https://ebookmass.com/product/analytical-methods-for-foodsafety-by-mass-spectrometry-volume-i-pesticides-guo-fang-
Instant digital products (PDF, ePub, MOBI) ready for you
Download now and discover formats that fit your needs...
Analytical Methods for Food Safety by Mass Spectrometry: Volume II Veterinary Drugs Guo-Fang Pang
https://ebookmass.com/product/analytical-methods-for-food-safety-bymass-spectrometry-volume-ii-veterinary-drugs-guo-fang-pang/
ebookmass.com
Applications in High Resolution Mass Spectrometry: Food Safety and Pesticide Residue Analysis 1st Edition RomeroGonz Lez
https://ebookmass.com/product/applications-in-high-resolution-massspectrometry-food-safety-and-pesticide-residue-analysis-1st-editionromero-gonz-lez/
ebookmass.com
Introduction to Spatial Mapping of Biomolecules by Imaging Mass Spectrometry Bindesh Shrestha
https://ebookmass.com/product/introduction-to-spatial-mapping-ofbiomolecules-by-imaging-mass-spectrometry-bindesh-shrestha/
ebookmass.com
(eTextbook PDF) for Research Methods: From Theory to Practice by
Ben Gorvine
https://ebookmass.com/product/etextbook-pdf-for-research-methods-fromtheory-to-practice-by-ben-gorvine/
ebookmass.com
Spring Awakened: A Wolf Shifter Paranormal Romance (Season Shifters Book 4) Kimberly Quay
https://ebookmass.com/product/spring-awakened-a-wolf-shifterparanormal-romance-season-shifters-book-4-kimberly-quay/
ebookmass.com
The life of John Worth Kern Claude G. Bowers
https://ebookmass.com/product/the-life-of-john-worth-kern-claude-gbowers/
ebookmass.com
UNCONVENTIONAL OILSEEDS AND OIL SOURCES 1st Edition
Abdalbasit Adam Mariod Alnadif
https://ebookmass.com/product/unconventional-oilseeds-and-oilsources-1st-edition-abdalbasit-adam-mariod-alnadif/
ebookmass.com
Feel Good Smoothies Sandra Wu
https://ebookmass.com/product/feel-good-smoothies-sandra-wu/
ebookmass.com
Human geography 10th Edition Michael Mercier
https://ebookmass.com/product/human-geography-10th-edition-michaelmercier/
ebookmass.com
Becoming Qualitative Researchers: An Introduction 5th Edition – Ebook PDF Version
https://ebookmass.com/product/becoming-qualitative-researchers-anintroduction-5th-edition-ebook-pdf-version/
ebookmass.com
AnalyticalMethods forFoodSafetybyMass Spectrometry
VolumeIPesticides
Guo-FangPang
Academician,ChineseAcademyofEngineering,Beijing,China
ChairmanoftheAcademicCommitteeandaChiefScientistofBeijing AdvancedInnovationCenterforFoodNutritionandHumanHealth, Beijing,China
AcademicPressisanimprintofElsevier 125LondonWall,LondonEC2Y5AS,UnitedKingdom 525BStreet,Suite1650,SanDiego,CA92101,UnitedStates 50HampshireStreet,5thFloor,Cambridge,MA02139,UnitedStates TheBoulevard,LangfordLane,Kidlington,OxfordOX51GB,UnitedKingdom
Copyright © 2018ChemicalIndustryPress.
PublishedbyElsevierInc.underanexclusivelicensewithChemicalIndustryPress.
Nopartofthispublicationmaybereproducedortransmittedinanyformorbyanymeans, electronicormechanical,includingphotocopying,recording,oranyinformationstorageand retrievalsystem,withoutpermissioninwritingfromthepublisher.Detailsonhowtoseek permission,furtherinformationaboutthePublisher’spermissionspoliciesandour arrangementswithorganizationssuchastheCopyrightClearanceCenterandtheCopyright LicensingAgency,canbefoundatourwebsite: www.elsevier.com/permissions.
Thisbookandtheindividualcontributionscontainedinitareprotectedundercopyrightbythe Publisher(otherthanasmaybenotedherein).
Notices
Knowledgeandbestpracticeinthisfieldareconstantlychanging.Asnewresearchand experiencebroadenourunderstanding,changesinresearchmethods,professionalpractices, ormedicaltreatmentmaybecomenecessary.
Practitionersandresearchersmustalwaysrelyontheirownexperienceandknowledgein evaluatingandusinganyinformation,methods,compounds,orexperimentsdescribedherein. Inusingsuchinformationormethodstheyshouldbemindfuloftheirownsafetyandthesafety ofothers,includingpartiesforwhomtheyhaveaprofessionalresponsibility.
Tothefullestextentofthelaw,neitherthePublishernortheauthors,contributors,oreditors, assumeanyliabilityforanyinjuryand/ordamagetopersonsorpropertyasamatterofproducts liability,negligenceorotherwise,orfromanyuseoroperationofanymethods,products, instructions,orideascontainedinthematerialherein.
