LC-LCMSD安全食品分析-总体解决方案

LC,LC/MSD安全食品分析－总体解决方案AgilentTechnologies安捷伦科技化学分析事业部

2002年5月04十一月20231第一部分安全食品分析2第一章安全食品分析概述3农药的分类目前在世界上正在使用的农药有超过750余种；在环境和食品中的农残对人类健康造成巨大威胁－－农残分析日益受到重视4农药残留物的分析概述农残分析的三个过程定性定量确认常用农残分析方法气相色谱法-FID,ECD,FPDandNPD薄层层析法液相色谱法-UVandFLD红外光谱法气质联用技术是目前最有效的方法,而且灵敏度很高。色质联用是最有效的农残确认方法液质联用技术5样品/分析的类型样品的制备方法样品的净化和浓缩分析仪器的选型数据分析质量控制(qualitycontrol)结果报告农残分析流程04十一月20236样品和农残的类型样品的类型高含水量的样品低含水量的样品含糖量高的样品含脂肪高的样品环境样品特殊样品分析农残物的类型含卤素的样品有机磷化合物氨基甲酸盐类有机氮化合物有机硫化合物除虫菊酯及拟除虫菊酯04十一月20237样品的制备方法样品的粉碎及均质溶剂萃取样品量:10g,20g,50g,or100g混合及Omni-mixer溶剂丙酮-USFADAcetonitrile-CDFAEthylacetate-Sweden04十一月20238提取方法

可根据待测农药的性质，样本种类和实验室条件选择适当的提取方法。常用方法有以下几种：浸渍，漂洗法：对附着在样本表面的农药有很好的提取效果。振荡法：样本+提取剂，振荡数小时，普遍采用。匀浆，捣碎法：样本放在匀浆杯（捣碎杯）中，加提取剂，快速匀浆几分钟。简便，快速，效果好，普遍采用。索氏提取法：经典提取法，也叫完全提取法，效果好，但时间过长，干扰物质较多。消化法：样本先消化，再用提取液提取，用于不易匀浆，不易捣碎的动物组织样本。其他方法：超声波提取法，吹扫蒸馏法，SFE等。 为提取充分，往往要经三次或多次提取。提取含水量高的样本中时,有时需加无水硫酸钠；提取含糖量高的样本中农药时，或干燥土壤中农药时，需加适量水，能提高提取效果。9样本的净化将样本中待测农药与干扰杂质分离的处理步骤液-液分配法：通常采用极性溶剂与非极性溶剂配成溶剂对进行多次分配，使干扰杂质和待测农药分离，达到净化目的。常用的溶剂对有：乙晴-正己烷（石油醚），二甲基甲酰胺（DMF）-正己烷（石油醚），二甲基亚砜（DMSO）-正己烷（石油醚），丙酮-正己烷，丙酮-二氯甲烷（石油醚），丙酮层需加10倍的2%或4%硫酸钠或氯化钠水溶液。吸附柱层析法：常用的吸附剂有：弗罗里硅土，三氧化二铝（酸性，中性，碱性），硅胶，活性碳，硅燥土。通常吸附剂在用前需经高温烘烤3小时以上活化。70年代后期，微型柱被应用于农药残留检测工作，提高了净化效果。10样本的净化（续）凝结沉淀法：待净化溶液中加入一定的凝结剂（如氯化铵+磷酸），能使溶液中的蛋白质，脂肪，腊质等干扰物沉淀析出，再经离心，可达到净化目的。冷冻法：低温处理样本提取液，使溶液中的蛋白质，脂肪，腊质等干扰物沉淀析出，过滤除掉杂质。其它方法：吹扫蒸馏法，薄层层析法，磺化法，凝胶渗透层析法，离子交换层析法，高压液谱柱净化法。11样品的制备方法(续)样品净化水相分离加NaCl加无水硫酸钠冷冻或吸附溶剂分配所有以上的组合净化-前或后-水相分离反相SPE-C18或活性炭04十一月202312样品的制备方法(续)样品净化凝胶过滤色谱(gelpermeationChromatography)SPEpHadjustmentofsolventextractsPhosphateBuffer(2M,limitvolumeadded)04十一月202313样品的制备方法(续)样品的浓缩K-D样品浓缩器氮气蒸发器开口烧杯(水浴)真空旋转蒸发仪04十一月202314

