Analysis of Pesticides in Food and Environmental Samples ß 2007 by Taylor & Francis Group, LLC. ß 2007 by Taylor & Francis Group, LLC. CRC Press is an imprint of the Taylor & Francis Group, an informa business Boca Raton London New York Edited by José L. Tadeo Analysis of Pesticides in Food and Environmental Samples ß 2007 by Taylor & Francis Group, LLC. CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2008 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed in the United States of America on acid-free paper 10 9 8 7 6 5 4 3 2 1 International Standard Book Number-13: 978-0-8493-7552-1 (Hardcover) This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. 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Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Analysis of pesticides in food and environmental samples / editor, Jose L. Tadeo. p. cm. Includes bibliographical references and index. ISBN 978-0-8493-7552-1 (alk. paper) 1. Pesticide residues in food. 2. Food Analysis. 3. Pesticides I. Tadeo, Jose L. TX571.P4A52 2008 664’.07 dc22 2007030736 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com ß 2007 by Taylor & Francis Group, LLC. Contents Preface Editor Contrib utors Chapt er 1 Pesticides : Classi fication and Properties José L. Tadeo, Consuel o Sánchez -Brunet e, and Lorena González Chapt er 2 Sample Hand ling of Pe sticides in Food and Env ironment al Samples Esther Turiel and Antoni o Mart ín-Esteban Chapt er 3 Analysis of Pesticides by Chroma togra phic Tec hnique s Coupled wi th Mass Spectromet ry Simon Hird Chapt er 4 Immunoas says and Biosens ors Jeanet te M. Van Emon, Jane C. Chuang, Kili an Di ll, and Guoh ua Xio ng Chapt er 5 Quality Assurance Árpád Ambru s Chapt er 6 Determinat ion of Pesticides in Food of Vegetal Origin Frank J. Schenck and Jon W. Wong Chapt er 7 Determinat ion of Pesticides in Food of Animal Origin Antoni a Garrido Frenich , Jose Luis Mart inez, and Adrian Covaci Chapt er 8 Determinat ion of Pesticides in Soil Con suelo Sánchez -Brunet e, Beatriz Albero, and José L. Tadeo Chapter 9 Determination of Pesticides in Water Jay Gan and Svetlana Bonda renko ß 2007 by Taylor & Francis Group, LLC. Chapter 10 Sampling and Analysis of Pesticides in the Atmosphere Maurice Millet Chapter 11 Levels of Pesticides in Food and Food Safety Aspects Kit Gra nby, Ann ette Peters en, Susan S. Her rmann, and Mett e Erecius Pou lsen Chapter 12 Monitoring of Pesticides in the Environment Ioannis Konstan tinou, Dimi tra Hela, Dimitra Lambrop oulou, and Tr iantafyllos Albani s ß 2007 by Taylor & Francis Group, LLC. Preface You should go on learning for as long as your ignorance lasts; and, if the proverb is to be believed, for the whole of your life. Lucius Annaeus Seneca Consumer concerns on food safety and society awareness of chemical contaminants in the environment have increased in the past few years. As a consequence , more restrictions in the use of chemical products have been imposed at national and international levels. Pesticides are widely used for the control of weeds, diseases, and pests of cultivated plants all over the world, mainly since after Second World War, with the discovery of some organic compounds with good insectici de or herbicide activity. At present, around 2.5 million tons of pesticides are used annually and the number of