LibraryofCongressCataloging-in-PublicationData
AcatalogrecordforthisbookisavailablefromtheLibraryofCongress
BritishLibraryCataloguing-in-PublicationData
AcataloguerecordforthisbookisavailablefromtheBritishLibrary
ISBN978-0-12-814167-0
ForinformationonallAcademicPresspublicationsvisitour websiteat https://www.elsevier.com/books-and-journals
Publisher: AndreGerhardWolff
AcquisitionEditor: PatriciaOsborn
EditorialProjectManager: JaclynTruesdell
ProductionProjectManager: PaulPrasadChandramohan
CoverDesigner: GregHarris
TypesetbySPiGlobal,India
MainResearchers/Editorsxiii
1.Introduction 1
1.1Insecticides 1
1.1.1OrganophosphateInsecticides1 1.1.2CarbamateInsecticides2
1.1.3OrganochlorineInsecticides2
1.1.4PyrethroidInsecticides2
1.1.5NeonicotinoidInsecticides2
1.2Herbicides 3
1.2.1PhenolicHerbicides3
1.2.2PhenoxyAcidHerbicides3
1.2.3BenzoicAcidHerbicides4
1.2.4DiphenylEtherHerbicides4
1.2.5DinitroanilineHerbicides4
1.2.6AmideHerbicides4
1.2.7CarbamateHerbicides5
1.2.8ThiocarbamateHerbicides5
1.2.9UreaHerbicides5
1.2.10SulfonylureaHerbicides5
1.2.11S-TriazineHerbicides5 1.2.12QuaternaryAmmoniumsHerbicides6
1.2.13OrganophosphateHerbicides6
1.2.14OtherHerbicides6 1.3Bactericides 6
1.3.1TriazoleBactericides7 1.3.2AmideBactericides7
1.3.3PyridinamineBactericides7 1.3.4StrobinBactericides7
1.3.5OxazoBactericides8 1.3.6PyrroleBactericides8
1.3.7AminoAcidBactericides8 1.3.8DerivantsofCinnamicAcid8 1.3.9Others8
1.4PesticidesBannedintheWorld 8
1.4.1PesticidesBannedinChina8
1.4.2PesticidesBannedinJapan9 1.4.3PesticidesBannedinEuropeanUnion9
2.AnalyticalMethodsfor793PesticidesandRelated ChemicalResiduesinProductsofPlantOrigin 11
2.1Determinationof512PesticidesandRelatedChemicalResidues inFruitJuiceandWine:LC-MS-MSMethod(GB/T23206-2008) 11
2.1.1Scope11
2.1.2Principle11
2.1.3ReagentsandMaterials11
2.1.4Apparatus21
2.1.5SamplePretreatment21
2.1.6Determination22
2.1.7Precision24 Researchers24
2.2Determinationof500PesticidesandRelatedChemicalResidues inFruitsandVegetables:GC-MSMethod(GB/T19648-2006) 25
2.2.1Scope25
2.2.2Principle25
2.2.3ReagentsandMaterials25
2.2.4Apparatus35
2.2.5SamplePretreatment35
2.2.6GC-MSDetermination36
2.2.7Precision37 Researchers37
2.3Determinationof450PesticidesandRelatedChemicalResidues inFruitsandVegetables:LC-MS-MSMethod (GB/T20769-2008) 37
2.3.1Scope37
2.3.2Principle45
2.3.3ReagentsandMaterials45
2.3.4Apparatus46
2.3.5SamplePretreatment46
2.3.6Determination47
2.3.7Precision49 Researchers50
2.4Determinationof475PesticidesandRelatedChemicalResidues inGrains:GC-MSMethod(GB/T19649-2006) 50
2.4.1Scope50
2.4.2Principle50
2.4.3ReagentsandMaterials50
2.4.4Apparatus59
2.4.5SamplePretreatment59
2.4.6GC-MSMethodDetermination60 2.4.7Precision61 Researchers61
2.5Determinationof486PesticidesandRelatedChemicalResidues inGrains:LC-MS-MSMethod(GB/T20770-2008) 61
2.5.1Scope61
2.5.2Principle69
2.5.3ReagentsandMaterials69
2.5.4Apparatus71
2.5.5SamplePretreatment71
2.5.6Determination72
2.5.7Precision73 Researchers73
2.6Determinationof519PesticidesandRelatedChemical ResiduesinTeaLeaves:GC-MSMethod(GB/T23204-2008) 74
2.6.1Scope74
2.6.2Determinationof490PesticidesandRelatedChemical ResiduesinTea:GC-MSMethod74
2.6.3Determinationof29AcidicHerbicidesinTea: GC-MSMethod85 Researchers91
2.7Determinationof448PesticidesandRelatedChemical ResiduesinTeaLeaves:LC-MS-MSMethod(GB/T23205-2008) 92 2.7.1Scope92
2.7.2Principle92
2.7.3ReagentsandMaterials92
2.7.4Apparatus101
2.7.5SamplePretreatment101
2.7.6Determination102
2.7.7Precision103 Researchers103
2.8Determinationof488PesticidesandRelatedChemical ResiduesinMulberryTwig,Honeysuckle,BarbaryWolfberry Fruit,andLotusLeaf:GC-MSMethod(GB/T23200-2008) 103
2.8.1Scope103
2.8.2Principle104
2.8.3ReagentsandMaterials104
2.8.4Apparatus113
2.8.5SamplePretreatment113
2.8.6Determination114
2.8.7Precision115 Researchers115
2.9Determinationof413PesticidesandRelatedChemical ResiduesinMulberryTwig,Honeysuckle,BarbaryWolfberry Fruit,andLotusLeaf:LC-MS-MSMethod(GB/T23201-2008) 115
2.9.1Scope115
2.9.2Principle115
2.9.3ReagentsandMaterials116
2.9.4Apparatus123
2.9.5SamplePretreatment123
2.9.6Determination124
2.9.7Precision126 Researchers126
2.10Determinationof503PesticidesandRelatedChemical ResiduesinMushrooms:GC-MSMethod(GB/T23216-2008) 126
2.10.1Scope126
2.10.2Principle126
2.10.3ReagentsandMaterials127
2.10.4Apparatus136
2.10.5SamplePretreatment136
2.10.6Determination137
2.10.7Precision138 Researchers138
2.11Determinationof440PesticidesandRelatedChemical ResiduesinEdibleFungus:LC-MS-MSMethod (GB/T23202-2008) 138
2.11.1Scope138
2.11.2Principle138
2.11.3ReagentsandMaterials146
2.11.4Apparatus147
2.11.5SamplePretreatment147
2.11.6Determination148
2.11.7Precision149 Researchers149
3.AnalyticalMethodsfor790PesticidesandRelated ChemicalResiduesinProductsofAnimalOrigin 151
3.1Determinationof511PesticidesandRelatedChemical ResiduesinMilkandMilkPowder:GC-MSMethod (GB/T23210-2008) 151
3.1.1Scope151
3.1.2Principle151
3.1.3ReagentsandMaterials151
3.1.4Apparatus162
3.1.5SamplePretreatment162
3.1.6Determination163
3.1.7Precision164 Researchers164
3.2Determinationof493PesticidesandRelatedChemical ResiduesinMilkandMilkPowder:LC-MS-MSMethod (GB/T23211-2008) 165
3.2.1Scope165
