SN-T 2575-2010进出口蜂王浆中多种菊酯类农药残留量检测方法

中华人民共和国出入境检验检疫行业标准进出口蜂王浆中多种菊酯类农药残留量检测方法2010-05-27发布I本标准按照GB/T1.1—2009给出的规则起草。本标准由国家认证认可监督管理委员会提出并归口。本标准起草单位：中华人民共和国浙江出入境检验检疫局。1SN/T2575—2010进出口蜂王浆中多种菊酯类农药残留量检测方法酯、氰戊菊酯、溴氰菊酯农药残留量的测定2方法提要试样中的菊酯类农药残留经正已烷十内酮(1上，体积比)混合溶剂提取，用弗罗里硅土固相萃取柱3试剂和材料除另有说明外，所用试剂均为分析理，水为蒸馆水或去离子水。3.4氯化钠。3.5无水硫酸钠：650℃灼烧46,在干燥器内冷却至室温，值于密封质中备用。酯标准物质：纯度大于等于99%,参见附录A。酯标准溶液：分别准确称取适量标准物质，用正己烷配成浓度为100μg/mL的标准储备液。根据需要用正己烷稀释混合至适当浓度的混合标准工作液。3.8弗罗里硅土固相萃取柱：(6ml,lg)或相当者。使用前柱内填约10mm高无水硫酸钠层，用5mL正己烷淋洗活化固相萃取柱。4仪器和设备4.1气相色谱仪：配电子俘获测定器(ECD)。4.2旋涡混合器。4.3离心机：转速大于5000r/min。4.4氮吹仪。4.5旋转蒸发器。25试样制备与保存5.1制样制备取代表性样品约500g,将其用力搅拌均匀，装入洁净容器内，密封，并标明标记。5.2试样保存于一18℃以下保存。在制样过程中，应防止样品受到污染或发生所测物残留量的变化。6测定步骤6.1提取称取2g试样(精确到0.01g)于50mL离心管中，加10mL水涡旋混匀1min,静置5min。加入20mL正己烷十丙酮(1+1,体积比)混合溶剂，涡旋混匀1min,以4000r/min离心3min,将上层有机相转移入浓缩瓶中。残渣中再加入10mL正己烷十丙酮(1+1,体积比)混合溶剂，重复提取一次，合并浓缩瓶中残留物用3mL正己烷溶解洗涤二次，转移到弗罗里硅土固相萃取柱(3.8)中。用5mL正己烷+乙醚(9+1,体积比)混合溶剂洗脱。收集洗脱液于10mL玻璃离心管中，在45℃水浴中用氮吹仪缓缓吹至近干，用正己烷溶解并定容至0.5mL,供气相色谱测定。6.3测定6.3.1气相色谱条件a)色谱柱：HP-50+石英毛细管柱，30m×0.32mm(内径)×0.25μm(膜厚),或相当者；b)色谱柱温度：70℃保持]min,以20℃/min的升温速率升至270℃,保持1min,以20℃/min的升温速率升至280℃,保持10min;c)进样口温度：270℃;d)测定器温度：325℃;e)载气：氮气，纯度99.999%,流速2.0mL/min,尾吹60mL/min;g)进样方式：不分流进样，开阀时间0.75min。6.3.2色谱测定根据样液中各种菊酯含量的情况，选定含量相近的标准工作溶液。标准工作溶液和样液中各种菊酯的响应值均应在仪器测定的线性范围内。标准工作溶液和样液等体积穿插进样测定。在上述色谱条件下联苯菊酯的保留时间约为12.9min;甲氰菊酯的保留时间约为13.6min;氯氟德菊酯的保留时间约为14.0min;氯菊酯各异构体的保留时间约为16.0min、16.2min;氟飘概菊酯各异构体的保留时间约为16.6min、16.7min、16.9min;氯氰菊酯各异构体的保留时间约为17.5min、17.6min、17.8min;氟胺钒菊酯各异构体的保留时间约为18.6min,18.8min;氰戊菊酯各异构体的保留时间约为.19.9min、20.5min;溴氰菊酯的保留时间约为23.0min。标准品的色谱图参见附录B中图B.1。3SN/T2575—2010 (1)农药名称添加浓度/(mg/kg)回收率/%联苯菊酯76.0～91.070.0～97.5甲氰菊酯78.4～10]79.5～10780.4～109氯氟氰菊酯78.8～10878.0～10477.6～104氯菊酯78.3～97.480.8～10876.4～103氟氯氰菊酯71.3～11073.2～1084表1样品的添加浓度及回收率的实验数据(续)农药名称添加浓度/(mg/kg)氯氛菊酯氟胺氰菊酯 领戊菊酯溴氟菊酯5(资料性附录)9种菊酯类农药中英文通用名称、化学分子式、CAS号信息中文通用名称英文通用名称化学分子式联苯菊酯甲氰菊酯氯氟氰菊酯C,H₁₉CIF₂No₃氯菊酯氟氯氛菊酯C₂HGFNO₃氯氛菊酯氟胺氰菊酯氰戊菊酯溴佩菊酯Heltamethrin】6(资料性附录)标准物质的色谱图t/min1——联苯菊酯；2——甲氰菊酯；3——氯氟氰菊酯；4——氯菊酯I;5——氯菊酯Ⅱ6——氟氯氰菊酯I;7——氟氯氰菊酯Ⅱ;8——氟氯氰菊酯Ⅲ;9——氯氰菊酯I;10——氯氰菊酯Ⅱ;11-—氯氰菊酯Ⅲ;12——氟胺氰菊酯I;13-—氟胺氰菊酯Ⅱ;14——氰戊菊酯I;图B.19种菊酯类农药标准物质气相色谱图7ThisstandardwasproposedbyandisunderthechargeofCertificationandAccreditationadministrationofthePeople'sRepublicofChina.ThisstandardwasdraftedbyZhejiangEntry-ExitInspectionandQuarantineBureauofthePeople'sThemaindraftersofthisstandardwereDingHuiying,XieWen,JiangXiaoying,Libo,YaoLiang.8SN/T2575—2010Thisstandardspecifiesthemethodfordeterminationofmultiplepyrethroidresiduesinroyal-jellyforimportandexportbygaschromatography(GC)ThisstandardisapplicabletodeterminationandconfirmationofBifenthrin,Fenpropathrin,Lanbda.Cyhalothrin.Permethrin,Cyfluthrin,Cypermethrin,Fvalerate,Fgnvalerate,Deltamethrinresiduesinroyal-jelly.Multiplepyrethroidresiduesareektractedfromthesamplewithn-hexane-acetone(1+1,V/V).Theextractiscleanedupwithflorisilcartridge.FinallyitisdeterminedbyGC-ECDandquantifiedbyexternalstandardmethod.Unlessotherwisespecified,allreagentsshouldbeanayticallypure,weatershouldberedistilledordei-onized.3.1Ether:HPLCgrade.3.3Acetone:HPLCgrade.3.4Sodiumchloride.3.5Sodiumsulfateanhydrous:Ignitefor4hat650℃,cooltoroomtemperatureindesiccatorandkeepinatightlyclosedcontainer.3.6Bifenthrin,fenpropathrin,lanbda-cyhalothrin,permethrin,cyfluthrin,cypermethrin,fluvalerate,fenvalerate,deltamethrinstandards:purity≥99.0%.SeetableA.1intheannexA.9SN/T2575—20103.7Bifenthrin,fenpropathrin,lanbda-cyhalothrin,permethrin,cyfluthrin,cypermethrin,fluvalerate,fenvalerate,deltamethrinstandardstocksolutions:Accuratelyweighanappropriateamountofstandardsanddissolvewithn-hexanetopreparestandardstocksolutionsof100μg/mL.Accordingtotheconcentrationrequired,pipetteappropriatevolumeoftheabovestandardsolutionsanddilutetoproposedmixworkingsolutionwithn-hexane.3.8FlorisilSPEcartridge(6mL,1g),orequivalent,eluatedwith5mLn-hexanebeforeuse.4ApparatusandEquipments4.1Gaschromatography(GC)tequippedwithelectroncapturedelector(ECD).4.2Vortexmixer.4.3Centrifuge:5000r/min.4.4Nitrogenevaporatorwithheatedbath.4.5Rotaryvacuumevaporator,5PreparationandStorage5.1PreparationoftestsampleTakeappropriately500gofrepresentativeSample,nixedthoroughY.ThenthehomogenizedsampleNote:Inthecourseofthesamplepreparation,precautionshaWeigh2g(accurateto0.01g)ofthetestsampleintoa50mLcentrifugetube.Add10mLdeionizedwater,vortexthesamplefor1minandstandingfor5min,thenadd20mLn-hexane-acetone(1+1,SN/T2575-2010V/V)tothesampleandcentrifugeitfor3min(4000r/min).Transferthesupernatantintoaconcen-tratingbottle.Theresidueisextractedagainwith10mLn-hexane-acetone(1+1,V/V).Mergetheorganicphasesandgentlyevaporatethesolventtonearbydrynessbyrotaryevaporateat45℃.Bereadyforcleanup.Dissolvetheresidueintheconcentratingbottletwicewith3mLn-hexaneandtransferthesolutionintotheflorisilSPEcartridge(3.8).Washthecartridgewithn-hexane-ether(9+1,V/V)inatotalvolumeof10mL.Gatherthewashingliquidinto10mLcentrifugetubeandgentlyevaporateittodrynessbynitrogenevaporatorat45℃.Theresidueisdissolvedin0.5mLn-hexanesolutionandreadyforthedeterminationbyGC.6.3Detectiona)Chromatographiccolumn:HP-50+fusedquartzcapillarycolumn,30m×0.32mm(i.d.)×0.25μmorequivalent;c)Injectionporttemperature:270℃;d)Detectortemperature:325℃:e)Carriergas:Nitrogen(purity>99.999%);Flowrateofcarriergas:2.0mL/min.Flowrateofmakeup:60mL/min;g)Injectionvolume:Splitless.purgetime:0.75min.6.3.2QuantificationAccordingtotheapproximateconcentrationsofmultiplepyrethroidinsamplesolution,selectthestandardworkingsolutionwithsimilarresponsestothatofsamplesolution.Theresponsesoftheanalyteinthestandardworkingsolutionandthesamplesolutionshouldbewithinthelinearrangeof theinstrumentdetection.Thestandardworkingsolutionshouldbeinjectedbeforeandbetweenthe injectionsofsamplesolutionofequalvolume.UndertheaboveGCoperatingcondition,theretentiontimeofBifenthrinisabout12.9min;theretentiontimeofFenpropathrinisabout13.6min;theretentiontimeofLanbda-Cyhalothrinisabout14.0min;theretentiontimesofPermethrinisomerareSN/T2575—2010about16.0minand16.2min;theretentiontimesofCyfuthrinisomerareabout16.6min,16.7mand16.9min;theretentiontimesofCypermethrinisomerareabout17.5min,17.6minand17.8min:theretentiontimesofFluvalerateisomerareabout18.6minand18.8min;theretentiontimesofFenvalerateisomerareabout19.9minand20.5min;theretentiontimeofDeltamethrinisabout23.0min.Forchromatogramofthestandard,seefigureB.1inannexB.Blanktestwillbeconductedaccordingtotheproceduresabovewithoutsampleaddition.6.4CalculationandexpressionofresultCalculationthecontentofmultiplepyrethroidresiduesinthetestsamplebyGCdataprocessororac-cordingtotheformula(1):……………WhereX—theresiduecontentofmultiplepyrethroidinthetestsample,mg/kg;A,—thepeakareaofmultiplepyrethroidinsamplesolution(Ifthepyrethroidhasisomer,peakareaistotalpeakareaofisomer);c;—theconcentrationofmultiplepyrethroidinthestandardworkingsolution,μg/mL;V-thefinalvolumeofthesamplesolution,mL;As₄-thepeakareaofmultiplepyrethroidinthestandardworkingsolution(Ifthepyrethroidha