分析仪器的选择GC/FPD(6890GC)-适合有机磷和有机硫农残化合物GC/ECD(6890GC)-适合有机氯农残化合物GC/NPD(6890GC)-适合有机氮和有机磷化合物GC/MSD

(5973NGC/MSD)通用的分析方法结合NIST98标准谱库和农药谱库可以进行农残化合物的鉴定高灵敏度,高选择性HPLC-柱后衍生用荧光检测(1100HPLCSeries)适合氨基甲酸盐类化合物的分析LC/MS-高灵敏度,高选择性的检测方法04十一月202315食品中的有机物分析总结挥发性极性亲水性的疏水性的挥发的非挥发性液相气相液相气相挥发性有机酸醛类/酮类乙二醇PG,OG,DG酚类化合物抗氧化剂脂肪酸脂溶性维生素三甘油三酯芳香酯多氯联苯多环芳烃C2/C6烃类化合物糖类物质的三硅氧烷衍生物脂肪酸甲酯食用油聚合物单体醇类化合物芳香胺有机农药磺胺药物亚硝胺磷酯类化合物天然食品色素黄曲霉素黄酮类化合物氨基酸无机离子糖类化合物草甘磷抗生素合成食品色素酶环氧化合物表面活性剂胶淀粉合成代谢物糖醇化合物16HP化学工作站(局域网,LAN)单用户多用户分析实验室一体化GC和GC/MS分析LC和LC/MS分析样品登录数据处理QA/QC结果报告

04十一月202317第二章安捷伦公司LC,LC/MSD仪器特点181100HPLC系列见HPLC19安捷伦公司新一代液相色谱/大气压电喷雾质谱

简单、耐用的离子源设计直角喷雾设计－减少系统污染。优化的设计不需要调节喷雾器位置。高温干燥气与直角喷雾器的设计可以产生更小的液滴。ES源与APCI源切换及清洗非常方便。清洗被不挥发性缓冲液污染的离子源0.5mm毛细传输管设计：调谐更稳定CID质谱图重复性好不容易阻塞及污染5000001000000150000020000002.2954.1765.7217.22210.08810.60311.47611.90212.05912.462Initialrunmin2.557.51012.5155000001000000150000020000002.3424.2785.8887.35910.30110.81211.71012.06612.26812.62414hourslater!!20在离子透镜区,准分子离子与氮气发生碰撞提高结构定性信息产生碎片离子,适合定量分析调节锥孔区电压,实现CID过程碰撞诱导解离－内源CID毛细管输入管碰撞诱导解离区锥孔区八极杆透镜四极杆质量滤过口M

n[M]+1[M]2+DETAIL21Turner-kruger透镜降低四级杆边缘效应自动调谐液输送系统，不需要在APCI或ES调谐时手动更换调谐瓶。加热气直接加热喷雾液滴，并不加热毛细传输管冷毛细传输管避免热不稳定化合物的分解四级杆提供SCAN和SIM方式扫描HED组件提高灵敏度，且更换方便22和二为一的工作站界面友好，方便质谱库检索检索用户自己创建的质谱库使用

NIST程序谱库可以包括分子结构自动或手动检索结合DAD/MSD两个谱库检索报告

23第三章LC，LC/MSD在安全食品中应用的24LC在安全食品中的应用25LC/MSD在安全食品中的应用26LC/MS联用技术的相对适用范围分子量分析物的极性电喷雾(ESI)GC/MS大气压化学电离源(APCI)1000100,00010,000非极性极性农药及兽残化和物

27用于食品/环境分析的液相检测器检测器灵敏度选择性定性能力化合物UV/VWD+--类酯UV/DAD+-+维生素,抗生素,氨基酸,农药,多环芳烃Fluorescence+++-霉菌毒素,氨基甲酸酯,氨基酸,维生素Electrochemical

