Editor-in-Chief Dr Philip W Lee DuPont Crop Protection USA Handbook of Residue Analytical Methods for Agrochemicals VOLUME 1 and VOLUME 2 Copyright C  2003 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester, West Sussex PO19 8SQ, England Telephone (+44) 1243 779777 Email (for orders and customer service enquiries): cs-books@wiley.co.uk Visit our Home Page on www.wileyeurope.com or www.wiley.com All Rights Reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except under the terms of the Copyright, Designs and Patents Act 1988 or under the terms of a licence issued by the Copyright Licensing Agency Ltd, 90 Tottenham Court Road, London W1T 4LP, UK, without the permission in writing of the Publisher. 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Works written by US government employees and classified as US Government Works are in the public domain in the United States of America. Preface The agrochemical industry is, globally, one of the most heavily regulated industries today. Extensive product chemistry, environmental fate, residue chemistry, ecotoxi- cology, and mammalian toxicology data are required to support the registration and reregistration of all crop protection products. This information is used not only to conduct human dietary and worker exposure risk assessments but also to determine the potential impact of the agrochemicals and their degradation products/metabolites on the environment and sensitive ecosystems. The quality of the residue data, includ- ing the reliability and sensitivities of the analytical methods and the validity of the collected biological/environmental samples,is critical to the acceptability and validity of the risk characterization/assessment. Differences in testing guidelines between the various regulatory authorities and the lack of standardization in test method specifica- tions further complicate the interpretation and broad application of the exposure data. Significant progress has been achieved in residue analytical technology in the past 50 years. Today’s residue analytical methodology detects multiple analytes routinely at the nanogram per kilogram (ppt) level in a wide variety of sample matrices with a high level of selectively and accuracy. The role of the residue analytical chemist is no longer limited to the development and validation of analytical methods but also includes design and conduct of complex field crop residue and environmental monitoring studies. This is a real challenge, especially when studies are conducted under the strict Good Laboratory Practices guidelines. Recognizing the diverse and rapid growth of residue chemistry as an important scientific discipline, Dr Terry Roberts, Founding Editor of the Handbook of the Residue Analytical Methods of Agrochemicals, organized this publication effort in 1999. The editorial team includes Dr Hiro Aizawa (Hiro Research Consultancy), Dr Al Barefoot (DuPont Crop Protection) and Dr John Murphy (Bayer CropScience). The scope/objective of this handbook is to present to the reader a comprehensive overview of current global regulatory requirements and the application of various analytical technologies (chromatographic and non-chromatographic) to residue anal- ysis. Best practices to conduct various crop residue and field monitoring studies and detailed method procedures for the determination of major classes of agrochemicals, as well as individual compounds, are key components of this handbook. This handbook consists of two volumes and approximately 80 individual chap- ters. The editorial team acknowledges the high quality of the contributions from the regulatory, academic, and industrial researchers around the world. It is their commit- ment in time and effort that make this a successful publication project. Each chapter was reviewed by at least one editor and often by other technical experts. The editorial team acknowledges the generous advice and reviews provided by our colleagues from DuPont Crop Protection (Dr Wynn John, Dr Chuck Powley) and Bayer CorpScience (Dr Lou Russo), the US EPA (Dr Alex Krynitsky) and the USDA ARS (Dr David Smith). We would also appreciate comments, feedback and upgrades from the readers, so that correction and improvement can be made for later editions or printings. xli xlii Preface The editorial team is also grateful for the valuable support from the Publisher (John Wiley & Sons Ltd.), in particular Ms Lynette James, and from the Project Manager (Gray Publishing), in particular Ms Lesley Gray, for their efficient coordination during the planning, review and production phase of this publication effort. Finally, this handbook is dedicated to all past and present residue analytical chemists. It is their vision and creativity that continues to push back the frontier of residue analytical technology. Philip W. Lee Newark, Delaware December, 2002 Editorial Board Editor-in-Chief Dr Philip W Lee DuPont Crop Protection Stine-Haskell Research Center Newark Delaware USA Associate Editors Professor Hiroyasu Aizawa Dr Aldos C Barefoot Dr John J Murphy Hiro Research Consultancy DuPont Crop Protection Dietary Exposure Inc.