registered active substances is higher than 500. However, as pesticides are toxic substances that may have undesirable effects, their use has to be regulated. Risk assessment of pesticides requires information on the toxicological and ecotoxicological properties of these compounds as well as on their levels in food and environmental compartments. Therefore, reliable analytical methods are needed to carry out the monitoring of pesticide residues in those matrices. Analysis of Pesticides in Food and Environmental Samples focuses on the analytical methodologies developed for the determination of these compounds and on their levels in food and in the environment. It includes infor mation on the different pesticides used, sample preparation methods, quality assurance, chromatographic techniques, immunoassays, pesticide determination in food, soil, water, and air, and the results of their monitoring in food and environmental compartments. I think that this timely and up-to-date work can significantly improve the information in this research area and contribute to a better understanding of the behavior of pesticides that will lead to an improvement of their use. My sincere thanks to everyone who has contributed and particularly to all the contributors of the different chapters of Analysis of Pesticides in Food and Environ- mental Samples. This work is dedicated to Teresa, my wife. José L. Tadeo ß 2007 by Taylor & Francis Group, LLC. ß 2007 by Taylor & Francis Group, LLC. Editor José L. Tadeo, PhD in chemistry, is a senior researcher at the National Institute for Agricultural and Food Research and Technology, Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria in Madrid, Spain. He graduated with a degree in chemistry in June 1972 from the University of Valencia and began his research career at the Institute of Agrochemistry and Food Technology, Spanish Council for Scientific Research, in Valencia, investigating natural components of plants with insecticide activity. In 1976, he was engaged in research of analytical methodologies for the determination of pesticide residues in food, water, and soil at the Jealott’s Hill Research Station in the United Kingdom. In 1977, Dr. Tadeo was a research scientist at the Institute for Agricultural Research in Valencia where his work focused on the study of the chemical compo- sition of citrus fruits and the behavior of fungicides used during postharvest of fruits. In 1988, he became a senior researcher at the Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria. During his stay at the Plant Protection Depart- ment, the main research lines were the analysis of herbicide residues and the study of their persistence and mobility in soil. His current research at the Environment Department of the Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria is the analysis of pesticides and other contaminants in food and environmental matrices and the evaluation of exposure to biocides and existing chemicals. He has published numerous scientific papers, monographs, and book chapters on these topics. He has been a member of national and international working groups for the evaluation of chemicals, and he is currently involved in the assessment of biocides at the international level. ß 2007 by Taylor & Francis Group, LLC. ß 2007 by Taylor & Francis Group, LLC. [...]