3.2.2Principle165
3.2.3ReagentsandMaterials165
3.2.4Apparatus175
3.2.5SamplePretreatment175
3.2.6Determination176
3.2.7Precision178 Researchers178
3.3Determinationof485PesticidesandRelatedChemical ResiduesinFugu,Eel,andPrawn:GC-MSMethod (GB/T23207-2008) 179
3.3.1Scope179
3.3.2Principle187
3.3.3ReagentsandMaterials187
3.3.4Apparatus188
3.3.5SamplePretreatment189
3.3.6Determination190
3.3.7Precision191 Researchers191
3.4Determinationof450PesticidesandRelatedChemical ResiduesinFugu,Eel,andPrawn:LC-MS-MSMethod (GB/T23208-2008) 192
3.4.1Scope192
3.4.2Principle200
3.4.3ReagentsandMaterials200
3.4.4Apparatus201
3.4.5SamplePretreatment201
3.4.6Determination203
3.4.7Precision204 Researchers204
3.5Determinationof497PesticidesandRelatedChemical ResiduesinHoney,FruitJuice,andWine:GC-MSMethod (GB/T19426-2006) 204
3.5.1Scope204
3.5.2Principle204
3.5.3ReagentsandMaterials213
3.5.4Apparatus214
3.5.5SamplePretreatment214
3.5.6Determination215
3.5.7Precision216 Researchers217
3.6Determinationof486PesticidesandRelatedChemical ResiduesinHoney:LC-MS-MSMethod(GB/T20771-2008) 217
3.6.1Scope217
3.6.2Principle217
3.6.3ReagentsandMaterials217
3.6.4Apparatus227
3.6.5SamplePretreatment227
3.6.6Determination228
3.6.7Precision232 Researchers232
3.7Determinationof478PesticidesandRelatedChemical ResiduesinAnimalMuscles:GC-MSMethod (GB/T19650-2006) 232
3.7.1Scope232
3.7.2Principle232
3.7.3ReagentsandMaterials232
3.7.4Apparatus242
3.7.5SamplePretreatment242
3.7.6Determination243
3.7.7Precision244 Researchers244
3.8Determinationof461PesticidesandRelatedChemical ResiduesinAnimalMuscles:LC-MS-MSMethod (GB/T20772-2008) 245
3.8.1Scope245
3.8.2Principle253
3.8.3ReagentsandMaterials253
3.8.4Apparatus254
3.8.5SamplePretreatment254
3.8.6Determination256
3.8.7Precision257 Researchers257
4.Determinationof450PesticidesandRelated ChemicalResiduesinDrinkingWater:LC-MS-MS Method(GB/T23214-2008) 259
4.1Scope
4.5.1PreparationofTestSample269
4.5.2Extraction269
4.5.3Clean-up269 4.6Determination
4.6.1LC-MS-MSOperatingCondition269
4.6.2QualitativeDetermination271
4.6.3QuantitativeDetermination271 4.7Precision 272 Researchers272
5.BasicResearchonChromatography-MassSpectroscopy CharacteristicParametersofPesticideandChemical Pollutants 273
5.1MassSpectrometryDataof1200PesticidesandChemical PollutantsDeterminedbyGC-MS,GC-MS-MS,andLC-MS-MS 277
5.1.1RetentionTimes,QuantifierandQualifierIonsof 567PesticidesandChemicalPollutantsDetermined byGC-MS277
5.1.2MonitoringofSelectedIonsfor567Pesticides andChemicalPollutantsDeterminedbyGC-MS311
5.1.3RetentionTime,QuantifierandQualifierIons,and CollisionEnergiesof454PesticidesandChemical PollutantsDeterminedbyGC-MS-MS321
5.1.4MonitoringofSelectedIonsfor454Pesticides andChemicalPollutantsDetermined byGC-MS-MS349
5.1.5RetentionTime,QuantifierandQualifierIons, andCollisionEnergiesof284EnvironmentalPollutants byGC-MS-MS356
5.1.6RetentionTimes,SelectiveIons,andRelativeAbundances ofEndosulfansDeterminedbyGC-NCI-MS374
5.1.7RetentionTimes,QuantifyingandQualifyingIons, DeclusteringPotentials,andCollisionEnergiesof9 EnvironmentalPollutantsDeterminedbyLC-MS-MS375
5.1.8RetentionTimes,QuantifyingandQualifyingIons, Fragmentor,andCollisionEnergiesof569Pesticides andChemicalPollutantsDeterminedbyLC-MS-MS376
5.1.9AccurateMasses,RetentionTimes,ParentIons, andCollisionEnergiesof492PesticidesandChemical PollutantsDeterminedbyLC-TOF-MS410
5.2LinearEquationParametersof1200Pesticidesand ChemicalPollutantsDeterminedbyGC-MS,GC-MS-MS, andLC-MS-MS 457
5.2.1LinearEquations,LinearRanges,andCorrelation Coefficientsof567PesticidesandChemicalPollutants DeterminedbyGC-MS457
5.2.2LinearEquations,LinearRanges,andCorrelation Coefficientsof466PesticidesandChemicalPollutants DeterminedbyGC-MS-MS491
5.2.3LinearEquations,LinearRanges,andCorrelation Coefficientsof284EnvironmentalPollutantsDetermined byGC-MS-MS519
5.2.4LinearEquations,LinearRanges,andCorrelation CoefficientsofEndosulfansDetermined byGC-MS(NCI)536
5.2.5LinearEquations,LinearRanges,andCorrelation Coefficientsof9EnvironmentalPollutantsDetermined byLC-MS-MS537
5.2.6LinearEquations,LinearRanges,andCorrelation Coefficientsof569PesticidesandChemicalPollutants DeterminedbyLC-MS-MS538
5.3GPCAnalyticalParametersofPesticidesandChemical Pollutants 572
5.3.1GPCAnalyticalParametersof744Pesticides andChemicalPollutants572
5.3.2GPCAnalyticalParametersof107Pesticides andChemicalPollutants599
AppendixA:Indexof1039PesticidesandChemicalPollutantsDetermined byGC-MS,GC-MS-MSandLC-MS-MS603
AppendixB:SolventSelectedandConcentrationofMixedStandard SolutionofPesticidesandChemicalPollutants661
AppendixC:PhysicochemicalPropertiesof900Pesticides andChemicalPollutants707
AppendixD:MRMChromatogramsof493Pesticides andRelatedChemicals791 Index857
MainResearchers/Editors
Guo-FangPang
Qiao-YingChang
Chun-LinFan
Yan-ZhongCao
Yong-MingLiu
Preface
Todaymoreandmorerequirementsandrestrictionsarebeingplacedontheresiduesofpesticidesandveterinarydrugsinedibleanimalandplant-derivedagriculturalproductsallovertheworld,andmoreandmorekindsofpesticidesmust becontrolled.Meanwhile,theindexofmaximumresiduelimit(MRL)forpesticidesisgettinglower,sothebarrierstointernationaltradeofedibleagriculturalproductsarebecominghigher.