(HRCI) Stine-Haskell Research Center Bayer CropScience Tokyo Newark Stilwell Japan Delaware Kansas USA USA Founding Editor Dr Terry Roberts Anglesey North Wales UK List of contributors Lutz Alder Federal Institute for Health Protection of Consumers and Veterinary Medicine (BgVV), Berlin, Germany Todd A. Anderson Texas Tech University, Lubbock, TX, USA Reiner Bacher PTRL Europe GmbH, Ulm, Germany Michael R. Barrett United States Environmental Protection Agency, Washington, DC, USA Elizabeth Behl United States Environmental Protection Agency, Washington, DC, USA Kimberly S. Billesbach Bayer CropScience, Stilwell, KS, USA James F. Brady Syngenta Crop Protection, Inc., Greensboro, NC, USA David J. Brookman Technology Sciences Group Inc., Washington, DC, USA Thomas J. Burnett Eli Lilly and Company, Greenfield, IN, USA Maria Elena Y. Cabusas DuPont Crop Protection, Newark, DE, USA Leslie S. Carver Waterborne Environmental, Inc., Leesburg, VA, USA Andrey Chen FMC, Princeton, NJ, USA Joseph R. Chepega Waterborne Environmental, Inc., Leesburg, VA, USA Mihai Cicotti Battelle Memorial Institute, Geneva, Switzerland Thomas J. Class PTRL Europe GmbH, Ulm, Germany George P. Cobb Texas Tech University, Lubbock, TX, USA Johannes Corley Rutgers, The State University of New Jersey, North Brunswick, NJ, USA Kay K. Curry Technology Sciences Group Inc., Washington, DC, USA William J. Englar Englar Food Laboratories, Inc., Moses Lake, WA, USA Cheryl M. Englar-Coulter Englar Food Laboratories, Inc., Moses Lake, WA, USA Neal Ewing National Food Laboratory, Inc., Dublin, CA, USA John Fuhrman Monsanto, St. Louis, MO, USA Richard J. Fussell Central Science Laboratory, York, UK Willa Garner GARNDAL Associates, Inc., Mount Airy, MD, USA Shirley J. Gee University of California, Davis, CA, USA Thomas J. Gould Bayer CropScience, Stilwell, KS, USA Timothy J. Grace Bayer CropScience, Stilwell, KS, USA Charles A. Green Valent USA Corporation, Dublin, CA, USA Amy Hackett Monsanto, St. Louis, MO, USA Bruce D. Hammock University of California, Davis, CA, USA Ralf H¨anel Federal Biological Research Centre for Agriculture and Forestry (BBA), Braunschweig, Germany Vincent Hebert Washington State University, Richland, WA, USA xliv List of contributors Andrew J. Hewitt Stewart Agricultural Research Services, Macon, MO, USA Richard Honeycutt H.E.R.A.C., Inc., Greensboro, NC, USA Mitsumasa Ikeda Kumiai Chemical Industry Co., Ltd, Shizuoka, Japan Yuji Ikemoto Nihon Nohyaku Co. Ltd, Osaka, Japan Fujio Ishijima Hokko Chemical Industry Co. Ltd, Kanagawa, Japan Scott H. Jackson BASF Corporation, Research Triangle Park, NC, USA Kathryn M. Jernberg DuPont Crop Protection, Newark, DE, USA William W. John DuPont Crop Protection, Stine Haskell Research Center, Newark, DE, USA Setsuko Katsurada Sankyo Co. Ltd, Shiga, Japan Guenther Kempe Landesuntersuchungsanstalt, Chemnitz, Germany Douglas E. Kiehl Eli Lilly and Company, Greenfield, IN, USA Philip James Kijak US Food and Drug Administration, Laurel, MD, USA Hiroko Kobayashi Research Institute of Japan Plant Protection Association, Ibaraki, Japan Alexander J. Krynitsky US Environmental Protection Agency, EPA Environmental Science Center, Fort Meade, MD, USA Chung K. Lam Bayer CropScience, Stilwell, KS, USA Steven J. Lehotay USDA Agricultural Research Service, Eastern Regional Research Center, Wyndmoor, PA, USA William M. Leimkuehler Bayer CropScience, Stilwell, KS, USA James S. LeNoir DuPont Crop Protection, Newark, DE, USA Yi Lin Syngenta Crop Protection, Inc., Greensboro, NC, USA Cynthia Lipton Byotix, Inc., Richmond, CA, USA Joseph H. Massey Mississippi State University, Starkville, MS, USA Greg C. Mattern Bayer CropScience, Stilwell, KS, USA Joseph P. McClory DuPont Crop Protection, Newark, DE, USA Carolyn Mentzer Agrisearch Incorporated, Thurmont, MD, USA D. Larry Merricks Agrisearch Incorporated, Frederick, MD, USA Sean M. Moore Bayer CropScience, Stilwell, KS, USA Kouji Nakamura Saitama Prefecture Agriculture and Forestry Research Center, Kuki, Japan Kazuo Ogura Agricultural Chemicals Inspection Station, Tokyo, Japan Jeff Old Inveresk Research, Tranent, UK Takeo Otsuka Sankyo Co. Ltd, Shiga, Japan John C. Peterson Englar Food Laboratories, Inc., Moses Lake, WA, USA Beth M. Polakoff Exponent, Inc., Washington, DC, USA Charles R. Powley DuPont Crop Protection, Newark, DE, USA