超高效液相色谱-四极杆/静电场轨道阱质谱同时回溯定性和精准定量粮食中多种农药残留  

UPLC-Q-Orbitrap HRMS for Simultaneous Accurate Quantitative and Retrospective Qualitative Screening of Pesticide Residues in Grain

作　　者：罗丽娟 赵小萌 叶金 吴宇 管骁[1] 张蕊 刘思思 王松雪 Luo Lijuan;Zhao Xiaomeng;Ye Jin;Wu Yu;Guan Xiao;Zhang Rui;Liu Sisi;Wang Songxue(School of Health Science and Engineering,University of Shanghai for Science and Technology,Shanghai 200093;Beijing Municipal Science&Technology Commission,Administrative Commission of Zhongguancun Science Park,Beijing Science and Technology Innovation Promotion Center,Beijing 100036;Academy of National Food and Strategic Reserves Administration,Beijing 100037)

机构地区：[1]上海理工大学健康科学与工程学院,上海200093 [2]北京市科学技术委员会、中关村科技园区管理委员会、北京科技创新促进中心,北京100036 [3]国家粮食和物资储备局科学研究院,北京100037

出　　处：《中国粮油学报》2025年第1期183-192,共10页Journal of the Chinese Cereals and Oils Association

基　　金：国家重点研发计划子课题项目(2022YFF1101105-05),中央级公益性科研院所基本科研业务费专项(ZX2231),全国粮食和物资储备青年拔尖人才项目(QN2022202),全国粮食和物资储备领军人才项目(LJ2022201)。

摘　　要：采用直接提取稀释结合超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法(UPLC-Q-Orbitrap HRMS),建立了粮食中回溯定性筛查和精准定量方法。通过UPLC-Q-Orbitrap HRMS采集农药标准品获得其一级和二级高分辨质谱图等信息,构建418种农药高分辨质谱数据库。样品经V_(乙腈)∶V_(水)∶V_(乙酸)溶液(70∶29∶1)提取,稀释,高速低温离心去除油脂,过滤膜后,采用UPLC-Q-Orbitrap HRMS进行检测。通过对数据依赖采集(ddMS^(2))、数据非依赖采集(DIA)和全离子碎裂(AIF)扫描模式的性能进行考察和优化,建立了基于农药高分辨质谱数据库的粮食中同时定性筛查和精准定量方法并进行系统验证。结果表明:稻谷、小麦和玉米3种基质中线性相关系数(R^(2))大于0.99的农药占比均大于90%,定量限(LOQ)在1~4μg/kg占比均大于90%;在50、100和200μg/kg 3个加标水平下,稻谷、小麦和玉米的平均回收率在70%~120%的农药占比均大于70%,相对标准偏差(RSD)<10%的农药占比均大于80%。该方法省时、快速、高效、低成本,无需重新采集样品即可对历史采集数据进行农药残留的回溯定性和半定量,有助于快速摸清粮食中主要污染农残种类和污染程度,缩短风险评估时间。In this study,dilute-and-shoot combined with ultra-high performance liquid chromatography coupled to quadrupole-orbitrap high resolution mass spectrometry(UPLC-Q-Orbitrap HRMS)was used to establish a retrospective qualitative screening and accurate quantitative method for grains.UPLC-Q-Orbitrap HRMS was used to collect data for pesticide standards to obtain the parent ion mass number,retention time,daughter ion mass number and optimal impact energy(NCE),etc.,and construct a high-resolution mass spectrometry database for 418 pesticides.Samples were extracted by acetonitrile:water:acetic acid solution(70∶29∶1),diluted,and centrifuged at high speed and low temperature to remove grease.After coating,the samples were detected by UPLC-Q-Orbitrap HRMS.By investigating the scanning patterns of Full MS/ddMS2,vDIA and AIF,the simultaneous qualitative screening and precise quantitative methods in grain were established.Results indicated that,the proportion of pesticides with linear correlation coefficient(R2)greater than 0.99 in rice,wheat and maize was greater than 90%,and the quantitative limit(LOQ)was greater than 90%in 1-4μg/kg.The average recovery of rice,wheat and maize at three spiked concentration levels was 70%-120%,and the proportion of pesticides was above 70%,with relative standard deviation(RSD)less than 10%was above 80%.This method had the advantages of simplicity,speed,accuracy,and high throughput.This method did not need to collect samples repeatedly,and could save time,quickly,efficiently and low-cost for analysis of pesticide residues from historical data collection retrospectively,helping to quickly identify the types and pollution degree of major polluting pesticide residues in grain and shorten the time of risk assessment.

关 键 词：粮食 农药残留 高分辨质谱数据库 直接提取稀释法 回溯定性和精准定量 

分 类 号：TS213.2[轻工技术与工程—粮食、油脂及植物蛋白工程]