+++-维生素,离子,碳水化合物Conductivity+++-离子Refractiveindex---碳水化合物，类酯LC-MS+/-++++全部28分析应用食品添加剂残留“天然”化合物酸类化合物抗生素氨基酸抗氧化剂霉菌毒素酯类化合物防腐剂无机离子糖人工甜味剂农药维生素香料化合物无机离子色素29检测蔬菜,水果及肉类食品中的农残,药残的一般检测方法CreatedbyTakinoandeditedbyLiPing2023/11/430利用LC/MS

技术检测食品中药残，兽残的必要性在许多国家,食品中的农残及药残的种类和数量快速增加此外,近来法规要求的农残的性质趋向高极性和热不稳定要求方法可以同时检测多种残留,以用于快速检测固定方法可以建立用于谱库检索的数椐库

CreatedbyTakinoandeditedbyLiPing31建议分析条件1.柱子:ZorbaxEclipsXDBC18(150mm,2.1mm,5μm)2.流动相:A:ACNB:10-30mMCH3COONH4

0.1-0.2%CH3COOH,HCOOH5mM二丁基胺醋酸盐

3.柱温: 40℃4.离子源:电喷雾(ESI)5.碎片碰撞电压:100or200V6.毛细管电压:4000V7.干燥气（Dryinggas）:10l/min350℃8.雾化气（Nebulizergas）:50psiCreatedbyTakinoandeditedbyLiPing32建立用于谱库检索的数椐库1.采用多种残留检测的通用方法2.碎片碰撞电压为100和

200V3.浓度是10ppm

(浓度的高低不会影响质谱图)CreatedbyTakinoandeditedbyLiPing33目标化和物(农药)CreatedbyTakinoandeditedbyLiPing34目标化和物(兽药残留)CreatedbyTakinoandeditedbyLiPing35色谱

液相

:HP-1100柱子

:Zorbax

EclipsXDBC18(150mm,2.1mm,5um)流动相

:A:MeCNB:10mMCH3COONH420%A/B---(30min)---100%A柱温 :40C进样体积

:10ul流速

:0.2ml/min质谱质谱

:HP1100MSDSL离子源

:ESI(Positive)扫描范围

:m/z100-500干燥气 :10l/minat350C雾化气:50psi碎片碰撞电压:100VEMgain:3氨基甲酸盐类化和物的分析条件CreatedbyTakinoandeditedbyLiPing361.Oxamyl2.Methiocarbsulfoxide3.Methiocarbsulfone4.Aldicarb5.Bendiocarb6.Pirimicarb7.Carbaryl8.Ethiofencarb9.Fenobcarb10.Methiocarbmin510152025050000100000150000200000250000300000350000123456789,10氨基甲酸盐标样的总离子流图(1ppm)1.杀线威2.甲硫威亚砜3.甲硫威砜4.涕灭威5.苯恶威6.抗蚜威7.甲奈威8.乙硫甲威9.仲丁威10.甲硫威CreatedbyTakinoandeditedbyLiPing37氨基甲酸盐标样的质谱图(1ppm)100000100150200250050000237(M+H)+100150200250050000242(M+H)+m/z10015020025001000020000275(M+NH4)+1.Oxamyl2.Methiocarbsulfoxide3.Methiocarbsulfone100150200250025000500001161001502002500100000224(M+H)+167m/z1001502002500100000200000239(M+H)+213(M+Na)+4.Aldicarb5.Bendiocarb6.Pirimicarb杀线威甲硫威亚砜甲硫威砜涕灭威苯恶威抗蚜威CreatedbyTakinoandeditedbyLiPing38氨基甲酸盐标样的质谱图(1ppm)10015020025002500050000202(M+H)+145219(M+NH4)+100150200250050000100000226(M+H)+107164m/z10015020025005000010000010:226(M+H)+9:208(M+H)+169243(M+NH4)+7.Carbaryl8.Ethiofencarb9.Fenobcarb10.Methiocarb甲奈威乙硫甲威9.仲丁威10.甲硫威CreatedbyTakinoandeditedbyLiPing39对1ppm

