色谱

色谱 ›› 2024, Vol. 42 ›› Issue (12): 1136-1144.DOI: 10.3724/SP.J.1123.2023.12021

• 研究论文 • 上一篇    下一篇

基于改性多壁碳纳米管净化的高效液相色谱-三重四极杆/复合线性离子阱质谱测定南美白对虾中66种农药残留

周锐东1,2, 文宇鹏1,2, 霍文迪2,3, 张超英2, 刘欢2, 孙慧武2, 吴立冬2, 李晋成2,*()   

  1. 1.上海海洋大学水产与生命学院, 上海 201306
    2.中国水产科学研究院农业农村部水产品质量安全控制重点实验室, 北京 100141
    3.北京石油化工学院新材料与化工学院, 北京 102617
  • 收稿日期:2023-12-18 出版日期:2024-12-08 发布日期:2024-12-09
  • 通讯作者: E-mail:lijc@cafs.ac.cn.
  • 作者简介:第一联系人：

    本文为“第24届全国色谱学术报告会优秀论文专辑”稿件.

  • 基金资助:
    中国水产科学研究院基本科研业务基金(2024A001);现代农业产业技术体系建设专项资金(CARS-48);中国水产科学研究院科技创新项目(2020TD75)

Determination of 66 pesticide residues in Litopenaeus vannamei by high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry based on modified multi-wall carbon nanotube purification

ZHOU Ruidong1,2, WEN Yupeng1,2, HUO Wendi2,3, ZHANG Chaoying2, LIU Huan2, SUN Huiwu2, WU Lidong2, LI Jincheng2,*()   

  1. 1. College of Fisheries and Life Science, Shanghai Ocean University, Shanghai 201306, China
    2. Key Laboratory of Control of Quality and Safety for Aquatic Products, Ministry of Agriculture and Rural Affairs, Chinese Academy of Fishery Sciences, Beijing 100141, China
    3. School of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China
  • Received:2023-12-18 Online:2024-12-08 Published:2024-12-09
  • Supported by:
    Basic Scientific Research Expenses of Chinese Academy of Fishery Sciences(2024A001);Special Funds for the Construction of Modern Agricultural Industrial Technology System(CARS-48);Science and Technology Innovation Project of Chinese Academy of Fishery Sciences(2020TD75)

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摘要：

针对水产品农药残留分析过程中基质干扰强的现状,本研究利用多壁碳纳米管(MWCNTs)和海藻酸钠(SAL)制备了一种MWCNTs-SAL复合净化材料,建立了高效液相色谱-三重四极杆/复合线性离子阱质谱(HPLC-QTRAP-MS/MS)快速测定水产品中66种农药残留的分析方法。采用电喷雾装置将MWCNTs和SAL的复合溶液快速喷入CaCl2溶液中进行交联,制备MWCNTs-SAL复合材料。将乙腈作为提取溶剂,基于推杆式震荡型净化技术对提取液进行净化。采用C18 RRHD色谱柱(150 mm×3.0 mm, 1.8 μm)对目标化合物进行分离,在多反应监测(MRM)模式下采集质谱数据,使用基质匹配混合标准溶液进行定量分析。实验比较了MWCNTs-SAL填料与商品化填料对南美白对虾提取液的净化效果,并考察了MWCNTs-SAL用量对目标化合物净化效果的影响。实验结果表明,66种农药在0.5~50 μg/L内线性关系良好,相关系数均>0.99,检出限和定量限分别为0.5~1 μg/kg和1~2 μg/kg;在低、中、高3个加标水平下,66种目标化合物的回收率为64.1%~107.3%,日内和日间精密度均小于20.4%。该方法经济快速,简便高效,具有较高的灵敏度和重复性,是水产品中农药残留分析的可行方法。

关键词: 多壁碳纳米管, 高效液相色谱-三重四极杆/复合线性离子阱质谱, 水产品, 农药残留

Abstract:

The complex composition of aquatic products, with high levels of protein and fat, significantly impacts the accuracy of liquid chromatography-mass spectrometry analysis for pesticide residue detection. Hence, developing effective purification materials is essential to mitigate these matrix interferences. To address strong matrix interference in pesticide residue analysis, a composite material, multi-walled carbon nanotubes (MWCNTs)-sodium alginate (SAL) (MWCNTs-SAL), was developed and used as purification material in a push-rod oscillation purification column to establish a rapid method for analyzing 66 pesticide residues in Litopenaeus vannamei. The composite solution of MWCNTs and SAL was quickly sprayed into CaCl2 solution by electrospray device for crosslinking, and MWCNTs-SAL materials were prepared. The results of scanning electron microscopy image proved the successful preparation of the MWCNTs-SAL. Acetonitrile, as the extraction solvent, was modified with acetic acid to augment the extraction efficiency of acidic pesticides, and anhydrous sodium sulfate was utilized to remove water from the matrix. Push-rod oscillation purification technology was used for purification of the post-centrifugation extract. The target compounds were separated using C18 RRHD column (150 mm×3.0 mm, 1.8 μm) and the mobile phases were consisted of 0.2% formic acid aqueous solution (containing 5 mmol/L ammonium acetate) and 0.2% formic acid methanol. The high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry (HPLC-QTRAP-MS/MS) was used for separation and determination, and the data was collected through the multiple reaction monitoring (MRM) mode. Due to the different properties of the target compounds, positive and negative ion acquisition scan modes were employed for mass spectrometry analysis. The quantitative analyses of the 66 pesticides were achieved by matrix-matched standard curves. The purification effects of MWCNTs-SAL and commercial sorbents on the extraction of the 66 pesticides were compared. The pretreatment parameters, such as the optimal dosage of MWCNTs-SAL and anhydrous sodium sulfate on the purification effects of the 66 pesticides were also assessed. When using 50 mg MWCNTs-SAL and 100 mg anhydrous sodium sulfate as the purification materials, the purification effect of aquatic products was the best. The 66 pesticides demonstrated good linearities in the range of 0.5-50 μg/L, with correlation coefficients of greater than 0.99. The limits of detection and quantification for the 66 pesticides were 0.5-1 μg/kg and 1-2 μg/kg, respectively. The recoveries of the 66 pesticides under three spiked levels (low, medium, high) were 64.1%-107.3%. The intra- and inter-day precisions were both less than 20.4%. This study provides an economical, quick, efficient, and sensitive approach for pesticide residue detection in aquatic products.

Key words: multi-walled carbon nanotubes (MWCNTs), high performance liquid chromatography-triple quadrupole/linear ion trap mass spectrometry (HPLC-QTRAP-MS/MS), aquatic products, pesticide residues

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