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前言农药是农业上用于防治病虫害及调节植物生长的化学试剂,广泛用于农林牧业生产、环境和家庭卫生除害防疫、工业品防霉和防蛀等。农药的大量使用容易会导致其在食物链及环境中残留,对人类健康和生态环境造成潜在的危害。因此,建立各类果蔬中农药残留的准确定性定量方法,为老百姓食品安全提供重要保障。本文参考《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》标准(GB 23200.113-2018),使用气相色谱-串联三重四极杆质谱联用仪对黄瓜基质中的107多种农药及相关化学品进行检测分析,通过定量限、精密度和准确度等指标评估仪器性能,证明GC-TQ 6000满足检测的需要。实验部分样品前处理准确称取10 g黄瓜样品于50 mL离心管中,加入10 mL乙腈和1包QuEChERS萃取盐包,盖上离心管,剧烈振荡3 min后4200 r/min离心5 min。吸取6 mL上清液加到内含净化盐包的15 mL离心管中,涡旋混匀2 min。4200 r/min离心5 min,准确吸取2 mL上清液于10 mL试管中,40℃水浴氮吹近干。加入10 μL内标溶液,1mL乙酸乙酯溶液复溶,过0.22 μm有机滤膜,待测。仪器条件表1. 仪器方法参数模块参数值色谱进样口温度280 °C进样方式不分流色谱柱VF-1701MS, 30 m × 0.25 mm × 0.25 μm升温程序起始温度40°C,保持1 min,以40°C/min升至120 °C,再以5 °C/min升至240 °C,再以12℃/min升至300℃,保持6min载气氦气柱流量1.0 mL/min 恒流模式质谱离子源EI,70eV离子源温度280 °C传输线温度280 °C检测器电压-1300 V溶剂延迟碰撞气流量射出电压(CXP)4min20psi3V采集模式MRM结果与讨论1、标准谱图和物质信息实验总离子流图见图1,107种农药目标化合物浓度为500 μg/L,内标物浓度为100 μg/L。107种目标化合物以及内标的保留时间以及特征离子信息见附录表3。图1 107种农药目标化合物总离子流图(500 μg/L)2、标准曲线黄瓜空白基质溶液氮吹近干,分别加入1 mL浓度为5 μg/L、10 μg/L、20 μg/L、50 μg/L、100 μg/L、200 μg/L、500 μg/L,内标含量为100 μg/L的混合标准曲线溶液进行分析。107种农药的线性相关系数R均大于0.995。 (a) 敌敌畏(b) 一溴二氯甲烷(c) 啶酰菌胺图2 三种代表性农药目标化合物的标准曲线图3、黄瓜加标回收实验3.1 精密度和准确度分别对10g黄瓜样品进行加标浓度为0.01 mg/kg、0.05 mg/kg、0.1 mg/kg各六次平行实验,对精密度和准确度进行评估,准确度具体信息详见附录表4。浓度为0.01 mg/kg、0.05 mg/kg和0.1 mg/kg时,107种农药化合物的相对标准偏差(RSD)分别为1.90%-14.54%、1.43%-9.32%和1.00%-4.81%,回收率分别为65.8%-121.2%、66.0%-117.8%、67.2%-113.3%。3.2 定量限按照标准GB/T 23200.113-2018《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》对10g黄瓜进行加标量为0.01 mg/kg的7次平行回收实验,计算其标准偏差(SD),根据方法定量限LOQ=10×SD计算目标化合物的方法定量限,通过计算可知107种农药化合物的方法定量限为0.001 mg/kg-0.010 mg/kg。表2.107种农药化合物黄瓜基质加标方法定量限序号化合物方法定量限(mg/kg)标准要求方法定量限(mg/kg)序号化合物方法定量限(mg/kg)标准要求方法定量限(mg/kg)1敌敌畏0.0100.01554,4'-滴滴伊0.0030.012甲胺磷0.0020.0156苯硫威0.0020.013敌草腈0.0100.0157嘧菌胺0.0030.014速灭磷0.0060.0158脱叶磷0.0100.015虫螨畏0.0050.0159甲拌磷砜0.0020.016禾草敌0.0100.0160除草定0.0050.017环草敌0.0030.0161三唑醇0.0050.018异丙威0.0030.0162溴苯烯磷0.0030.019乙酰甲胺磷0.0030.0163丙草胺0.0030.0110六氯苯0.0060.01642,4'-滴滴滴0.0040.0111灭线磷0.0030.0165醚菌酯0.0100.0112乙丁烯氟灵0.0020.0166异狄氏剂0.0100.0113残杀威0.0030.0167灭菌磷0.0020.0114治螟磷0.0030.0168噁草酮0.0030.0115α-六六六0.0040.01692,4-滴滴涕0.0020.0116脱乙基莠去津0.0040.0170抑霉唑0.0050.0117特丁硫磷0.0020.0171地胺磷0.0020.0118敌噁磷0.0060.0172环氟菌胺0.0100.0119野麦畏0.0020.0173虫螨磷0.0050.0120环丙氟灵0.0050.0174乙嘧酚磺酸酯0.0040.0121地虫硫磷0.0030.0175乙氧氟草醚0.0040.0122丁基嘧啶磷0.0020.0176噁唑啉0.0040.0123扑灭津0.0030.0177氟酰胺0.0030.0124氯硝胺0.0040.01784,4'-滴滴滴0.0030.0125胺丙畏0.0030.0179β-硫丹0.0060.0126异稻瘟净0.0100.0180喹氧灵0.0020.0127除线磷0.0020.0181苯草醚0.0020.0128抗蚜威0.0030.0182肟菌酯0.0040.0129久效磷0.0030.0183三硫磷0.0050.0130乐果0.0070.0184增效醚0.0040.0131乙草胺0.0040.0185敌瘟磷0.0020.0132甲草胺0.0030.0186丰索磷0.0040.0133甲基嘧啶磷0.0040.0187联苯菊酯0.0030.0134甲基对氧磷0.0040.0188三唑磷0.0050.0135乙烯菌核利0.0040.0189吡螨胺0.0020.0136嗪草酮0.0020.0190溴螨酯0.0020.0137甲霜灵0.0090.0191胺菊酯0.0090.0138禾草丹0.0090.0192氟环唑0.0030.0139异丙甲草胺0.0100.0193戊唑醇0.0040.0140安硫磷0.0050.0194吡丙醚0.0050.0141三氯杀螨醇0.0050.0195哌草磷0.0040.0142倍硫磷0.0030.0196苯硫磷0.0090.0143溴硫磷0.0040.0197环嗪酮0.0020.0144对氧磷0.0100.0198咪唑菌酮0.0030.0145三唑酮0.0060.0199三氯杀螨砜0.0100.0146烯丙菊酯0.0070.01100莎稗磷0.0060.0147对硫磷0.0050.01101氯菊酯0.0050.0148甲基异柳磷0.0010.01102氯苯嘧啶醇0.0040.0149异柳磷0.0050.01103哒螨灵0.0080.0150α-硫丹0.0100.01104氯氰菊酯0.0090.0151喹硫磷0.0020.01105啶酰菌胺0.0030.0152戊菌唑0.0030.01106氰戊菊酯0.0100.0153甲拌磷亚砜0.0030.01107溴氰菊酯0.0100.0154噻唑滕0.0030.01结论本文依据GB 23200.113-2018《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》,采用禾信GC-TQ 6000对黄瓜进行加标回收实验,结果显示107种农药化合物的线性相关系数R均大于0.995;黄瓜基质加标精密度在1.00%-14.54%范围,加标回收率在65.8%-121.2%范围;方法定量限范围为0.001 mg/kg-0.010 mg/kg。上述结果表明禾信GC-TQ 6000具有优异的重现性和检测灵敏度,满足检测需求。参考文献1. GB 23200.113-2018《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》附录表3. 107种农药和内标的保留时间和特征离子信息表序号名 称CAS RT,min定量离子对碰撞能V定性离子对碰撞能V1敌敌畏62-73-78.858109.0->79.05185.0->93.0102甲胺磷10265-92-610.635141.0->95.05141.0->79.0103敌草腈1194-65-611.228171.0->100.020171.0->136.0104速灭磷17786-34-713.057127.0->109.05127.0->95.0105速灭磷27786-34-713.268127.0->109.05127.0->95.0106虫螨畏62610-77-913.800207.9->180.05207.9->93.0107禾草敌2212-67-113.814126.2->55.110126.2->83.158环草敌1134-23-215.421154.1->83.15154.1->72.159异丙威2631-40-515.589121.0->77.110136.0->121.0510乙酰甲胺磷30560-19-115.736136.0->94.010136.0->42.0511六氯苯118-74-115.981283.8->248.810283.8->213.92512灭线磷13194-48-416.486157.9->97.010157.9->114.0513乙丁烯氟灵55283-68-616.878275.9->202.110315.9->275.9514残杀威114-26-117.473110.0->64.010110.0->63.02015治螟磷3689-24-517.634237.8->145.910201.8->145.9516α-六六六319-84-618.174218.9->183.05216.9->181.0517脱乙基莠去津6190-65-419.077187.0->172.05172.0->94.01018特丁硫磷13071-79-919.093230.9->129.020230.9->175.01019敌噁磷78-34-219.093125.0->97.05153.0->97.0520野麦畏2303-17-519.264268.0->184.110142.9->83.01021环丙氟灵26399-36-019.413317.9->199.010317.9->54.81022地虫硫磷944-22-919.545136.9->109.05245.9->137.0523丁基嘧啶磷96182-53-519.662260.8->137.210233.9->110.11024扑灭津139-40-220.044214.2->172.25229.1->58.11025氯硝胺99-30-920.271206.1->176.05160.1->124.1526胺丙畏31218-83-420.388138.0->110.05138.0->64.01027异稻瘟净26087-47-820.874203.9->91.05121.9->121.01028除线磷97-17-620.992278.9->222.910222.9->204.91029抗蚜威23103-98-221.056238.0->166.210166.0->55.11030久效磷6923-22-421.316127.1->109.010127.1->95.01031乐果60-51-521.61786.9->46.010142.9->111.0532乙草胺34256-82-121.917222.9->132.210222.9->147.2533甲草胺15972-60-822.304188.1->160.25160.2->132.1534甲基嘧啶磷29232-93-722.486290.0->125.015232.9->151.0535甲基对氧磷950-35-622.652229.9->136.05229.9->106.01036乙烯菌核利50471-44-822.762197.9->145.010187.0->124.01037嗪草酮21087-64-922.92198.0->82.010198.0->55.02538甲霜灵57837-19-123.015234.0->146.110220.0->192.1539禾草丹28249-77-623.173100.0->72.05124.9->89.01040异丙甲草胺51218-45-223.684238.0->162.210162.2->133.21041安硫磷2540-82-123.771170.0->93.010197.9->92.9542三氯杀螨醇115-32-223.899139.0->111.010250.9->138.91043倍硫磷55-38-923.986278.0->109.010278.0->169.01044溴硫磷2104-96-324.04330.8->315.810328.8->313.81045对氧磷311-45-524.328108.9->91.05148.9->119.0546环氧七氯B(内标)1024-57-324.415352.8->262.915354.8->264.91547三唑酮43121-43-324.844208.0->181.15208.0->111.01048烯丙菊酯584-79-224.851123.0->81.05107.0->91.0549对硫磷56-38-225.005290.9->109.010138.9->109.0550甲基异柳磷99675-03-325.072199.0->121.010241.1->199.1551异柳磷25311-71-125.404212.9->121.110212.9->185.1552α-硫丹959-98-825.436194.9->159.05194.9->125.02053喹硫磷13593-03-825.56146.0->118.010146.0->91.03054戊菌唑66246-88-625.835248.0->157.025248.0->192.01055甲拌磷亚砜2588-03-626.134199.0->142.9596.9->64.92056噻唑滕198886-44-326.296195.0->103.05195.0->60.020574,4'-滴滴伊72-55-926.327246.1->176.225315.8->246.01058噻唑滕298886-44-326.396195.0->103.05195.0->60.02059苯硫威62850-32-226.477160.1->72.01072.0->56.01560嘧菌胺110235-47-726.706223.2->222.210222.2->207.21061脱叶磷78-48-826.753202.0->147.010169.0->57.11062甲拌磷砜2588-04-726.912153.0->97.05124.9->96.9