Chromatographic-Mass Spectrometric Food Analysis for Trace Determination of Pesticide Residues, Volume 43 (Comprehensive Analytical Chemistry)

490 Pages·2005·2.39 MB·English

by  A.R. Fernández Alba

CONTRIBUTORS TO VOLUME XLIII
Joaquin Abidn
Pesticide Residue Group, University of Almeria, Ctra Sacramento sin,
04120 La Canada de San Urbano,A lmeria, Spain
Ana Agiiera
Pesticide Residues Group, University of Almeria, Ctra Sacramento s/n,
04120 La Canada de San Urbano, Almeria, Spain
Lutz Alder
Federal Institute for Risk Assessment, Thieleallee 88-92, Berlin D-14195,
Germany
Michelangelo Anastassiades
Stuttgart Regional Chemical and Veterinary Control Laboratory,
Schaflandstrasse3 /2, 70736 Fellbach, Germany
Andre de Kok
PesticidesA nalysis Group, VWA - Food and Consumer Product Safety
Authority, Hoogte Kadijk 401, 1018 BKAmsterdam, The Netherlands
Amadeo R. Ferndndez-Alba
Pesticide Residue Group, University of Almeria, Ctra Sacramento s/n,
04120 La Canada de San Urbano, Almeria, Spain
Amadeo R. FernAndez-Alba
Pesticide Residue Research Group, University of Almeria, 04071 Almeria,
Spain
Imma Ferrer
Pesticide Residue Group, University of Almeria, Ctra Sacramento s/n,
04120 La Caiada de San Urbano, Almeria, Spain
Richard J. Fussell
Central Science Laboratory, Departmentf or Food, Environment and Rural
Affairs, Sand Hutton, York Y041 1LZ, UK
Alan R.C. Hill
Central Science Laboratory, Departmentf or Food, Environment and Rural
Affairs, Sand Hutton, York Y041 1LZ, UK
Silvia Lacorte
Department of Environmental Chemistry, IIQAB-CSIC, Jordi Girona
18-26, 08034 Barcelona, Spain
E. Michael Thurman
Pesticide Residue Research Group, University of Almeria, Almeria, Spain
Luis Martin Plaza
EuropeanC ommission. Health and ConsumerP rotectionD irectionG eneral.
Rue Froissart1 01, Bureau 6/86-1040 Bruxelles, Belgium
vii
Contributors to Volume XLIII
Stewart L. Reynolds
Central Science Laboratory, Sand Hutton, York YO41 ILZ, UK
Ellen Scherbaum
Stuttgart Regional Chemical and Veterinary Control Laboratory,
Schaflandstrasse 3/2, 70736 Fellbach, Germany
Hans-Jiirgen Stan
Institute of Food Chemistry, Technical University, Gustau-Meyer-Allee 25,
0-13355 Berlin, Germany
James R. Startin
Central Science Laboratory, Department for Food, Environment and
Rural Affairs, Sand Hutton, York YO41 1LZ, UK
Christoph von Holst
European Commission, DG Joint Research Centre, Institute for Reference
Materials and Measurements, B-2440 Geel, Belgium
WILSON AND WILSON'S
COMPREHENSIVE ANALYTICAL CHEMISTRY
VOLUMES IN THE SERIES
Vol. IA Analytical Processes
Gas Analysis
Inorganic Qualitative Analysis
Organic Qualitative Analysis
Inorganic Gravimetric Analysis
Vol. IB Inorganic Titrimetric Analysis
Organic Quantitative Analysis
Vol. IC Analytical Chemistry of the Elements
Vol. IIA Electrochemical Analysis
Electrodeposition
Potentiometric Titrations
Conductometric Titrations
High-Frequency Titrations
Vol. IIB Liquid Chromatography in Columns
Gas Chromatography
Ion Exchangers
Distillation
Vol. IIC Paper and Thin Layer Chromatography
Radiochemical Methods
Nuclear Magnetic Resonance and Electron Spin Resonance Methods
X-Ray Spectrometry
Vol. IID Coulometric Analysis
Vol. III Elemental Analysis with Minute Sample
Standards and Standardization
Separation by Liquid Amalgams
Vacuum Fusion Analysis of Gases in Metals
Electroanalysis in Molten Salts