的添加样品的药残分析的谱库检索结果=====================================================InjectionDate:2001/01/2411:59:17AMSampleName:100ppmfiaLocation:Vial1Acq.Instrument:Instrument1InjVolume:5ｵlAcq.Method:C:\HPCHEM\1\METHODS\CARBA.MAnalysisMethod:C:\HPCHEM\1\METHODS\ANY1_POS.M=====================================================NISTMSlibrarysearchmode:AutomaticlibrarysearchNISTMSlibraryfilename:foodpestRetTimeSigMWLibraryMatchFormulaName[min]#Id-------------|----|-------|--|---------|-----------|------------------------|--------------------------------------------------------3.289121911915C7H13N3O3SOxyamyl(pos,100V)5.302124113901C11H15NO3SMethiocarbsulfoxide(pos,100v)11.464125715922C11H15NO4SMethiocarbsulfon(pos,100)14.140119017903C7H14N2O2SAldicarb(pos,100v)23.715122319961C11H13NO4Bendiocarb(pos,100v)26.1561238111970C11H18N4O2Pirimicarb(pos,100v)27.5081201113832C12H11NO2Carbaryl(pos,100v)29.61712251101929C11H15NO2SEthiofencarb(pos,100v)43.4611225117934C11H15NO2SMethiocarb(pos,100v)43.6871207119757C12H17NO2Fenobucarb(pos,100v)======================================================CreatedbyTakinoandeditedbyLiPing40氨基甲酸盐标样(1ppb)

的选择离子模式的谱图5101520250200400600800510152025020040060080010001200min51015202501002003004005006001.Oxamyl2.Methiocarbsulfoxide3.Methiocarbsulfonem/z=237m/z=242m/z=2755101520250500100015002000250005101520250500100015002000min51015202505001500250035004.Aldicarb5.Bendiocarb6.Pirimicarbm/z=239m/z=224m/z=116杀线威甲硫威亚砜甲硫威砜涕灭威苯恶威抗蚜威CreatedbyTakinoandeditedbyLiPing41氨基甲酸盐标样(1ppb)

的选择离子模式的谱图510152025040080012005101520250500100015002000min510152025040080012007.Carbaryl8.Ethiofencarb9.Fenobcarb10.Methiocarbm/z=116m/z=208m/z=226甲奈威乙硫甲威仲丁威甲硫威CreatedbyTakinoandeditedbyLiPing42ChromatogramHPLC:HP-1100SLColumn:Zorbax

EclipsXDBC18(150mm,2.1mm,5um)Mobilepahse:A:MeCNB:15mMCH3COONH4+0.05%CH3COOH30%A/B---(30min)--100%A/BFlowrate:0.2ml/minColumnntemp:40CSamplevolume:10ulMSMS:HP1100MSDIonization:ESI(Positive)Pentoxazone(Negative)Scanrange:m/z100-900SIMion:basepeakDryinggas:10,l/minat350CNebulizergas:50psiFragmentor:100vEMgain:3食品中7种必检的农药残留的分析条件CreatedbyTakinoandeditedbyLiPing43食品中7种必检的农药残留的总离子流图（1ppm)1.Azimsulfuron2.Flazasulfron3.Dimethomorph4.Cyclosulfamuron5.Quizalfop-ethyl6.Pentoxazone7.Emamectin510152025050000100000150000200000min51015202560000650007000075000800001234567这些化合物必须用液质联用确认C13H16N10O5SC13H12F3N5O5SC21H22ClNO4C17H19N5O6SC17H13ClN2O4C17H17ClFNO4C49H75NO13+C48H73NO13杀虫剂CreatedbyTakinoandeditedbyLiPing44463(M+K)+1001502002503003504004500447(M+Na)+425(M+H)+100150200250300350400450010000408(M+H)+430(M+Na)+100150200250300350400450020000388(M+H)+410(M+Na)+426(M+K)+m/z100150200250300350400450020000422(M+H)+444(M+Na)+460(M+K)+200001.Azimsulfuron2.Flazasulfron3.Dimethomorph4.Cyclosulfamuron食品中7种必检的农药残留的总离子流图（1ppm)C13H16N10O5SC13H12F3N5O5SC21H22ClNO4C17H19N5O6SCreatedbyTakinoandeditedbyLiPing45100200300400500600700800900200004000060000