TheresearchteamofGuo-FangPangtooktheleadinresearchfocusingon thestrategicdevelopmentoffoodsafety.Theymetthechallenge,andaseriesof low-costandhighlyefficientdetectionmethodshavebeenestablished.
Inthefieldofpesticideresiduesdetermination,theauthorsconductedasystematicstudyofthedetectionofmulticlassesandmultitypesofpesticideresiduesindifferentedibleagriculturalproducts,and20high-throughput samplepreparationandanalyticalmethodsweredevelopedforsimultaneous extraction,separation,enrichmentanddeterminationof400–500pesticide residueswithaonce-for-allsamplepreparation.Thesemethodsareapplicable tothesimultaneousdeterminationofmultipesticideresiduesinanimaland plant-derivedagriculturalproducts,suchasfruitjuices,vegetablejuices,fruit wines,fruits,vegetables,cereals,tea,Chinesemedicinalherbs(suchasramulus mori,honeysuckle,Chinesewolfberry,andlotusleaf),ediblefungi(suchas mushrooms),honey,milk,milkpowder,aquaticproducts(suchasglobefish, eel,andprawn),animalmuscletissues,anddrinkingwater.Ahigh-selectivity, high-sensitivity,high-resolution,andhigh-throughputanalysismethodology forthedetectionofmorethan1000pesticideresidueshasbeenestablished. Thesemethodsareconsideredtobetheinternationalleadersinthetypeand quantityofpesticidesthatcanbedetectedsimultaneously.
Inveterinarydrugresiduedetection,theauthorshaveestablished65highselectivity,high-sensitivityveterinarydrugresiduedetectionmethodsforthe determinationof20typesofnearly200commonlyusedveterinarydrugsthat mayberesidualinedibleanimal-derivedagriculturalproducts,andthemethods areapplicabletosampleswithcomplicatedbases,suchasedibleanimaltissue (suchasmuscle,liver,kidney,andfat),milk,milkpowder,beeproducts(such ashoney,royaljelly,anditslyophilizedpowder),aquaticproducts(suchas globefish,eel,andprawn),andanimalurine.
ThisbookisasystemicsummaryoftheresearchofGuo-FangPang’s teamonthetheoryandappliedpracticeofdetectiontechnologyofpesticide residuesoverthepast20years.Theinnovativeresearchachievementsatan
internationallyadvancedlevelinthisfieldarefullydemonstratedinthiswork. Inaddition,theprogressoffoodsafetydetectiontechnologyhasbeenpromoted. Thisismainlyreflectedinthefollowingaspects:
1. High-throughputsamplepretreatmenttechnology:Aseriesoftechnical problemssuchastheextractionofpesticideandveterinarydrugresidues atthelevelofmicrogramsperkilograminvariouscomplexmatrixsamples andtheeffectivepurificationoftheCO-extracteddisruptingchemicalshave beenovercome,andhigh-throughputsamplepreparationandpurification technologyataninternationalleadinglevelhasbeendeveloped.Implementationofthedetectionof400–500pesticideresiduessimultaneouslyusing onesamplepreparationhasbeenachieved.
2. Themostcomprehensivedatabaseavailableofpesticidemassspectrometry hasbeenconstructed:gaschromatography-(tandem)massspectrometryand liquidchromatography-(tandem)massspectrometrycharacteristicsof1000 commonlyusedpesticidesworldwideweresystematicallystudiedandadatabasewithtensofthousandsofmassspectrahasbeenconstructed.Thedatabase canprovideaqualitativeandquantitativebasisandhaslaidthefoundationfor researchanddevelopmentofhigh-throughputdetectiontechnology.
3. Anewtechniqueofgroupdetectionbytimeintervalsusingchromatography andmassspectrometryisproposed:pesticideswithsimilarchemicalpropertiesandretentiontimesaredividedintoseveralgroupsinturn;thus,theselectivityofthemethodcanbeenhanced.Eachgroupofpesticidesisdetected accordingtothepeakorderandthetimeintervals,sotheselectivityofthesensitivityofthemethodscanbeimprovedandthemonitoringrangeexpanded.
Furthermore,academicianPang’steamalsocooperatedfullywithunitsfromthe qualityinspectionsystemofChina,institutionsofhigherlearning,andscientific researchinstitutesforcollaborativeverificationofthereliabilityandapplicability ofthemethods,thusleadingtotheformationofChinesenationalstandards(GB/T seriesstandards).Thesemethodshavebeenwidelyusedinthedetectionofpesticideandveterinarydrugresiduesinedibleanimalandplant-derivedagricultural productsandtheyhavemadeagreatcontributiontotheguaranteeoffoodsafety inChina.Webelievethesemethodswillprovideausefulreferencevalueforedible animalandplant-derivedagriculturalproductsafetydetectionallovertheworld. Thebookissuitableforscientificresearchersintheresiduestestingareas andtechniciansworkinginagriculturalproductstestingandinspection,aswell asteachersandscholarsofhigherlearninginstitutionsastheirreadingmaterial orreferenceliterature.