563除草定314-40-926.99205.0->188.010207.0->190.01064三唑醇55219-65-327.093168.0->70.05128.0->65.01065溴苯烯磷33399-00-727.093266.9->159.110268.9->161.11066丙草胺51218-49-627.251162.0->132.010262.0->202.05672,4'-滴滴滴53-19-027.402235.0->165.220237.0->165.22068醚菌酯143390-89-027.465116.0->89.05116.0->63.03069异狄氏剂72-20-827.536262.8->193.025244.8->173.02070灭菌磷5131-24-827.536130.0->102.110148.0->130.11571噁草酮19666-30-927.567174.9->112.015174.9->76.035722,4-滴滴涕789-02-627.888235.0->165.020237.0->165.02073抑霉唑35554-44-027.916214.9->173.05216.8->175.0574地胺磷950-10-728.137168.0->139.95196.0->139.91075环氟菌胺180409-60-328.156118.1->90.05118.1->89.01076虫螨磷160238-56-428.292324.8->268.910296.8->268.9577乙嘧酚磺酸酯41483-43-628.382272.9->193.15272.9->108.01078乙氧氟草醚42874-03-328.687252.0->146.025252.0->196.01579虫螨磷260238-56-428.741324.8->268.910296.8->268.9580噁唑啉18854-01-828.754177.1->130.05177.1->116.01081氟酰胺66332-96-528.828173.0->145.110280.9->173.010824,4'-滴滴滴72-54-828.922234.9->165.120236.9->165.22083β-硫丹33213-65-929.029206.9->172.010194.9->124.92084喹氧灵124495-18-729.19237.0->208.120271.9->237.11085苯草醚74070-46-529.357264.1->194.210212.1->182.21086肟菌酯141517-21-729.371116.0->89.010131.0->89.02087三硫磷786-19-629.438153.0->96.95199.0->143.0588增效醚51-03-629.585176.0->103.020176.0->131.01589敌瘟磷17109-49-829.93172.9->109.010201.0->109.01090丰索磷115-90-230.103291.8->156.010291.8->108.81091联苯菊酯82657-04-330.197181.2->165.220181.2->166.21092三唑磷24017-47-830.217161.2->134.25161.2->106.11093吡螨胺119168-77-330.689275.9->171.110332.9->171.01594溴螨酯18181-80-130.904185.0->157.010183.0->155.01095胺菊酯17696-12-030.911164.0->107.010164.0->77.02096氟环唑133855-98-830.974192.0->138.05192.0->111.01597胺菊酯27696-12-031.079164.0->107.010164.0->77.02098戊唑醇107534-96-331.142250.0->125.010250.0->153.0599吡丙醚95737-68-131.339136.0->78.010136.0->96.010100哌草磷24151-93-731.479320.0->122.010140.0->98.05101苯硫磷2104-64-531.556169.0->141.15169.0->77.110102环嗪酮51235-04-231.605171.0->71.15171.0->85.110103咪唑菌酮161326-34-731.633238.0->237.25268.0->180.220104三氯杀螨砜116-29-031.931158.9->131.05226.9->199.010105莎稗磷64249-01-032.043225.9->184.010255.9->157.05106氯菊酯152645-53-132.424183.1->168.110183.1->153.010107氯菊酯252645-53-132.659183.1->168.110183.1->153.010108氯苯嘧啶醇60168-88-932.702251.0->139.110219.0->107.010109哒螨灵96489-71-333.026147.2->132.210147.2->117.120110氯氰菊酯152315-07-834.393163.0->91.010163.0->109.010111氯氰菊酯252315-07-834.659163.0->91.010163.0->109.010112氯氰菊酯352315-07-834.729163.0->91.010163.0->109.010113氯氰菊酯452315-07-834.877163.0->91.010163.0->109.010114啶酰菌胺188425-85-635.391140.0->112.05140.0->76.015115氰戊菊酯151630-58-136.018167.0->125.010224.9->119.010116氰戊菊酯251630-58-136.484167.0->125.010224.9->119.010117溴氰菊酯52918-63-537.812250.7->172.05252.9->93.010表4.107种农药化合物黄瓜基质加标精密度序号化合物加标量(mg/kg)序号化合物加标量(mg/kg)0.010.050.10.010.050.11敌敌畏70.6%74.6%72.47%554,4'-滴滴伊100.3%101.6%98.0%2甲胺磷72.3%80.7%83.43%56苯硫威87.8%97.7%99.2%3敌草腈73.2%68.6%70.3%57嘧菌胺85.5%87.0%84.8%4速灭磷77.4%91.4%92.3%58脱叶磷81.7%89.0%88.6%5虫螨畏78.7%85.6%79.0%59甲拌磷砜82.9%92.8%97.9%6禾草敌71.3%81.2%80.6%60除草定79.0%101.6%104.6%7环草敌75.9%90.7%86.6%61三唑醇86.5%97.6%99.9%8异丙威84.8%90.5%91.2%62溴苯烯磷81.1%100.4%92.9%9乙酰甲胺磷76.0%78.6%83.5%63丙草胺86.2%94.7%99.6%10六氯苯83.5%77.6%82.1%642,4'-滴滴滴95.7%108.9%101.6%11灭线磷78.2%92.2%91.0%65醚菌酯95.4%103.8%100.4%12乙丁烯氟灵72.0%89.2%88.7%66异狄氏剂93.7%99.9%98.1%13残杀威84.5%97.7%93.4%67灭菌磷65.8%66.0%68.1%14治螟磷75.9%95.2%89.3%68噁草酮91.8%98.2%98.0%15α-六六六75.6%90.2%85.7%692,4-滴滴涕75.1%85.6%89.2%16脱乙基莠去津88.0%94.3%96.8%70抑霉唑84.7%95.7%94.2%17特丁硫磷75.4%98.2%88.6%71地胺磷89.4%94.0%95.7%18敌噁磷82.2%97.2%90.9%72环氟菌胺99.4%107.7%105.2%19野麦畏89.5%97.0%92.1%73虫螨磷88.6%87.7%97.6%20环丙氟灵83.8%85.1%95.4%74乙嘧酚磺酸酯86.9%91.0%97.1%21地虫硫磷89.1%92.5%93.5%75乙氧氟草醚90.4%104.3%104.5%22丁基嘧啶磷82.6%95.4%92.2%76噁唑啉94.8%88.1%94.1%23扑灭津88.2%102.4%94.1%77氟酰胺115.6%101.1%108.5%24氯硝胺93.6%96.8%100.5%784,4'-滴滴滴95.2%108.1%103.8%25胺丙畏82.3%89.7%99.4%79β-硫丹95.6%99.8%101.1%26异稻瘟净95.4%90.9%86.4%80喹氧灵84.5%92.4%94.8%27除线磷83.8%93.2%92.6%81苯草醚99.2%103.5%102.6%28抗蚜威87.0%91.8%92.7%82肟菌酯83.9%98.4%101.2%29久效磷85.1%102.4%98.3%83三硫磷90.1%95.1%101.1%30乐果98.8%110.9%103.1%84增效醚92.0%100.2%102.4%31乙草胺88.7%103.3%92.8%85敌瘟磷85.7%94.8%96.3%32甲草胺87.9%92.3%94.0%86丰索磷121.2%115.6%109.5%33甲基嘧啶磷87.7%96.2%92.8%87联苯菊酯116.8%109.8%108.7%34甲基对氧磷87.0%97.0%100.6%88三唑磷92.6%99.4%96.3%35乙烯菌核利87.4%97.4%94.5%89吡螨胺87.5%98.3%95.7%36嗪草酮86.5%99.4%95.3%90溴螨酯94.7%103.7%100.9%37甲霜灵112.9%117.8%113.3%91胺菊酯101.7%107.9%102.6%38禾草丹89.6%106.0%93.4%92氟环唑91.5%101.2%100.7%39异丙甲草胺95.4%99.2%95.1%93戊唑醇90.1%103.6%99.3%40安硫磷68.6%66.38%67.2%94吡丙醚93.0%94.3%104.6%41三氯杀螨醇98.1%111.5%113.0%95哌草磷90.5%95.9%100.7%42倍硫磷83.8%91.0%94.1%96苯硫磷95.6%104.7%105.0%43溴硫磷81.8%81.4%90.6%97环嗪酮92.9%98.9%98.7%44对氧磷103.9%112.1%108.0%98咪唑菌酮96.9%106.7%102.5%45三唑酮88.7%98.4%95.4%99三氯杀螨砜92.9%97.3%104.3%46烯丙菊酯77.3%79.7%70.5%100莎稗磷86.9%97.0%93.6%47对硫磷82.5%98.9%90.4%101氯菊酯99.0%104.8%99.6%48甲基异柳磷84.7%94.7%95.6%102氯苯嘧啶醇90.9%105.1%95.7%49异柳磷86.2%91.0%88.4%103哒螨灵101.4%94.9%90.9%50α-硫丹108.4%101.1%99.9%104氯氰菊酯90.6%97.6%96.3%51喹硫磷82.4%88.6%96.3%105啶酰菌胺88.65%92.0%100.1%52戊菌唑86.3%100.5%96.4%106氰戊菊酯91.6%100.2%99.5%53甲拌磷亚砜85.7%95.2%96.0%107溴氰菊酯77.7%76.9%82.6%54噻唑滕88.3%96.8%95.5%GB 23200.113-2018 B组分析果蔬中113种农药前言农药是农业上用于防治病虫害及调节植物生长的化学试剂,广泛用于农林牧业生产、环境和家庭卫生除害防疫、工业品防霉和防蛀等。农药的大量使用容易会导致其在食物链及环境中残留,对人类健康和生态环境造成潜在的危害。因此,建立各类果蔬中农药残留的准确定性定量方法,为老百姓食品安全提供重要保障。本文参考《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》标准(GB 23200.113-2018),使用气相色谱-串联三重四极杆质谱联用仪对黄瓜基质中的113多种农药及相关化学品进行检测分析,通过定量限、精密度和准确度等指标评估仪器性能,证明GC-TQ 6000满足检测的需要。实验部分样品前处理准确称取10 g黄瓜样品于50 mL离心管中,加入10 mL乙腈和1包QuEChERS萃取盐包,盖上离心管,剧烈振荡3 min后4200 r/min离心5 min。吸取6 mL上清液加到内含净化盐包的15 mL离心管中,涡旋混匀2 min。4200 r/min离心5 min,准确吸取2 mL上清液于10 mL试管中,40℃水浴氮吹近干。加入10 μL内标溶液,1mL乙酸乙酯溶液复溶,过0.22 μm有机滤膜,待测。仪器条件表1. 仪器方法参数模块参数值色谱进样口温度280 °C进样方式不分流色谱柱VF-1701MS, 30 m × 0.25 mm × 0.25 μm升温程序起始温度40°C,保持1 min,以40°C/min升至120 °C,再以5 °C/min升至240 °C,再以12℃/min升至300℃,保持6min载气氦气柱流量1.0 mL/min 恒流模式质谱离子源EI,70eV离子源温度280 °C传输线温度280 °C检测器电压-1300 V溶剂延迟碰撞气流量射出电压(CXP)4min20psi3V采集模式MRM结果与讨论1、标准谱图和物质信息实验总离子流图见图1,113种农药目标化合物浓度为500 μg/L,内标物浓度为100 μg/L。113种目标化合物以及内标的保留时间以及特征离子信息见附录表3。图1 113种农药目标化合物总离子流图(500 μg/L)2、标准曲线黄瓜空白基质溶液氮吹近干,分别加入1 mL浓度为5 μg/L、10 μg/L、20 μg/L、50 μg/L、100 μg/L、200 μg/L、500 μg/L,内标含量为100 μg/L的混合标准曲线溶液进行分析。113种农药的线性相关系数R均大于0.995。 (a)硫草敌 (b)水胺硫磷 (c)蝇毒磷图2 三种代表性农药目标化合物的标准曲线图3、黄瓜加标回收实验3.1 精密度和准确度分别对10g黄瓜样品进行加标浓度为0.01 mg/kg、0.05 mg/kg、0.1 mg/kg各六次平行实验,对精密度和准确度进行评估,准确度具体信息详见下附录表4。浓度为0.01 mg/kg、0.05 mg/kg和0.1 mg/kg时,113种农药化合物的相对标准偏差(RSD)分别为4.02%-15.54%、1.14%-9.29%和1.26%-7.66%,回收率分别为70.6%-119.8%、82.1%-119.7%、74.4%-119.3%。3.2 定量限按照标准GB/T 23200.113-2018《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》对10g黄瓜进行加标量为0.01 mg/kg的7次平行回收实验,计算其标准偏差(SD),根据方法定量限LOQ=10×SD计算目标化合物的方法定量限,通过计算可知113种农药化合物的方法定量限为0.003 mg/kg-0.010 mg/kg。