Forensic Science Progress

184 Pages·1991·9.239 MB·English

by  Jehuda Yinon (auth.), Prof. Dr. A. Maehly, Prof. Dr. R. L. Williams (eds.)

5 Forensic Science Progress
Editorial Board
Ass.-Prof. Dr. Dr. Hans-J. Battista
Institut für Gerichtliche Medizin der Universität Innsbruck,
Abt. für Forensische und Chemisch-Analytische Toxikologie,
Müllerstraße 44, 6020 Innsbruck/Austria
Dr. B. S. Finkle
Associate Director, Center for Human Toxicology
Research Professor, University of Utah,
417 Wakara Way RM 290, Salt Lake City, Utah 84108/USA
Dr. H. Kobus
Forensic Science Centre, 21 Divett Place,
Adelaide 5000/South Australia
Prof. Dr. K. Sellier
Institut für Gerichtliche Medizin, Stiftsplatz 13,
W-5300 Bonn/FRG
Prof. Dr. George Sensabaugh
Department of Biomedical & Environmental Health Science,
School of Public Health, University of California, Berkeley,
CA 97420/USA
Dr. R. N. Totty
Assistant Director, Home Office Forensic Science Laboratory,
Priory House, Gooch Street North,
Birmingham B5 6QQ/United Kingdom
Prof. Dr. Rokus A. de Zeeuw
Rijkuniversiteit, Afd. Toxicologic, Antonius Deusinglaan 2,
9713 AW Groningen/The Netherlands
Editorial
During the years 1962-1965 Interscience Publishers produced
a four-volume series called "Methods in Forensic Science".
Since then no major effort seems to have been made to review
the progress in the rapidly expanding field of fornesic science.
Our new series "Forensic Science Progress" represents a
serious effort to take up a neglected venture. The series intends
to cover all aspects of forensic science but does not include
forensic medicine which is well represented in other publica
tions.
The aim of the publisher and the board of editors is to produce
contributions of high quality by leading scientists in the field of
forensic science. Suggestions for such contributions from the
forensic community at large are of course also very welcome.
The volumes will not be topic-oriented but will give balanced
views ön various aspects of the science. The editors believe that
the forensic worker should be informed about all branches of
the science even if he may very well be specialised in one or few
of them. Ideally, contributions should be from 40-80 type
written pages. Experimental details, except when not published
previously, should be covered by citing the appropriate refer
ences. Polemic passages should be avoided but this does not
include objective criticism.
The publisher has tried to choose an editorial board which is
representative not only of various topics but also of the various
geographical regions of the world.
Editors Publisher
Table of Contents
MS/MS Techniques in Forensic Science
J. Yinon 1
Forensic Science Aspects of Ethanol Metabolism
A. W.Jones 31
Recent Developments in Handwriting Examination
R. N. Totty 91
Forensic Entomology
B. D. Turner 129
Elements of Forensic Science Laboratory Management
B.A.J. Fisher 153
Author Index Volumes 1-5 177
Subject Index 179
Forensic
Science
Progress
Volume 5
With contributions by
B. A. J. Fisher, A. W. Jones, R. N. Totty,
B.D.Turner, J.Yinon
With 38 Figures
Springer-Verlag Berlin Heidelberg GmbH
Editors-in-Chief
Prof. Dr. A. Maehly
Forensic Science Centre, 21 Divett Place
Adelaide 5000 S. A./Australia
Prof. Dr. R. L. Williams
Ardmore, 9 Meon Road, Boscombe East
Bournemouth BH7 6PN, England
ISBN 978-3-642-63510-6 ISBN 978-3-642-58233-2 (eBook)
DOI 10.1007/978-3-642-58233-2
Library of Congress Catalog Card Number: 86-640073
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© Springer-Verlag Berlin Heidelberg 1991
Originally published by Springer-Verlag Berlin Heidelberg in 1991
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MSjMS Techniques in Forensic Science
lehuda Yinon
Weizmann Institute of Science, 76100 Rehovot, Israel
Tandem mass spectrometry. or MS/MS. is now a well established analytical technique which can serve as
a fast separation and identification method for mixtures. and has proven to be useful for trace analysis of
selected components in complex matrices. This chapter describes the principles and instrumentation of
MS/MS and its applications in forensic science. These applications include detection and identification
of drugs and toxic substances in body fluids and other matrices. analysis of drugs in sports testing.
identification of explosives in bombing residues. and detection of hidden explosives in luggage. mail.
vehicles and aircraft.
