超高效液相色谱-四级杆/静电场轨道阱高分辨质谱联用快速测定水产品及干制水产品制品中的116种农药和24种生物毒素残留

Simultaneous Determination and Confirmation of 116 Pesticides Residues and 24 Biotoxins in Aquatic Product and Dried Aquatic Product by Ultra Liquid Chromatography Coupled with Quadrupole/Exactive Orbitrap Mass Spectrometry

采用了一种新型脂肪吸附剂去除样品基质中脂肪和磷脂等杂质的干扰,利用超高效液相色谱-四级杆/静电场轨道阱质谱法(UPLC-Q Exactive Orbitrap MS)的同时定性定量功能,建立了水产品及干制水产品制品中116种农药和24种生物毒素残留量的检测方法。样品前处理采用QuEChERS方法,经乙腈/水(90:10,V/V)溶液提取,高效基质脂肪吸附剂(EMR-Lipid)净化,平行定量浓缩仪浓缩,C18色谱柱分离,5 mmol甲酸水溶液(含0.1%甲酸铵)和5 mmol甲酸甲醇溶液(含0.1%甲酸铵)梯度洗脱;质谱数据采集使用Q Exactive高分辨质谱的Full MS/dd-MS2监测模式,以Full MS一级质谱全扫描提取母离子精确质量数所得的色谱峰面积进行定量,以保留时间和dd-MS2数据依赖子离子扫描所得的二级子离子质谱图进行定性确证。140种目标物的精确质量数偏差不大于3×10^(-6),浓度与母离子峰面积的线性关系良好,相关系数≥0.991,检出限为0.02~0.4μg/kg。基质加标回收率在70.1%~109.1%之间,相对标准偏差(RSD)为1.0%~14.1%。该方法学结果满足GB/T 27417-2017《合格评定化学分析方法确认和验证指南》的技术要求。本方法具有操作简单快捷、灵敏度高等优点。

A method for determination of 116 pesticides and 24 biotoxin residues in aquatic product and dried aquatic product by ultra high performance liquid chromatography coupled with quadrupole/exactive orbitrap mass spectrometry(UPLC-Q exactive orbitrap MS)was developed.During the sample preparation,a novel lipid removal product was applied,and also QuEChERS extraction was involved.The sample was firstly extracted followed by acetonitrile(containing 30%(V/V)water),cleaned up by enhanced matrix removal of lipids(EMR-Lipid),and concentrated using syncore analyst.The separation of 140 target compounds was performed on a C;column using gradient elution of 5 mmol/L ammonium formate in methanol(containing 0.1%formic acid)and 5 mmol/L ammonium formate water(containing 0.1%formic acid)as mobile phase.In the process of quantification and qualification,a full MS/dd-MS2 experiment was adopted in mass spectrometry acquisition,the chromatographic peak area obtained by extracting the accurate mass number of parent ions by full MS first-order mass spectrometry was quantified,and the retention time and dd-MS2 data were qualitatively confirmed by the second-order ionization mass spectrometry obtained by daughter ion scanning.The mass accuracy error was less than 3×10^(-6),and the calibration curves were linear well with correlation coefficient over 0.991.The limits of detection ranged from 0.02μg/kg to 0.4μg/kg.The average spiked recoveries for 140 target compounds were between 70.1%and 109.1%,with relative standard derivations(RSDs)from 1.0%to 14.1%.The results of the methodology met the requirements of GB/T 27417-2017.Compared to previous methods,the new procedure is characteristics of simple sample preparation and higher sensitivity.