Handbook of Residue Analytical Methods for Agrochemicals

1428 Pages·2003·7.2 MB·English

by  Lee Ph.W.

Handbook of Residue
Analytical Methods
for Agrochemicals
VOLUME 1
and VOLUME 2
Editor-in-Chief
Dr Philip W Lee
DuPont Crop Protection
USA
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Preface
Theagrochemicalindustryis,globally,oneofthemostheavilyregulatedindustries
today.Extensiveproductchemistry,environmentalfate,residuechemistry,ecotoxi-
cology,andmammaliantoxicologydataarerequiredtosupporttheregistrationand
reregistration of all crop protection products. This information is used not only to
conducthumandietaryandworkerexposureriskassessmentsbutalsotodetermine
thepotentialimpactoftheagrochemicalsandtheirdegradationproducts/metabolites
ontheenvironmentandsensitiveecosystems.Thequalityoftheresiduedata,includ-
ing the reliability and sensitivities of the analytical methods and the validity of the
collectedbiological/environmentalsamples,iscriticaltotheacceptabilityandvalidity
oftheriskcharacterization/assessment.Differencesintestingguidelinesbetweenthe
variousregulatoryauthoritiesandthelackofstandardizationintestmethodspecifica-
tionsfurthercomplicatetheinterpretationandbroadapplicationoftheexposuredata.
Significantprogresshasbeenachievedinresidueanalyticaltechnologyinthepast
50years.Today’sresidueanalyticalmethodologydetectsmultipleanalytesroutinely
atthenanogramperkilogram(ppt)levelinawidevarietyofsamplematriceswith
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
underthestrictGoodLaboratoryPracticesguidelines.
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),
DrAlBarefoot(DuPontCropProtection)andDrJohnMurphy(BayerCropScience).
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
analyticaltechnologies(chromatographicandnon-chromatographic)toresidueanal-
ysis.Bestpracticestoconductvariouscropresidueandfieldmonitoringstudiesand
detailedmethodproceduresforthedeterminationofmajorclassesofagrochemicals,
aswellasindividualcompounds,arekeycomponentsofthishandbook.
This handbook consists of two volumes and approximately 80 individual chap-
ters.Theeditorialteamacknowledgesthehighqualityofthecontributionsfromthe
regulatory,academic,andindustrialresearchersaroundtheworld.Itistheircommit-
mentintimeandeffortthatmakethisasuccessfulpublicationproject.Eachchapter
wasreviewedbyatleastoneeditorandoftenbyothertechnicalexperts.Theeditorial
teamacknowledgesthegenerousadviceandreviewsprovidedbyourcolleaguesfrom
DuPontCropProtection(DrWynnJohn,DrChuckPowley)andBayerCorpScience
(Dr Lou Russo), the US EPA (Dr Alex Krynitsky) and the USDA ARS (Dr David
Smith).Wewouldalsoappreciatecomments,feedbackandupgradesfromthereaders,
sothatcorrectionandimprovementcanbemadeforlatereditionsorprintings.
xli
xlii Preface
TheeditorialteamisalsogratefulforthevaluablesupportfromthePublisher(John
Wiley&SonsLtd.),inparticularMsLynetteJames,andfromtheProjectManager
(GrayPublishing),inparticularMsLesleyGray,fortheirefficientcoordinationduring
theplanning,reviewandproductionphaseofthispublicationeffort.
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
ofresidueanalyticaltechnology.