... 1- ( 4,6-Dimethoxypyrimidin-2-yl )-3 -( 3-trifluoromethyl2-pyridylsulfonyl)urea 1- ( 2-Chloroimidazo [1, 2-a]pyridin-3-ylsulfonyl) 3-( 4,6-dimethoxypyrimidin-2-yl)urea Methyl- 2-( 4-methoxy-6-methyl -1 , 3,5-triazin2-ylcarbamoylsulfamoyl)benzoate 1- ( 4,6-Dimethoxypyrimidin-2-yl )-3 -( 3-ethylsulfonyl2-pyridylsulfonyl)urea Methyl 3-( 4-methoxy-6-methyl -1 , 3,5-triazin2-ylcarbamoylsulfamoyl)thiophen-2-carboxylate 1- [ 2-( 2-Chloroethoxy)phenylsulfonyl ]-3 -( 4-methoxy6-methyl -1 , 3,5-triazin-2-yl)urea... 2-( 4-Chloro-6-ethylamino1,3,5-triazin-2-ylamino)2-methylpropionitrile 4-Amino-6-tert-butyl4,5-dihydro-3-methylthio1,2,4-triazin-5-one N2,N4-Diisopropyl-6methylthio -1 , 3,5triazine-2,4-diamine 6-Chloro-N2,N4-diethyl1,3,5-triazine-2,4-diamine N2-tert-Butyl-N4-ethyl6-methylthio -1 , 3,5triazine-2,4-diamine Vapor Pressure mPa (258C) Kow log P (258C) 3.8 3 10 À2 2.5 33a 35–50 2.0 3 10 À4a 2 .1 1 71 ca 14 0.058a 1. 6a 10 50a 40 0 .16 5 3 .1 33 50 2.9 3 10 À3 2 .1 6.2a 27 10 2 0.225... Flazasulfuron C13H12F3N5O5S Imazosulfuron C14H13ClN6O5S Metsulfuron-methyl C14H15N5O6S Rimsulfuron C14H17N5O7S2 Thifensulfuron-methyl C12H13N5O6S2 Triasulfuron C14H16ClN5O5S Tribenuron-methyl C15H17N5O6S Sources: a 208C IUPAC Name 1- ( 4,6-Dimethoxypyrimidin-2-yl )-3 - [ 1- methyl- 4-( 2-methyl2H-tetrazol-5-yl)-pyrazol-5-ylsulfonyl]urea 1- ( 2-Chlorophenylsulfonyl )-3 -( 4-methoxy-6-methyl1,3,5-triazin-2-yl)urea 1- ( 4,6-Dimethoxypyrimidin-2-yl )-3 -( 3-trifluoromethyl2-pyridylsulfonyl)urea... Chemical Names and Properties of Nitroaniline Herbicides Common Name Butralin C14H21N3O4 Ethalfluralin C13H14F3N3O4 Pendimethalin C13H19N3O4 Trifluralin C13H16F3N3O4 IUPAC Name N-sec-Butyl-4-tert-butyl-2, 6-dinitroaniline N-Ethyl-a,a,a-trifluoro-N(2-methylallyl )-2 ,6-dinitrop-toluidine N- ( 1- Ethylpropyl )-2 ,6dinitro-3,4-xylidine a,a,a-Trifluoro-2,6-dinitroN,N-dipropyl-p-toluidine Water Solubility mg=L (258C)... Permethrin C21H20Cl2O3 IUPAC Name (S)-a-Cyano-3-phenoxybenzyl (Z )-( 1R,3S )-2 ,2-dimethyl 3-[ 2-( 2,2,2-trifluoro -1 - trifluoromethyl ethoxycarbonyl)vinyl] cyclopropanecarboxylate (RS)-a-Cyano- 4- uoro-3-phenoxybenzyl(1RS,3RS; 1RS,3SR )-3 -( 2,2-dichlorovinyl )-2 ,2-dimethyl cyclopropanecarboxylate (RS)-a -Cyano-3-phenoxybenzyl(1RS,3RS; 1RS,3SR) 3-( 2,2-dichlorovinyl )-2 ,2-dimethyl cyclopropanecarboxylate (S)-a-Cyano-3-phenoxybenzyl(1R,3R )-3 -( 2,2-dibromovinyl)2,2-dimethyl... p,p0 -DDT C14H9Cl5 Dieldrin C12H8Cl6O Dicofol C14H9Cl5O Endosulfan C9H6Cl6O3S g-HCH C6H6Cl6 Methoxychlor C16H15Cl3O2 Tetradifon C12H6Cl4O2S 1, 2,3,4 ,10 ,10 -Hexachloro -1 , 4,4a,5,8,8a-hexahydro-exo1,4-endo-5,8-dimethanonaphthalene 1, 1 , 1- Trichloro-2,2-bis(4-chlorophenyl)ethane 3.08 5.0–7.4 . Pyridines and Quaternary Ammonium Compounds 12 1. 2.9 Pyridazines and Pyridazinones 13 1. 2 .10 Triazines 14 1. 2 .11 Ureas 15 1. 2 .11 .1 Phenylureas 15 1. 2 .11 .2 Sulfonylureas 16 1. 3 Insecticides 16 1. 3 .1. 1 30 Butachlor C 17 H 26 ClNO 2 N-Butoxymethyl-2-chloro-2 0 ,6 0 - diethylacetanilide 0.24 — 23 a 12 Metolachlor C 15 H 22 ClNO 2 2-Chloro-6-ethyl- N- (2-methoxy -1 - methylethyl) acet- o-toluidide. Group, LLC. 1. 5 .1. 3 Photosynthesis Inhibitors 30 1. 5.2 Insecticides 30 1. 5.2 .1 Signal Interference in the Nervous System 30 1. 5.2.2 Inhibitors of Cholinesterase 31 1.5.2.3 Inhibitors of Chitin Synthesis