德国农药残留标准.pdf

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1、November 1999(C:Eigene DateienS&PPestizideL 00.00-34-englischJuni2002.docCollection of Official Methods under Article 35 of the German Federal Food Act00.00LAnalysis of Foodstuffs Modular Multiple Analytical Method for the Determination of PesticideResidues in Foodstuffs(Extended and Revised Version

2、 of the DFG Method S 19)341 Aim and scopeThis official method specifies a procedure for the residueanalysis of organochlorine,organophosphorus,nitrogen-containing and other pesticides in foodstuffs.It reflectsthe DFG Multiresidue Method S 19 in its original 1 aswell as in its modified version 2 and

3、affords a muchbroader field of application.2DefinitionThe term pesticide residue content of a foodstuff is de-fined as the content determined by using this method.Itis expressed in mg/kg.3IntroductionThe Multiresidue Method S 19 of the DFG Manual in-cluding the Cleanup Method 6(gel chromatographiccl

4、eanup)3 has proved to be used successfully in manylaboratories because of its broad applicability for the gaschromatographic determination of pesticide residues infoodstuffs.It was also included into the respective Euro-pean Standards 4,5.In the meantime a modification of the extraction and par-titi

5、on step has been implemented 2.It requires less ex-perimental efforts and manages without dichloromethanewhich is undesirable for toxicological and ecological rea-sons.As the results from validation studies demonstrate,this modification has the same broad field of applicationas the original DFG Meth

6、od S 19,and it is included inthe German Collection of Official Methods as Method L00.00-34.In both cases the entire method consists of four stages:extraction and partition,gel permeation chromatography(GPC),mini silica gel column chromatography,and gaschromatographic determination.Except for the cen

7、tralGPC,several variations occur on each stage dependingon the kind of the sample material and the residues to beanalyzed.They can be combined with each other in a va-riety of ways according to the requirements.This is difficult to realize in the references published pre-viously.However,every labora

8、tory analyzing pesticideresidues is constrained to provide a detailed descriptionof the specific analytical conditions used together with itsresults.This is easier to see when the individual stagesare presented just as“modules”which can be listed inthe particular test report.At the same time this fa

9、cilitatesthe course of work in the residue laboratory,when it canbe clearly specified with which modules an individualsample has to be processed.If the analyst,however,in-troduces any deviations,this should be recorded in thetest report.In addition,this modular form facilitates the introductionof ne

10、w and approved techniques in the future,e.g.theHPLC as a module for cleanup or for determination pur-poses.For all these reasons,the Analytical Working Group ofthe Pesticides Commission at BgVV publishes here anextended version of the latest available and reliablemethodology.It takes the mentioned p

11、oints into accountand makes the modular structure transparent.Sinceeach module is completely described thus avoidingcomplicating cross-references,the reiteration of severaltexts had to be accepted.4Sampling4.1 Sampling study planThe sampling procedure for the official control of resi-dues of pestici

12、des on and in fruit and vegetables has tocomply with the provision given in L 29.00-1 in the Ger-man Collection of Official Methods.4.2 Sample preparationReference is given to the recommendations of the DFGManual 6 and of the Pesticide Working Group of“Le-bensmittelchemische Gesellschaft”(GDCh)7.5Pr

13、ocedureThe extraction and liquid/liquid partition steps are de-scribed in the Modules E.The extracts are cleaned up bygel permeation chromatography(Module GPC)and ad-ditionally if required on a small silica gel column(Module C).The residue-containing eluate from the GPC step isevaporated and is anal

14、yzed by gas chromatography withthe flame photometric detector(FPD)or a mass spec-trometric detector(MS),under appropriate conditionsalso with a nitrogen/phosphorus detector(NPD)(Mod-ules D 2 to D 4).For gas chromatography with the electron capture de-tector(ECD)(Module D 1),the GPC eluate requires a