This contribution is intended to introduce MS/MS to the forensic scientist and to demonstrate by
examples from various forensic fields. the different modes of operation and the range of uses and
capabilities of this technique. Before long it will become a routine analytical tool in forensic analysis.
1 Introduction 2
2 Tandem Mass Spectrometry (MS/MS) 2
2.1 Principles of Operation . 2
2.2 Instrumentation . . . . 4
2.2.1 Two-Sector MS/MS 4
2.2.2 Hybrid Instruments 6
2.2.3 Four-Sector MS/MS 7
2.2.4 Ion-Trap MS/MS . 7
2.3 Range of Applications. . 9
2.3.1 Biochemical and Biomedical Applications. 9
2.3.2 Environmental Applications . . . . . . 9
3 Analysis of Drugs . . . . . . . . . . . . . . . . . . .. 10
3.1 Trace Analysis of Drugs and Toxic Substances in Body Fluids. 10
3.2 Analysis of Drugs in Sports Testing . . . 14
3.3 Identification of Drugs in Various Matrices 19
3.4 Molecular Structure Determination 20
4 Analysis of Explosive. . . . . . . . 22
4.1 Identification of Explosives in Mixtures 22
4.2 Detection of Hidden Explosives 26
5 References. . . . . . . . . . 28
Forensic Science Progress 5
© Springer-Verlag Berlin Heidelberg 1991
2 lehuda Yinon
1 Introduction
The use of mass spectrometry, especially as a gas chromatograph/mass
spectrometer (GC/MS) combination with an on-line computer, has added a new
dimension to the capabilities of the forensic laboratory: the sensitivity of
detection has been enhanced, the ability to isolate and identify minor constituents
in complex matrices has improved, and the time required for an analysis has
diminished. The introduction of coated capillary columns and the use of alternate
ionization techniques, like electron impact (EI) and chemical ionization (CI),
have made GC/MS the method of choice in the forensic laboratory.
With the development of new interfacing techniques such as thermospray
(TSP) and particle-beam (PB), liquid chromatography/mass spectrometry
(LC/MS) has become complimentary to GC/MS, especially for non-volatile
compounds.
Based on a different concept is tandem mass spectrometry (MS/MS), which is
now a well established analytical technique. MS/MS can provide an extra
dimension of structural information for pure compounds and can serve as a fast
separation and identification method for mixtures. It has proven to be useful for
trace analysis of selected components in complex matrices.
MS/MS has been adopted as a routine technique in many analytical
laboratories dealing with biomedical and environmental applications. In the
forensic field, MS/MS has been mainly used in research and development and to a
smaller extent in routine work. But before long it will find its place as an analytical
tool in many forensic laboratories.
2 Tandem Mass Spectrometry (MS/MS)
2.1 Principles of Operation
Tandem mass spectrometry or mass spectrometry/mass spectrometry (MS/MS)
is a field in mass spectrometry which has grown rapidly during the last 10 years
and has established itself in numerous analytical applications as well as in
research. Several reviews [1-4] and books [5-6] have been published which
describe the technique and many of its applications.
As can be understood from its name, MS/MS is a technique which is based on
the combination of two mass spectrometers in tandem, with a collision cell
between them. A schematic illustration of an MS/MS is shown in Fig. 1. The
sample can be one single component or a mixture. Accordingly one would use
either EI or CI, or any other ionization method.