October10,2017
BriefIntroduction
Foodsafetyisamajorsecurityissuenecessarytoensurethesounddevelopment ofhumansociety.Thewidespreaduseofpesticides,veterinarydrugs,andother agriculturalchemicalshavecontributedtowidespreadcontaminationin agriculturalproducts.Thelong-termconsumptionoffoodwithhighresidues ofpesticidesandveterinarydrugswillcausebothacuteandchronictoxicity inhumansandinduceresistantstrains,thusresultinginallergies,cancer, mutation,andteratogenicity.Inordertoensurehumanhealthandfoodsafety, countriesallovertheworldhaveissuedstrictfoodsafetyandhygienestandards. ThePeople’sRepublicofChina(PRC)hasimplementedstrictmonitoringof pesticideandveterinarydrugresidues,suchasmaximumresiduelimitsfor veterinarydrugsinfoodofanimalorigin(AnnouncementNo.235ofthe MinistryofAgricultureofthePeople’sRepublicofChina)andnationalfood safetystandards:Maximumresiduelimitsforpesticidesinfood(GB27632016).ThecommonlyusedpesticidesandveterinarydrugsapprovedinChina andthemainagriculturalproductsofurbanresidents’dailyconsumptionare almostallcovered.
Thebookisasystematicsummaryofthehigh-throughputchromatographymassspectrometrytechniquefortheanalysisofmultipesticides,veterinary drugs,andotheragriculturalchemicalresiduesinagricultureproductsofplant andanimalorigin.Itstechnicalcharacteristicsaremainlyembodiedinthe simultaneousdeterminationofhundredsofcompounds,aswellaslowcost andhighefficiency.
Thisbookisdividedintotwovolumes.InVolume1,pesticidesandrelated chemicalsareselectedasthemainresearchobject,whilegaschromatographymassspectrometry(GC-MS),gaschromatography-tandemmassspectrometry (GC-MS-MS),andliquidchromatography-tandemmassspectrometry(LC-MSMS)areconcerned.Thisvolumeincludesmorethan20analyticalmethodsfor thehigh-throughputanalysisofmultipesticideresidues,andmorethan1000 pesticidesandrelatedchemicalsinmorethan10kindsofagriculturalproducts anddrinkingwatercanbedetected,and400–500kindsofpesticideresiduescan bedetectedsimultaneouslywiththepretreatmentundertakenjustonce.The methodsfortheanalysisof793pesticidesandrelatedchemicalresiduesin foodsofplantoriginapplicabletofruitjuices,vegetablejuices,fruitwines, fruits,vegetables,cereals,tea,Chinesemedicinalherbs(ramulusmori,honeysuckle,Chinesewolfberry,andlotusleaf),andediblefungi(mushroom)are introducedinPart1;themethodsfortheanalysisof790pesticidesandrelated chemicalresiduesinfoodsofanimaloriginapplicabletohoney,milk,milk
powder,aquaticproducts(globefish,eel,andprawn),andanimalmuscletissues arepresentedinPart2;whilethemethodsfortheanalysisof450pesticidesand relatedchemicalresiduesindrinkingwaterareintroducedinPart3.Furthermore,thethreemajorparameterdatabasesadoptedintheanalysisofmore than1000pesticidesandrelatedchemicalsarealsoincludedinthisvolume: ①chromatography-massspectrometrycharacteristicparametersincluderetentiontime,quantitativeandqualitativeions,fragmentvoltageandcollision energy,etc.; ②performanceparametersofthemethodsincludelinearequation, linearrangeandcorrelationcoefficient,etc.;and ③gelpermeationchromatography(GPC)purificationanalysisparameters.
InVolume2,themethodsfortheanalysisof20species(nearly200kinds)of veterinarydrugresiduesinedibleanimaltissues(muscle,liver,kidney,andfat), dairies(milkandmilkpowder),beeproducts(honey,royaljelly,anditslyophilizedpowder),aquaticproducts(globefish,eel,androastedeel)andanimal urineareselectedasmainsubjectsofstudy.The65analyticalmethodsfor theanalysisofmultiveterinarydrugresiduesaredescribedindifferentchapters bycategory(sulfonamides, β-adrenergicagonists,aminoglycosides,chloramphenicols, β-lactams,macrolides,nitrofurans,anabolicsteroids,nonsteroidal anabolicsteroids,glucocorticoids,fluoroquinolones,tetracyclines,sedatives, pyrazolones,quinoxalines,nitromidazoles,benzimidazoles,levamisole,thioureapyrimidines,andpolyethers),and90%ofthemethodsareLC-MS-MS. Meanwhilethephysicalandchemicalproperties,efficacy,sideeffects,and maximumallowableresiduallimitofallthecompoundsarealsoprovided.
Inshort,thisbookisthesummaryoftheworkoftheauthorteamwho,for morethan20years,engagedintheresearchandpracticeofdetectiontechnologyofpesticidesandveterinarydrugresidues.Thesemethodsfortheanalysis ofpesticidesandveterinarydrugsareinnovativeresearchresultsbasedonthe internationalfrontierofpesticidesandveterinarydrugresidueanalysis,andthe analyticaltechniquesadoptedarenewtechnologieswidelyconcernedinthe fieldofresidueanalysisintheworldtoday.Theperformanceindexesofthe methodscanmeettherequirementsoftheCodexAlimentariusCommission andtheworld’smajordevelopedcountries;meanwhilethemethodsarein conformitywiththedevelopingtrendofinternationalresidueanalysisandthey areadvancedintheworld.Inaddition,themethodsestablishedinthisbookhave becomethecurrenteffectivenationalstandardmethodsinChinaandtheycan beusedasthedetectionbasisofrelevanttestinginstitutionsandthelawbasisof therelevantgovernmentdepartments.Nevertheless,duetothelimitationsofthe level,theremaybeunavoidableerrors.Wewouldkindlyasktheusersofthis publicationtoprovidefeedbacktotheauthorssothatsubsequenteditionsmay beimprovedupon. Guo-FangPang xviii BriefIntroduction
Chapter1
Introduction
Pesticidesarechemicalandbiologicalproductsusedtocontrol,destroy,repel,or attackorganismssuchaspests,mites,eelworms,pathogens,weeds,andmice. Accordingtotheirfunctions,pesticidescanbecategorizedasinsecticides, fungicides,nematocides,molluscicides,bacteriocides,attractants,fumigants, rodenticides,defoliants,desiccants,insectgrowthandplantgrowthregulators, etc.Alternatively,basedonthefunctionalgroupsoftheirmolecularstructures,pesticidescanbecategorizedasinorganicpesticides,organochlorineinsecticides, organophosphatepesticides,carbamatepesticides,triazineherbicides,etc.
