超高效液相色谱-串联质谱法对比11种净化方式对当归中50种农药残留检测的影响

doi:10.11944/j.issn.1000-0518.2019.08.190011

摘要/Abstract

摘要：

采用超高效液相色谱-串联质谱仪(UPLC-MS/MS)同时测定当归药材中50种农药残留,对比了11种净化方式对检测结果的影响,筛选出最有效的基质净化方法。以回收率为考察指标,评估了不同基质净化方法对当归中多农残的提取净化效果,最终确定样品经乙腈提取,NaCl净化,在电喷雾正负离子扫描、依赖保留时间的动态多反应监测模式(dMRM)下,以基质匹配内标法定量。结果表明,50种农药在NaCl净化法下回收率最高,在各自的浓度范围内线性关系良好(R²>0.99);3个添加水平(10、50、100 μg/kg)下,大多数农药的回收率为70.1%~117.7%,相对标准偏差(RSD,n=6)不大于 20.0%,50种农药的定量限为1.0~20.0 μg/kg。该方法为当归中准确、高效、经济的检测目标物提供了可靠依据。

关键词: 基质净化方法, 农药残留, 当归

Abstract:

Fifty pesticides in Angelica sinensis, were determined by ultra-high performance liquid chromatography/tandem mass spectrometry(UPLC-MS/MS). Through comparing 11 kinds of purification methods, the best effective matrix purification method was selected. The pesticide residues were extracted from samples with acetoniteile, cleaned-up with NaCl and then analyzed using UPLC-MS/MS in dynamic multiple reaction monitoring(dMRM) mode with positive and negative electrospray ionization. The pesticide residues were quantified by matrix matched standard solution-internal standard method. All calibration curves showed good linearity(R²>0.99) within the test ranges. The average recoveries of most pesticides at the spiked levels of 10, 50, 100 μg/kg ranged from 70.1%~117.7% with RSDs of 1.0%~20.0%. The limits of quantification of 50 pesticides were 1.0~20.0 μg/kg. The method provides a reliable basis for accurate, efficient and economical detection of targeted analytes in Angelica sinensis.

Key words: matrix purification method, pesticide residues, Angelica sinensis

刘志荣. 超高效液相色谱-串联质谱法对比11种净化方式对当归中50种农药残留检测的影响[J]. 应用化学, 2019, 36(8): 968-976.

LIU Zhirong. Evaluation on Efficiencies of 11 Purification Methods Toward 50 Pesticide Residues in Angelica sinensis by Ultra-high Performance Liquid Chromatography/Tandem Mass Spectrometry[J]. Chinese Journal of Applied Chemistry, 2019, 36(8): 968-976.