373(M+H)+395(M+Na)+411(M+K)+100200300400500600700800900200040006000301.2

352(M-H)-141m/z1002003004005006007008009002500050000886(M+H)+590.4546.3502.4634.45.Quizalfop-ethyl6.Pentoxazone7.Emamectin食品中7种必检的农药残留的总离子流图（1ppm)C17H13ClN2O4C17H17ClFNO4C49H75NO13+C48H73NO13CreatedbyTakinoandeditedbyLiPing46510152025010030050051015202501003005005101520250400800min510152025020060010001.Azimsulfuron2.Flazasulfron3.Dimethomorph4.Cyclosulfamuronm/z=425m/z=408m/z=388m/z=422食品中7种必检的农药残留的选择离子流图（0.1ppb)CreatedbyTakinoandeditedbyLiPing475101520250501502503505101520250100030005000min510152025600100014005.Emamectin6.Quizalfop-ethyl(1ppb)7.Pentoxazone(20ppb)m/z=886m/z=373m/z=354食品中7种必检的农药残留的选择离子流图（0.1ppb)CreatedbyTakinoandeditedbyLiPing48ChromatogramHPLC:HP-1100SLColumn:Zorbax

EclipsXDBC18(150mm,2.1mm,5um)Mobilepahse:A:MeCNB:30mMCH3COONH420%A/B---(30min)--100%A/BFlowrate:0.2ml/minColumnntemp:40CSamplevolume:7ulMSMS:HP1100MSDIonization:ESI(Positive,Negative)Scanrange:m/z100-600SIMion:basepeakDryinggas:10l/minat350CNebulizergas:50psiFragmentor:100vEMgain:5食品中7种农药残留的分析条件CreatedbyTakinoandeditedbyLiPing49食品中7种农药残留的总离子流图（1ppm)051015202501000002000003000004000005000006000001234min051015202501000002000003000004000005000006000005671.Chrorimuron-ethyl2.Mepanipyrimmetabolite3.Mepanipyrim4.Ethobenzanid5.hexaflumuron6.Fulfenoxuron7.HexathizoxCreatedbyTakinoandeditedbyLiPing50食品中7种农药残留的质谱图（1ppm)10015020025030035040045050001000015000415(M+H)+100150200250300350400450100000200000100150200250300350400450200000400000244(M+H)+224(M+H)+m/z10015020025030035040045010000200003000040000340(M+H)+m/z1001502002503003504004504000080000120000459(M-H)-4391.Chlorimuron-ethyl2.Mepanipyrimmetabolite3.Mepanipyrim4.Ethobenzanid5.hexaflumuronm/z氯嘧磺隆乙酯CreatedbyTakinoandeditedbyLiPing51食品中7种农药残留的质谱图（1ppm)10015020025030035040045020000400006000080000

487(M-H)-m/z10015020025030035040045050001000015000

353(M+H)+6.Flufenoxuron7.HexythiazoxC17H21ClN2O2S噻螨酮C21H11ClF6N2O3CreatedbyTakinoandeditedbyLiPing52食品中7种农药残留的选择离子流图（1ppm)0510152025500100015002000min05101520255000100001500020000051015202520004000600080001000012000min051015202550015002500350045001.Chrorimuron-ethyl(0.2ppb)2.Mepanipyrim

metabolite(0.2ppb)3.Mepanipyrim(0.2ppb)4.Ethobenzanid(1ppb)m/z=415m/z=244m/z=224m/z=340CreatedbyTakinoandeditedbyLiPing53食品中7种农药残留的选择离子流图（1ppm)05101520251000200030004000min05101520255001000150020002500min05101520252000400060008000100005.hexaflumuron(1ppb)6.Fulfenoxuron(1ppb)7.Hexathizox(5ppb)m/z=459m/z=487m/z=353CreatedbyTakinoandeditedbyLiPing540510152025500150025003500min051015202520000400006000080000100000051015202520000400006000080000100000min05101520252000400060008000花茎甘蓝萃取物中添加农残物(10ppb)的选择离子流图1.Chrorimuron-ethyl2.Mepanipyrim