表2.113种农药化合物黄瓜基质加标方法定量限序号化合物方法定量限(mg/kg)标准要求方法定量限(mg/kg)序号化合物方法定量限(mg/kg)标准要求方法定量限(mg/kg)1硫草敌0.0060.0158水胺硫磷0.0060.012联苯0.0070.0159氯丹-反式0.0070.013土菌灵0.0060.0160四氟醚唑0.0080.014氯苯甲醚0.0070.0161丁草胺0.0070.015四氯硝基苯0.0040.0162丙硫磷0.0050.016虫线磷0.0050.0163氟丁酰草胺0.0060.017二苯胺0.0050.0164杀虫畏0.0060.018仲丁威0.0070.0165腐霉利0.0070.019乙丁氟灵0.0060.0166狄氏剂0.0030.0110二溴磷0.0080.0167杀扑磷0.0050.0111甲拌磷0.0090.0168丙溴磷0.0070.0112氯苯胺灵0.0100.0169敌草胺0.0060.0113五氯硝基苯0.0100.0170己唑醇0.0090.0114氧乐果0.0050.0171抑草磷0.0030.0115阿特拉通0.0070.0172多效唑0.0060.0116二嗪磷0.0080.0173杀螨酯0.0080.0117异噁草酮0.0060.0174吡氟禾草灵0.0070.0118百治磷0.0060.0175稻瘟灵0.0070.0119嘧霉胺0.0060.0176硫环磷0.0060.0120γ-六六六0.0080.0177乙酯杀螨醇0.0060.0121乙嘧硫磷0.0050.0178除草醚0.0080.0122克百威0.0060.0179乙硫磷0.0060.0123莠去津0.0070.0180三氟硝草醚0.0080.0124西玛津0.0100.01814,4'-滴滴涕0.0070.0125特丁津0.0070.0182烯唑醇0.0050.0126绿谷隆0.0060.0183腈菌唑0.0050.0127五氯苯胺0.0060.0184环丙唑醇0.0070.0128氯唑磷0.0050.0185苯霜灵0.0070.0129炔苯酰草胺0.0050.0186氟虫腈0.0060.0130甲基毒死蜱0.0040.0187丙环唑0.0080.0131艾氏剂0.0070.0188禾草灵0.0070.0132皮蝇磷0.0060.0189倍硫磷亚砜0.0100.0133敌草净0.0060.0190倍硫磷砜0.0100.0134甲基立枯磷0.0050.0191咯菌腈0.0080.0135扑草净0.0040.0192噁霜灵0.0070.0136莠灭净0.0070.0193乙螨唑0.0090.0137β-六六六0.0070.0194异菌脲0.0100.0138特丁净0.0070.0195甲氧滴滴涕0.0070.0139毒死蜱0.0080.0196伐灭磷0.0080.0140磷胺0.0060.0197甲氰菊酯0.0070.0141马拉氧磷0.0060.0198哒嗪硫磷0.0060.0142异丙净0.0050.0199溴苯磷0.0060.0143甲基对硫磷0.0060.01100亚胺硫磷0.0030.0144毒壤滕0.0050.01101甲羧除草醚0.0100.0145δ-六六六0.0060.01102氯氟氰菊酯0.0090.0146嘧啶磷0.0060.01103氟丙菊酯0.0090.0147马拉硫磷0.0060.01104伏杀硫磷0.0080.0148烯虫酯0.0050.01105苯噻酰草胺0.0090.0149杀螟硫磷0.0050.01106益棉磷0.0100.0150乙氧呋草黄0.0080.01107氟喹唑0.0060.0151嘧菌环胺0.0060.01108氟氯氰菊酯0.0100.0152氧异柳磷0.0050.01109蝇毒磷0.0060.0153二甲戊灵0.0050.01110氟氰戊菊酯0.0080.0154毒虫畏0.0030.01111腈苯唑0.0070.0155敌稗0.0070.01112氟胺氰菊酯0.0090.0156o,p'-DDE0.0080.01113苯醚甲环唑0.0060.0157乙基溴硫磷0.0060.01结论本文依据GB 23200.113-2018《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》,采用禾信GC-TQ 6000对黄瓜进行加标回收实验,结果显示113种农药化合物的线性相关系数R均大于0.995;黄瓜基质加标精密度在1.14%-15.54%范围,加标回收率在70.6%-119.8%范围;方法定量限在0.003 mg/kg-0.010 mg/kg范围内。上述结果表明禾信GC-TQ 6000具有优异的重现性和检测灵敏度,满足检测需求。参考文献1. GB 23200.113-2018《食品安全国家标准 植物源性食品中208种农药及其代谢物残留量的测定 气相色谱-质谱联用法》附录表3. 113种农药和内标的保留时间和特征离子信息表序号名 称CAS RT,min定量离子对碰撞能V定性离子对碰撞能V1硫草敌2941-55-17.154100.0->72.05161.0->100.052联苯92-52-410.299154.0->153.010153.0->152.0103土菌灵2593-15-911.761211.0->183.05183.0->140.0104氯苯甲醚2675-77-613.539191.0->113.010191.0->141.055四氯硝基苯117-18-015.111260.9->203.010214.9->179.056虫线磷297-97-216.186143.0->79.05175.0->79.057二苯胺122-39-416.699169.0->168.210168.0->167.2108仲丁威3766-81-216.96121.0->77.015121.0->103.1109乙丁氟灵1861-40-117.347292.0->264.05292.0->206.0510二溴磷300-76-517.506108.9->79.05144.9->109.0511甲拌磷298-02-217.632260.0->75.05230.9->128.91512氯苯胺灵101-21-317.924153.0->125.15153.0->90.01513五氯硝基苯82-68-818.312295.0->237.010236.9->142.91514氧乐果1113-02-618.972156.0->110.05110.0->79.0515阿特拉通1610-17-919.081169.0->154.05211.0->169.0516二嗪磷331-41-519.161137.0->84.05137.0->54.01517异噁草酮81777-89-119.322125.0->89.010204.0->107.01518百治磷141-66-219.497127.0->109.010127.0->95.01019嘧霉胺53112-28-019.607198.0->183.010198.0->118.02520γ-六六六58-89-919.877217.0->181.05181.0->145.01021乙嘧硫磷38260-54-720.052181.0->153.05168.0->153.0522克百威1563-66-220.096164.0->149.05164.0->131.01023莠去津1912-24-920.213215.0->200.05215.0->58.01024西玛津122-34-920.315201.0->173.05201.0->186.0525特丁津5915-41-320.483229.0->173.05173.0->172.0526绿谷隆1746-81-220.774126.0->99.05214.0->61.0527五氯苯胺527-20-821.028263.0->192.015265.0->194.01528氯唑磷42509-80-821.02161.0->119.05161.0->146.0529炔苯酰草胺23950-58-521.204173.0->145.010175.0->147.01030甲基毒死蜱5598-13-021.502286.0->93.020288.0->93.01531艾氏剂309-00-221.783263.0->193.025255.0->220.01032皮蝇磷299-84-322.002285.0->270.010287.0->272.01033敌草净1014-69-322.072213.0->171.05213.0->58.01034甲基立枯磷57018-04-922.142265.0->250.010265.0->93.02035扑草净7287-19-622.528199.0->184.05226.0->184.0536莠灭净834-12-822.677227.0->170.05227.0->58.01037β-六六六319-85-722.905217.0->181.05181.0->145.01038特丁净886-50-023.037185.0->170.05241.0->170.01039毒死蜱2921-88-223.045197.0->169.010199.0->171.01040磷胺-113171-21-623.344127.0->109.05127.0->95.01041马拉氧磷1634-72-823.344127.0->99.05127.0->55.0542异丙净4147-51-723.405255.0->222.05255.0->180.01043磷胺-213171-21-623.528127.0->109.05127.0->95.01044甲基对硫磷298-00-023.536263.0->109.05233.0->109.01545毒壤滕327-98-023.387299.0->271.010297.0->269.01046δ-六六六319-86-823.811217.0->181.05181.0->145.01047嘧啶磷23505-41-123.797318.0->182.05318.0->166.0548马拉硫磷121-75-524.078127.0->99.05173.0->99.01049烯虫酯40596-69-824.232153.0->111.05111.0->55.01050杀螟硫磷122-14-524.288277.0->260.05277.0->109.01051环氧七氯B1024-57-324.449352.8->262.915354.8->264.91552乙氧呋草黄26225-79-624.575207.0->161.05161.0->105.0553嘧菌环胺121552-61-224.393225.2->224.35224.2->208.21554氧异柳磷31120-85-124.825229.0->200.95229.0->121.02055二甲戊灵40487-42-124.899252.0->162.25252.0->161.11556毒虫畏470-90-625.609266.9->159.110322.8->266.81057敌稗709-98-825.569161.0->99.020161.0->90.01558o,p'-DDE3424-82-625.073246.0->176.225248.0->176.22559乙基溴硫磷4824-78-625.348358.7->302.810302.8->284.71060水胺硫磷24353-61-525.65135.9->108.010135.9->69.02061氯丹-反式5103-74-225.683372.8->265.820271.7->236.91062四氟醚唑112281-77-326.219336.0->203.825336.0->217.91063丁草胺23184-66-926.259236.9->160.25188.1->160.2564丙硫磷34643-46-426.454267.0->239.05309.0->239.01065氟丁酰草胺113614-08-727.058176.1->91.110221.0->193.1566杀虫畏22248-79-926.814329.0->109.015331.0->109.01067腐霉利32809-16-827.02196.0->67.1596.0->53.01068狄氏剂60-57-126.856263.0->193.025277.0->241.0569杀扑磷950-37-827.162144.9->85.05144.9->58.11070丙溴磷41198-08-727.223338.8->268.710207.9->63.02571敌草胺15299-99-727.448128.0->72.15128.0->100.1572己唑醇79983-71-427.577231.0->175.05256.0->82.11073抑草磷36335-67-827.619286.0->202.010200.0->92.0574多效唑76738-62-027.986236.0->125.110236.0->167.0575杀螨酯80-33-127.863175.0->111.05111.0->75.01076吡氟禾草灵69806-50-428.003281.9->91.010281.9->238.01077稻瘟灵50512-35-128.135162.1->134.05162.1->85.01078硫环磷947-02-428.258196.0->140.05168.0->140.0579乙酯杀螨醇510-15-628.521139.1->111.010251.1->139.11080除草醚1836-75-528.731202.0->139.115282.9->253.0581乙硫磷563-12-229.021230.9->129.015230.9->175.01082三氟硝草醚15457-05-329.336190.0->126.015190.0->132.010834,4'-滴滴涕50-29-329.389235.0->165.215237.0->165.21584烯唑醇83657-24-329.354267.9->232.05269.9->232.0585腈菌唑88671-89-029.529179.0->125.010179.0->90.02086环丙唑醇-1113096-99-429.573222.0->125.010139.1->111.01087苯霜灵71626-11-429.573148.0->77.025148.0->105.11088环丙唑醇-2113096-99-429.675222.0->125.010139.1->111.01089氟虫腈120068-37-329.696366.8->212.820368.8->214.82090丙环唑-160207-90-129.889172.9->145.010172.9->74.02591丙环唑-260207-90-130.011172.9->145.010172.9->74.02592禾草灵51338-27-329.976339.9->252.95253.0->162.01093倍硫磷亚砜