色谱

色谱 ›› 2019, Vol. 37 ›› Issue (12): 1321-1330.DOI: 10.3724/SP.J.1123.2019.06018

• 研究论文 • 上一篇    下一篇

基于超高效液相色谱-高分辨质谱的非衍生化法测定面粉和燕麦中草甘膦及氨甲基膦酸残留

潘胜东1, 童廷德2, 叶美君3, 陈晓红1, 金米聪1   

  1. 1.宁波市疾病预防控制中心, 浙江省微量有毒化学物健康风险评估技术研究重点实验室, 浙江 宁波 315010;
    2.赛默飞世尔科技(中国)有限公司, 上海 201206;
    3.中华全国供销总社杭州茶叶研究院, 浙江 杭州 310016
  • 收稿日期:2019-06-19 出版日期:2019-12-08 发布日期:2020-12-11
  • 通讯作者: 潘胜东.E-mail:panshengdong0714@163.com.
  • 基金资助:
    浙江省自然科学基金项目（LQ19B050001）；宁波市自然科学基金项目（2018A610404，2016A610178）；浙江省公共卫生应急检测关键技术重点实验室开放基金；宁波市领军和拔尖人才计划.

Determination of residual glyphosate and aminomethylphosphonic acid in wheat flour and oats samples by non-derivatization method based on ultra-performance liquid chromatography-high resolution mass spectrometry

PAN Shengdong1, TONG Tingde2, YE Meijun3, CHEN Xiaohong1, JIN Micong1   

  1. 1. Key Laboratory of Health Risk Appraisal for Trace Toxic Chemicals of Zhejiang Province, Ningbo Municipal Center for Disease Control and Prevention, Ningbo 315010, China;
    2. Thermo Fisher Scientific(China) Co., Ltd., Shanghai 201206, China;
    3. Hangzhou Tea Research Institute, China COOP, Hangzhou 310016, China
  • Received:2019-06-19 Online:2019-12-08 Published:2020-12-11
  • Supported by:
    Zhejiang Provincial Natural Science Foundation (No. LQ19B050001); Ningbo Municipal Natural Science Foundation of China (Nos. 2018A610404, 2016A610178); Opening Foundation of Key Laboratory of Emergency Detection for Public Health of Zhejiang Province; Ningbo Municipal Program for Leading and Top-Notch Talents.

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摘要： 建立了固相萃取-超高效液相色谱-高分辨质谱（UPLC-HRMS）快速准确测定面粉和燕麦中残留草甘膦（GLY）及其代谢物氨甲基膦酸（AMPA）的分析方法。面粉和燕麦样品经水涡旋和超声提取，用混合阳离子交换固相萃取（MCX）小柱净化与乙腈沉淀蛋白质后，以5 mmol/L乙酸铵水溶液（pH=10.5）和乙腈溶液作为流动相在Dikma Polyamino HILIC色谱柱（150 mm×2.0 mm，5 μm）上进行梯度洗脱与分离，采用电喷雾电离源、负离子模式和平行反应监测（PRM）模式下，内标法定量分析。系统优化了液相色谱与高分辨质谱等仪器条件和样品前处理条件对GLY及其代谢物AMPA测定的影响，并比对了不同分析方法的基质效应，研究了进样系统残留。实验结果表明，GLY和AMPA在5.0~100.0 μg/L范围内呈现良好的线性关系（线性相关系数R2>0.999），检出限分别为0.005和0.05 mg/kg；低（0.1 mg/kg）、中（0.5 mg/kg）、高（2.0 mg/kg）3个添加水平下，GLY和AMPA的加标回收率分别为93.8%~115%和89.8%~110%，相对标准偏差均小于10%。基质效应实验结果表明，利用同位素内标物能有效降低方法的基质抑制效应（基质效应参数|η|<3%）；进样系统的残留率小于1.0%。本方法与文献报道的衍生化法方法进行比对，结果表明，两种检测方法与靶值的相对偏差分别为2.19%和3.07%。将该方法用于弗帕斯（FAPAS）能力验证样品的测定（编号为09122，燕麦中GLY的测定），结果满意，测定值与真值之间的偏离程度（z值）=0.2。FAPAS质控样品（编号为T09119QC，面粉中GLY的测定）检测结果显示本方法的准确度为102.2%。该方法具有快速、简便、灵敏和准确等优点，适合面粉与燕麦样品中GLY及其代谢物AMPA的日常监测。

关键词: 超高效液相色谱-高分辨质谱, 草甘膦, 氨甲基膦酸, 面粉, 燕麦

Abstract: A rapid and accurate analysis method based on ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) was developed for the determination of residual glyphosate (GLY) and aminomethylphosphonic acid (AMPA) in wheat flour and oats samples. The wheat flour and oats samples were firstly subjected to vortex and ultrasound extraction; then, the extract solution was purified by MCX solid-phase extraction (SPE) cartridges as well as protein precipitation using acetonitrile. The chromatographic separation was carried out on a Dikma Polyamino HILIC column (150 mm×2.0 mm, 5 μm) by linear gradient elution procedure using 5 mmol/L ammonium acetate in water (pH=10.5) and acetonitrile as the elution solvent. An electrospray ion source in negative mode and parallel reaction monitor (PRM) mode was used for quantification by the internal standard method. The instrument conditions for liquid chromatography (LC) and HRMS, and the sample pretreatment conditions for GLY and its metabolite AMPA were systematically optimized. In addition, the matrix effect and injection system residue were investigated, and a comparison of different analytical methods was carried out. The results indicated that GLY and AMPA showed good linearities in the range of 5.0-100.0 μg/L with coefficients (R2) higher than 0.999. The limits of detection (LODs) were found to be 0.005 and 0.05 mg/kg for GLY and AMPA, respectively. The recoveries of GLY and AMPA in the wheat flour and oats samples were in the range of 93.8%-115% and 89.8%-110% at the spiked levels of 0.1, 0.5, and 2.0 mg/kg, respectively, while the relative standard deviations (RSDs) were all less than 10%. The results of the matrix effect test revealed that the matrix inhibition effect could be reduced by using an isotopic internal standard with the matrix effect parameter |η|<3%. Moreover, the injection system residue was effectively controlled with a residual level of less than 1.0%. A comparison of the developed method with the reported derivatization method indicated little difference, with RSDs of 2.19% and 3.07% to the assigned value, respectively. The established analytical method was used for the Food Analysis Performance Assessment Scheme (FAPAS) proficiency test (No. 09122, GLY in oats), and the results were satisfactory with a z value of 0.2. Moreover, the result obtained using this method was very closed to the assigned value of the FAPAS QC sample, with a recovery of 102.2% (No. T09119QC, GLY in wheat flour). The proposed method is fast, simple, sensitive, and accurate, and it can be applied for the daily monitoring of GLY and its metabolite AMPA in wheat flour and oats samples.

Key words: ultra-performance liquid chromatography-high resolution mass spectrum (UPLC-HRMS), glyphosate, aminomethylphosphonic acid (AMPA), wheat flour, oats

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