metabolite3.Mepanipyrim4.Ethobenzanidm/z=415m/z=244m/z=224m/z=340CreatedbyTakinoandeditedbyLiPing5505101520255000100001500020000min05101520252000400060008000min05101520251000002000003000004000005000006000007000005.hexaflumuron6.Fulfenoxuron7.Hexathizoxm459m/z=487m/z=353花茎甘蓝萃取物中添加农残物(10ppb)的选择离子流图CreatedbyTakinoandeditedbyLiPing56ChromatogramHPLC:HP-1100Column:ZorbaxEclipsXDBC18(150mm,2.1mm,5μm)Mobilepahse:A:MeCNB:10%CH3COONH420%A/B---(30min)--100%A/B/7minFlowrate:0.2ml/minColumnntemp:40CSamplevolume:10ulMSMS:HP1100MSDSLIonization:ESI(Positive/Negative)Scanrange:m/z100-600SIMion:basepeakDryinggas:10l/minat350CNebulizergas:50psiFragmentor:100V/200VEMgain:59种农药残留的分析条件CreatedbyTakinoandeditedbyLiPing579种农药残留的总离子流图（1ppm)510152025300200000400000600000800000min5101520253001000002000003000004000005000001.Quinclorac2.Sethoxydim3.Iprodione4.Tebufenozide5.Ethoxyquin6.Pencycuron7.Fenproxymate8.Etofenprox9.Silafluofen12345678923469CreatedbyTakinoandeditedbyLiPing589种农药残留的质谱图（1ppm,正离子模式)10020030040002000040000242(M+H)+m/z1002003004000100000200000328(M+H)+10020030040002000400060008000352(M+Na)+330(M+H)+m/z1002003004000100000200000300000400000500000297(M+H)+3531.Quinclorac2.Sethoxydim3.Iprodione4.Tebufenozide二氯喹啉酸异菌脲稀禾定一种新杀虫剂CreatedbyTakinoandeditedbyLiPing599种农药残留的质谱图（1ppm,正离子模式)1001502002503003504000100000200000300000218(M+H)+m/z1001502002503003504000100000200000300000400000329(M+H)+1001502002503003504004500200000400000600000422(M+H)+m/z1001502002503003504004500100000200000

394(M+H)+5.Ethoxyquin6.Pencycuron7.Fenproxymate8.Etofenprox乙氧三甲喹啉杀螨酯禾穗宁唑螨酯CreatedbyTakinoandeditedbyLiPing609种农药残留的质谱图（1ppm,正离子模式)m/z10015020025030035040045050001000200030004000287(M+H)+9.SilafluofenCreatedbyTakinoandeditedbyLiPing619种农药残留的质谱图（1ppm,负离子模式)100150200250300350020000400006000080000326(M-H)-119163m/z10015020025030035005000100002431502002503003500100000200000300000351(M-H)-m/z150200250300350050000100000150000327(M-H)-2.Sethoxydim3.Iprodione6.Pencycuron4.TebufenozideCreatedbyTakinoandeditedbyLiPing629种农药残留的质谱图（1ppm,负离子模式)m/z10015020025030035040005000100001500020000407(M-H)-1419.SilafluofenCreatedbyTakinoandeditedbyLiPing639种农残(1ppb)的选择离子流图510152025303505001000150020005101520253035010002000300040005000min510152025303501003005007001.Quinclorac(68.2)2.Sethoxydim(14.5)3.Iprodione(2)2ppbm/z=242m/z=328m/z=243CreatedbyTakinoandeditedbyLiPing649种农残(1ppb)的选择离子流图51015202530350200040006000800051015202530350200400600800min510152025303502000400060008000100004.Tebufenozide(74)m/z=2975.Ethoxyquin(14)6.Pencycuron(295)m/z=218m/z=329CreatedbyTakinoandeditedbyLiPing659种农残(1ppb)的选择离子流图510152025303501000300050007000510152025303505000100001500020000min51015202530350500100015002000m/z=422m/z=394m/z=4077.Fenproxymate(112)8.Etofenprox(139)9.Silafluofen(2)2ppbCreatedbyTakinoandeditedbyLiPing66ChromatogramHPLC:HP-1100Column:Zorbax

