Key Laboratory of Testing and Evaluation for Aquatic Product Safety and Quality, Ministry of Agriculture and Rural Affairs; Yellow Sea Fisheries Research Institute, Chinese Academy of Fishery Sciences, Qingdao, 266071, Shandong, People's Republic of China.
Weifang Institute of Inspection on Product Quality, Weifang, 266000, People's Republic of China.
Anal Bioanal Chem. 2021 Oct;413(25):6239-6252. doi: 10.1007/s00216-021-03579-y. Epub 2021 Aug 13.
Triazine herbicides are used extensively in agriculture and aquaculture worldwide because of their broad effectiveness in weed control. However, after they are discharged into the sea, they seriously contaminate aquatic ecosystems and threaten aquatic organisms, especially shellfish. Currently, there are no established methods for the detection and confirmation of triazine herbicides and their metabolites in biological matrixes. Hence, the food safety of aquatic products cannot be accurately evaluated, which creates a technical barrier against international aquatic product trade. In this study, for the first time, a method was developed for the analysis and confirmation of seven triazine herbicides and 13 metabolites in shellfish, based on alkaline acetonitrile extraction and neutral AlO cartridge purification coupled with internal standard calibration. Specifically, quantitative and qualitative analysis was conducted using high-performance liquid chromatography-triple quadrupole mass spectrometry (HPLC-MS/MS), and accurate identification was carried out by quadrupole orbitrap high-resolution mass spectrometry (Q/E Orbitrap HRMS). The results showed that target analytes demonstrated good linearity within the corresponding range (R > 0.995). The limit of detection and limit of quantitation of the proposed method were 0.1 and 0.3 μg/kg, respectively. The average recoveries of analytes were between 70.0% and 120% when spiked at three levels with blank oyster (Crassostrea gigas) as the matrix, and the relative standard deviations (RSDs) were all less than 12% (n=6). The proposed method was successfully applied for the detection of triazine herbicide residues in oyster samples during actual breeding, and the presence of DIP, HP, DEHA, and other metabolites in positive samples was confirmed by Q/E Orbitrap HRMS. This method exhibits high accuracy, high sensitivity, and good reproducibility. It has promising application prospects in the field of hazard analysis and the positive identification of aquatic products.
三嗪类除草剂由于其在杂草防治方面的广泛有效性，在世界范围内被广泛用于农业和水产养殖。然而，它们被排放到海洋后，会严重污染水生生态系统并威胁水生生物，尤其是贝类。目前，在生物基质中还没有建立检测和确认三嗪类除草剂及其代谢物的方法。因此，无法准确评估水产品的食品安全，这对水产品国际贸易造成了技术障碍。在这项研究中，首次建立了基于碱性乙腈提取和中性 AlO 柱净化结合内标校准的贝类中 7 种三嗪类除草剂和 13 种代谢物的分析和确证方法。具体来说，采用高效液相色谱-三重四极杆质谱联用技术（HPLC-MS/MS）进行定量和定性分析，并采用四极杆轨道阱高分辨率质谱（Q/E Orbitrap HRMS）进行准确鉴定。结果表明，目标分析物在相应范围内具有良好的线性关系（R > 0.995）。该方法的检测限和定量限分别为 0.1 和 0.3 μg/kg。当以空白牡蛎（Crassostrea gigas）为基质进行 3 个水平的加标时，分析物的平均回收率在 70.0%至 120%之间，相对标准偏差（RSD）均小于 12%（n=6）。该方法成功应用于实际养殖过程中牡蛎样品中三嗪类除草剂残留的检测，并通过 Q/E Orbitrap HRMS 确认阳性样品中 DIP、HP、DEHA 等代谢物的存在。该方法具有准确度高、灵敏度高、重现性好的特点，在危害分析和水产品阳性鉴定领域具有广阔的应用前景。
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