Vol. IV Instrumentation for Spectroscopy
Atomic Absorption and Fluorescence Spectroscopy
Diffuse Reflectance Spectroscopy
Vol. V Emission Spectroscopy
Analytical Microwave Spectroscopy
Analytical Applications of Electron Microscopy
Vol. VI Analytical Infrared Spectroscopy
Vol. VII Thermal Methods in Analytical Chemistry
Substoichiometric Analytical Methods
Vol. VIII Enzyme Electrodes in Analytical Chemistry
Molecular Fluorescence Spectroscopy
Photometric Titrations
Analytical Applications of Interferometry
Vol. IX Ultraviolet Photoelectron and Photoion Spectroscopy
Auger Electron Spectroscopy
Plasma Excitation in Spectrochemical Analysis
Vol. X Organic Spot Tests Analysis
The History of Analytical Chemistry
ix
Volumes in the series
Vol. XI The Application of Mathematical Statistics in
Analytical Chemistry Mass Spectrometry
Ion Selective Electrodes
Vol. XII Thermal Analysis
Part A. Simultaneous Thermoanalytical Examination by Means of
the Derivatograph
Part B. Biochemical and Clinical Applications of Thermometric and
Thermal Analysis
Part C. Emanation Thermal Analysis and other Radiometric
Emanation Methods
Part D. Thermophysical Properties of Solids
Part E. Pulse Method of Measuring Thermophysical Parameters
Vol. XIII Analysis of Complex Hydrocarbons
Part A. Separation Methods
Part B. Group Analysis and Detailed Analysis
Vol. XIV Ion-Exchangers in Analytical Chemistry
Vol. XV Methods of Organic Analysis
Vol. XVI Chemical Microscopy
Thermomicroscopy of Organic Compounds
Vol. XVII Gas and Liquid Analysers
Vol. XVIII Kinetic Methods in Chemical Analysis
Application of Computers in Analytical Chemistry
Vol. XIX Analytical Visible and Ultraviolet Spectrometry
Vol. XX Photometric Methods in Inorganic Trace Analysis
Vol. XXI New Developments in Conductometric and Oscillometric Analysis
Vol. XXII Titrimetric Analysis in Organic Solvents
Vol. XXIII Analytical and Biomedical Applications of Ion-Selective Field-Effect
Transistors
Vol. XXIV Energy Dispersive X-Ray Fluorescence Analysis
Vol. XXV Preconcentration of Trace Elements
Vol. XXVI Radionuclide X-Ray Fluorescence Analysis
Vol. XXVII Voltammetry
Vol. XXVIII Analysis of Substances in the Gaseous Phase
Vol. XXIX Chemiluminescence Immunoassay
Vol. XXX Spectrochemical Trace Analysis for Metals and Metalloids
Vol. XXXI Surfactants in Analytical Chemistry
Vol. XXXII Environmental Analytical Chemistry
Vol. XXXIII Elemental Speciation -New Approaches for Trace Element Analysis
Vol. XXXIV Discrete Sample Introduction Techniques for Inductively Coupled
Plasma Mass Spectrometry
Vol. XXXV Modern Fourier Transform Infrared Spectroscopy
Vol. XXXVI Chemical Test Methods of Analysis
Vol. XXXVII Sampling and Sample Preparation for Field and Laboratory
Vol. XXXVIII Countercurrent Chromatography: The Support-Free liquid
Stationary Phase
Vol. XXXIX Integrated Analytical Systems
Vol. XL Analysis and Fate of Surfactants in the Aquatic Environment
Vol. XLI Sample Preparation for Trace Element Analysis
Vol. XLII Non-destructive Microanalysis of Cultural Heritage Materials
x
Series Editor's Preface
Pesticides play an important role in many areas of science and industrial
activity, ranging in scope from the production of pesticides and their formula-
tions to their wide range of applications in agriculture, especially in tropical
countries, the environment and domestic applications.