15、nadditional cleanup on a small silica gel column.The Tables 1 to 4 schedule a short description of themodules,notes for their application and several exam-ples.The water contents of important foodstuffs arelisted in Table A 1 in the Appendix.Plant foodstuffs andtheir fat content,which determines the

16、 extraction moduleto be used,are compiled in Table A 2.The individual modules are described in the working pro-cedures in this method.Page 2 November 1999 L 00.0034Official Methods under Article 35Table 1:Extraction(E)ModuleDescriptionUse/ApplicationExamplesE 1Extraction and subsequentliquid/liquid

17、partition 2Plant material and foodstuffswith a water content exceeding 70 g/100 gand a fat content below 2.5 g/100 gFruit,vegetables,juicesE 2Extraction and subsequentliquid/liquid partition 2Plant material and foodstuffswith a water content below 70 g/100 g and afat content below 2.5 g/100 gCereals

18、 and cereal prod-ucts,spices,fruit powderE 3Extraction and subsequentliquid/liquid partition 2Plant material and foodstuffswith a water content exceeding 70 g/100 g,a fat content below 2.5 g/100 g and a highacid contentFruit,tomatoesE 4Two-stage extraction andliquid/liquid partition 1Plant material

19、and foodstuffswith a water content exceeding 70 g/100 gand a fat content below 2.5 g/100 gFruit,vegetables,juicesE 5Two-stage extraction andliquid/liquid partition 1Plant material and foodstuffswith a water content below 70 g/100 g and afat content below 2.5 g/100 gCereals and cereal prod-ucts,spice

20、s,fruit powderE 6Dissolving fat in GPC elutingmixturePlant and animal fats(containing no water)Edible fats and oils,es-sential oilsE 7Extraction in the presence oflarge amounts of fat 8Plant and animal fats with low water content,if the limit of determination is not sufficientwith E 6,and dry food w

21、ith a fat content exceeding2.5 g/100 g Edible fats and oils,wheatand rye germs,oats,nuts,oil seedE 8Extraction of fat with hex-ane/acetone 9Fat-containing foodstuffs with high watercontentMeat,fish,cheeseE 9Accelerated solvent extraction(ASE)Plant material and foodstuffs with a watercontent below 20

22、 g/100 g and a fat contentbelow 2.5 g/100 gTea,cereals and cerealproducts,spicesTable 2:Gel permeation chromatographyModuleDescriptionUse/ApplicationExamplesGPCGel permeation chromatographyExtract from E 1 to E 9All samplesTable 3:Cleanup(C)ModuleDescriptionUse/ApplicationExamplesC 1Column chromatog

23、raphy on asmall silica gel columnGPC eluate,PCB residues not expectedC 2Column chromatography on asmall silica gel columnGPC eluate,PCB residues expectedAnimal fatsTable 4:Detection(D)ModuleDescriptionUse/ApplicationExamplesD 1Gas chromatography with ECDEluate from C 1 or C 2Organochlorine com-pound

24、s,pyrethroids,PCBD 2Gas chromatography with FPDGPC eluate or eluate from C 1 or C 2Organophosphorus andsulfur-containing com-poundsD 3Gas chromatography with NPDGPC eluate or eluate from C 1 or C 2Organophosphorus andnitrogen-containing com-poundsD 4Gas chromatography with MSGPC eluate or eluate fro

25、m C 1 or C 2Compounds containingnitrogen,compounds notdetectable with D 1 to D 3Official Methods under Article 35L 00.0034 November 1999 page 36Evaluation6.1Identification and confirmationIn multiresidue analysis an analyte is identified by itsrelative retention time,e.g.relative to aldrin when usin

26、gan ECD or relative to parathion or chlorpyrifos when us-ing a FPD and a NPD.Such relative retention times aretaken from corresponding lists for the columns used.Further evidence for the identity of an analyte is providedby the selectivity of the different detectors(modules D 1to D 3),by its elution