3761-41-930.24278.0->109.015278.0->169.01094倍硫磷砜3761-42-030.668309.9->105.010135.9->92.0595咯菌腈131341-86-130.922248.0->182.010248.0->154.01596噁霜灵77732-09-330.944163.0->132.05163.0->117.02097乙螨唑153233-91-130.922141.0->113.010141.0->63.02098异菌脲36734-19-731.59187.0->124.010245.0->161.01599甲氧滴滴涕72-43-530.88227.1->169.015227.1->141.030100伐灭磷52-85-731.156218.0->109.010218.0->79.020101甲氰菊酯39515-41-831.156207.9->181.05264.9->210.05102哒嗪硫磷119-12-031.548340.0->199.05204.0->203.15103溴苯磷21609-90-531.41171.0->77.115154.9->77.110104亚胺硫磷732-11-631.845160.0->77.115160.0->133.15105甲羧除草醚42576-02-331.982189.1->126.015340.9->309.95106氯氟氰菊酯-168085-85-832.301197.0->141.010197.0->161.05107氟丙菊酯101007-06-132.301207.9->181.05288.9->92.85108氯氟氰菊酯-268085-85-832.396197.0->141.010197.0->161.05109伏杀硫磷2310-17-032.417182.0->111.010182.0->102.010110苯噻酰草胺73250-68-732.555192.0->136.110192.0->109.120111益棉磷2642-71-933.149132.0->77.110160.0->77.110112氟喹唑136426-54-533.597340.0->298.010108.0->57.010113氟氯氰菊酯-168359-37-534.171226.0->206.010198.9->170.115114氟氯氰菊酯-268359-37-534.424226.0->206.010198.9->170.115115氟氯氰菊酯-368359-37-534.494226.0->206.010198.9->170.115116蝇毒磷56-72-434.536361.9->109.010210.0->182.05117氟氯氰菊酯-468359-37-534.641226.0->206.010198.9->170.115118氟氰戊菊酯-170124-77-535.124156.9->107.110198.9->157.05119氟氰戊菊酯-270124-77-535.495156.9->107.110198.9->157.05120腈苯唑119611-00-635.712197.9->129.05128.9->102.010121氟胺氰菊酯-169409-94-536.777250.0->200.010250.0->55.010122氟胺氰菊酯-269409-94-536.91250.0->200.010250.0->55.010123苯醚甲环唑-1119446-68-337.464322.8->264.910264.9->202.010124苯醚甲环唑-2119446-68-337.464322.8->264.910264.9->202.010表4.113种农药化合物黄瓜基质加标精密度序号化合物加标量(mg/kg)序号化合物加标量(mg/kg)0.010.050.10.010.050.11硫草敌82.4%83.8%94.1%58水胺硫磷88.3%93.3%96.0%2联苯101.0%106.8%107.2%59氯丹-反式86.5%87.9%92.2%3土菌灵87.2%89.6%98.3%60四氟醚唑91.7%90.4%98.4%4氯苯甲醚94.6%94.9%96.2%61丁草胺89.5%94.1%99.4%5四氯硝基苯80.6%85.1%89.9%62丙硫磷86.7%90.0%94.9%6虫线磷86.2%91.7%94.6%63氟丁酰草胺91.9%93.6%99.6%7二苯胺92.7%79.2%87.8%64杀虫畏89.9%92.1%98.4%8仲丁威73.7%81.3%80.8%65腐霉利92.8%86.2%95.1%9乙丁氟灵70.6%78.4%74.4%66狄氏剂93.9%94.3%99.3%10二溴磷90.4%94.2%92.0%67杀扑磷88.4%92.0%98.4%11甲拌磷90.4%85.1%89.5%68丙溴磷85.9%84.1%84.3%12氯苯胺灵104.2%100.3%107.3%69敌草胺93.6%93.3%91.8%13五氯硝基苯85.8%82.1%87.8%70己唑醇96.1%91.3%90.1%14氧乐果82.9%88.3%84.7%71抑草磷76.2%82.4%81.8%15阿特拉通87.2%91.1%87.6%72多效唑96.4%97.0%99.9%16二嗪磷78.2%84.5%86.8%73杀螨酯107.9%108.2%106.0%17异噁草酮74.6%81.5%83.7%74吡氟禾草灵92.4%93.6%99.4%18百治磷87.1%93.0%90.2%75稻瘟灵96.7%95.5%101.9%19嘧霉胺86.2%85.7%92.3%76硫环磷82.2%87.4%86.3%20γ-六六六75.3%79.9%77.2%77乙酯杀螨醇105.7%100.6%105.6%21乙嘧硫磷78.9%83.6%83.6%78除草醚90.7%93.9%91.5%22克百威92.0%97.8%101.0%79乙硫磷99.4%101.2%104.8%23莠去津95.5%96.0%101.4%80三氟硝草醚81.0%90.5%93.8%24西玛津97.6%95.4%102.8%814,4'-滴滴涕95.8%103.8%101.5%25特丁津95.6%95.3%99.3%82烯唑醇92.1%92.3%100.9%26绿谷隆87.4%86.4%92.5%83腈菌唑101.4%98.8%99.2%27五氯苯胺78.7%82.1%88.0%84环丙唑醇95.1%96.0%104.4%28氯唑磷82.0%87.9%88.3%85苯霜灵104.0%97.5%107.9%29炔苯酰草胺93.4%95.1%101.1%86氟虫腈95.1%98.6%100.9%30甲基毒死蜱79.9%85.2%84.6%87丙环唑111.9%101.0%106.7%31艾氏剂79.8%82.6%79.8%88禾草灵99.9%91.3%106.9%32皮蝇磷81.4%83.9%84.7%89倍硫磷亚砜104.7%108.1%106.1%33敌草净98.8%95.3%101.1%90倍硫磷砜98.55%92.5%98.2%34甲基立枯磷84.7%88.3%90.2%91咯菌腈106.4%103.4%105.5%35扑草净94.1%93.5%101.5%92噁霜灵98.7%98.4%99.4%36莠灭净94.2%93.3%100.1%93乙螨唑97.0%94.7%95.5%37β-六六六89.5%92.4%97.5%94异菌脲102.6%110.2%108.6%38特丁净93.6%92.6%99.9%95甲氧滴滴涕98.3%100.5%92.7%39毒死蜱89.9%91.5%95.0%96伐灭磷101.0%100.1%107.3%40磷胺84.2%89.5%86.8%97甲氰菊酯96.7%94.3%96.2%41马拉氧磷91.9%93.4%89.9%98哒嗪硫磷95.4%89.9%95.4%42异丙净88.5%89.2%87.2%99溴苯磷97.7%95.3%100.3%43甲基对硫磷80.0%83.6%85.1%100亚胺硫磷87.4%87.1%86.2%44毒壤滕84.4%85.9%82.5%101甲羧除草醚97.65%98.8%104.1%45δ-六六六94.1%92.5%90.9%102氯氟氰菊酯97.0%97.6%99.6%46嘧啶磷83.1%86.9%92.8%103氟丙菊酯92.0%92.5%95.6%47马拉硫磷89.1%91.8%88.2%104伏杀硫磷96.1%94.2%93.7%48烯虫酯85.7%82.7%88.1%105苯噻酰草胺114.4%118.4%119.2%49杀螟硫磷76.4%82.3%87.0%106益棉磷103.5%97.5%95.5%50乙氧呋草黄97.8%97.2%103.1%107氟喹唑94.4%90.8%98.1%51嘧菌环胺119.8%119.7%119.3%108氟氯氰菊酯100.6%106.3%104.9%52氧异柳磷107.7%113.1%113.4%109蝇毒磷96.7%93.9%103.6%53二甲戊灵70.6%81.5%83.9%110氟氰戊菊酯101.5%101.1%107.4%54毒虫畏87.5%91.6%87.4%111腈苯唑98.1%106.7%105.7%55敌稗92.7%95.2%93.8%112氟胺氰菊酯97.4%97.2%104.7%56o,p'-DDE104.4%107.1%103.3%113苯醚甲环唑94.6%89.8%92.0%57乙基溴硫磷87.1%87.6%90.5%禾信质谱 股票代码HEXIN MASS SPECTROMETRY688622 GB23200.113-2018 分析果蔬中1208 种农药 LAN FHH CT060DA 添信用 C C GC-TQ 6000 GB 23200.113-2018 A组分析果蔬中 107种农药 前言 农药是农业上用于防治病虫害及调 节植物生长的化学试剂,广泛用于农林牧 业生产、环境和家庭卫生除害防疫、工业 品防霉和防蛀等。农药的大量使用容易会 导致其在食物链及环境中残留,对人类健 康和生态环境造成潜在的危害。因此,建 立各类果蔬中农药残留的准确定性定量 方法,为老百姓食品安全提供重要保障。 本文参考《食品安全国家标准植物 源性食品中 208种农药及其代谢物残留 量的测定气相色谱-质谱联用法》标准 (GB23200.113-2018),使用气相色谱-串联三重四极杆质谱联用仪对黄瓜基质 中的 107多种农药及相关化学品进行检 测分析,通过定量限、精密度和准确度等 指标评估仪器性能,证明GC-TQ 6000满 足检测的需要。 实验部分 样品前处理 准确称取 10 g黄瓜样品于 50 mL离 心管中,加入 10 mL乙腈和 1包 QuEChERS萃取盐包,盖上离心管,剧 烈振荡 3 min后 4200 r/min离心 5 min。吸取6 mL上清液加到内含净化盐包的15mL离心管中,涡旋混匀 2 min。4200 r/min 离心 5 min,准确吸取 2 mL上清液于 10 mL试管中,40℃水浴氮吹近干。加入 10μL内标溶液,1mL乙酸乙酯溶液复溶,过 0.22 μm有机滤膜,待测。 仪器条件 表1.仪器方法参数 模块 参数 值 色谱 进样口温度 280 °C 进样方式 不分流 色谱柱 VF-1701MS, 30 m × 0.25 mm × 0.25 μm 升温程序 起始温度 40°C,保持 1 min,以 40°C/min升至 120 °C,再以5 °C/min升 至240 °C,再以12℃/min 升至300℃,保持6min 载气 氦气 柱流量 1.0 mL/min恒流模式 质谱 离子源 EI,70eV 离子源温度 280 °C 传输线温度 280 °C 检测器电压 -1300 V 溶剂延迟 4min 碰撞气流量 20psi 射出电压(CXP) 3V 采集模式 MRM 结果与讨论 1、标准谱图和物质信息 实验总离子流图见图1,107种农药目标化合物浓度为500 μg/L,内标物浓度为100 μg/L。107种目标化合物以及内标的保留时间以及特征离子信息见附录表3。 图1 107种农药目标化合物总离子流图(500 μg/L) 2、标准曲线 黄瓜空白基质溶液氮吹近干,分别加入 1 mL浓度为 5 μg/L、10 μg/L、20 μg/L、50 μg/L、100 μg/L、200 μg/L、500 μg/L,内标含量为 100 μg/L的混合标准曲线溶液进行分析。107种农药的线性相关系数R均大于 0.995。 (a)敌敌畏 (b)一溴二氯甲烷 (c)啶酰菌胺 图 2三种代表性农药目标化合物的标准曲线图 3、黄瓜加标回收实验 3.1精密度和准确度 分别对 10g黄瓜样品进行加标浓度为 0.01 mg/kg、0.05 mg/kg、0.1 mg/kg各六次平行 实验,对精密度和准确度进行评估,准确度具体信息详见附录表 4。浓度为 0.01 mg/kg、0.05 mg/kg和 0.1 mg/kg时,107种农药化合物的相对标准偏差(RSD)分别为 1.90%-14.54%、1.43%-9.32%和 1.00%-4.81%,回收率分别为 65.8%-121.2%、66.0%-117.8%、67.2%-113.3%。 3.2定量限 按照标准GB/T23200.113-2018《食品安全国家标准植物源性食品中 208种农药及其 代谢物残留量的测定气相色谱-质谱联用法》对 10g黄瓜进行加标量为 0.01 mg/kg的 7次 平行回收实验,计算其标准偏差(SD),根据方法定量限 LOQ=10×SD计算目标化合物的 方法定量限,通过计算可知 107种农药化合物的方法定量限为 0.001 mg/kg-0.010 mg/kg。 