Eclipsbonus(250mm,4.6mm,5um)Mobilepahse:A:MeCNB:5mMNonafluoropentanoicacid15%A/BColumnntemp:40CSamplevolume:15ulFlowrate:0.2ml/minMSMS:HP1100MSDSLIonization:ESI(Positive)Scanrange:m/z50-400SIMion:basepeakDryinggas:12l/minat350CNebulizergas:60psiFragmentor:100V,200vEMgain:7碱性农药的分析条件Volatileion-pairingreagentCreatedbyTakinoandeditedbyLiPing67碱性农药的总离子流图(1ppm)min12345678750001250001750002250002750001.Amitrol2.Cyromazin1250100150200250020000400006000085(M+H)+m/z50100150200250050000100000150000167(M+H)+1.Amitrol2.Cyromazin杀草强三嗪胺CreatedbyTakinoandeditedbyLiPing68碱性农药的选择离子流图(1ppb)123456780500100015002000250030003500min1234567802000400060008000100001.Amitrol(S/N=22)2.Cyromazin(S/N=100)m/z=85m/z=167杀草强三嗪胺CreatedbyTakinoandeditedbyLiPing69ChromatogramHPLC:HP-1100Column:ZorbaxEclipsXDBC18(150mm,2.1mm,5μm)Mobilepahse:A:MeCNB:10%CH3COONH420%A/B---(30min)--100%A/BFlowrate:0.2ml/minColumnntemp:40CSamplevolume:10ulMSMS:HP1100MSDSLIonization:ESI(Positive/Negative)Scanrange:m/z100-600SIMion:basepeakDryinggas:10l/minat350CNebulizergas:50psiFragmentor:100V/200VEMgain:510种农药化合物的分析条件CreatedbyTakinoandeditedbyLiPing7010种农残(1ppm)的总离子流图51015202530350250000500000750000100000012345678910117min5101520253035010000020000030000040000050000046101.Prohexadione-Ca2.Nitenpyram3.Cymoxanil4.Furametpyr-OH-15.diclomezine6.Cumylron7.Daimuron8.Imazalil9.Furametpyr-OH-210.Trifulmizole11.Pyridate

Positive(100V)Negative(100V)CreatedbyTakinoandeditedbyLiPing7110种农药残留的质谱图（1ppm,正离子模式)1001502002503003500200002441001502002503003500271(M+H)+1001502002503003500199(M+H)+m/z1001502002503003500332(M+H)+2000020000100001.Prohexadione-Ca2.Nitenpyram3.Cymoxanil4.Furametpyr-OH-1霜脲氰CreatedbyTakinoandeditedbyLiPing7210种农药残留的质谱图（1ppm,正离子模式)1001502002503003500255(M+H)+1001502002503003500303(M+H)+1001502002503003500500000269(M+H)+m/z1001502002503003500297(M+H)+1000002000002000005.diclomezine6.Cumylron7.Daimuron8.ImazalilCreatedbyTakinoandeditedbyLiPing7310种农药残留的质谱图（1ppm,正离子模式)1001502002503003500100000332(M+H)+386.11001502002503003500250000500000346(M+H)+278m/z1001502002503003500250000500000379(M+H)+9.Furametpyr-OH-210.Triflumizole11.Pyridate哒草特氟菌唑CreatedbyTakinoandeditedbyLiPing7410种农药残留的质谱图（1ppm,负离子模式)1001502002503003500200003481001502002503003500361(M+CH3COO)-1001502002503003500250000327(M+CH3COO)-267.1m/z1001502002503003500344(M-H)-4.Furametpyr-OH-16.Cumylron7.Daimuron10.TrifulmizoleCreatedbyTakinoandeditedbyLiPing75对1ppm