After pesticide application the target compound may degrade and residues
will remain not only in the plant, leaves or fruits but also in various environ-
mental matrices, like water, soil or sediments. Pesticide analysis requires a
comprehensive approach and for this reason it is very difficult to compile in
a single book all the analytical methods applied to the great variety and
complexity of pesticides used and found nowadays in the environment. This
book, edited by my old friend and colleague Amadeo R. Ferndndez-Alba, offers
a focussed approach and presents analytical methods for the trace determi-
nation of pesticides in food. It is a useful addition to the Comprehensive
Analytical Chemistry series since there is an urgent need for such a book due
to the the large number of analytical chemists working in this emerging field.
Its 10 chapters are devoted to sample preparation techniques, chromato-
graphic-mass spectrometric methods, including GC-MS and LC-MS
protocols, and quality control and proficiency testing schemes. The content
of the book should enable the analyst to solve most of the problems encoun-
tered in pesticide analysis, and be useful both for newcomers as well as
analysts in expert food laboratories looking either for a multiresidue analysis
or for a tailor-made determination of a specific pesticide. The various chapters
on mass spectrometry should also be useful to gain an insight into the
techniques that are now routinely used in pesticide analysis, partly due
to the lower costs of the MS instruments and also to the recently developed
instruments like time-of-flight or hybrid instruments, based on triple
quadrupoles followed by other mass analysers like ion traps.
As well as being an applied book covering the increasingly growing field
of pesticide residue analysis in food, it also contains some fundamental
information on the techniques that are used. Food laboratories are well
organised around the world since exports and imports of fruits and vegetables
are a key issue in most economies. For this reason laboratories in the food area
should be aware of new developments for ensuring quality control of pesticide
xix
Series Editor's Preface
residues in the various food matrices. Harmonisation of the methods is a key
element to avoid any economic losses and to be able to sell any food product in
any part of the world. This book will be of great help to those trading in this
global economic market, being a useful tool-box that should help the analyst
avoid pitfalls and assure method harmonisation in pesticide food control
laboratories.
Overall, this book covers most of the aspects of pesticide analysis in food
and I expect it to become a key reference in the community of pesticide residue
specialists. Finally I would like to thank not only the editor but also the
various authors, some of whom have been my co-workers for several years,
for their contributions in compiling this excellent book on pesticides in food.
D. Barcel6
June 2004
xx
Preface
Far from being a mature analytical field, the trace determination of
pesticides* continues to be a target topic for analytical chemists working in
research centres, government and universities. This is a consequence of (i)
new compounds, based on new chemical structures, continually being
introduced into the market, (ii) new regulations, which are becoming ever
more restrictive concerning the maximum residue limits legally permitted in
food, and (iii) an increasing social, economic and academic interest in food
safety, which has important trade implications.
As a consequence of the specific characteristics of pesticides (i.e. high
number of compounds, extremely diverse physical and chemical properties,
analysis levels per day for effective control, system robustness, analytical
performance, etc.) chromatography-based techniques are clearly the main
choice for the practitioner. Traditionally, the introduction of mass spectro-
metric analysers/detectors coupled to gas chromatography (GC) or liquid
chromatography (LC) has received less attention in this field compared to
others, such as the environment. This is probably a consequence of special
difficulties with these types of matrices/analytes, the high cost of these
systems and the difficulties present in routine operation.
However, during the last few years this situation has completely changed
and chromatography-mass spectrometry (GC and LC) based techniques have
become the core of pesticide food analysis. This change has been a result of
important developments in and improvements of these techniques, making
the great majority of pesticides/levels/commodities amenable to mass spectro-
metric detection with adequate analytical performance and robustness.