表2.107种农药化合物黄瓜基质加标方法定量限 序 方法 标准要求 序 方法 标准要求 化合物 定量限 方法定量限 化合物 定量限 方法定量限 号 号 (mg/kg) (mg/kg) (mg/kg) (mg/kg) 1 敌敌畏 0.010 0.01 55 4,4'-滴滴伊 0.003 0.01 2 甲胺磷 0.002 0.01 56 苯硫威 0.002 0.01 3 敌草腈 0.010 0.01 57 嘧菌胺 0.003 0.01 4 速灭磷 0.006 0.01 58 脱叶磷 0.010 0.01 5 虫螨畏 0.005 0.01 59 甲拌磷砜 0.002 0.01 6 禾草敌 0.010 0.01 60 除草定 0.005 0.01 7 环草敌 0.003 0.01 61 三唑醇 0.005 0.01 8 异丙威 0.003 0.01 62 溴苯烯磷 0.003 0.01 9 乙酰甲胺磷 0.003 0.01 63 丙草胺 0.003 0.01 10 六氯苯 0.006 0.01 64 2,4'-滴滴滴 0.004 0.01 11 灭线磷 0.003 0.01 65 醚菌酯 0.010 0.01 12 乙丁烯氟灵 0.002 0.01 66 异狄氏剂 0.010 0.01 13 残杀威 0.003 0.01 67 灭菌磷 0.002 0.01 14 治螟磷 0.003 0.01 68 噁草酮 0.003 0.01 15 α-六六六 0.004 0.01 69 2,4-滴滴涕 0.002 0.01 16 脱乙基莠去津 0.004 0.01 70 抑霉唑 0.005 0.01 17 特丁硫磷 0.002 0.01 71 地胺磷 0.002 0.01 18 敌噁磷 0.006 0.01 72 环氟菌胺 0.010 0.01 19 野麦畏 0.002 0.01 73 虫螨磷 0.005 0.01 20 环丙氟灵 0.005 0.01 74 乙嘧酚磺酸酯 0.004 0.01 21 地虫硫磷 0.003 0.01 75 乙氧氟草醚 0.004 0.01 22 丁基嘧啶磷 0.002 0.01 76 噁唑啉 0.004 0.01 23 扑灭津 0.003 0.01 77 氟酰胺 0.003 0.01 24 氯硝胺 0.004 0.01 78 4,4'-滴滴滴 0.003 0.01 25 胺丙畏 0.003 0.01 79 β-硫丹 0.006 0.01 26 异稻瘟净 0.010 0.01 80 喹氧灵 0.002 0.01 27 除线磷 0.002 0.01 81 苯草醚 0.002 0.01 28 抗蚜威 0.003 0.01 82 肟菌酯 0.004 0.01 29 久效磷 0.003 0.01 83 三硫磷 0.005 0.01 30 乐果 0.007 0.01 84 增效醚 0.004 0.01 31 乙草胺 0.004 0.01 85 敌瘟磷 0.002 0.01 32 甲草胺 0.003 0.01 86 丰索磷 0.004 0.01 33 甲基嘧啶磷 0.004 0.01 87 联苯菊酯 0.003 0.01 34 甲基对氧磷 0.004 0.01 88 三唑磷 0.005 0.01 35 乙烯菌核利 0.004 0.01 89 吡螨胺 0.002 0.01 序 方法 标准要求 序 方法 标准要求 化合物 定量限 方法定量限 化合物 定量限 方法定量限 号 号 (mg/kg) (mg/kg) (mg/kg) (mg/kg) 36 嗪草酮 0.002 0.01 90 溴螨酯 0.002 0.01 37 甲霜灵 0.009 0.01 91 胺菊酯 0.009 0.01 38 禾草丹 0.009 0.01 92 氟环唑 0.003 0.01 39 异丙甲草胺 0.010 0.01 93 戊唑醇 0.004 0.01 40 安硫磷 0.005 0.01 94 吡丙醚 0.005 0.01 41 三氯杀螨醇 0.005 0.01 95 哌草磷 0.004 0.01 42 倍硫磷 0.003 0.01 96 苯硫磷 0.009 0.01 43 溴硫磷 0.004 0.01 97 环嗪酮 0.002 0.01 44 对氧磷 0.010 0.01 98 咪唑菌酮 0.003 0.01 45 三唑酮 0.006 0.01 99 三氯杀螨砜 0.010 0.01 46 烯丙菊酯 0.007 0.01 100 莎稗磷 0.006 0.01 47 对硫磷 0.005 0.01 101 氯菊酯 0.005 0.01 48 甲基异柳磷 0.001 0.01 102 氯苯嘧啶醇 0.004 0.01 49 异柳磷 0.005 0.01 103 哒螨灵 0.008 0.01 50 α-硫丹 0.010 0.01 104 氯氰菊酯 0.009 0.01 51 喹硫磷 0.002 0.01 105 啶酰菌胺 0.003 0.01 52 戊菌唑 0.003 0.01 106 氰戊菊酯 0.010 0.01 53 甲拌磷亚砜 0.003 0.01 107 溴氰菊酯 0.010 0.01 54 噻唑滕 0.003 0.01 结论 本文依据GB 23200.113-2018《食品安全国家标准植物源性食品中 208种农药及其代 谢物残留量的测定气相色谱-质谱联用法》,采用禾信GC-TQ 6000对黄瓜进行加标回收 实验,结果显示 107种农药化合物的线性相关系数R均大于 0.995;黄瓜基质加标精密度 在1.00%-14.54%范围,加标回收率在 65.8%-121.2%范围;方法定量限范围为0.001mg/kg-0.010 mg/kg。上述结果表明禾信GC-TQ 6000具有优异的重现性和检测灵敏度,满 足检测需求。 参考文献 1. GB 23200.113-2018《食品安全国家标准植物源性食品中 208种农药及其代谢物残 留量的测定气相色谱-质谱联用法》 附录 表3. 107种农药和内标的保留时间和特征离子信息表 序 名称 CAS RT,min 定量离子对 碰撞能 定性离子对 碰撞能 号 V V 1 敌敌畏 62-73-7 8.858 109.0->79.0 5 185.0->93.0 10 2 甲胺磷 10265-92-6 10.635 141.0->95.0 5 141.0->79.0 10 序 号 名称 CAS RT,min 定量离子对 碰撞能 V 定性离子对 碰撞能 V 3 敌草腈 1194-65-6 11.228 171.0->100.0 20 171.0->136.0 10 4 速灭磷 1 7786-34-7 13.057 127.0->109.0 5 127.0->95.0 10 5 速灭磷 2 7786-34-7 13.268 127.0->109.0 5 127.0->95.0 10 6 虫螨畏 62610-77-9 13.800 207.9->180.0 5 207.9->93.0 10 7 禾草敌 2212-67-1 13.814 126.2->55.1 10 126.2->83.1 5 8 环草敌 1134-23-2 15.421 154.1->83.1 5 154.1->72.1 5 9 异丙威 2631-40-5 15.589 121.0->77.1 10 136.0->121.0 5 10 乙酰甲胺磷 30560-19-1 15.736 136.0->94.0 10 136.0->42.0 5 11 六氯苯 118-74-1 15.981 283.8->248.8 10 283.8->213.9 25 12 灭线磷 13194-48-4 16.486 157.9->97.0 10 157.9->114.0 5 13 乙丁烯氟灵 55283-68-6 16.878 275.9->202.1 10 315.9->275.9 5 14 残杀威 114-26-1 17.473 110.0->64.0 10 110.0->63.0 20 15 治螟磷 3689-24-5 17.634 237.8->145.9 10 201.8->145.9 5 16 α-六六六 319-84-6 18.174 218.9->183.0 5 216.9->181.0 5 17 脱乙基莠去津 6190-65-4 19.077 187.0->172.0 5 172.0->94.0 10 18 特丁硫磷 13071-79-9 19.093 230.9->129.0 20 230.9->175.0 10 19 敌噁磷 78-34-2 19.093 125.0->97.0 5 153.0->97.0 5 20 野麦畏 2303-17-5 19.264 268.0->184.1 10 142.9->83.0 10 21 环丙氟灵 26399-36-0 19.413 317.9->199.0 10 317.9->54.8 10 22 地虫硫磷 944-22-9 19.545 136.9->109.0 5 245.9->137.0 5 23 丁基嘧啶磷 96182-53-5 19.662 260.8->137.2 10 233.9->110.1 10 24 扑灭津 139-40-2 20.044 214.2->172.2 5 229.1->58.1 10 25 氯硝胺 99-30-9 20.271 206.1->176.0 5 160.1->124.1 5 26 胺丙畏 31218-83-4 20.388 138.0->110.0 5 138.0->64.0 10 27 异稻瘟净 26087-47-8 20.874 203.9->91.0 5 121.9->121.0 10 28 除线磷 97-17-6 20.992 278.9->222.9 10 222.9->204.9 10 29 抗蚜威 23103-98-2 21.056 238.0->166.2 10 166.0->55.1 10 30 久效磷 6923-22-4 21.316 127.1->109.0 10 127.1->95.0 10 31 乐果 60-51-5 21.617 86.9->46.0 10 142.9->111.0 5 32 乙草胺 34256-82-1 21.917 222.9->132.2 10 222.9->147.2 5 33 甲草胺 15972-60-8 22.304 188.1->160.2 5 160.2->132.1 5 34 甲基嘧啶磷 29232-93-7 22.486 290.0->125.0 15 232.9->151.0 5 35 甲基对氧磷 950-35-6 22.652 229.9->136.0 5 229.9->106.0 10 36 乙烯菌核利 50471-44-8 22.762 197.9->145.0 10 187.0->124.0 10 37 嗪草酮 21087-64-9 22.92 198.0->82.0 10 198.0->55.0 25 38 甲霜灵 57837-19-1 23.015 234.0->146.1 10 220.0->192.1 5 39 禾草丹 28249-77-6 23.173 100.0->72.0 5 124.9->89.0 10 40 异丙甲草胺 51218-45-2 23.684 238.0->162.2 10 162.2->133.2 10 41 安硫磷 2540-82-1 23.771 170.0->93.0 10 197.9->92.9 5 42 三氯杀螨醇 115-32-2 23.899 139.0->111.0 10 250.9->138.9 10 43 倍硫磷 55-38-9 23.986 278.0->109.0 10 278.0->169.0 10 44 溴硫磷 2104-96-3 24.04 330.8->315.8 10 328.8->313.8 10 碰撞能 碰撞能 序 号 名称 CAS RT,min 定量离子对 碰撞能 V 定性离子对 碰撞能 V 45 对氧磷 311-45-5 24.328 108.9->91.0 5 148.9->119.0 5 46 环氧七氯B 1024-57-3 24.415 352.8->262.9 15 354.8->264.9 15 (内标) 47 三唑酮 43121-43-3 24.844 208.0->181.1 5 208.0->111.0 10 48 烯丙菊酯 584-79-2 24.851 123.0->81.0 5 107.0->91.0 5 49 对硫磷 56-38-2 25.005 290.9->109.0 10 138.9->109.0 5 50 甲基异柳磷 99675-03-3 25.072 199.0->121.0 10 241.1->199.1 5 51 异柳磷 25311-71-1 25.404 212.9->121.1 10 212.9->185.1 5 52 α-硫丹 959-98-8 25.436 194.9->159.0 5 194.9->125.0 20 53 喹硫磷 13593-03-8 25.56 146.0->118.0 10 146.0->91.0 30 54 戊菌唑 66246-88-6 25.835 248.0->157.0 25 248.0->192.0 10 55 甲拌磷亚砜 2588-03-6 26.134 199.0->142.9 5 96.9->64.9 20 56 噻唑滕 1 98886-44-3 26.296 195.0->103.0 5 195.0->60.0 20 57 4,4'-滴滴伊 72-55-9 26.327 246.1->176.2 25 315.8->246.0 10 58 噻唑滕 2 98886-44-3 26.396 195.0->103.0 5 195.0->60.0 20 59 苯硫威 62850-32-2 26.477 160.1->72.0 10 72.0->56.0 15 60 嘧菌胺 110235-47-7 26.706 223.2->222.2 10 222.2->207.2 10 61 脱叶磷 78-48-8 26.753 202.0->147.0 10 169.0->57.1 10 62 甲拌磷砜 2588-04-7 26.912 153.0->97.0 5 124.9->96.9 5 63 除草定 314-40-9 26.99 205.0->188.0 10 207.0->190.0 10 64 三唑醇 55219-65-3 27.093 168.0->70.0 5 128.0->65.0 10 65 溴苯烯磷 33399-00-7 27.093 266.9->159.1 10 268.9->161.1 10 66 丙草胺 51218-49-6 27.251 162.0->132.0 10 262.0->202.0 5 67 2,4'-滴滴滴 53-19-0 27.402 235.0->165.2 20 237.0->165.2 20 68 醚菌酯 143390-89-0 27.465 116.0->89.0 5 116.0->63.0 30 69 异狄氏剂 72-20-8 27.536 262.8->193.0 25 244.8->173.0 20 70 灭菌磷 5131-24-8 27.536 130.0->102.1 10 148.0->130.1 15 71 噁草酮 19666-30-9 27.567 174.9->112.0 15 174.9->76.0 35 72 2,4-滴滴涕 789-02-6 27.888 235.0->165.0 20 237.0->165.0 20 73 抑霉唑 35554-44-0 27.916 214.9->173.0 5 216.8->175.0 5 74 地胺磷 950-10-7 28.137 168.0->139.9 5 196.0->139.9 10 75 环氟菌胺 180409-60-3 28.156 118.1->90.0 5 118.1->89.0 10 76 虫螨磷 1 60238-56-4 28.292 324.8->268.9 10 296.8->268.9 5 77 乙嘧酚磺酸酯 41483-43-6 28.382 272.9->193.1 5 272.9->108.0 10 78 乙氧氟草醚 42874-03-3 28.687 252.0->146.0 25 252.0->196.0 15 79 虫螨磷 2 60238-56-4 28.741 324.8->268.9 10 296.8->268.9 5 80 噁唑啉 18854-01-8 28.754 177.1->130.0 5 177.1->116.0 10 81 氟酰胺 66332-96-5 28.828 173.0->145.1 10 280.9->173.0 10 82 4,4'-滴滴滴 72-54-8 28.922 234.9->165.1 20 236.9->165.2 20 83 β-硫丹 33213-65-9 29.029 206.9->172.0 10 