参考文献

[1]	Abbas M S,Soliman A S,Elgammal H A, et al. Development and Validation of a Multiresidue Method for the Determination of 323 Pesticide Residues in Dry Herbs Using QuEChERS Method and LC-ESI-MS/MS[J]. Int J Environ Anal Chem,2017:1-21.
[2]	Anastassiades M,Lehotay S J,Stajnbaher D, et al. Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and “Dispersive Solid-Phase Extraction” for the Determination of Pesticide Residues in Produce[J]. J AOAC Int,2003,86(2):412-431.
[3]	Anastassiades M,Masstovska K,Lehotay S J.Evaluation of Analyte Protectants to Improve Gas Chromatographic Analysis of Pesticides[J]. J Chromatogr A,2003,1015(1):163-184.
[4]	Yang X,Zhang H,Liu Y, et al. Multiresidue Method for Determination of 88 Pesticides in Berry Fruits Using Solid-Phase Extraction and Gas Chromatography-Mass Spectrometry:Determination of 88 Pesticides in Berries Using SPE and GC-MS[J]. Food Chem,2011,127(2):855-865.
[5]	Chen Y,Altaher F,Juskelis R, et al. Multiresidue Pesticide Analysis of Dried Botanical Dietary Supplements Using an Automated Dispersive SPE Cleanup for QuEChERS and High-Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. J Agric Food Chem,2012,60(40):9991-9999.
[6]	Filho A M,Fábio Neves dos Santos,Pereira P A D P . Development, Validation and Application of a Method Based on DI-SPME and GC MS for Determination of Pesticides of Different Chemical Groups in Surface and Groundwater Samples[J]. Microchem J,2010,96(1):139-145.
[7]	Wang J,Tuduri L,Mercury M, et al. Sampling Atmospheric Pesticides with SPME:Laboratory Developments and Field Study[J]. Environ Pollut,2009,157(2):365-370.
[8]	Raeppel C,Fabritius M,Nief M, et al. Coupling ASE, Sylilation and SPME-GC/MS for the Analysis of Current-Used Pesticides in Atmosphere[J]. Talanta,2014,121:24-29.
[9]	Mahmood S F,Sultana T,Rahman M A.Supercritical Fluid Extraction as a Successful Technique for Pesticides Estimation[J]. Bangladesh J Sci Ind Res,2010,45(1):47-56.
[10]	Nam K,King J W.Coupled SFE/SFC/GC for the Trace Analysis of Pesticide Residues in Fatty Food Samples[J]. J Sep Sci,2015,17(8):577-582.
[11]	Eskilsson C S,Mathiasson L.Supercritical Fluid Extraction of the Pesticides Carbosulfan and Imidacloprid from Process Dust Waste[J]. J Agric Food Chem,2000,48(11):5159-5164.
[12]	Lee J M,Park J W,Jang G C, et al. Comparative Study of Pesticide Multi-residue Extraction in Tobacco for Gas Chromatography-Triple Quadrupole Mass Spectrometry[J]. J Chromatogr A,2008,1187(1):25-33.
[13]	Lin Q B,Xue Y Y,Song H.Determination of the Residues of 18 Carbamate Pesticides in Chestnut and Pine Nut by GPC Cleanup and UPLC-MS-MS[J]. J Chromatogr Sci,2010,48(1):7-11.
[14]	Banerjee K,Oulkar D P,Dasgupta S, et al. Validation and Uncertainty Analysis of a Multi-residue Method for Pesticides in Grapes Using Ethyl Acetate Extraction and Liquid Chromatography-Tandem Mass Spectrometry[J]. J Chromatogr A,2007,1173(1):98-109.
[15]	Plácido A,Paíga P,Lopes D H, et al. Determination of Methiocarb and Its Degradation Products, Methiocarb Sulfoxide and Methiocarb Sulfone, in Bananas Using QuEChERS Extraction[J]. J Agric Food Chem,2013,61(2):325-331.
[16]	Chamkasem N,Ollis L W,Harmon T, et al. Analysis of 136 Pesticides in Avocado Using a Modified QuEChERS Method with LC-MS/MS and GC-MS/MS[J]. J Agric Food Chem,2013,61(10):2315-2329.
[17]	Souza C S,Marian B C,Jaime d M E, et al. A Vortex-Assisted MSPD Method for the Extraction of Pesticide Residues from Fish Liver and Crab Hepatopancreas with Determination by GC-MS[J]. Talanta,2013,112(15):63-68.
[18]	Lee J,Shin Y,Lee J, et al. Simultaneous Analysis of 310 Pesticide Multiresidues Using UHPLC-MS/MS in Brown Rice, Orange, and Spinach[J]. Chemosphere,2018,207:519-526.
[19]	Xiao J J,Duan J S,Xu X, et al. Behavior of Pesticides and Their Metabolites in Traditional Chinese Medicine Paeoniae Radix Alba During Processing and Associated Health Risk[J]. J Pharmaceut Biomed,2018,161:20-27.
[20]	Zhao P,Alvarez P,Li X, et al. Development of an Analytical Method for Pesticide Residues in Berries with Dispersive Dolid Phase Extraction Using Multiwalled Carbon Nanotubes and Primary Secondary Amine Sorbents[J]. Anal Methods,2018,10:757-766.
[21]	Dou X,Chu X,Kong W, et al. Carbon Nanotube-Based QuEChERS Extraction and Enhanced Product Ion Scan-Assisted Confirmation of Multi-pesticide Residue in Dried Tangerine Peel[J]. RSC Adv,2015,5:86163-86171.