Handbook of Residue Analytical Methods for Agrochemicals VOLUME 1 and VOLUME 2 doc

The role of the residue analytical chemist is no longer limited to the development and validation of analytical methods butalso includes design and conduct of complex field crop residue

for Agrochemicals

VOLUME 1

and VOLUME 2

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The agrochemical industry is, globally, one of the most heavily regulated industriestoday Extensive product chemistry, environmental fate, residue chemistry, ecotoxi-cology, and mammalian toxicology data are required to support the registration andreregistration of all crop protection products This information is used not only toconduct human dietary and worker exposure risk assessments but also to determinethe potential impact of the agrochemicals and their degradation products/metabolites

on the environment and sensitive ecosystems The quality of the residue data, ing the reliability and sensitivities of the analytical methods and the validity of thecollected biological/environmental samples, is critical to the acceptability and validity

includ-of the risk characterization/assessment Differences in testing guidelines between thevarious 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 butalso includes design and conduct of complex field crop residue and environmentalmonitoring studies This is a real challenge, especially when studies are conductedunder 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 comprehensiveoverview of current global regulatory requirements and the application of variousanalytical technologies (chromatographic and non-chromatographic) to residue anal-ysis Best practices to conduct various crop residue and field monitoring studies anddetailed 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 ters The editorial team acknowledges the high quality of the contributions from theregulatory, academic, and industrial researchers around the world It is their commit-ment in time and effort that make this a successful publication project Each chapterwas reviewed by at least one editor and often by other technical experts The editorialteam acknowledges the generous advice and reviews provided by our colleagues fromDuPont 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 DavidSmith) We would also appreciate comments, feedback and upgrades from the readers,

chap-so that correction and improvement can be made for later editions or printings

xli

The editorial team is also grateful for the valuable support from the Publisher (JohnWiley & Sons Ltd.), in particular Ms Lynette James, and from the Project Manager(Gray Publishing), in particular Ms Lesley Gray, for their efficient coordination duringthe planning, review and production phase of this publication effort.

Finally, this handbook is dedicated to all past and present residue analyticalchemists It is their vision and creativity that continues to push back the frontier

of residue analytical technology

Philip W LeeNewark, DelawareDecember, 2002

Associate Editors

Professor Hiroyasu Aizawa Dr Aldos C Barefoot Dr John J MurphyHiro Research Consultancy DuPont Crop Protection Dietary ExposureInc.(HRCI) Stine-Haskell Research Center Bayer CropScience

Founding Editor

Dr Terry RobertsAngleseyNorth WalesUK

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,

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,

John Fuhrman Monsanto, St Louis, MO, USA

Richard J Fussell Central Science Laboratory, York,UK

Willa Garner GARNDAL Associates, Inc., MountAiry, 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,

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,

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,

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,

Sean M Moore Bayer CropScience, Stilwell, KS, USA

Kouji Nakamura Saitama Prefecture Agriculture andForestry Research Center, Kuki, Japan

Kazuo Ogura Agricultural Chemicals InspectionStation, 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,

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-EnvironmentalSciences, 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 PlantProtection 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

Relationship of pesticide residue analysis, regulation, and risk assessment 4

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

Regulatory considerations for residue analysis and methods on crops and food:the approach of Japan

Kazuo Ogura, Hisayoshi Yamagishi and Shigeji Sugimoto 38

Preferred methodology for conducting supervised field trials 41Field data (field report) presentation 46Extrapolation among the formulation types 47

General approaches for residue analytical method development and validation

Approaches to analytical method development 51

Availability and practicality of analytical instrumentation 54Consideration of time, throughput, ruggedness and quality 54

Extending the scope of the multi-residue method DFG S19 55

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 76

Evaluation of data and recommendation for use 92

Validation of analytical methods for post-registration control and monitoring

purposes in the European Union

Evaluation of enforcement methods for food provided by manufacturers 95

The need for enforcement methods from the applicant 95

Elements and format of method description 98

Validation of European standard (CEN) methods 110

CEN requirements for widely accepted multi-matrix/multi-residue methods 112Requirements for (newer) methods with limited scope 112Assessment and documentation of validation results 113Validation of official methods of EU member states 115Overview of existing method collections and validation requirements 115Single-laboratory validation in the UK 115Validation procedures of the Nordic countries 119Validation of official methods in Germany 124The problem of appropriate documentation of validation data