194.9->124.9 20 84 喹氧灵 124495-18-7 29.19 237.0->208.1 20 271.9->237.1 10 85 苯草醚 74070-46-5 29.357 264.1->194.2 10 212.1->182.2 10 序 号 名称 CAS RT,min 定量离子对 碰撞能 V 定性离子对 碰撞能 V 86 肟菌酯 141517-21-7 29.371 116.0->89.0 10 131.0->89.0 20 87 三硫磷 786-19-6 29.438 153.0->96.9 5 199.0->143.0 5 88 增效醚 51-03-6 29.585 176.0->103.0 20 176.0->131.0 15 89 敌瘟磷 17109-49-8 29.93 172.9->109.0 10 201.0->109.0 10 90 丰索磷 115-90-2 30.103 291.8->156.0 10 291.8->108.8 10 91 联苯菊酯 82657-04-3 30.197 181.2->165.2 20 181.2->166.2 10 92 三唑磷 24017-47-8 30.217 161.2->134.2 5 161.2->106.1 10 93 吡螨胺 119168-77-3 30.689 275.9->171.1 10 332.9->171.0 15 94 溴螨酯 18181-80-1 30.904 185.0->157.0 10 183.0->155.0 10 95 胺菊酯 1 7696-12-0 30.911 164.0->107.0 10 164.0->77.0 20 96 氟环唑 133855-98-8 30.974 192.0->138.0 5 192.0->111.0 15 97 胺菊酯 2 7696-12-0 31.079 164.0->107.0 10 164.0->77.0 20 98 戊唑醇 107534-96-3 31.142 250.0->125.0 10 250.0->153.0 5 99 吡丙醚 95737-68-1 31.339 136.0->78.0 10 136.0->96.0 10 100 哌草磷 24151-93-7 31.479 320.0->122.0 10 140.0->98.0 5 101 苯硫磷 2104-64-5 31.556 169.0->141.1 5 169.0->77.1 10 102 环嗪酮 51235-04-2 31.605 171.0->71.1 5 171.0->85.1 10 103 咪唑菌酮 161326-34-7 31.633 238.0->237.2 5 268.0->180.2 20 104 三氯杀螨砜 116-29-0 31.931 158.9->131.0 5 226.9->199.0 10 105 莎稗磷 64249-01-0 32.043 225.9->184.0 10 255.9->157.0 5 106 氯菊酯 1 52645-53-1 32.424 183.1->168.1 10 183.1->153.0 10 107 氯菊酯 2 52645-53-1 32.659 183.1->168.1 10 183.1->153.0 10 108 氯苯嘧啶醇 60168-88-9 32.702 251.0->139.1 10 219.0->107.0 10 109 哒螨灵 96489-71-3 33.026 147.2->132.2 10 147.2->117.1 20 110 氯氰菊酯 1 52315-07-8 34.393 163.0->91.0 10 163.0->109.0 10 111 氯氰菊酯 2 52315-07-8 34.659 163.0->91.0 10 163.0->109.0 10 112 氯氰菊酯 3 52315-07-8 34.729 163.0->91.0 10 163.0->109.0 10 113 氯氰菊酯 4 52315-07-8 34.877 163.0->91.0 10 163.0->109.0 10 114 啶酰菌胺 188425-85-6 35.391 140.0->112.0 5 140.0->76.0 15 115 氰戊菊酯 1 51630-58-1 36.018 167.0->125.0 10 224.9->119.0 10 116 氰戊菊酯 2 51630-58-1 36.484 167.0->125.0 10 224.9->119.0 10 117 溴氰菊酯 52918-63-5 37.812 250.7->172.0 5 252.9->93.0 10 表 4.107种农药化合物黄瓜基质加标精密度 序号 加标量(mg/kg) 化合物 序号 0.01 0.05 0.1 化合物 加标量(mg/kg) 0.01 0.05 0.1 1 敌敌畏 70.6% 74.6% 72.47% 55 4,4'-滴滴伊 100.3% 101.6% 98.0% 2 甲胺磷 72.3% 80.7% 83.43% 56 苯硫威 87.8% 97.7% 99.2% 3 敌草腈 73.2% 68.6% 70.3% 57 嘧菌胺 85.5% 87.0% 84.8% 4 速灭磷 77.4% 91.4% 92.3% 58 脱叶磷 81.7% 89.0% 88.6% 5 虫螨畏 78.7% 85.6% 79.0% 59 甲拌磷砜 82.9% 92.8% 97.9% 6 禾草敌 71.3% 81.2% 80.6% 60 除草定 79.0% 101.6% 104.6% 7 环草敌 75.9% 90.7% 86.6% 61 三唑醇 86.5% 97.6% 99.9% 加标量(mg/kg) 加标量(mg/kg) 序号 化合物 加标量(mg/kg) 序号 0.01 0.05 0.1 化合物 加标量(mg/kg) 0.01 0.05 0.1 8 异丙威 84.8% 90.5% 91.2% 62 溴苯烯磷 81.1% 100.4% 92.9% 9 乙酰甲胺磷 76.0% 78.6% 83.5% 63 丙草胺 86.2% 94.7% 99.6% 10 六氯苯 83.5% 77.6% 82.1% 64 2,4'-滴滴滴 95.7% 108.9% 101.6% 11 灭线磷 78.2% 92.2% 91.0% 65 醚菌酯 95.4% 103.8% 100.4% 12 乙丁烯氟灵 72.0% 89.2% 88.7% 66 异狄氏剂 93.7% 99.9% 98.1% 13 残杀威 84.5% 97.7% 93.4% 67 灭菌磷 65.8% 66.0% 68.1% 14 治螟磷 75.9% 95.2% 89.3% 68 噁草酮 91.8% 98.2% 98.0% 15 α-六六六 75.6% 90.2% 85.7% 69 2,4-滴滴涕 75.1% 85.6% 89.2% 16 脱乙基莠去津 88.0% 94.3% 96.8% 70 抑霉唑 84.7% 95.7% 94.2% 17 特丁硫磷 75.4% 98.2% 88.6% 71 地胺磷 89.4% 94.0% 95.7% 18 敌噁磷 82.2% 97.2% 90.9% 72 环氟菌胺 99.4% 107.7% 105.2% 19 野麦畏 89.5% 97.0% 92.1% 73 虫螨磷 88.6% 87.7% 97.6% 20 环丙氟灵 83.8% 85.1% 95.4% 74 乙嘧酚磺酸酯 86.9% 91.0% 97.1% 21 地虫硫磷 89.1% 92.5% 93.5% 75 乙氧氟草醚 90.4% 104.3% 104.5% 22 丁基嘧啶磷 82.6% 95.4% 92.2% 76 噁唑啉 94.8% 88.1% 94.1% 23 扑灭津 88.2% 102.4% 94.1% 77 氟酰胺 115.6% 101.1% 108.5% 24 氯硝胺 93.6% 96.8% 100.5% 78 4,4'-滴滴滴 95.2% 108.1% 103.8% 25 胺丙畏 82.3% 89.7% 99.4% 79 β-硫丹 95.6% 99.8% 101.1% 26 异稻瘟净 95.4% 90.9% 86.4% 80 喹氧灵 84.5% 92.4% 94.8% 27 除线磷 83.8% 93.2% 92.6% 81 苯草醚 99.2% 103.5% 102.6% 28 抗蚜威 87.0% 91.8% 92.7% 82 肟菌酯 83.9% 98.4% 101.2% 29 久效磷 85.1% 102.4% 98.3% 83 三硫磷 90.1% 95.1% 101.1% 30 乐果 98.8% 110.9% 103.1% 84 增效醚 92.0% 100.2% 102.4% 31 乙草胺 88.7% 103.3% 92.8% 85 敌瘟磷 85.7% 94.8% 96.3% 32 甲草胺 87.9% 92.3% 94.0% 86 丰索磷 121.2% 115.6% 109.5% 33 甲基嘧啶磷 87.7% 96.2% 92.8% 87 联苯菊酯 116.8% 109.8% 108.7% 34 甲基对氧磷 87.0% 97.0% 100.6% 88 三唑磷 92.6% 99.4% 96.3% 35 乙烯菌核利 87.4% 97.4% 94.5% 89 吡螨胺 87.5% 98.3% 95.7% 36 嗪草酮 86.5% 99.4% 95.3% 90 溴螨酯 94.7% 103.7% 100.9% 37 甲霜灵 112.9% 117.8% 113.3% 91 胺菊酯 101.7% 107.9% 102.6% 38 禾草丹 89.6% 106.0% 93.4% 92 氟环唑 91.5% 101.2% 100.7% 39 异丙甲草胺 95.4% 99.2% 95.1% 93 戊唑醇 90.1% 103.6% 99.3% 40 安硫磷 68.6% 66.38% 67.2% 94 吡丙醚 93.0% 94.3% 104.6% 41 三氯杀螨醇 98.1% 111.5% 113.0% 95 哌草磷 90.5% 95.9% 100.7% 42 倍硫磷 83.8% 91.0% 94.1% 96 苯硫磷 95.6% 104.7% 105.0% 43 溴硫磷 81.8% 81.4% 90.6% 97 环嗪酮 92.9% 98.9% 98.7% 44 对氧磷 103.9% 112.1% 108.0% 98 咪唑菌酮 96.9% 106.7% 102.5% 45 三唑酮 88.7% 98.4% 95.4% 99 三氯杀螨砜 92.9% 97.3% 104.3% 46 烯丙菊酯 77.3% 79.7% 70.5% 100 莎稗磷 86.9% 97.0% 93.6% 47 对硫磷 82.5% 98.9% 90.4% 101 氯菊酯 99.0% 104.8% 99.6% 48 甲基异柳磷 84.7% 94.7% 95.6% 102 氯苯嘧啶醇 90.9% 105.1% 95.7% 49 异柳磷 86.2% 91.0% 88.4% 103 哒螨灵 101.4% 94.9% 90.9% 序号 化合物 加标量(mg/kg) 序号 化合物 加标量(mg/kg) 0.01 0.05 0.1 0.01 0.05 0.1 50 α-硫丹 108.4% 101.1% 99.9% 104 氯氰菊酯 90.6% 97.6% 96.3% 51 喹硫磷 82.4% 88.6% 96.3% 105 啶酰菌胺 88.65% 92.0% 100.1% 52 戊菌唑 86.3% 100.5% 96.4% 106 氰戊菊酯 91.6% 100.2% 99.5% 53 甲拌磷亚砜 85.7% 95.2% 96.0% 107 溴氰菊酯 77.7% 76.9% 82.6% 54 噻唑滕 88.3% 96.8% 95.5% GB 23200.113-2018 B组分析果蔬中 113种农药 前言 农药是农业上用于防治病虫害及调节 植物生长的化学试剂,广泛用于农林牧业 生产、环境和家庭卫生除害防疫、工业品 防霉和防蛀等。农药的大量使用容易会导 致其在食物链及环境中残留,对人类健康 和生态环境造成潜在的危害。因此,建立 各类果蔬中农药残留的准确定性定量方法,为老百姓食品安全提供重要保障。 本文参考《食品安全国家标准植物源 性食品中 208种农药及其代谢物残留量的 测定 气相色谱-质谱联用法》标准(GB 23200.113-2018),使用气相色谱-串联三重 四极杆质谱联用仪对黄瓜基质中的 113多 种农药及相关化学品进行检测分析,通过 定量限、精密度和准确度等指标评估仪器 性能,证明GC-TQ 6000满足检测的需要。 实验部分 样品前处理 准确称取 10 g黄瓜样品于 50 mL离心 管中,加入 10 mL乙腈和 1包QuEChERS 萃取盐包,盖上离心管,剧烈振荡3min 后 4200 r/min离心 5 min。吸取 6 mL上清 液加到内含净化盐包的 15 mL离心管中,涡旋混匀 2 min。4200 r/min离心 5 min, 准确吸取 2 mL上清液于 10mL试管中,40℃水浴氮吹近干。加入 10 μL内标溶液,1mL乙酸乙酯溶液复溶,过 0.22 μm有机 滤膜,待测。 仪器条件 表1. 仪器方法参数 模块 参数 值 色谱 进样口温度 280 °C 进样方式 不分流 色谱柱 VF-1701MS, 30 m × 0.25 mm × 0.25 μm 升温程序 起始温度 40°C,保持 1 min,以 40°C/min升至 120 °C,再以5 °C/min升 至240 °C,再以12℃/min 升至300℃,保持6min 载气 氦气 柱流量 1.0 mL/min 恒流模式 质谱 离子源 EI,70eV 离子源温度 280 °C 传输线温度 280 °C 检测器电压 -1300 V 溶剂延迟 4min 碰撞气流量 20psi 射出电压(CXP) 3V 采集模式 MRM 结果与讨论 1、标准谱图和物质信息 实验总离子流图见图1,113种农药目标化合物浓度为500 μg/L,内标物浓度为100 μg/L。113种目标化合物以及内标的保留时间以及特征离子信息见附录表3。 图1 113种农药目标化合物总离子流图(500 μg/L) 2、标准曲线 黄瓜空白基质溶液氮吹近干,分别加入1 mL浓度为5 μg/L、10 μg/L、20 μg/L、50μg/L、100 μg/L、200 μg/L、500 μg/L,内标含量为100 μg/L的混合标准曲线溶液进行分 析。113种农药的线性相关系数R均大于0.995。 图2三种代表性农药目标化合物的标准曲线图 3、黄瓜加标回收实验 3.1精密度和准确度 分别对 10g黄瓜样品进行加标浓度为 0.01 mg/kg、0.05 mg/kg、0.1 mg/kg各六次平行 实验,对精密度和准确度进行评估,准确度具体信息详见下附录表 4。浓度为 0.01 mg/kg、0.05 mg/kg和 0.1 mg/kg时,113种农药化合物的相对标准偏差(RSD)分别为 4.02%-15.54%、1.14%-9.29%和 1.26%-7.66%,回收率分别为 70.6%-119.8%、82.1%-119.7%、74.4%-119.3%。 