27、 behaviour during column chroma-tography(modules C 1 and C 2)and in some caseseven by the peak form in a gas chromatogram.In a spe-cific analysis for only some individual analytes,their re-tention times are compared directly with the corre-sponding retention times of the analytes from standardsoluti

28、ons.As a rule,a confirmatory gas chromatographic meas-urement is performed with a capillary column of differentpolarity and/or a different detector.The mass selectivedetector MS(module D 4)is especially suitable for theconfirmation of results.Confirmation of the identity of an analyte should be per-

29、formed particularly in those cases in which it would ap-pear that a maximum residue limit(MRL)has been ex-ceeded or in which a compound seems to be present,which is not to expected in the sample analyzed.6.2CalculationThe residue,WR in mg/kg,of an identified analyte is cal-culated using the sample e

30、quivalent CEx from modules E,the dilution factors FGPC and FC from modules GPC andC,respectively,and the concentration CA from modulesD.The following equation is used:CAWR =FGPC FCCExwhere:CAis the concentration of the identified analyte in the sample test solution frommodules D,in g/mLCExis the sam

31、ple equivalent in the extract from modules E,in g/mLFGPCis the dilution factor(module GPC)FCis the dilution factor(modules C)6.3 Reliability of the methodThe recoveries from untreated control samples of a widevariety of analytical materials of plant and animal originfortified with the analytes at le

32、vels of 0.01 to 1 mg/kggenerally ranged from 70 to 110%.Details on collaborative studies determining the precisionare given in Table A 4 in the Appendix.The data wasacquired in accordance with ISO 5725:1994 and maynot be applicable to analyte concentration ranges andmatrices other than as given in T

33、able A 4 10.7Test reportThe test report shall contain a reference to this officialmethod and at least the following information:Kind,origin and description of the sampleType and date of samplingDate of receipt of sample in the laboratory and date oftestEnumeration of the modules and any particular p

34、ointsobserved in course of the test The analytical resultsReasons for any deviation from this official method8Explanations and notesReference is made to the explanations given in the intro-ductory part of the Collection of Official Methods.This extended,modular version was outlined by R.-D.Weeren an

35、d S.Pelz(Labor Dr.Specht&Partner,Ham-burg)and was recommended for inclusion into the Ger-man Collection of Official Methods after detailed discus-sions in the Analytical Working Group of the PesticidesCommission at BgVV.This translation of the method L00.00-34 was drafted by B.Walker,H.-P.Thier and

36、J.Kirchhoff.9References1DFG,Deutsche Forschungsgemeinschaft:Man-ual of Pesticide Residue Analysis,Method S 19.VCH Verlagsgesellschaft Weinheim,Vol.1(1987),383400;Vol.2(1992),3173222Specht W.,Pelz,S.,Gilsbach,W.:Gaschromato-graphic determination of pesticide residues afterclean-up by gel permeation c

37、hromatography andmini-silica gel-column chromatography.6.Comm.:Replacement of dichloromethane byethyl acetate/cyclohexane in liquid-liquid partitionand simplified conditions for extraction and liquid-liquid partition,Fresenius J.Anal.Chem.353,183190(1995)3DFG,Deutsche Forschungsgemeinschaft:Man-ual

38、of Pesticide Residue Analysis,Cleanup Me-thod 6.VCH Verlagsgesellschaft Weinheim,Vol.1(1987),7578;Vol.2(1992);31364European Standard EN 1528-3:1996,Fatty food Determination of pesticides and polychlorinatedbiphenyls(PCBs)Part 3:Clean-up methods,Method G5European Standard EN 12393-2:1998,Non-fattyfoo

39、ds Multiresidue methods for the gas chro-matographic determination of pesticide residues Part 2:Methods for extraction and clean-up,Me-thod N6DFG,Deutsche Forschungsgemeinschaft:Man-ual of Pesticide Residue Analysis,Preparation ofSamples.VCH Verlagsgesellschaft Weinheim,Vol.1(1987),17207Arbeitsgrupp

