Simultaneous determination of triazine herbicides and their metabolites in shellfish by HPLC-MS/MS combined with Q/E-Orbitrap HRMS.

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 Al ₂ O ₃ 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 ² > 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.
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