的添加样品的10种药残分析的谱库检索结果==================================================InjectionDate:2001/01/2311:37:56AMSampleName:100ppmfiaLocation:Vial1Acq.Operator:Inj:1Acq.Instrument:Instrument1InjVolume:5ｵlAcq.Method:C:\HPCHEM\1\METHODS\NETPE.MAnalysisMethod:C:\HPCHEM\1\METHODS\ANY1_POS.M==================================================NISTMSlibraryfilename:foodpestRetTimeSigMWLibraryMatchFormulaName[min]Id-------------|----|-------|--|---------|---------|---------------------------|------------------------------------------------1.74412491107868C10H9CaO5Prohexadione-Ca(pos,100v)3.12412701108950C11H15ClN4O2Nitenpyram(pos,100v)10.04111981110950C7H10N4O3Cymoxanil(pos,100v)18.26112541113940C11H8Cl2N2ODiclomezine(pos,100v)20.48013021114889C17H19ClN2OCumyluron(pos,100v)20.95112681116945C17H20N2ODaimuron(pos,100v)21.37812961118963C14H14Cl2N2OImazalil(pos,100v)21.64713311120935C17H18ClN3O2Furametpyr-OH(pos,100v)24.89313451122838C15H15ClF3N3OTriflumizole(pos,100v)33.26213781124961C19H23ClN2O2SPyridate(pos,100v)==================================================CreatedbyTakinoandeditedbyLiPing7610种农残(1ppb)的选择离子流图():S/N51015202530350200400600800510152025303501000200030004000510152025303502004006008001000min510152025303502000400060008000100001.Prohexadione-Ca(8)m/z=213m/z=271m/z=199m/z=3322.Nitenpyram(115)3.Cymoxanil(20)4.Furametpyr-OH(175)CreatedbyTakinoandeditedbyLiPing7710种农残(1ppb)的选择离子流图():S/N5101520253035020040060080051015202530350200040006000800010000min510152025303502500500075001000012500150005.diclomezine(10)6.Cumylron(45)7.Daimuron(20)m/z=255m/z=303m/z=269CreatedbyTakinoandeditedbyLiPing7810种农残(1ppb)的选择离子流图5101520253035020004000600080001000051015202530350100020003000400050006000min510152025303502500500075001000012500150001750010ppb8.Imazalil(42)10.Trifulmizole(67)11.Pyridate(20)m/z=297m/z=346m/z=379():S/NCreatedbyTakinoandeditedbyLiPing79ChromatogramHPLC:HP-1100Column:Zorbax

EclipsXDBC18(150mm,2.1mm,5um)Mobilepahse:A:MeCNB:10mMCH3COONH420%A/B---(20min)--100%AFlowrate:0.2ml/minColumnntemp:40CSamplevolume:10ulMSMS:HP1100MSDIonization:ESI(Positive)Scanrange:m/z100-600SIMion:basepeakDryinggas:10l/minat350CNebulizergas:50psiFragmentor:100vEMgain:３5种磺酰脲类农药的分析条件CreatedbyTakinoandeditedbyLiPing805种磺酰脲类农药的总离子流图(1ppm)min510152025020000400006000080000100000120000140000160000180000123451.Metsulfuron-methyl2.Imazosulfuron3.Tribenuron-methyl4.Bensulfuron-methyl5.MethabenzthiazuronCreatedbyTakinoandeditedbyLiPing815种磺酰脲类农药的质谱图(1ppm)150200250300350400450020000400006000080000

411(M+H)+433(M+Na)+449(M+K)+m/z15020025030035040045004000080000120000222(M+H)+1651002003004005000200004000060000382(M+H)+

404(M+Na)+

420(M+K)+10020030040050002000040000413(M+H)+451(M+K)+435(M+Na)+m/z1002003004005000200004000060000

396(M+H)+418(M+Na)+

434(M+K)+1.Metsulfuron-methyl2.Imazosulfuron3.Tribenuron-methyl4.Bensulfuron-methyl5.Methabenzthiazuron甲黄隆苄嘧黄隆甲酯苯黄隆甲酯冬播隆CreatedbyTakinoandeditedbyLiPing825种磺酰脲类农药的选择离子流图(1ppm)246810121440080012002468101214100300500700min246810121440080012001.Metsulfuron-methyl(0.5ppb)2.Imazosulfuron(0.5ppb)3.Tribenur