PhilipW.Lee
Newark,Delaware
December,2002
Editorial Board
Editor-in-Chief
DrPhilipWLee
DuPontCropProtection
Stine-HaskellResearchCenter
Newark
Delaware
USA
Associate Editors
ProfessorHiroyasuAizawa DrAldosCBarefoot DrJohnJMurphy
HiroResearchConsultancy DuPontCropProtection DietaryExposure
Inc.(HRCI) Stine-HaskellResearchCenter BayerCropScience
Tokyo Newark Stilwell
Japan Delaware Kansas
USA USA
Founding Editor
DrTerryRoberts
Anglesey
NorthWales
UK
List of contributors
LutzAlder FederalInstituteforHealthProtectionof JohannesCorley Rutgers,TheStateUniversityofNew
ConsumersandVeterinaryMedicine(BgVV),Berlin, Jersey,NorthBrunswick,NJ,USA
Germany
KayK.Curry TechnologySciencesGroupInc.,
ToddA.Anderson TexasTechUniversity,Lubbock, Washington,DC,USA
TX,USA
WilliamJ.Englar EnglarFoodLaboratories,Inc.,
ReinerBacher PTRLEuropeGmbH,Ulm,Germany MosesLake,WA,USA
MichaelR.Barrett UnitedStatesEnvironmental CherylM.Englar-Coulter EnglarFoodLaboratories,
ProtectionAgency,Washington,DC,USA Inc.,MosesLake,WA,USA
ElizabethBehl UnitedStatesEnvironmentalProtection NealEwing NationalFoodLaboratory,Inc.,Dublin,
Agency,Washington,DC,USA CA,USA
KimberlyS.Billesbach BayerCropScience,Stilwell, JohnFuhrman Monsanto,St.Louis,MO,USA
KS,USA
RichardJ.Fussell CentralScienceLaboratory,York,
JamesF.Brady SyngentaCropProtection,Inc., UK
Greensboro,NC,USA
WillaGarner GARNDALAssociates,Inc.,Mount
DavidJ.Brookman TechnologySciencesGroupInc., Airy,MD,USA
Washington,DC,USA
ShirleyJ.Gee UniversityofCalifornia,Davis,CA,
ThomasJ.Burnett EliLillyandCompany,Greenfield, USA
IN,USA
ThomasJ.Gould BayerCropScience,Stilwell,KS,
MariaElenaY.Cabusas DuPontCropProtection, USA
Newark,DE,USA
TimothyJ.Grace BayerCropScience,Stilwell,KS,
LeslieS.Carver WaterborneEnvironmental,Inc., USA
Leesburg,VA,USA
CharlesA.Green ValentUSACorporation,Dublin,
AndreyChen FMC,Princeton,NJ,USA CA,USA
JosephR.Chepega WaterborneEnvironmental,Inc., AmyHackett Monsanto,St.Louis,MO,USA
Leesburg,VA,USA
BruceD.Hammock UniversityofCalifornia,Davis,
MihaiCicotti BattelleMemorialInstitute,Geneva, CA,USA
Switzerland
RalfHa¨nel FederalBiologicalResearchCentrefor
ThomasJ.Class PTRLEuropeGmbH,Ulm,Germany AgricultureandForestry(BBA),Braunschweig,Germany
GeorgeP.Cobb TexasTechUniversity,Lubbock,TX, VincentHebert WashingtonStateUniversity,Richland,
USA WA,USA
xliv Listofcontributors
AndrewJ.Hewitt StewartAgriculturalResearch JamesS.LeNoir DuPontCropProtection,Newark,DE,
Services,Macon,MO,USA USA
RichardHoneycutt H.E.R.A.C.,Inc.,Greensboro,NC, YiLin SyngentaCropProtection,Inc.,Greensboro,NC,
USA USA
MitsumasaIkeda KumiaiChemicalIndustryCo.,Ltd, CynthiaLipton Byotix,Inc.,Richmond,CA,USA
Shizuoka,Japan
JosephH.Massey MississippiStateUniversity,
YujiIkemoto NihonNohyakuCo.Ltd,Osaka,Japan Starkville,MS,USA
FujioIshijima HokkoChemicalIndustryCo.Ltd, GregC.Mattern BayerCropScience,Stilwell,KS,
Kanagawa,Japan USA
ScottH.Jackson BASFCorporation,Research JosephP.McClory DuPontCropProtection,Newark,