40、e“Pestizide”:5.Empfehlung.Kriteri-en zur Vorbereitung von Proben pflanzlicher Le-bensmittel fr die Rckstandsanalytik von Pflan-zenschutz-und Schdlingsbekmpfungsmit-teln,Lebensmittelchemie 49,4042(1995)8DFG,Deutsche Forschungsgemeinschaft:Man-ual of Pesticide Residue Analysis,Cleanup Me-thod 5.VCH Ve

41、rlagsgesellschaft Weinheim,Vol.1(1987),71749Ernst,W.,Schaefer,R.G.,Goerke,H.,Eder,G.:Aufarbeitung von Meerestieren fr die Bestim-mung von PCB,DDT,DDE,DDD,-HCH undPage 4 November 1999 L 00.0034Official Methods under Article 35HCB,Fresenius Z.Anal.Chem.272,358363(1974)10European Commission(1998):bcr i

42、nformation;report EUR 18639 EN;“Intercomparison study oftwo multiresidue methods for the enforcement ofEU MRLs for pesticides in fruit,vegetables andgrain”,ISSN 1018-5593Official Methods under Article 35L 00.0034 November 1999 page 5MODULE E 1 Extraction and subsequent liquid/liquid partition for ma

43、terials with awater contentexceeding 70 g/100 g and a fat content below 2.5 g/100 g1Outline The sample is extracted with acetone,after addition ofwater,depending on the natural water content of thematerial,in order to ensure an acetone/water ratio of 2+1(v/v)during the extraction.For liquid/liquid p

44、artitioning,sodium chloride and a mix-ture of cyclohexane and ethyl acetate are added to thehomogenate.The mixture is again intensively mixed andallowed to stand until the phases separate.An aliquotportion of the organic phase is dried with sodium sulfateand concentrated.To the residue obtained,ethy

45、l acetateis added followed by the same volume of cyclohexane.Remaining water is eliminated with a mixture of sodiumsulfate and sodium chloride and the solution is filtered.The extract is used for cleanup by gel permeation chro-matography(module GPC).2Reagents2.1Sodium chloride,p.a.2.2Sodium sulfate,

46、p.a.,anhydrous,powder,heated at 550 C for at least 2 h2.3Salt mixture:sodium sulfate+sodium chloride1:1(w/w)2.4Cotton wool,extracted exhaustively with ace-tone2.5Acetone,for residue analysis2.6Water,bi-distilled or equivalent 2.7Cyclohexane,for residue analysis2.8Ethyl acetate,for residue analysis2.

47、9GPC eluting mixture:cyclohexane+ethyl ace-tate 1:1(v/v);alternatively,redistilled as an azeotropicmixture3Apparatus3.1High-speed homogenizer,e.g.Ultra-Turrax(Janke u.Kunkel,Staufen/Br)3.2Glass jar,500 mL or 750 mL,with a screw caplined with aluminium foil3.3Graduated cylinder,250 mL3.4Round-bottome

48、d flask,500 mL,with groundjoint3.5Glass funnels,45 mm and 100 mm dia.3.6Rotary vacuum evaporator,water bath tem-perature 40 C3.7Volumetric pipette,10 mL3.8Ultrasonic bath3.9Fluted filter paper,6 cm dia.,fast flow rate,ex-tracted exhaustively with acetone3.10Membrane filter,0.45 m pore size,25 mm dia

49、.(e.g.Chromafil,type 0-45/25 organic,Macherey-NagelNr.718 005)Note:Glassware cleaned with detergents must be thor-oughly rinsed with water and acetone.4ProcedureIn a portion of the material,determine the water contentin g/100 g.As an alternative,take the approximate watercontent from Table A 1 in th

50、e Appendix or from a litera-ture source.As the test portion,weigh 25 to 100 g(mA)of the mate-rial having a water content of x g/100 g into a glass jar.Then add sufficient water to adjust the total water pres-ent to 100 g.The amount of water mW to be added iscalculated as follows:mW=100 mA x/100.Next