Pesticidesareimportantmaterialsinmodernagricultureproductionbecause theyplayakeyroleinpreventingandcontrollinginfectiousdiseasesand enhancingproductionyieldsatharvest.However,thelong-termuseofpesticideshasalsoresultedinsignificantcontaminationofthesoil,theairwe breathe,andtheenvironment.
1.1INSECTICIDES
Insecticidesareusedinagriculture,medicine,industry,andourhomesagainst insectsatalldevelopmentalstages.Manyinsecticidesarealsousedagainsteggs andlarvaeofinsects,suchasomethoate,monocrotophosandfenpropathrin,etc. Insecticidesfallintotwotypes:inorganicandorganic.Inorganicinsecticides arecompoundscontainingarsenic,copper,lead,ormercury.Theyarehighly persistentinterrestrialenvironments,andareslowlydispersedthroughleaching anderosionbywindandwater.Inorganicinsecticidesareusedmuchlessnow thanpreviously,havingbeenwidelyreplacedbysyntheticorganicinsecticides. Organicinsecticidescanbecategorizedasnaturalandsynthetic.Naturalinsecticidesincludebotanicalandbiologicalinsecticides.Therearemanytypesof syntheticorganicinsecticides,includingorganophosphates,carbamates,organochlorines,andpyrethroids.
1.1.1OrganophosphateInsecticides
Thefunctionoforganophosphateinsecticidesistoinhibittheactivityof cholinesteraseofnervetissueininsectsandeventuallytokillthem.Usageof organophosphateinsecticideshasalonghistory.Today,manyorganophosphateinsecticides,includingparathion,dichlorvos,fenitrothion,fenthion, AnalyticalMethodsforFoodSafetybyMassSpectrometry. https://doi.org/10.1016/B978-0-12-814167-0.00001-6
Copyright © 2018ChemicalIndustryPress. PublishedbyElsevierInc.underanexclusivelicensewithChemicalIndustryPress.
cyanofenphos,trichlorfon,tetrachlorvinphos,dimethoate,phorate,phosphamidon,monocrotophos,menazon,pirimiphos-ethyl,diazinon,trichloronate, chlorpyrifos,phoxim,malathion,methamidophos,temephos,fenchlorphos, profenofos,etc.,arestillwidelyused.
1.1.2CarbamateInsecticides
Thehydrogenatomthatconnectswithcarboninacarbamateesterderivativeis substitutedbyanarylgroup.Carbamateinsecticidesarenotusedaswidelyas organophosphateinsecticides,buttheireffectismorerapidandmoreselective. Theseinsecticidesincludecarbaryl,isoprocarb,carbafuran,aldicarb,etc.
1.1.3OrganochlorineInsecticides
Thisgroupofinsecticideswasusedwidelyinagriculturalproductionearlier thanotherinsecticides.Inparticular,theinventionofDDTisconsideredthe beginningofmodernpesticideuse.Theseinsecticideshaveroad-spectrum activityandareverypersistent.Therearetwokindsoforganochlorineinsecticides.Onetypeismadewithbenzene,suchasDDTandhexachlorobenzene;the otherismadewithoutbenzene,suchascyclopentadieneandcamphechlor,etc.
1.1.4PyrethroidInsecticides
Pyrethroidinsecticideswereinventedinthe1970s.Theappearanceofpyrethroidinsecticideschangedthefeaturesofinsecticidesinnotonlyproduction technologyandfarmingpractice,butalsoinpracticesforincreasingproduction. Pyrethroidinsecticidescurrentlyusedarecalled“super-efficiency”insecticides.Theyrequiretheapplicationoflessthan1.5g,oratmost30gper 1000m2,ofland.Thus,withonlyasmallamount,pyrethyroidinsecticides cankillpestsandstimulategrowth,andsohaveamarkedeffectonincreasingproduction.Theymainlyincluderesmethrin,tetramethrin,phenothrin, cyphenothrin,fenpropathrin,permethrin,cypermethrin,deltamethrin,and fenvalerate.
1.1.5NeonicotinoidInsecticides
Neonicotinoidinsecticidesareofhighkillingactivityandattracttheattentionof differentindustriesowingtotheirinfluencesonmanyaspectssuchasthereproductivesystemofpollinatinginsectsandavianaswellastherespiratorysystem ofrats.Neonictonioidinsecticidesareclassifiedasthreegenerationssuch aschloronicotineandthionicotineandfurannicotineincludingimidacloprid, acetamiprid,thiamethoxam,furosemide,fluidoximide,chlorothiazoline,enipramine,thiacloprid,thiamethoxam.In2013,EUannouncedamoratorium ontheuseofthreestapleneonicotinoidinsecticidesforcertaincrops,while
thedraftofthenewregulationproclaimedthebanontheuseofneonicotinoid insecticidesonallthefieldcropsexceptthegreenhousecrops.In2016,officials fromDepartmentofHealthinCanadaconveyedthemessagethattheirFederal PesticidesSupervisoryInstitutionsplannedtoeliminateadisputativeinsecticide-imidacloprid.In2018,Franceannouncedabanontheneonicotinoidinsecticide,whichwouldbeprohibitedfromuseonallthecropsinduetimeincluding onthetreatmentofseeds.Atpresent,therearealreadyliteraturesonthe analyticalmethodsfordeterminationofneonicotinoidinsecticidesinredwine, whitewine,environmentalwater,honeyorangeleaves,fruitsandvegetables, sunflowerseeds,teasoups,pollens,atmosphericparticulatesamples,soilsamplesandhematuria,andthecleanuptechniquesadoptedareSPE,DLLME, solid-liquidextraction,QuEchERS,etc.,whileLC-MS-MSareadoptedmostly.