Robin S. Readnour Eli Lilly and Company, Greenfield, IN, USA Valerie B. Reeves US Food and Drug Administration, Rockville, MD, USA List of contributors xlv Stewart L. Reynolds Central Science Laboratory, York, UK Neil J. Robinson Syngenta, Bracknell, UK Janine E. Rose PTRL West, Inc., Hercules, CA, USA Louis Russo Bayer CropScience, Kansas City, MO, USA Mariko Sabi Sankyo Co. Ltd, Shiga, Japan Shingo Sadakane Sankyo Co. Ltd, Shiga, Japan Manasi Saha BASF Corporation, Research Triangle Park, NC, USA Takashi Saito Sankyo Co. Ltd, Shiga, Japan Yoshihiro Saito Kumiai Chemical Industry Co., Ltd, Shizuoka, Japan Thomas Schreier Valent USA Corporation, Dublin, CA, USA James N. Seiber Western Regional Research Center, USDA Agricultural Research Service, Albany, CA, USA Robert J. Seymour Bayer CropScience, Research Triangle Park, NC, USA Guomin Shan Dow AgroSciences LLC, Indianapolis, IN, USA Weilin L. Shelver US Department of Agriculture, Agricultural Research Service, Fargo, ND, USA Johannes Siebers Federal Biological Research Centre for Agriculture and Forestry (BBA), Braunschweig, Germany David J. Smith US Department of Agriculture, Agricultural Research Service, Fargo, ND, USA Craig A. Smitley Scynexis, Research Triangle Park, NC, USA Lisa D. Spurlock-Brouwer Eli Lilly and Company, Greenfield, IN, USA Guy R. Stehly USGS, Biological Resources Division, La Crosse, WI, USA Shigeji Sugimoto Nippon Soda Co. Ltd, Tokyo, Japan Manabu Toujigamori Sankyo Co. Ltd, Shiga, Japan Yasuhiro Tsujino Sankyo Co. Ltd, Shiga, Japan Michael P. Turberg Eli Lilly and Company, Greenfield, IN, USA Takashi Ueda Sankyo Co. Ltd, Shiga, Japan Masako Ueji National Institute for Agro-Environmental Sciences, Tsukuba, Japan Noriharu Umetsu Otsuka Chemical Co. Ltd, Naruto, Japan David L. Valcore Dow AgroSciences, Indianapolis, IN, USA Chantel Van Bellinghan Monsanto, Brussels, Belgium Michael F. Wilson Central Science Laboratory, York, UK James E. Woodrow University of Nevada, Reno, NV, USA Akira Yagi Kumiai Chemical Industry Co., Ltd, Shizuoka, Japan Katsura Yagi Otsuka Chemical Co. Ltd, Naruto, Japan Hisayoshi Yamagishi Research Institute of Japan Plant Protection Association, Ibaraki, Japan Hiroki Yamamoto Shimane University, Matsue, Japan Robert A. Yokley Syngenta Crop Protection, Inc., Greensboro, NC, USA Sabrina X. Zhao Pfizer Inc., Groton, CT, USA Eberhard Zietz Institut Fresenius, Taunusstein, Germany Contents of Volume 1 Preface xli List of contributors xliii Introduction James N. Seiber 1 Introduction 1 Relationship of pesticide residue analysis, regulation, and risk assessment 4 Who does residue analysis and why 5 Challenges 7 References 8 Regulatory guidance and scientific consideration for residue analytical method development and validation Assessment of residue analytical methods for crops, food, feed, and environmental samples: the approach of the European Union Johannes Siebers and Ralf H ¨ anel 13 Introduction 13 Legal background 14 General 14 Council Directive 91/414/EEC 14 Legislation related to MRLs 15 Legislation related to residues limits for soil, water, and air 18 Provisions for residue analytical methods 18 Evaluation of the submitted methods 20 Institutional background 20 Validation parameters 21 Requirements for post-registration and monitoring (enforcement) methods 23 General requirements 23 Specific requirements 27 Requirements for data generation methods 31 General requirements 32 Specific requirements 33 Availability of analytical methods 34 Perspectives 35 Acknowledgement 36 References 36 v vi Contents of Volume 1 Regulatory considerations for residue analysis and methods on crops and food: the approach of Japan Kazuo Ogura, Hisayoshi Yamagishi and Shigeji Sugimoto 38 Background 38 Plant metabolism studies 40 Residue studies on crops 41 Residue analytical method 41 Preferred methodology for conducting supervised field trials 41 Field data (field report) presentation 46 Extrapolation among the formulation types 47 Residue definition 47 Market basket survey in Japan 48 Conclusion 49 Further reading 49 General approaches for residue analytical method development and validation Thomas J. Class and Reiner Bacher 50 Introduction 50 Approaches to analytical method development 51 Properties of the analyte(s) 51 Functional groups of the analyte(s) 52 Properties of the sample material 53 Availability and practicality of analytical instrumentation 54 Consideration of time, throughput, ruggedness and quality 54 Practical examples 55 Extending the scope of the multi-residue method DFG S19 55 What can go wrong? 