3.2定量限 按照标准GB/T23200.113-2018《食品安全国家标准植物源性食品中 208种农药及其 代谢物残留量的测定气相色谱-质谱联用法》对 10g黄瓜进行加标量为 0.01 mg/kg的 7次 平行回收实验,计算其标准偏差(SD),根据方法定量限 LOQ=10×SD计算目标化合物的 方法定量限,通过计算可知 113种农药化合物的方法定量限为 0.003 mg/kg-0.010 mg/kg。 表2.113种农药化合物黄瓜基质加标方法定量限 序 方法 标准要求 序 方法 标准要求 化合物 定量限 方法定量限 化合物 定量限 方法定量限 号 号 (mg/kg) (mg/kg) (mg/kg) (mg/kg) 1 硫草敌 0.006 0.01 58 水胺硫磷 0.006 0.01 2 联苯 0.007 0.01 59 氯丹-反式 0.007 0.01 3 土菌灵 0.006 0.01 60 四氟醚唑 0.008 0.01 4 氯苯甲醚 0.007 0.01 61 丁草胺 0.007 0.01 5 四氯硝基苯 0.004 0.01 62 丙硫磷 0.005 0.01 6 虫线磷 0.005 0.01 63 氟丁酰草胺 0.006 0.01 7 二苯胺 0.005 0.01 64 杀虫畏 0.006 0.01 8 仲丁威 0.007 0.01 65 腐霉利 0.007 0.01 9 乙丁氟灵 0.006 0.01 66 狄氏剂 0.003 0.01 10 二溴磷 0.008 0.01 67 杀扑磷 0.005 0.01 11 甲拌磷 0.009 0.01 68 丙溴磷 0.007 0.01 12 氯苯胺灵 0.010 0.01 69 敌草胺 0.006 0.01 13 五氯硝基苯 0.010 0.01 70 己唑醇 0.009 0.01 14 氧乐果 0.005 0.01 71 抑草磷 0.003 0.01 15 阿特拉通 0.007 0.01 72 多效唑 0.006 0.01 16 二嗪磷 0.008 0.01 73 杀螨酯 0.008 0.01 17 异噁草酮 0.006 0.01 74 吡氟禾草灵 0.007 0.01 18 百治磷 0.006 0.01 75 稻瘟灵 0.007 0.01 19 嘧霉胺 0.006 0.01 76 硫环磷 0.006 0.01 20 γ-六六六 0.008 0.01 77 乙酯杀螨醇 0.006 0.01 21 乙嘧硫磷 0.005 0.01 78 除草醚 0.008 0.01 22 克百威 0.006 0.01 79 乙硫磷 0.006 0.01 23 莠去津 0.007 0.01 80 三氟硝草醚 0.008 0.01 24 西玛津 0.010 0.01 81 4,4'-滴滴涕 0.007 0.01 25 特丁津 0.007 0.01 82 烯唑醇 0.005 0.01 26 绿谷隆 0.006 0.01 83 腈菌唑 0.005 0.01 27 五氯苯胺 0.006 0.01 84 环丙唑醇 0.007 0.01 28 氯唑磷 0.005 0.01 85 苯霜灵 0.007 0.01 29 炔苯酰草胺 0.005 0.01 86 氟虫腈 0.006 0.01 30 甲基毒死蜱 0.004 0.01 87 丙环唑 0.008 0.01 31 艾氏剂 0.007 0.01 88 禾草灵 0.007 0.01 序 方法 标准要求 序 方法 标准要求 化合物 定量限 方法定量限 化合物 定量限 方法定量限 号 号 (mg/kg) (mg/kg) (mg/kg) (mg/kg) 32 皮蝇磷 0.006 0.01 89 倍硫磷亚砜 0.010 0.01 33 敌草净 0.006 0.01 90 倍硫磷砜 0.010 0.01 34 甲基立枯磷 0.005 0.01 91 咯菌腈 0.008 0.01 35 扑草净 0.004 0.01 92 噁霜灵 0.007 0.01 36 莠灭净 0.007 0.01 93 乙螨唑 0.009 0.01 37 β-六六六 0.007 0.01 94 异菌脲 0.010 0.01 38 特丁净 0.007 0.01 95 甲氧滴滴涕 0.007 0.01 39 毒死蜱 0.008 0.01 96 伐灭磷 0.008 0.01 40 磷胺 0.006 0.01 97 甲氰菊酯 0.007 0.01 41 马拉氧磷 0.006 0.01 98 哒嗪硫磷 0.006 0.01 42 异丙净 0.005 0.01 99 溴苯磷 0.006 0.01 43 甲基对硫磷 0.006 0.01 100 亚胺硫磷 0.003 0.01 44 毒壤滕 0.005 0.01 101 甲羧除草醚 0.010 0.01 45 δ-六六六 0.006 0.01 102 氯氟氰菊酯 0.009 0.01 46 嘧啶磷 0.006 0.01 103 氟丙菊酯 0.009 0.01 47 马拉硫磷 0.006 0.01 104 伏杀硫磷 0.008 0.01 48 烯虫酯 0.005 0.01 105 苯噻酰草胺 0.009 0.01 49 杀螟硫磷 0.005 0.01 106 益棉磷 0.010 0.01 50 乙氧呋草黄 0.008 0.01 107 氟喹唑 0.006 0.01 51 嘧菌环胺 0.006 0.01 108 氟氯氰菊酯 0.010 0.01 52 氧异柳磷 0.005 0.01 109 蝇毒磷 0.006 0.01 53 二甲戊灵 0.005 0.01 110 氟氰戊菊酯 0.008 0.01 54 毒虫畏 0.003 0.01 111 腈苯唑 0.007 0.01 55 敌稗 0.007 0.01 112 氟胺氰菊酯 0.009 0.01 56 o,p'-DDE 0.008 0.01 113 苯醚甲环唑 0.006 0.01 57 乙基溴硫磷 0.006 0.01 结论 本文依据GB 23200.113-2018《食品安全国家标准植物源性食品中 208种农药及其代 谢物残留量的测定气相色谱-质谱联用法》,采用禾信GC-TQ 6000对黄瓜进行加标回收 实验,结果显示 113种农药化合物的线性相关系数R均大于 0.995;黄瓜基质加标精密度 在 1.14%-15.54%范围,加标回收率在 70.6%-119.8%范围;方法定量限在 0.003 mg/kg-0.010mg/kg范围内。上述结果表明禾信GC-TQ 6000具有优异的重现性和检测灵敏度,满足检 测需求。 参考文献 1. GB 23200.113-2018《食品安全国家标准植物源性食品中 208种农药及其代谢物残留量的 测定气相色谱-质谱联用法》 附录 表3. 113种农药和内标的保留时间和特征离子信息表 序号 名称 CAS RT,min 定量离子对 碰撞能 定性离子对 碰撞能 V V 1 硫草敌 2941-55-1 7.154 100.0->72.0 5 161.0->100.0 5 2 联苯 92-52-4 10.299 154.0->153.0 10 153.0->152.0 10 3 土菌灵 2593-15-9 11.761 211.0->183.0 5 183.0->140.0 10 4 氯苯甲醚 2675-77-6 13.539 191.0->113.0 10 191.0->141.0 5 5 四氯硝基苯 117-18-0 15.111 260.9->203.0 10 214.9->179.0 5 6 虫线磷 297-97-2 16.186 143.0->79.0 5 175.0->79.0 5 7 二苯胺 122-39-4 16.699 169.0->168.2 10 168.0->167.2 10 8 仲丁威 3766-81-2 16.96 121.0->77.0 15 121.0->103.1 10 9 乙丁氟灵 1861-40-1 17.347 292.0->264.0 5 292.0->206.0 5 10 二溴磷 300-76-5 17.506 108.9->79.0 5 144.9->109.0 5 11 甲拌磷 298-02-2 17.632 260.0->75.0 5 230.9->128.9 15 12 氯苯胺灵 101-21-3 17.924 153.0->125.1 5 153.0->90.0 15 13 五氯硝基苯 82-68-8 18.312 295.0->237.0 10 236.9->142.9 15 14 氧乐果 1113-02-6 18.972 156.0->110.0 5 110.0->79.0 5 15 阿特拉通 1610-17-9 19.081 169.0->154.0 5 211.0->169.0 5 16 二嗪磷 331-41-5 19.161 137.0->84.0 5 137.0->54.0 15 17 异噁草酮 81777-89-1 19.322 125.0->89.0 10 204.0->107.0 15 18 百治磷 141-66-2 19.497 127.0->109.0 10 127.0->95.0 10 19 嘧霉胺 53112-28-0 19.607 198.0->183.0 10 198.0->118.0 25 20 γ-六六六 58-89-9 19.877 217.0->181.0 5 181.0->145.0 10 21 乙嘧硫磷 38260-54-7 20.052 181.0->153.0 5 168.0->153.0 5 22 克百威 1563-66-2 20.096 164.0->149.0 5 164.0->131.0 10 23 莠去津 1912-24-9 20.213 215.0->200.0 5 215.0->58.0 10 24 西玛津 122-34-9 20.315 201.0->173.0 5 201.0->186.0 5 25 特丁津 5915-41-3 20.483 229.0->173.0 5 173.0->172.0 5 26 绿谷隆 1746-81-2 20.774 126.0->99.0 5 214.0->61.0 5 27 五氯苯胺 527-20-8 21.028 263.0->192.0 15 265.0->194.0 15 28 氯唑磷 42509-80-8 21.02 161.0->119.0 5 161.0->146.0 5 29 炔苯酰草胺 23950-58-5 21.204 173.0->145.0 10 175.0->147.0 10 30 甲基毒死蜱 5598-13-0 21.502 286.0->93.0 20 288.0->93.0 15 31 艾氏剂 309-00-2 21.783 263.0->193.0 25 255.0->220.0 10 32 皮蝇磷 299-84-3 22.002 285.0->270.0 10 287.0->272.0 10 33 敌草净 1014-69-3 22.072 213.0->171.0 5 213.0->58.0 10 34 甲基立枯磷 57018-04-9 22.142 265.0->250.0 10 265.0->93.0 20 35 扑草净 7287-19-6 22.528 199.0->184.0 5 226.0->184.0 5 36 莠灭净 834-12-8 22.677 227.0->170.0 5 227.0->58.0 10 37 β-六六六 319-85-7 22.905 217.0->181.0 5 181.0->145.0 10 38 特丁净 886-50-0 23.037 185.0->170.0 5 241.0->170.0 10 39 毒死蜱 2921-88-2 23.045 197.0->169.0 10 199.0->171.0 10 碰撞能 碰撞能 序号 名称 CAS RT,min 定量离子对 碰撞能 定性离子对 碰撞能 V V 40 磷胺-1 13171-21-6 23.344 127.0->109.0 5 127.0->95.0 10 41 马拉氧磷 1634-72-8 23.344 127.0->99.0 5 127.0->55.0 5 42 异丙净 4147-51-7 23.405 255.0->222.0 5 255.0->180.0 10 43 磷胺-2 13171-21-6 23.528 127.0->109.0 5 127.0->95.0 10 44 甲基对硫磷 298-00-0 23.536 263.0->109.0 5 233.0->109.0 15 45 毒壤滕 327-98-0 23.387 299.0->271.0 10 297.0->269.0 10 46 δ-六六六 319-86-8 23.811 217.0->181.0 5 181.0->145.0 10 47 嘧啶磷 23505-41-1 23.797 318.0->182.0 5 318.0->166.0 5 48 马拉硫磷 121-75-5 24.078 127.0->99.0 5 173.0->99.0 10 49 烯虫酯 40596-69-8 24.232 153.0->111.0 5 111.0->55.0 10 50 杀螟硫磷 122-14-5 24.288 277.0->260.0 5 277.0->109.0 10 51 环氧七氯B 1024-57-3 24.449 352.8->262.9 15 354.8->264.9 15 52 乙氧呋草黄 26225-79-6 24.575 207.0->161.0 5 161.0->105.0 5 53 嘧菌环胺 121552-61-2 24.393 225.2->224.3 5 224.2->208.2 15 54 氧异柳磷 31120-85-1 24.825 229.0->200.9 5 229.0->121.0 20 55 二甲戊灵 40487-42-1 24.899 252.0->162.2 5 252.0->161.1 15 56 毒虫畏 470-90-6 25.609 266.9->159.1 10 322.8->266.8 10 57 敌稗 709-98-8 25.569 161.0->99.0 20 161.0->90.0 15 58 o,p'-DDE 3424-82-6 25.073 246.0->176.2 25 248.0->176.2 25 59 乙基溴硫磷 4824-78-6 25.348 358.7->302.8 10 302.8->284.7 10 60 水胺硫磷 24353-61-5 25.65 135.9->108.0 10 135.9->69.0 20 61 氯丹-反式 5103-74-2 25.683 372.8->265.8 20 271.7->236.9 10 62 四氟醚唑 112281-77-3 26.219 336.0->203.8 25 336.0->217.9 10 63 丁草胺 23184-66-9 26.259 236.9->160.2 5 188.1->160.2 5 64 丙硫磷 34643-46-4 26.454 267.0->239.0 5 309.0->239.0 10 65 氟丁酰草胺 113614-08-7 27.058 176.1->91.1 10 221.0->193.1 5 66 杀虫畏 22248-79-9 26.814 329.0->109.0 15 331.0->109.0 10 67 腐霉利 32809-16-8 27.021 