-
蔬菜是我国不可或缺的主要食物,在种植过程中不合理使用农药可能造成蔬菜中农药残留量超标,影响人体的健康. 随着人们越来越关注农药残留问题,对蔬菜中的农药残留进行快速检测显得尤其重要. 近年QuEChERS 技术因其简单、低廉、快速有效等特点在农药残留分析中得以迅速发展,传统的前处理技术如固相萃取法[1]、凝胶色谱法[1]、液液萃取法[2]也在被逐步取代. 气相色谱串联质谱仪也凭借其选择性好、灵敏度高、准确定量等优势而成为农药分析的首选仪器[3]. 分析时间过长严重制约了农药残留检测的快速和高效,无法体现QuEChERS技术所带来的前处理优势,不利于食用农产品质量安全监管的快速处理.
传统的仪器检测方法时间长、化合物少,不能快速高效的应对如今频繁爆发的食品安全事件. 本文建立的采用QuEChERS前处理,基于LPGC快速定量测定黄瓜中120种农药残留的检测方法,适用性广、操作简便、灵敏度高、快速高效,为突发的食品安全事件提供了有效的技术支撑手段.
低压气相色谱柱10 min内测定黄瓜中120种农药残留
Determination of 120 pesticide residues in cucumber within 10 minutes by low-pressure gas chromatography column
-
摘要: 采用低压气相色谱柱(LPGC)结合三重四极杆串联质谱技术( GC-MS /MS)测定黄瓜中120种农药残留的分析方法. 该方法中120种农药在0.010—0.400 mg·L−1范围内具有良好的线性相关性,相关系数(R2)均大于0.995. 在0.02、0.04、0.10 mg·kg−1不同质量浓度水平下做加标实验,回收率为73.6%—115%,相对标准偏差为 (SRSD,n=3)0.0560%—12.6%,定量限为0.01 mg·kg−1. 该方法操作简便、高效快速,适用于黄瓜中农药多残留的快速筛查.Abstract: An analysis method was established for the determination of 120 kinds of pesticides in cucumber by Low-pressure Gas Chromatography column(LPGC)and triple quadrupole tandem mass spectrometry(GC-MS/MS). The 120 pesticides in this method have a good linear correlation in the range of 0.010—0.400 mg·L−1, the correlation coefficients(R2) are all greater than 0.995. In three differen concentration levels of 0.02 mg·kg−1, 0.04 mg·kg−1 and 0.10 mg·kg−1, the average recovery was 73.6% —115%, the relative standard deviations (
SRSD, n=3) of the recoveries between 0.0560% and 12.6% in cucumber,and the limit of quantification is 0.01 mg·kg−1. The method is simple, rapid and accurate, which was suitable for determination of pesticide residues in cucumber. -
表 1 120种农药的保留时间、相关系数
Table 1. Retention time, lcorrelation coefficient, of the 120 pesticides
农药 保留时间/ min R2 农药 保留时间/ min R2 农药 保留时间/ min R2 Acephate 3.78 0.9986 Fenthion-sulfoxide 6.40 0.9992 Fenthion 5.63 0.9985 Alachlor 5.40 0.9992 Fenvalerate 7.93 0.9989 Fenthion-sulfone 6.42 0.9980 Aldrin 5.67 0.9994 Fipronil 5.87 0.9979 Permethrin 7.41 0.9986 Benfluralin 4.63 0.9984 Fluazifop 6.26 0.9997 Phorate 4.72 0.9985 Bifenox 6.98 0.9985 Flucythrinate 7.76 0.9991 Phorate-sulfone 5.61 0.9988 Bifenthrin 6.86 0.9988 Fludioxonil 6.17 0.9990 Phorate-sulfoxide 5.57 0.9994 Bromopropylat 6.89 0.9982 Fluorodifen 6.10 0.9972 Phosalone 7.10 0.9989 Butachlor 6.04 0.9989 Flutolanil 6.10 0.9990 Phosfolan 5.88 0.9990 Chlorfenvinphos 5.87 0.9986 Fluvalinate 7.97 0.9980 Phosmet 6.90 0.9994 Chloroneb 4.07 0.9993 Fonofos 5.02 0.9989 Phosphamidon 5.06 0.9983 Chlorpropham 4.56 0.9994 Hexaconazole 6.13 0.9989 Piperonyl-butoxide 6.70 0.9988 Chlorpyrifos 5.63 0.9993 Imazalil 6.15 0.9991 Pirimicarb 5.21 0.9990 Chlorpyrifos-methyl 5.36 0.9989 Iprodione 6.81 0.9985 Pirimiphos-methyl 5.50 0.9988 Clomazone 4.94 0.9991 Isazofos 5.13 0.9991 Pretilachlor 6.16 0.9990 Coumaphos 7.48 0.9981 