TrianglePark,NC,USA DE,USA
KathrynM.Jernberg DuPontCropProtection, CarolynMentzer AgrisearchIncorporated,Thurmont,
Newark,DE,USA MD,USA
WilliamW.John DuPontCropProtection,Stine D.LarryMerricks AgrisearchIncorporated,Frederick,
HaskellResearchCenter,Newark,DE,USA MD,USA
SetsukoKatsurada SankyoCo.Ltd,Shiga,Japan SeanM.Moore BayerCropScience,Stilwell,KS,USA
GuentherKempe Landesuntersuchungsanstalt, KoujiNakamura SaitamaPrefectureAgricultureand
Chemnitz,Germany ForestryResearchCenter,Kuki,Japan
DouglasE.Kiehl EliLillyandCompany,Greenfield, KazuoOgura AgriculturalChemicalsInspection
IN,USA Station,Tokyo,Japan
PhilipJamesKijak USFoodandDrugAdministration, JeffOld InvereskResearch,Tranent,UK
Laurel,MD,USA
TakeoOtsuka SankyoCo.Ltd,Shiga,Japan
HirokoKobayashi ResearchInstituteofJapanPlant
ProtectionAssociation,Ibaraki,Japan JohnC.Peterson EnglarFoodLaboratories,Inc.,
MosesLake,WA,USA
AlexanderJ.Krynitsky USEnvironmentalProtection
Agency,EPAEnvironmentalScienceCenter,FortMeade, BethM.Polakoff Exponent,Inc.,Washington,DC,
MD,USA USA
ChungK.Lam BayerCropScience,Stilwell,KS,USA CharlesR.Powley DuPontCropProtection,Newark,
DE,USA
StevenJ.Lehotay USDAAgriculturalResearch
Service,EasternRegionalResearchCenter,Wyndmoor, RobinS.Readnour EliLillyandCompany,Greenfield,
PA,USA IN,USA
WilliamM.Leimkuehler BayerCropScience,Stilwell, ValerieB.Reeves USFoodandDrugAdministration,
KS,USA Rockville,MD,USA
Listofcontributors xlv
StewartL.Reynolds CentralScienceLaboratory,York, GuyR.Stehly USGS,BiologicalResourcesDivision,
UK LaCrosse,WI,USA
NeilJ.Robinson Syngenta,Bracknell,UK ShigejiSugimoto NipponSodaCo.Ltd,Tokyo,Japan
JanineE.Rose PTRLWest,Inc.,Hercules,CA,USA ManabuToujigamori SankyoCo.Ltd,Shiga,Japan
LouisRusso BayerCropScience,KansasCity,MO, YasuhiroTsujino SankyoCo.Ltd,Shiga,Japan
USA
MichaelP.Turberg EliLillyandCompany,Greenfield,
MarikoSabi SankyoCo.Ltd,Shiga,Japan IN,USA
TakashiUeda SankyoCo.Ltd,Shiga,Japan
ShingoSadakane SankyoCo.Ltd,Shiga,Japan
MasakoUeji NationalInstituteforAgro-Environmental
ManasiSaha BASFCorporation,ResearchTriangle
Sciences,Tsukuba,Japan
Park,NC,USA
NoriharuUmetsu OtsukaChemicalCo.Ltd,Naruto,
TakashiSaito SankyoCo.Ltd,Shiga,Japan
Japan
YoshihiroSaito KumiaiChemicalIndustryCo.,Ltd,
DavidL.Valcore DowAgroSciences,Indianapolis,IN,
Shizuoka,Japan
USA
ThomasSchreier ValentUSACorporation,Dublin,
ChantelVanBellinghan Monsanto,Brussels,Belgium
CA,USA
MichaelF.Wilson CentralScienceLaboratory,York,
JamesN.Seiber WesternRegionalResearchCenter,
UK
USDAAgriculturalResearchService,Albany,CA,USA
JamesE.Woodrow UniversityofNevada,Reno,NV,
RobertJ.Seymour BayerCropScience,Research USA
TrianglePark,NC,USA
AkiraYagi KumiaiChemicalIndustryCo.,Ltd,
GuominShan DowAgroSciencesLLC,Indianapolis, Shizuoka,Japan
IN,USA
KatsuraYagi OtsukaChemicalCo.Ltd,Naruto,
WeilinL.Shelver USDepartmentofAgriculture, Japan
AgriculturalResearchService,Fargo,ND,USA
HisayoshiYamagishi ResearchInstituteofJapanPlant