The first mass analyzer separates the ions produced in the source. A precursor
ion (also called primary ion or parent ion) is selected and focused into the collision
MSjMS Techniques in Forensic Science 3
ION SOURCE
SAMPLE SAMPLE
INTRODUCTlON IONIZATION
FlRST MASS !ANALYZE R
PRIMARY MASS
SEPARATION
COLLISlON !CELL
INTRODUCTION OF CID
COLLISION GAS OF SELECTED
ION
SECOND MASS! ANALYZE R
SECONDARY
MASS
ANALYSIS
DETECTOR AND! DATA SYS TEM
MASS SPECTRUM
OF DAUGHTER
Fig. 1. Schematic illustration of an MSjMS system IONS
cell. In the cell, the primary ion beam collides with an inert gas, such as helium,
nitrogen or argon, resulting in collision induced dissociation (CID) [also called
collision ally activated dissociation (CAD)]. The fragment ions (or daughter ions)
thus produced in the collision cell are mass analyzed by the second mass analyzer
and recorded. This secondary mass spectrum (or CID spectrum) provides a
"fingerprint" of the primary ion beam.
There are two types of CID in the collision cell, depending on the type of the
first mass analyzer:
1) High energy CID, if the first mass analyzer is a magnetic sector analyzer. The
primary ion has then an energy of several ke V.
2) Low energy CID, if the first mass analyzer is a quadrupole analyzer. In this
case the primary ion has an energy of 0-100 eV .
In high energy CID, when the beam of precursor ions, having translational
kinetic energies of several ke V, collides with the molecules of the inert gas in the
collision cell, part of the translational energy of the precursor ion is transformed
into internal excitation energy, resulting in its dissociation.
In low energy CID, the transfer of momentum plays a more important role
than the transfer of energy. Therefore larger molecules, such as nitrogen, are more
effective than small atomic species, such as helium, as collision gas.
4 lehuda Yinon
The MS/MS can be used for analytical applications in several modes of
operation [7]:
1) Daughter ion mode. This mode of operation allows a survey of specific
compounds in complex mixtures. Each component of the mixture is
represented by a characteristic ion (molecular ion or typical fragment ion in EI
or MH + ion in CI). This ion undergoes CID in the collision cell and is
identified by its daughter ion mass spectrum obtained in the second mass
analyzer.
2) Parent ion mode. In this mode of operation the first mass analyzer is scanned,
while the second one is set at a specific mass. This experiment can identify all
parent ions that dissociate to form a specific predetermined daughter
(fragment) ion. For example, trinitroaromatic compounds could be identified
by the NO + fragment ion; while nitrate esters by the NOt fragment ion.
3) Neutral loss mode. In this mode of operation the two mass analyzers are set to
detect a constant neutral loss. For example, the first mass analyzer is scanned
from m/z 37 to 300, while the second mass analyzer is scanned simultaneously
from m/z 20 to 283. In this example the neutral loss of 17 mass units may
represent a series of nitrocompounds losing OH.
2.2 Instrumentation
There are many types of MS/MS instruments including those which are
commercially available and others which are home-built.
2.2.1 Two-Sector MS/MS
a) Reversed-geometry double-focusing mass spectrometer (Fig. 2). In this
configuration the magnetic field is used as first mass analyzer and the
electrostatic analyzer as the second one. This particular MS/MS is called
MIKES: mass analyzed ion kinetic energy spectrometer (8), because mass
selection-by momentum analysis-is followed by an ion kinetic energy
analysis of the product ions. The mass scale of the daughter ions formed by
CID in the collision cell of the MIKE spectrometer is a linear function of the
electric sector voltage.
b) B-B configuration (Fig. 3). This home-built MS/MS (9) consists of two
magnetic sector analyzers with a collision cell located in the region between
the two analyzers. The primary ion beam is monitored by the off-line electron
multiplier detector No. 1. A voltage of 30 V applied to the deflection plate
deflects about 5% of the ion beam, while the other 95% continues on its path
into the collision cell. It is thus possible to monitor simultaneously the
daughter ions on detector No.2, and the primary ion on detector No.1.
c) Triple Quadrupole System (Fig. 4). This MS/MS consists basically of two
quadrupole analyzers (first and third quadrupole). The second quadrupole