1.2HERBICIDES
Chemicalherbicidescanincreaseoutputofcropsmarkedlybyselectivelykillingweedsandstimulatinggrowth.Withchemicalherbicides,anincreaseof 10%inoutputcanbeobtainedcomparedtomanualwork.Theemployment ofchemicalherbicidescouldsavetheuseof75–300laborersinthepaddyfield and30–45intheglebe.Theapplicationofchemicalherbicidespromotesgood agriculturalpractices,includingplantingtechniquesandmethods,boosting productionofsoya,corn,wheat,andcotton,buttheirresidueshavebeen detectedonsoya,corn,wheat,rice,andcottonplantsinChina.Thereareseveral kindsofsyntheticherbicides,includingphenolic,phenoxyacid,benzoicacid, diphenylether,dinitroaniline,amide,carbamate,urea,sulfonylurea,s-triazine, quarternaryammonium,organophosphateherbicides,andothers.
1.2.1PhenolicHerbicides
Theearliestappliedinthefield,phenolicherbicidesaresyntheticorganicherbicides.Therearetwotypesbasedonstructuraldifferences.Onegrouphasa substitutedphenolandtheothergrouphasasubstitutedchlorophenolgroup. Allphenolicherbicideshavelowwatersolubilityandhighfatsolubilityand mosthavecontactpoisoningandbadselectivity.Thefunctionofphenolicherbicidesistokillplantsbyinhibitingrespiration.Sodiumpentachlorophenolis themostwidelyused.
1.2.2PhenoxyAcidHerbicides
Themainmolecularstructureofphenoxyacidherbicidescontainsphenoxyacetic acid,phenoxypropionicacid,andaryloxy-phenoxypropionicacid.Mosteffectiveoncaulinesandleaves,thecommoncharacteristicsoftheseherbicides includehighselectivity,broadspectrum,lowdosage,lowcost,andsafety.Phenoxyacidherbicideissafeforhumans,livestock,andtheenvironmentwhen
4 AnalyticalMethodsforFoodSafetybyMassSpectrometry
normaldosagesareused.However,thesynthesisof2,4,5-trichlorophenoxyacetic acid(2,4,5-T)generatesdioxin,whichisastrongteratogen.2,4,5-Tis,therefore, restrictedorbannedinmanycountries.Phenoxyacidherbicidesmainlyinclude 2,4-D,MCPA,diclofop-methyl,andfluazifop-butyl.
1.2.3BenzoicAcidHerbicides
Exceptforchloramben,benzoicacidherbicideshaveactivitybothonleavesand soil.Theynotonlyhaveweedingactivity,butalsohavetheactionofauxin. Benzoicacidherbicidescanbeabsorbedandtransmittedthroughtheroot,stem, andleaves.Benzoicacidherbicidesmainlyincludechlorambenanddicamba.
1.2.4DiphenylEtherHerbicides
Theseherbicideshavelowwatersolubilityandtendtobeadsorbedbysoilcolloid.Theyarehardtoalleviate,andhaveamoderatepersistency.Mostdiphenyl etherherbicidesareusedonsoilbeforeseedingtopreventannualweedingand haveafunctionofcontactpoisoning.Whensubstitutionisattheorthoposition, ithasweedingactivityonlyinillumination,suchaschlornitrofen,polytetramethyleneoxide,bifenox,oxyfluorfen,etc.Mostareusedinthepaddyfields, duetolowpoisonouseffectonfishandshellfish.Diphenyletherherbicides includenitrofen,acifluorfensodium,fomesafen,oxyfluorfen,fluoroglycofen, attackweed,farmaid,lactofen,andchloromethoxynil.
1.2.5DinitroanilineHerbicides
Dinitroanilineherbicideswerescreenedstartingfrom1953.Trifluralin,witha highactivityandselectivity,wassuccessfullyselectedfrom80compoundsin 1959.Sincethen,dinitroanilineherbicideshavebecomeaveryimportantherbicide.Theircommoncharacteristicsarebroadspectrum,highefficiency, tendencytovolatilizeandphotolyze,steadyeffect,andsafety.Theyincludetrifluralin,butralin,pendimethalin,etc.
1.2.6AmideHerbicides
In1956,P.C.Hammreportedthatpethoxamidecouldpreventthegrowthof annualgramineousspeciesandsomebroadleafweeds.Inthesameyear,pethoxamidewaspopularizedbyMonsantoCorporation.Thiswasthebeginningofthe developmentofamideherbicides.Sincethen,amideherbicideshavedeveloped rapidly.Amongthem,propanil,aselectiveherbicidethatwasinventedin1960, isthemostfrequentlyusedamideherbicideinthepaddyfields.Themaincompoundsofamideherbicidesincludepropanil,alachlor,metolachlor,pretilachlor,napropamide,mefluidideanddiflufenican.
1.2.7CarbamateHerbicides
Carbamateherbicideusestartedin1945whenTemplemanandSextondiscoveredtheweedcharacteristicsofpropham.Afterthereportoftheweedingeffect ofchlorprophamin1951,barban,swep,phenmedipham,asulam,desmedipham,andlatifolinineweresynthesizedandutilizedsubsequently.
1.2.8ThiocarbamateHerbicides
Thiocarbamateherbicidesweredevelopedfrom1945whentheStauffeCorporationdiscoveredtheweedingcharacteristicofEPTC.In1960and1961,MonsantoCompanyinventeddiallateandtriallatetopreventwildoatssuccessively. In1965,aJapanesecombinatorialchemistrycompanyproducedthiobencarb,a highlyefficientherbicideforkillingbarnyardgrass.Thiswasagreatadvancementforthiskindofherbicide.Themaincompoundsofthiocarbamateherbicidesincludethiobencarb,molinate,andvernolate.
1.2.9UreaHerbicides
Itwasreportedinthe1940sthatureacompoundscouldrestrainthegrowthof plants,buttheirweedingfunctionwasnotfound.Until1951,whenH.C.Bucha andC.W.Todddiscoveredtheweedingfunctionofmonuron,ureaherbicides hadbeendevelopedgraduallyandbecamepopularinusewithdifferentcompounds.Ureaherbicidesmainlyincludediuron,linuron,andchlortoluron.
1.2.10SulfonylureaHerbicides
Sulfonylureaherbicidesareanewkindofherbicide,whichhasbeendeveloped rapidly,withthehighestweedingfunction.G.Levittin1978andD.W.Finnerty in1979gavetheearliestreportsthatchlorsulfuronpossessedweedingactivity. Fromthenon,thestudyofsulfonylureaherbicidesenteredintoanewera.They representagreatadvancementinthehistoryofherbicides,bringingherbicides intotheeraofsuperefficiency.Sulfonylureaherbicidesmainlyincludechlorsulfuron,metsulfuron-methyl,andtribenuron-methyl.