96.0->67.1 5 96.0->53.0 10 68 狄氏剂 60-57-1 26.856 263.0->193.0 25 277.0->241.0 5 69 杀扑磷 950-37-8 27.162 144.9->85.0 5 144.9->58.1 10 70 丙溴磷 41198-08-7 27.223 338.8->268.7 10 207.9->63.0 25 71 敌草胺 15299-99-7 27.448 128.0->72.1 5 128.0->100.1 5 72 己唑醇 79983-71-4 27.577 231.0->175.0 5 256.0->82.1 10 73 抑草磷 36335-67-8 27.619 286.0->202.0 10 200.0->92.0 5 74 多效唑 76738-62-0 27.986 236.0->125.1 10 236.0->167.0 5 75 杀螨酯 80-33-1 27.863 175.0->111.0 5 111.0->75.0 10 76 吡氟禾草灵 69806-50-4 28.003 281.9->91.0 10 281.9->238.0 10 77 稻瘟灵 50512-35-1 28.135 162.1->134.0 5 162.1->85.0 10 78 硫环磷 947-02-4 28.258 196.0->140.0 5 168.0->140.0 5 79 乙酯杀螨醇 510-15-6 28.521 139.1->111.0 10 251.1->139.1 10 80 除草醚 1836-75-5 28.731 202.0->139.1 15 282.9->253.0 5 81 乙硫磷 563-12-2 29.021 230.9->129.0 15 230.9->175.0 10 序号 名称 CAS RT,min 定量离子对 碰撞能 定性离子对 碰撞能 V V 82 三氟硝草醚 15457-05-3 29.336 190.0->126.0 15 190.0->132.0 10 83 4,4'-滴滴涕 50-29-3 29.389 235.0->165.2 15 237.0->165.2 15 84 烯唑醇 83657-24-3 29.354 267.9->232.0 5 269.9->232.0 5 85 腈菌唑 88671-89-0 29.529 179.0->125.0 10 179.0->90.0 20 86 环丙唑醇-1 113096-99-4 29.573 222.0->125.0 10 139.1->111.0 10 87 苯霜灵 71626-11-4 29.573 148.0->77.0 25 148.0->105.1 10 88 环丙唑醇-2 113096-99-4 29.675 222.0->125.0 10 139.1->111.0 10 89 氟虫腈 120068-37-3 29.696 366.8->212.8 20 368.8->214.8 20 90 丙环唑-1 60207-90-1 29.889 172.9->145.0 10 172.9->74.0 25 91 丙环唑-2 60207-90-1 30.011 172.9->145.0 10 172.9->74.0 25 92 禾草灵 51338-27-3 29.976 339.9->252.9 5 253.0->162.0 10 93 倍硫磷亚砜 3761-41-9 30.24 278.0->109.0 15 278.0->169.0 10 94 倍硫磷砜 3761-42-0 30.668 309.9->105.0 10 135.9->92.0 5 95 咯菌腈 131341-86-1 30.922 248.0->182.0 10 248.0->154.0 15 96 噁霜灵 77732-09-3 30.944 163.0->132.0 5 163.0->117.0 20 97 乙螨唑 153233-91-1 30.922 141.0->113.0 10 141.0->63.0 20 98 异菌脲 36734-19-7 31.59 187.0->124.0 10 245.0->161.0 15 99 甲氧滴滴涕 72-43-5 30.88 227.1->169.0 15 227.1->141.0 30 100 伐灭磷 52-85-7 31.156 218.0->109.0 10 218.0->79.0 20 101 甲氰菊酯 39515-41-8 31.156 207.9->181.0 5 264.9->210.0 5 102 哒嗪硫磷 119-12-0 31.548 340.0->199.0 5 204.0->203.1 5 103 溴苯磷 21609-90-5 31.41 171.0->77.1 15 154.9->77.1 10 104 亚胺硫磷 732-11-6 31.845 160.0->77.1 15 160.0->133.1 5 105 甲羧除草醚 42576-02-3 31.982 189.1->126.0 15 340.9->309.9 5 106 氯氟氰菊酯-1 68085-85-8 32.301 197.0->141.0 10 197.0->161.0 5 107 氟丙菊酯 101007-06-1 32.301 207.9->181.0 5 288.9->92.8 5 108 氯氟氰菊酯-2 68085-85-8 32.396 197.0->141.0 10 197.0->161.0 5 109 伏杀硫磷 2310-17-0 32.417 182.0->111.0 10 182.0->102.0 10 110 苯噻酰草胺 73250-68-7 32.555 192.0->136.1 10 192.0->109.1 20 111 益棉磷 2642-71-9 33.149 132.0->77.1 10 160.0->77.1 10 112 氟喹唑 136426-54-5 33.597 340.0->298.0 10 108.0->57.0 10 113 氟氯氰菊酯-1 68359-37-5 34.171 226.0->206.0 10 198.9->170.1 15 114 氟氯氰菊酯-2 68359-37-5 34.424 226.0->206.0 10 198.9->170.1 15 115 氟氯氰菊酯-3 68359-37-5 34.494 226.0->206.0 10 198.9->170.1 15 116 蝇毒磷 56-72-4 34.536 361.9->109.0 10 210.0->182.0 5 117 氟氯氰菊酯-4 68359-37-5 34.641 226.0->206.0 10 198.9->170.1 15 118 氟氰戊菊酯-1 70124-77-5 35.124 156.9->107.1 10 198.9->157.0 5 119 氟氰戊菊酯-2 70124-77-5 35.495 156.9->107.1 10 198.9->157.0 5 120 腈苯唑 119611-00-6 35.712 197.9->129.0 5 128.9->102.0 10 121 氟胺氰菊酯-1 69409-94-5 36.777 250.0->200.0 10 250.0->55.0 10 122 氟胺氰菊酯-2 69409-94-5 36.91 250.0->200.0 10 250.0->55.0 10 123 苯醚甲环唑-1 119446-68-3 37.464 322.8->264.9 10 264.9->202.0 10 序号 名称 CAS RT,min 定量离子对 碰撞能 定性离子对 碰撞能 V V 124 苯醚甲环唑-2 119446-68-3 37.464 322.8->264.9 10 264.9->202.0 10 表 4.113种农药化合物黄瓜基质加标精密度 序号 化合物 加标量(mg/kg) 序号 0.01 0.05 0.1 化合物 加标量(mg/kg) 0.01 0.05 0.1 1 硫草敌 82.4% 83.8% 94.1% 58 水胺硫磷 88.3% 93.3% 96.0% 2 联苯 101.0% 106.8% 107.2% 59 氯丹-反式 86.5% 87.9% 92.2% 3 土菌灵 87.2% 89.6% 98.3% 60 四氟醚唑 91.7% 90.4% 98.4% 4 氯苯甲醚 94.6% 94.9% 96.2% 61 丁草胺 89.5% 94.1% 99.4% 5 四氯硝基苯 80.6% 85.1% 89.9% 62 丙硫磷 86.7% 90.0% 94.9% 6 虫线磷 86.2% 91.7% 94.6% 63 氟丁酰草胺 91.9% 93.6% 99.6% 7 二苯胺 92.7% 79.2% 87.8% 64 杀虫畏 89.9% 92.1% 98.4% 8 仲丁威 73.7% 81.3% 80.8% 65 腐霉利 92.8% 86.2% 95.1% 9 乙丁氟灵 70.6% 78.4% 74.4% 66 狄氏剂 93.9% 94.3% 99.3% 10 二溴磷 90.4% 94.2% 92.0% 67 杀扑磷 88.4% 92.0% 98.4% 11 甲拌磷 90.4% 85.1% 89.5% 68 丙溴磷 85.9% 84.1% 84.3% 12 氯苯胺灵 104.2% 100.3% 107.3% 69 敌草胺 93.6% 93.3% 91.8% 13 五氯硝基苯 85.8% 82.1% 87.8% 70 己唑醇 96.1% 91.3% 90.1% 14 氧乐果 82.9% 88.3% 84.7% 71 抑草磷 76.2% 82.4% 81.8% 15 阿特拉通 87.2% 91.1% 87.6% 72 多效唑 96.4% 97.0% 99.9% 16 二嗪磷 78.2% 84.5% 86.8% 73 杀螨酯 107.9% 108.2% 106.0% 17 异噁草酮 74.6% 81.5% 83.7% 74 吡氟禾草灵 92.4% 93.6% 99.4% 18 百治磷 87.1% 93.0% 90.2% 75 稻瘟灵 96.7% 95.5% 101.9% 19 嘧霉胺 86.2% 85.7% 92.3% 76 硫环磷 82.2% 87.4% 86.3% 20 γ-六六六 75.3% 79.9% 77.2% 77 乙酯杀螨醇 105.7% 100.6% 105.6% 21 乙嘧硫磷 78.9% 83.6% 83.6% 78 除草醚 90.7% 93.9% 91.5% 22 克百威 92.0% 97.8% 101.0% 79 乙硫磷 99.4% 101.2% 104.8% 23 莠去津 95.5% 96.0% 101.4% 80 三氟硝草醚 81.0% 90.5% 93.8% 24 西玛津 97.6% 95.4% 102.8% 81 4,4'-滴滴涕 95.8% 103.8% 101.5% 25 特丁津 95.6% 95.3% 99.3% 82 烯唑醇 92.1% 92.3% 100.9% 26 绿谷隆 87.4% 86.4% 92.5% 83 腈菌唑 101.4% 98.8% 99.2% 27 五氯苯胺 78.7% 82.1% 88.0% 84 环丙唑醇 95.1% 96.0% 104.4% 28 氯唑磷 82.0% 87.9% 88.3% 85 苯霜灵 104.0% 97.5% 107.9% 29 炔苯酰草胺 93.4% 95.1% 101.1% 86 氟虫腈 95.1% 98.6% 100.9% 30 甲基毒死蜱 79.9% 85.2% 84.6% 87 丙环唑 111.9% 101.0% 106.7% 31 艾氏剂 79.8% 82.6% 79.8% 88 禾草灵 99.9% 91.3% 106.9% 32 皮蝇磷 81.4% 83.9% 84.7% 89 倍硫磷亚砜 104.7% 108.1% 106.1% 33 敌草净 98.8% 95.3% 101.1% 90 倍硫磷砜 98.55% 92.5% 98.2% 34 甲基立枯磷 84.7% 88.3% 90.2% 91 咯菌腈 106.4% 103.4% 105.5% 35 扑草净 94.1% 93.5% 101.5% 92 噁霜灵 98.7% 98.4% 99.4% 36 莠灭净 94.2% 93.3% 100.1% 93 乙螨唑 97.0% 94.7% 95.5% 37 β-六六六 89.5% 92.4% 97.5% 94 异菌脲 102.6% 110.2% 108.6% 38 特丁净 93.6% 92.6% 99.9% 95 甲氧滴滴涕 98.3% 100.5% 92.7% 序号 化合物 加标量(mg/kg) 序号 化合物 加标量(mg/kg) 0.01 0.05 0.1 0.01 0.05 0.1 39 毒死蜱 89.9% 91.5% 95.0% 96 伐灭磷 101.0% 100.1% 107.3% 40 磷胺 84.2% 89.5% 86.8% 97 甲氰菊酯 96.7% 94.3% 96.2% 41 马拉氧磷 91.9% 93.4% 89.9% 98 哒嗪硫磷 95.4% 89.9% 95.4% 42 异丙净 88.5% 89.2% 87.2% 99 溴苯磷 97.7% 95.3% 100.3% 43 甲基对硫磷 80.0% 83.6% 85.1% 100 亚胺硫磷 87.4% 87.1% 86.2% 44 毒壤滕 84.4% 85.9% 82.5% 101 甲羧除草醚 97.65% 98.8% 104.1% 45 δ-六六六 94.1% 92.5% 90.9% 102 氯氟氰菊酯 97.0% 97.6% 99.6% 46 嘧啶磷 83.1% 86.9% 92.8% 103 氟丙菊酯 92.0% 92.5% 95.6% 47 马拉硫磷 89.1% 91.8% 88.2% 104 伏杀硫磷 96.1% 94.2% 93.7% 48 烯虫酯 85.7% 82.7% 88.1% 105 苯噻酰草胺 114.4% 118.4% 119.2% 49 杀螟硫磷 76.4% 82.3% 87.0% 106 益棉磷 103.5% 97.5% 95.5% 50 乙氧呋草黄 97.8% 97.2% 103.1% 107 氟喹唑 94.4% 90.8% 98.1% 51 嘧菌环胺 119.8% 119.7% 119.3% 108 氟氯氰菊酯 100.6% 106.3% 104.9% 52 氧异柳磷 107.7% 113.1% 113.4% 109 蝇毒磷 96.7% 93.9% 103.6% 53 二甲戊灵 70.6% 81.5% 83.9% 110 氟氰戊菊酯 101.5% 101.1% 107.4% 54 毒虫畏 87.5% 91.6% 87.4% 111 腈苯唑 98.1% 106.7% 105.7% 55 敌稗 92.7% 95.2% 93.8% 112 氟胺氰菊酯 97.4% 97.2% 104.7% 56 o,p'-DDE 104.4% 107.1% 103.3% 113 苯醚甲环唑 94.6% 89.8% 92.0% 57 乙基溴硫磷 87.1% 87.6% 90.5%
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