In addition, we must not consider the detection step as separate from
other stages of the analytical methodology, especially sample treatment and
clean-up, which are closely-linked and together determine the quality and
performance of the analyses as a whole. Therefore, developments in these
* Note: The term "pesticide" covers a very diverse range of substances, not only single chemicals of
natural or synthetic origin but additionally, among other things, micro-organisms. Throughout
this text, the word "pesticide" is typically used in the restricted sense of a synthetic organic
molecule and its degradation products.
xxi
Preface
areas have also contributed to improvements in pesticide food analysis and, in
many cases, to the MS-based method itself.
As far as pesticide residues are concerned, consumer confidence, food trade
decisions and regulatory controls depend heavily on the quality of analysis.
Thus, laboratories analysing food samples for the determination of pesticide
residues need to be assured of the quality of their data and whether they are
appropriate. The "fit-for-purpose" quality requirements are obviously related
to the analytical procedures applied, as well as the legislative driving forces.
Therefore, these topics are always relevant to get an adequate and realistic
perspective of the proposed food analytical methods.
On account of all the points mentioned above, the core of this book contains
four chapters (chapters 6-9) devoted to chromatography-mass spectrometry
methods. This part draws a clear and concise pathway between the relevant
analytical aspects, allowing the reader to understand the analytical basis,
technical characteristics and possibilities to evaluate pesticides in food by
GC-MS and LC-MS. Furthermore, the book also gives a well-defined and
critical compilation of the sample treatment and clean-up procedures, as well
as injection techniques applied in GC and LC food analysis (chapters 3-5).
Finally the book deals with aspects related to analytical quality control
requirements for pesticide residues, in addition to the pesticide regulation
aspects, which allows laboratories involved in residue analyses to meet the
requirements of a recognised accreditation scheme (chapters 1, 2 and 10).
These issues are considered in order to give to the readers a "field" dimension
with regard to the proposed analytical tools. I give my heartfelt thanks to the
authors who have contributed their expertise here. I must especially thank
those authors who prepared their manuscripts early on, for their patience,
while they waited for us to tidy up the remainder. I am impressed by the
energy and work expended by all the authors and I hope they feel well-
rewarded when seeing the final product. I would also like to thank Dr. Damia
Barcel6 (Series Editor) for his help and support throughout this time.
Amadeo Ferndndez-Alba
xxii
Chapter 1
Quality control for pesticide residues
analysis
Alan R.C. Hill, James R. Startin and Richard J. Fussell
1.1 INTRODUCTION
The determination of pesticide residues presents analysts with challenges
ranging from moderately to extremely difficult. Some of the complexities and
problems are sufficiently subtle, or lacking robust solutions, that it has always
been uncomfortably easy to generate spurious results. The term "pesticide"
has a very diverse range of meanings in terms of biological activity but it also
encompasses many hundreds of chemicals, exhibiting extremely diverse
physical and chemical properties. Consequently the analytical methods
involved are also diverse, although the majority of pesticides are amenable
to mass spectrometric detection.
Amongst the most problematic for the analyst are those pesticides that are
labile, or volatile, or have no chemical or physical features that differentiate
them from co-extractives, or are zwitterionic, or are insoluble in anything, or
are of incompletely-defined structure. Such analytes tend to require so-called
single residues methods (SRMs) and therefore the cost per result of analysis
tends to be very high. In contrast, certain large groups of pesticides share
physico-chemical properties that render them amenable to the use of multi-
residue methods (MRMs). Some MRMs are capable of detecting the presence
of several hundred pesticides as a part of a single determination, whereas
others are intended for a much smaller group, so that "typical" MRMs and
SRMs represent the extremes of a continuum. Mass spectrometry (MS)
coupled with gas or liquid chromatographic separation, and certain tech-
niques based on detection of a common moiety, are particularly suited for use
with MRMs. However, MRMs can provide special challenges for analytical
quality control (AQC).
Comprehensive Analytical Chemistry XLIII
FernAndez-Alba (Ed.)
© 2005 Elsevier B.V. All rights reserved I