57 Beyond the limits 58 References 58 Best practices in establishing detection and quantification limits for pesticide residues in foods Johannes Corley 59 Introduction 59 Definitions 61 Methods for defining LOD and LOQ 63 IUPAC method 63 Propagation of errors method 66 Hubaux–Vos approach 67 Two-step approach (proposed by the US EPA) 67 RMSE method 68 The t 99 s LLMV method 70 Confirmation 71 Representative data 72 Conclusions 73 Acknowledgements 74 References 74 [...]... Contents of Volume 1 Regulatory guidelines Inter-laboratory/collaborative studies Conclusion References 319 321 321 321 Compound class Anilides Hiroko Kobayashi Introduction Residue analytical methods for plant materials Nature of the residue Analytical method Residue analytical methods for soil Nature of the residues Analytical method Analytical methodology for water Nature of the residues Analytical. .. Introduction Analytical methodology for plant and animal products Nature of the residue Rationale for the presented methods Description of methodology Analytical methodology for water and soil Nature of the residue Rationale for the methods presented Description of methodology Analytical method for the determination of acetochlor and its metabolites in plants and animals Outline of method Apparatus Reagents Analytical. .. Evaluation of data and recommendation for use Conclusion References Validation of analytical methods for post-registration control and monitoring purposes in the European Union Lutz Alder Introduction Evaluation of enforcement methods for food provided by manufacturers The need for enforcement methods from the applicant The problem with residue definition Elements and format of method description Assessment of. .. 361 361 361 362 363 363 366 Contents of Volume 1 Calculation of residues Evaluation Multi -residue analytical method for the determination of acetochlor, alachlor, and metolachlor in aqueous samples Outline of method Apparatus Reagents Analytical standards Analytical procedure Calculation of residues Evaluation Multi -residue analytical method for the determination of acetochlor, alachlor, and metolachlor... multi-matrix/multi -residue methods Requirements for (newer) methods with limited scope Assessment and documentation of validation results Validation of official methods of EU member states Overview of existing method collections and validation requirements Single-laboratory validation in the UK Validation procedures of the Nordic countries Validation of official methods in Germany The problem of appropriate... Outline of method Apparatus Reagents Analytical standards Analytical procedures Calculation of residues Evaluation Future directions for environmental monitoring Acknowledgements References Dinitroaniline herbicides Masako Ueji Introduction Analytical methodology for plant materials Nature of the residues Method principle Analytical methodology for soil Nature of the residues Method principle Analytical. .. methodology for biological fluids Analytical methodology for air samples Instrumentation Gas chromatography Liquid chromatography Supercritical fluid chromatography Electrochemical analysis Other techniques Future directions References Diphenyl ethers Masako Ueji Introduction Analytical methodology for plant materials Nature of the residues Analytical method Analytical methodology for soil Nature of the residues...Contents of Volume 1 The process of development and validation of animal drug residue methods for US Food and Drug Administration regulatory use Philip James Kijak and Valerie B Reeves Introduction The method Determinative procedures Confirmatory procedures Development of methods for regulatory use Practicability of methods Analyte selection Specificity Ruggedness... Agrochemical residue immunoassay applications Detection of veterinary medicine residues Other therapeutic agents Other antibody-based technologies Conclusion Abbreviations Acknowledgements References Validated immunoassay methods James F Brady Introduction Enzyme immunoassays Choice of tube or plate format Calculation of residues Comparison with chromatography-based methods Requirements for validating a residue. .. experiments Test of multi -residue methods Independent laboratory validation Statement on extraction efficiency Perspectives 76 76 78 79 79 80 80 80 81 81 82 82 83 83 83 84 84 85 85 85 87 87 88 88 88 89 91 91 92 92 93 94 94 95 95 96 98 101 105 107 108 108 109 vii viii Contents of Volume 1 Validation of European standard (CEN) methods Scope and format of CEN methods CEN requirements for widely accepted . 327 Residue analytical methods for plant materials 327 Nature of the residue 327 Analytical method 329 Residue analytical methods for soil 336 Nature of. growth of residue chemistry as an important scientific discipline, Dr Terry Roberts, Founding Editor of the Handbook of the Residue Analytical Methods of Agrochemicals,