JohannesSiebers FederalBiologicalResearchCentre ProtectionAssociation,Ibaraki,Japan
forAgricultureandForestry(BBA),Braunschweig,
Germany HirokiYamamoto ShimaneUniversity,Matsue,
Japan
DavidJ.Smith USDepartmentofAgriculture,
AgriculturalResearchService,Fargo,ND,USA RobertA.Yokley SyngentaCropProtection,Inc.,
Greensboro,NC,USA
CraigA.Smitley Scynexis,ResearchTrianglePark,
NC,USA SabrinaX.Zhao PfizerInc.,Groton,CT,USA
LisaD.Spurlock-Brouwer EliLillyandCompany, EberhardZietz InstitutFresenius,Taunusstein,
Greenfield,IN,USA Germany
Contents of Volume 1
Preface xli
Listofcontributors xliii
Introduction
JamesN.Seiber 1
Introduction 1
Relationshipofpesticideresidueanalysis,regulation,andriskassessment 4
Whodoesresidueanalysisandwhy 5
Challenges 7
References 8
Regulatoryguidanceandscientificconsiderationforresidue
analyticalmethoddevelopmentandvalidation
Assessmentofresidueanalyticalmethodsforcrops,food,feed,and
environmentalsamples:theapproachoftheEuropeanUnion
JohannesSiebersandRalfHa¨nel 13
Introduction 13
Legalbackground 14
General 14
CouncilDirective91/414/EEC 14
LegislationrelatedtoMRLs 15
Legislationrelatedtoresidueslimitsforsoil,water,andair 18
Provisionsforresidueanalyticalmethods 18
Evaluationofthesubmittedmethods 20
Institutionalbackground 20
Validationparameters 21
Requirementsforpost-registrationandmonitoring(enforcement)methods 23
Generalrequirements 23
Specificrequirements 27
Requirementsfordatagenerationmethods 31
Generalrequirements 32
Specificrequirements 33
Availabilityofanalyticalmethods 34
Perspectives 35
Acknowledgement 36
References 36
v
vi ContentsofVolume1
Regulatoryconsiderationsforresidueanalysisandmethodsoncropsandfood:
theapproachofJapan
KazuoOgura,HisayoshiYamagishiandShigejiSugimoto 38
Background 38
Plantmetabolismstudies 40
Residuestudiesoncrops 41
Residueanalyticalmethod 41
Preferredmethodologyforconductingsupervisedfieldtrials 41
Fielddata(fieldreport)presentation 46
Extrapolationamongtheformulationtypes 47
Residuedefinition 47
MarketbasketsurveyinJapan 48
Conclusion 49
Furtherreading 49
Generalapproachesforresidueanalyticalmethoddevelopmentandvalidation
ThomasJ.ClassandReinerBacher 50
Introduction 50
Approachestoanalyticalmethoddevelopment 51
Propertiesoftheanalyte(s) 51
Functionalgroupsoftheanalyte(s) 52
Propertiesofthesamplematerial 53
Availabilityandpracticalityofanalyticalinstrumentation 54
Considerationoftime,throughput,ruggednessandquality 54
Practicalexamples 55
Extendingthescopeofthemulti-residuemethodDFGS19 55
Whatcangowrong? 57
Beyondthelimits 58
References 58
Bestpracticesinestablishingdetectionandquantificationlimitsforpesticide
residuesinfoods
JohannesCorley 59
Introduction 59
Definitions 61
MethodsfordefiningLODandLOQ 63
IUPACmethod 63
Propagationoferrorsmethod 66
Hubaux–Vosapproach 67
Two-stepapproach(proposedbytheUSEPA) 67
RMSEmethod 68
Thet s method 70
99 LLMV
Confirmation 71
Representativedata 72
Conclusions 73
Acknowledgements 74
References 74