 (2017) 1075–1082.
III E.-G. Kobrin, H. Lees, M. Fomitšenko, P. Kubáň, M. Kaljurand, Fingerprinting
postblast explosive residues by portable capillary electrophoresis with contactless
conductivity detection, Electrophoresis. 35 (2014) 1165–1172.
IV H. Lees, F. Zapata, M. Vaher, C. García-Ruiz, Simple multispectral imaging approach
for determining the transfer of explosive residues in consecutive fingerprints,
Talanta. 184 (2018) 437–445.

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THE AUTHOR’S CONTRIBUTION

The contributions made by the author to the publications included are the following:

I. The author was responsible for the analysis part of this article. She carried out
the experiments for the optimization and validation of the capillary zone
electrophoresis method with UV detection for the quantitative analysis of the
acyclic degradation products of sulfur mustard in water samples. The author
participated in the preparation of the manuscript.
II. The author planned and carried out all the experiments for the development of
the HPLC and MEKC methods with UV detection for the analysis of the cyclic
degradation products of sulfur mustard. The author interpreted the obtained
results, wrote the manuscript, and is the first and corresponding author.
III. The author participated in the expedition to Hanko, Finland. The author
performed a considerable part of the sample collection, preparation, and
analysis using a portable CE instrument with conductivity detection.
IV. The author was responsible for planning the experiments. She carried out all the
experiments with the aim of studying the transfer of different explosives to
different materials through successive fingerprints. She participated in setting
up the purpose-built photo studio, and performed imaging of fingerprints on
surfaces using a reflex camera and image analysis in MATLAB. The author wrote
the manuscript and is the first author.

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ABBREVIATIONS
ACN Acetonitrile
ANOVA Analysis of variance
BGE Background electrolyte
C4D Capacitively coupled contactless conductivity detector
CE Capillary electrophoresis
CMC Critical micelle concentration
CTAB Cetyltrimethylammonium bromide
CW Chemical weapon
CWA Chemical warfare agent
CWC The Chemical Weapons Convention
CZE Capillary zone electrophoresis
DAD Diode array detector
DOEI Dual opposite end injection
GC Gas chromatography
HD Sulfur mustard
HMTD Hexamethylene triperoxide diamine
HPLC High performance liquid chromatography
i.d. Internal diameter
IC Ion chromatography
IED Improvised explosive device
IMS Ion mobility spectrometry
IR Infrared
IS Internal standard
LD Median lethal dose
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LOD Limit of detection
LOQ Limit of quantification
MANOVA Multivariate analysis of variance
MEKC Micellar electrokinetic chromatography
MES 2-(N-morpholino)ethanesulfonic acid
MODUM Towards the Monitoring of Dumped Munitions Threat (project)
MS Mass spectrometry
MSI Multispectral imaging
NIR Near-infrared
NMR Nuclear magnetic resonance
PC Principal component
PCA Principal component analysis
PETN Pentaerythritol tetranitrate
R2 Square of the correlation coefficient/Coefficient of determination
RDX 1,3,5-Trinitroperhydro-1,3,5-triazine
RGB Red-green-blue
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ROI Region of interest
RSD Relative standard deviation
S/N Signal-to-noise ratio
SDS Sodium dodecyl sulfate
SPE Solid phase extraction
SSB Sum of squares between groups
SST Total sum of squares
SSW Sum of squares within groups
TDG Thiodiglycol
TDGO Thiodiglycol sulfoxide
TDGOO Thiodiglycol sulfone
TNT 2,4,6-Trinitrotoluene
VIS Visible
WW World War

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