Simultaneous Determination of Residues of 46 Pesticides in Lycium Ruthenicum Murr. by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry after QuEChERS Purification
摘 要
提出了QuEChERS净化-超高效液相色谱-串联质谱法同时测定黑枸杞中46种农药残留量的方法。将黑枸杞样品冷冻干燥、粉碎、过筛,分取5.00 g,加入100 μg·L-1内标溶液15 μL和水5 mL,涡旋混匀,浸泡10 min,然后用含1%(体积分数)乙酸的乙腈溶液10 mL提取,接着加入无水硫酸镁4.0 g和氯化钠1.0 g,摇散、振荡、离心后,将上清液全部转移至预先装有1.0 g无水硫酸镁的离心管中,再次振荡、离心,分取上清液2 mL于装有N-丙基乙二胺20 mg、十八烷基硅烷键合硅胶20 mg和石墨化碳黑25 mg的离心管中,振荡、离心后,取上清液待测。以Eclipse Plus C18色谱柱为固定相,以含10 mmol·L-1甲酸铵的0.1%(体积分数)甲酸溶液-乙腈为流动相体系进行梯度洗脱。分离后的目标物在三重四极杆质谱检测器(设置干燥气温度为350℃,鞘气温度为300℃)中进行检测,以基质匹配的混合标准溶液绘制工作曲线,内标法定量。结果显示:经QuEChERS净化后的黑枸杞样品中46种农药的基质效应值为-48.4%~39.5%;46种农药工作曲线的线性范围均为6.0~600.0 μg·kg-1,检出限为0.2~4.2 μg·kg-1;对空白样品进行3个浓度水平的加标回收试验,回收率为47.5%~129%,测定值的相对标准偏差(n=6)为3.0%~17%。方法用于12批黑枸杞样品分析,6批黑枸杞样品中有13种农药被检出,其余农药均未检出;参考GB 2763-2021,12种农药的检出量均符合要求,仅1批样品中克百威的检出量[(22.9±2.3)μg·kg-1]不符合残留限量要求(20 μg·kg-1)。
Abstract
A method for the simultaneous determination of residues of 46 pesticides in Lycium ruthenicum Murr. by ultra-high performance liquid chromatography-tandem mass spectrometry after QuEChERS purification was proposed. Lycium ruthenicum Murr. sample was freeze-dried, crushed and sieved. An aliquot (5.00 g) was taken, and 15 μL of 100 μg·L-1 internal standard solution and 5 mL of water were added. The mixture was swirled well, soaked for 10 min, and extracted with 10 mL of acetonitrile solution containing 1% (volume fraction) acetic acid, and 4.0 g of anhydrous magnesium sulfate and 1.0 g of sodium chloride were added. After shake, vibration and centrifugation, the supernatant was transferred to the centrifuge tube preloaded with 1.0 g of anhydrous magnesium sulfate. After vibration and centrifugation again, 2 mL of the supernatant was added into the centrifuge tube containing 20 mg of N-propyl ethylene diamineethy, 20 mg of octadecylsilane bonded silica gel and 25 mg of graphitized carbon black. After vibration and centrifugation, the supernatant was taken for determination. Eclipse Plus C18 column was used as the stationary phase, and 0.1% (volume fraction) formic acid solution containing 10 mmol·L-1 ammonium formate-acetonitrile were used as the mobile phase system for gradient elution. The separated targets were detected by triple quadrupole mass spectrometry detector with drying temperature of 350℃ and sheath temperature of 300℃. Standard curves were drawn with the matrix matching mixed standard solutions, and internal standard method was used for quantification. It was shown that the matrix effect values of 46 pesticides in the sample purified by QuEChERS ranged from -48.4% to 39.5%, and the linear ranges of working curves of 46 pesticides were 6.0-600.0 μg·kg-1, with detection limits in the range of 0.2-4.2 μg·kg-1. Test for recovery was made on the blank samples by standard addition method, giving results in the range of 47.5%-129%, and RSDs (n=6) of the determined values were in the range of 3.0%-17%. This method was applied to analysis of 12 batches of Lycium ruthenicum Murr. samples. Thirteen pesticides were detected in 6 batches of Lycium ruthenicum Murr. samples, and the other pesticides were not detected. According to GB 2763-2021, the detection amounts of 12 pesticides met the requirements, but the detection amount of carbofuran[(22.9±2.3)μg·kg-1] in 1 batch of sample did not meet the requirements for residue limits (20 μg·kg-1).
中图分类号 O657.63 DOI 10.11973/lhjy-hx202210005
所属栏目 工作简报
基金项目 国家中药及饮片质量控制重点实验室项目(2021GSMPA-KL06、2021GSMPA-KL04、2020GSMPA-KL06-1、2020GSMPA-KL15);甘肃省药品产业技术扶持项目(2019KF008、2019KF011);甘肃省2020年重点人才项目(2020RCXM084);甘肃海智计划特色示范项目(2019);甘肃省药品科研项目(2019GSMPA018)
收稿日期 2022/1/28
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备注刘志荣,工程师,硕士,主要从事药品质量研究
引用该论文: LIU Zhirong,LIU Dongsheng,ZHANG Mingtong,XIE Nan,LI Donghua. Simultaneous Determination of Residues of 46 Pesticides in Lycium Ruthenicum Murr. by Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry after QuEChERS Purification[J]. Physical Testing and Chemical Analysis part B:Chemical Analysis, 2022, 58(10): 1144~1153
刘志荣,刘东升,张明童,谢楠,李冬华. QuEChERS净化-超高效液相色谱-串联质谱法同时测定黑枸杞中46种农药残留量[J]. 理化检验-化学分册, 2022, 58(10): 1144~1153
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【3】ANASTASSIADES M, LEHOTAY S J, ŠTAJNBAHER 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]. Journal of AOAC INTERNATIONAL, 2019,86(2):412-431.
【4】GONZÁLEZ-CURBELO M Á, SOCAS-RODRÍGUEZ B, HERRERA-HERRERA A V, et al. Evolution and applications of the QuEChERS method[J]. TrAC Trends in Analytical Chemistry, 2015,71:169-185.
【5】DA COSTA MORAIS E H, COLLINS C H, JARDIM I C S F. Pesticide determination in sweet peppers using QuEChERS and LC-MS/MS[J]. Food Chemistry, 2018,249:77-83.
【6】谢楠,张明童,刘志荣,等.改进QuEChERS/超高效液相色谱-串联质谱法同时测定当归中86种农药残留[J].化学试剂, 2021,43(2):196-203.
【7】刘志荣,张明童,谢楠,等.改进QuEChERS-超高效液相色谱-串联质谱法同时测定甘草中86种农药残留[J].质谱学报, 2020,41(6):624-636.
【8】张明童,刘志荣,李冬华,等.超高效液相色谱-串联质谱法测定白芷中51种禁用农药的残留量[J].理化检验-化学分册, 2020,56(4):381-388.
【9】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.
【10】NI Y X, YANG H, ZHANG H T, et al. Analysis of four sulfonylurea herbicides in cereals using modified Quick, Easy, Cheap, Effective, Rugged, and Safe sample preparation method coupled with liquid chromatography-tandem mass spectrometry[J]. Journal of Chromatography A, 2018,1537:27-34.
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