1.2.11S-TriazineHerbicides
S-Triazineherbicidesweredevelopedfrom1932whenA.Gastetal.foundthe weedingactivityofchlorazineforthefirsttime.Inparticular,afterthehigh weedingeffectofsimazineandtrietazinewasfoundandbroughttoindustrializedproduction,thedevelopmentofs-Triazineherbicidesproceededmore quicklyandtheherbicidebecameoneofthemostimportantmodernherbicides. Todays-Triazineherbicidesstayintheleadintheaspectsofapplicability, selectivity,output,andsale.Thistypeofherbicidemainlyincludessimazine, atrazine,andprometryne.
6 AnalyticalMethodsforFoodSafetybyMassSpectrometry
1.2.12QuaternaryAmmoniumsHerbicides
Synthesizedinthe1950s,theseherbicidesarealsocalledbipyridineherbicides.TheICICompanyisthepioneerinresearchingthebiologicactivity ofbipyridinecompoundsandbroughtthefirstquaternaryammoniumsherbicide,diquat,intoindustrializedproductionin1957.Thesecondvarietywas carriedoutbytheBritishPlantProtec tingCompanyin1958.Afterward,some similarcompoundswerefoundandproduced,butmostofthemhadnolarge output.Quaternaryammoniumsherbicidesmainlyincludeparaquatand diquat.
1.2.13OrganophosphateHerbicides
Theproductionoforganophosphateherbicidesbeganin1958whenUniroyal Companyfoundthefirstorganophosphateherbicide,2,4-DEP.Subsequently, somevarietieswereemployedsuccessivelyforuseondryland,paddyfields, andinfield.Amongthem,glyphosatedrewthemostattentionandwasused mostwidelybecauseofitshighefficiency,broadspectrum,lowleveloftoxicity,lowlevelsofresidualcontamination,andsafetytotheenvironment.There aremanyvarietiesoforganophosphateherbicides,butthemostimportantones arebensulide,amiprophos,2,4-DEP,andglyphosate.
1.2.14OtherHerbicides
Thereareotherherbicidesbesidesthe13describedhere,includingnitrileherbicidecontainingdichlorobenil,ioxynil,ioxynil-octanoateandbromoxynil,aliphaticherbicidecontainingMCA,TCA,anddalapon,imidazolinonesherbicide containingimazaquin,irnazamethabenz,andimazathapyr,cyclohexenoneherbicidecontainingclethodim,cycloxydim,tralkoxydim,sethoxydim,andalloxydim,pyridineherbicidecontainingpicloram,clopyralid,trichlopyr, haloxydine,fluridone,andfluroxypyr,pyrazoleherbicidecontainingpyrazolate,pyrazoxyfen,benzofenap,metazachlor,anddifenzoquat,pyrimidineherbicidecontainingisocil,bromacil,lenacil,andbentazon,quinolinecarboxylic acidsherbicidecontainingquinmeracandquinclorac,andotherheterocyclic herbicidescontainingoxadiazon,dimethazone,andcinmethylin.
1.3BACTERICIDES
Inordertoincreasefoodproduction,itisimportanttopreventdiseasesinadditiontokillinginsectsandclearingweeds.Bactericidesaretheoldestmedicationsinhumanhistoryandtheyincludesulfur,limesulfur,bordeaux mixture,mercurial,anilinopyrimidines,andstrobins.Comparedtoinsecticides andherbicides,bactericideshavefewervarietiesandamorestablemarket.
However,greatadvancementshavebeenmadesincethe1980sinthedevelopmentofbactericidessuchastriazoles,amide,anilinopyrimidines,andstrobins.
1.3.1TriazoleBactericides
TriazolebactericidedrewmuchattentionwhenBayerCompanyproducedtriadimefon,whichisthefirstcommercialbactericidewiththechiralcarbonatom. Currently,therearemorethan40commercialvarietiesoftriazoles.Theycan affecttheformationofthecellwallbyblockingthesynthesisofergosterin inepiphyte.Also,theycanpreventandcuremostharmfuloriginatedepiphytes forcrops.Mostofthetriazolesbactericideshavethecharacteristicsofhigh efficiency,broadspectrum,persistency,strongsystemiceffect,andstereoselectivity.Theymainlyincludetebuconazole,propiconazol,cyprodinil,epoxiconazole,metconazole,andtetraconazole.
1.3.2AmideBactericides
Amidebactericideshaveahistoryofseveraldecadesandhavemorethan30 varieties.Asthespecialmedicamentforpreventingandcuringperonosporales fungal,thiskindofbactericidehasremarkablecapabilitiesofprotecting,curing, anderadicating.Itiswidelyusedinpreventinglateblightoftomatoesandpotatoes.Themaincompoundsofthisbactericideincludemetalaxyl,oxadixyl anchor,benalaxyl,mefloamide,fenhexamid,andethaboxam.
1.3.3PyridinamineBactericides
Pyridinamineisanimportantbactericidedevelopedintheearly1990s.Ithas lowpowerwhenunorganized,butexhibitsastrongpreventioneffectwhenused onhostplants.Itcanpreventpathogeninbreakingtothehostbyrestrainingthe synthesisofmethionineandexudationofcellwall-degradingenzyme.Pyridinaminebactericidesincludepyrimethanil,mepanipyrim,cymoxanil,and diflumetorim.
1.3.4StrobinBactericides
StrobinsarederivedfromthecrudeantibioticstrobilurinsA,whichpossesssterilizationactivity.Strobinshaveauniqueabilitytoblockthesynthesisofcellular ATPbylockingtheelectrontransferbetweencytochromebandc1,rendering theirbactericidalcapacitybyrestrainingthebreathofthemitochondrion.They mainlyincludeazoxystrobin,kresoximmethyl,trifloxystrobin,kresoximmethyl,picoxystrobin,pyraclostrobin,fluoxastrobinand1-octylalcohol. Introduction Chapter 1 7