Isocarbophos 5.68 0.9992 Procymidone 5.93 0.9984 Cyfluthrin 7.60 0.9991 Isofenphos-methyl 5.78 0.9991 Profenofos 6.15 0.9992 Cypermethrin 7.70 0.9989 Isoprocarb 4.17 0.9984 Prometryn 5.41 0.9984 Cyproconazole 6.32 0.9990 Isoprothiolane 6.14 0.9997 Propanil 5.30 0.9990 Cyprodinil 5.79 0.9992 Kresoxim-methyl 6.23 0.9989 Propiconazole 6.63 0.9994 Deltamethrin 8.17 0.9984 Lambda-cyhalothrin 7.15 0.9982 Pyridaben 7.45 0.9991 Diazinon 5.03 0.9991 Malathion 5.55 0.9989 Pendimethalin 5.82 0.9984 Dichlobenil 3.47 0.9985 Metalaxyl 5.42 0.9985 Pentachloroaniline 5.28 0.9991 Dichlorvos 3.03 0.9986 Methamidophos 2.96 0.9982 Pyriproxyfen 7.09 0.9990 Dicloran 4.85 0.9983 Methidathion 5.99 0.9991 Quinalphos 5.89 0.9997 Dicofol 6.36 0.9979 Methoxychlor 6.92 0.9996 Quinoxyfen 6.60 0.9984 Dieldrin 6.24 0.9996 Metolachlor 5.62 0.9988 Quintozene 5.02 0.9981 Difenoconazole 8.10 0.9987 Metribuzin 5.31 0.9980 Sulfotep 4.67 0.9983 Dimethoate 4.85 0.9985 Mevinphos 3.75 0.9991 Tebuconazole 6.70 0.9985 Diphenylamine 4.48 0.9988 Molinate 4.18 0.9986 Tebufenpyrad 6.93 0.9980 Edifenphos 6.60 0.9986 Monocrotophos 4.67 0.9990 Tecnazene 4.45 0.9994 Endosulfan-1 6.09 0.9980 Myclobutanil 6.22 0.9982 Terbufos 4.98 0.9986 Endosulfan-2 6.41 0.9992 Naled 3.02 0.9990 Terbufos-sulfone 5.84 0.9983 Epoxiconazole 6.79 0.9983 Omethoate 4.40 0.9986 Tetrachlorvinphos 6.03 0.9993 Ethoprophos 4.50 0.9979 Oxadiazon 6.19 0.9984 Tetraconazole 5.67 0.9989 Etofenprox 7.73 0.9980 Oxadixy 6.45 0.9990 Tolclofos-methyl 5.39 0.9987 Etoxazole 6.92 0.9999 Oxyfluorfen 6.19 0.9989 Triadimefon 5.65 0.9993 Fenamidone 3.78 0.9989 Paclobutrazol 6.02 0.9994 Triadimenol 5.90 0.9989 Fenbuconazole 5.40 0.9983 Parathion 5.64 0.9963 Triazophos 6.49 0.9981 Fenitrothion 5.67 0.9992 Parathion-methyl 5.36 0.9986 Trifloxystrobin 6.56 0.9988 Fenpropathrin 4.63 0.9986 Penconazole 5.84 0.9990 Vinclozolin 5.35 0.9989 表 2 不同方法测定黄瓜中甲胺磷和溴氰菊酯的结果
Table 2. Results of determination of methamidophos and deltamethrin in cucumber by different methods
样品
Sample甲胺磷/ (mg·kg−1) 溴氰菊酯/(mg·kg−1) LPGC TG-5MS LPGC TG-5MS Cucumber 1 0.0603 0.0616 0.0661 0.0673 Cucumber 2 0.0622 0.0619 0.0676 0.0643 Cucumber 3 0.0569 0.0551 0.0657 0.0654 Cucumber 4 0.0402 0.0402 0.0478 0.0458 Cucumber 5 0.0336 0.0338 0.0471 0.0431 Cucumber 6 0.0334 0.0343 0.0473 0.0448 -
[1] 姚家彪, 赵颖, 潘伟, 等. 蔬菜和食用菌中氨基甲酸酯类农药残留检测技术 [J]. 应用化学, 2010, 27(4): 488-493. [2] LI J X, SUN M Y, CHANG Q Y, et al. Determination of pesticide residues in teas via QuEChERS combined with dispersive liquid–liquid microextraction followed by gas chromatography–tandem mass spectrometry [J]. Chromatographia, 2017, 80(9): 1447-1458. doi: 10.1007/s10337-017-3362-7 [3] 张丽静, 任召珍. GC-MS/MS法快速筛查鲜西洋参中40种农药残留 [J]. 中国果菜, 2022, 42(8): 59-63,69. doi: 10.19590/j.cnki.1008-1038.2022.08.010