全自动固相萃取结合UPLC-MS/MS测定茶叶中的草甘膦及其代谢物

易华娟; 朱洁灵; 周瑞铮; 郑耀林; 张树权; 杨乐; 苏雍伦

doi:10.13305/j.cnki.jts.2023.06.010

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茶叶科学 ›› 2023, Vol. 43 ›› Issue (6) : 857-869. DOI: 10.13305/j.cnki.jts.2023.06.010

研究报告

全自动固相萃取结合UPLC-MS/MS测定茶叶中的草甘膦及其代谢物

易华娟¹, 朱洁灵¹, 周瑞铮¹, 郑耀林¹, 张树权¹, 杨乐¹, 苏雍伦²

作者信息 +

Determination of Glyphosate and Its Metabolites in Tea by Automatic Solid Phase Extraction Combined with UPLC-MS/MS

YI Huajuan¹, ZHU Jieling¹, ZHOU Ruizheng¹, ZHENG Yaolin¹, ZHANG Shuquan¹, YANG Le¹, SU Yonglun²

Author information +

文章历史 +

摘要

建立超高效液相色谱-质谱/质谱法（UPLC-MS/MS）测定茶叶中草甘膦及其代谢物氨甲基膦酸的分析方法。用水-二氯甲烷体系对样品进行提取和初步除杂,在全自动固相萃取仪中通过聚苯乙烯键合苯磺酸混合型阳离子交换柱进一步净化样品溶液基质,利用正交试验和方差分析得出最优的衍生条件为5%硼酸钠缓冲溶液和10 mg·mL^-1的9-芴基甲基三氯甲烷（FMOC-Cl）衍生剂在室温下衍生2 h,衍生后的样品溶液在HSS T₃色谱柱和5 mmol·L^-1乙酸铵溶液（含0.1%甲酸）-乙腈流动相体系下进行梯度洗脱分离,经UPLC-MS/MS进行内标法定量分析。草甘膦和氨甲基膦酸在0.2~50 ng·mL^-1质量浓度范围内线性关系良好,相关系数（R²）均大于0.999,该方法的检出限为2 μg·kg^-1,定量限为5 μg·kg^-1。低、中、高3个加标水平（5、50 μg·kg^-1和250 μg·kg^-1）的回收率为94.2%~106.7%,相对标准偏差为3.8%~4.9%。该方法具有高效率、高准确度、高通量、基质干扰小和自动化程度高等优点,适用于实验室日常大批量茶叶样品筛查草甘膦及氨甲基膦酸残留的工作需求。

Abstract

An analytical method for the determination of glyphosate and its metabolite aminomethylphosphonic acid in tea was established by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were extracted and preliminarily purified using a water dichloromethane system and the sample matrix was further purified by mixed-mode cation exchanger column filled with polystyrene bonded benzenesulfonic acid in an automatic solid phase extractor. The optimal derivation conditions obtained by orthogonal test and variance analysis were 5% sodium borate buffer solution and 10 mg·mL^-1 FMOC-Cl derivatizing agent for derivatization at room temperature for 2 h. The derived sample solution was subjected to gradient elution separation on HSS T₃ column and 5 mmol·L^-1 ammonium acetate solution (containing 0.1% formic acid)-acetonitrile mobile phase system. The targets were analyzed by UPLC-MS/MS and quantified by internal standard method. The linearity of glyphosate and aminomethylphosphonic acid was good in the concentration range of 0.2-50 ng·mL^-1 and the correlation coefficient (R²) was greater than 0.999. The detection limit of the method was 2 μg·kg^-1, and the quantitation limit was 5 μg·kg^-1. The recoveries of 5, 50 and 250 μg·kg^-1 were in range of 94.2%-106.7% with relative standard deviations of 3.8%-4.9%, at low, medium and high spiked levels. The method is suitable for the determination of glyphosate and aminomethylphosphonic acid residues in daily large quantities of tea samples in the laboratory with the advantages of high efficiency, high accuracy, high throughput, low matrix interference and high degree of automation.

导出引用

易华娟, 朱洁灵, 周瑞铮, 郑耀林, 张树权, 杨乐, 苏雍伦. 全自动固相萃取结合UPLC-MS/MS测定茶叶中的草甘膦及其代谢物[J]. 茶叶科学. 2023, 43(6): 857-869 https://doi.org/10.13305/j.cnki.jts.2023.06.010

YI Huajuan, ZHU Jieling, ZHOU Ruizheng, ZHENG Yaolin, ZHANG Shuquan, YANG Le, SU Yonglun. Determination of Glyphosate and Its Metabolites in Tea by Automatic Solid Phase Extraction Combined with UPLC-MS/MS[J]. Journal of Tea Science. 2023, 43(6): 857-869 https://doi.org/10.13305/j.cnki.jts.2023.06.010

中图分类号： S571.1 S482

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