Description of the different types of field crop residue studies 137

Best practices in conducting field study 148

Conducting crop residue field trials in Europe

General issues and considerations in conducting residue studies in Europe 169

European comparable climatic zones/weather influences 170

Role and responsibility of study personnel 173

Test site requirements, evaluation and selection 177

Best practices to conduct field studies 178

Evaluation and selection of field investigators and testing personnel 178

Preparation of field testing study plan 179

Test item (previously termed test substance) 179

Growing and maintenance of trial site crops 181

Calibration/servicing of application equipment 181

Field QA audits and study involvement 194

Planning a field residue trial in Latin America 201

Preparation of the field notebook formats 207

GLP training and protocol discussion 210

First application 211

Food Quality Protection Act (FQPA) considerations 213

Food processing of raw agricultural commodities for residue analysis

William J Englar, Neal Ewing, John C Peterson and

Summary report of processing procedures 228

Case study (Organophosphates Market Basket Survey) 232

Role and responsibilities of study personnel 235Selection of products and of properties to be evaluated 236

Sample collection, storage, shipment, receipt, and documentation 240

Assignment of products to laboratories 242Standardization of results reporting 243Presentation and review of study findings 245

Quality assurance functions 246

Procedures and best practices for conducting residue studies of animal health

drugs in food animals

David J Smith, Guy R Stehly and Michael P Turberg 248

Studies sponsored by the animal health industry 249

Animal considerations for GLP studies 262

Other considerations in animal selection 264

Other methods of drug administration 272

Animal weights, feed and water intakes, and dose 275

Nutritional and environmental considerations 276

Sampling and analyses of foodstuffs from animal origin

Robin S Readnour, Thomas J Burnett, Douglas E Kiehl

Regulatory guidelines 319Inter-laboratory/collaborative studies 321

Residue analytical methods for plant materials 327

Analytical methodology for plant and animal products 347

Analytical methodology for water and soil 348

Analytical method for the determination of acetochlor and its metabolites

Analytical method for the determination of propachlor and its metabolites

Calculation of residues 367

Multi-residue analytical method for the determination of acetochlor, alachlor,

Multi-residue analytical method for the determination of acetochlor, alachlor,

and metolachlor soil metabolites in aqueous samples 378

Analytical methodology for plant materials 390

Analytical method for soil metabolites 397

Triazine herbicide methodology

Analytical methodology for water samples 416

Analytical methodology for soil samples 429

Analytical methodology for crops, food, feed, and animal tissues 435Analytical methodology for biological fluids 437Analytical methodology for air samples 438

Analytical methodology for plant materials 453

Analytical method for the metabolites of diphenyl ether herbicides in soil 460

Analytical procedures for nonoil crop matrices 480

Sample extraction, filtration and concentration 480

Determination of carfentrazone-ethyl 480

Analytical procedures for crop refined oils 482

Analytical procedures for animal matrices 483

Automated procedure using a Zymark Benchmate Workstation with

Method for extraction of pyriminobac-methyl from soil 555

Extraction of pyriminobac-methyl from rice grain and rice straw 556

Analytical procedures for nonoil crop matrices 569

Sample extraction, filtration and concentration 569

Second reflux (conversion of SCA to DMS and release of conjugated HMS)

C8SPE cartridge/first slica gel SPE cartridge 570

Derivatization (silylation of 3-hydroxymethyl sulfentrazone) 570

Second (post-derivatization) silica gel SPE cartridge 570

Analytical procedures for oily crop matrices 571

Analytical procedures for crop refined oils 571

Preface xli

Recent advances in analytical technology, immunoassay and other nonchromatographic methods

Regulatory considerations for environmental analytical methods for

environmental fate and water quality impact assessments of agrochemicals

Michael R Barrett and Elizabeth Behl 603

Acceptance criteria of environmental analytical methods for pesticide regulation 606Method submission and evaluation criteria 606Validation and availability of methods and standards 608

Identification of unknowns/selection of analyte(s) 609

Specific environmental sample analysis issues 614Identification of target population in monitoring programs 614Sample collection strategy: study design 615

Immunoassay, biosensors and other nonchromatographic methods

Guomin Shan, Cynthia Lipton, Shirley J Gee and Bruce D Hammock 623

Development of pesticide immunoassays 631

PCR for products of agricultural biotechnology 653Basic principles of agricultural biotechnology 654

xxii

Basic principles of the PCR 659

Applications of PCR to agricultural biotechnology 668

Recent advances in nucleic acid amplification and detection 669

Immunoassays and animal production agriculture 680

Considerations involved in immunoassay development 681

Assay validation using incurred or fortified tissues 691

General sample treatments for eggs, milk, and meat 692

Agrochemical residue immunoassay applications 695

Detection of veterinary medicine residues 698

Comparison with chromatography-based methods 718

Requirements for validating a residue method 721

Examples of validated immunoassay methods 723

Advances in methods for pesticide residues in food

Michael F Wilson, Stewart L Reynolds and Richard J Fussell 727

Immunochemical and biosensor techniques 746

Gas chromatography/mass spectrometry (GC/MS) 762

Best practices in the analysis of residues in environmental samples:

groundwater and soil-water monitoring procedures

Leslie S Carver and Joseph R Chepega 789

Sources for the collection of groundwater samples 790

Sample collection techniques 800

Sampling of other groundwater sources 811

Suction lysimeter installation and sampling procedures 812

Current technology: Mass spectrometry 828

Selected reaction monitoring (SRM)/confirmation 831

Matrix effects, calibration and quantitation 832

Sampling and analysis of soil

Joseph H Massey, Scott H Jackson, Manasi Saha and Eberhard Zietz 840

Phase III: sample processing and analysis 872

Analytical detection and quantitation techniques 878

Models for agrochemical dissipation in soil 881

Determining water balance and leaching potential 884Weather data requirements for water balance and mobility assessments 888

Sampling sediment and water in rice paddy fields and adjacent water bodies

Hiroki Yamamoto and Kouji Nakamura 892

Regulatory requirements and guidelines 893

Quality control (QC) and quality assurance (QA) 904Data presentation and interpretation 905

Monitoring of agrochemical residues in air

James E Woodrow, Vincent Hebert and James S LeNoir 908

Biological sampling: determining routes of wildlife exposure to pesticides

George P Cobb and Todd A Anderson 936

Regulatory requirements and guidelines 938

Test systems 942

Data presentation and interpretation 946

Best practices in conducting dislodgeable foliar residue studies

Joseph P McClory and D Larry Merricks 960

Regulatory requirements and experimental field design 961

Materials and methods – test substance 963

Best practices to conduct spray drift studies

Andrew J Hewitt and David L Valcore 974

Covariate study designs 985

Correcting field and analytical data 1024

Electronic record keeping in a regulated environment

Management and integration of electronic records and documents 1028

Electronic data management of protocols and SOPs 1029Management of field data and information 1034Management of laboratory data and information 1036

Validation of chromatography software 1058Validation priority setting and risk assessment 1058

Open and closed systems 1064

Electronic records and electronic signatures 1065

EPA Office of Enforcement (OE) perspective 1077

Regulatory enforcement of electronic data management 1078

Analytical method for the determination of alkylenebis(dithiocarbamates) in plant

commodities by hot acid decomposition and spectrophotometric determination 1092

Methyl xanthate spectrophotometric method 1095

Analytical method for the determination of alkylenebis(dithiocarbamates) in plant

commodities by headspace GC and flame photometric (FPD) detection 1095

Multi-residue methods (S19) to measure azole fungicides in crop samples

General overview of the various modules 1102

Module E1: extraction and subsequent liquid/liquid partition for materials with

a water content exceeding 70 g/100 g and a fat content below 2.5 g/100 g 1104Module E2: extraction and subsequent liquid/liquid partition for materials with

a water content below 70 g/100 g and a fat content below 2.5 g/100 g 1107Module E3: extraction and subsequent liquid/liquid partition for materials with

a water content exceeding 70 g/100 g, a fat content below 2.5 g/100 g and a highacid content (highly recommended for determining acid-sensitive analytes) 1108Module E4: two-stage extraction and liquid/liquid partition for materials with

a water content exceeding 70 g/100 g and a fat content below 2.5 g/100 g 1110Module E5: two-stage extraction and liquid/liquid partition for materials with

a water content below 70 g/100 g and a fat content below 2.5 g/100 g 1111Module GPC: gel permeation chromatography 1113Module C1: column chromatography on a small silica gel column 1115

Analytical methodology for plant materials 1128

Conclusions and future directions 1161