Cao Yi-Lin, Li Nan, Li Yun, Qiu Jing, Sui Hai-Xia, Yang Dao-Yuan, Qian Yong-Zhong
Institute of Quality Standards and Testing Technology for Agro-Products, Key Laboratory of Agro-Product Quality and Safety, Chinese Academy of Agricultural Sciences; Key Laboratory of Agri-Food Quality and Safety, Ministry of Agriculture and Rural Affairs, Beijing 100081, PR China.
Institute of Quality Standards and Testing Technology for Agro-Products, Key Laboratory of Agro-Product Quality and Safety, Chinese Academy of Agricultural Sciences; Key Laboratory of Agri-Food Quality and Safety, Ministry of Agriculture and Rural Affairs, Beijing 100081, PR China; College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102627, PR China.
J Hazard Mater. 2025 Mar 5;485:136920. doi: 10.1016/j.jhazmat.2024.136920. Epub 2024 Dec 16.
The rapid sulfhydrylation of chlorothalonil (CHT) in sulfur-rich vegetable matrices was observed in our previous study. However, the formation pathway, residual behavior, and toxicity of sulfhydrylated CHT remain unclear. In this study, we reveal that 4-sulfhydryl chlorothalonil (4-SH-CHT) can be formed by the reaction of CHT with HS species. CHT sulfhydrylation mainly occurs in tissue-destroyed pak choi, as HS and various HS donors are released along with tissue destruction. Over 50 % of CHT was transformed during pak choi homogenization at room temperature (25 °C). Liquid nitrogen with solvent acidification has been proposed to inhibit rapid sulfhydrylation during the analysis of CHT and its degradation products. The analytical method developed to simultaneously detect CHT, 4-SH-CHT, and 4-hydroxy chlorothalonil demonstrated good accuracy, high sensitivity, and satisfactory repeatability. At the maximum recommended dose of CHT, the terminal concentration of CHT in pak choi was higher than the maximum residue level, suggesting a potential chronic risk. The acute toxicity of 4-SH-CHT was higher than that of CHT, and the main target organs were the liver and heart. The consumption of 4-SH-CHT in several tissue-destroyed pak choi samples was higher than the threshold level. This study provides valuable information for further comprehensive safety evaluations of CHT in sulfur-rich vegetables and related foods.
我们之前的研究观察到，在富硫蔬菜基质中百菌清（CHT）会迅速发生巯基化反应。然而，巯基化百菌清的形成途径、残留行为和毒性仍不清楚。在本研究中，我们揭示了4-巯基百菌清（4-SH-CHT）可由百菌清与HS物种反应形成。百菌清的巯基化主要发生在组织被破坏的小白菜中，因为随着组织破坏会释放出HS和各种HS供体。在室温（25°C）下小白菜匀浆过程中，超过50%的百菌清发生了转化。已提出在分析百菌清及其降解产物时，加入溶剂酸化的液氮来抑制快速巯基化反应。所开发的同时检测百菌清、4-巯基百菌清和4-羟基百菌清的分析方法具有良好的准确性、高灵敏度和令人满意的重复性。在百菌清的最大推荐剂量下，小白菜中百菌清的最终浓度高于最大残留限量，表明存在潜在的慢性风险。4-巯基百菌清的急性毒性高于百菌清，主要靶器官为肝脏和心脏。在几个组织被破坏的小白菜样品中，4-巯基百菌清的摄入量高于阈值水平。本研究为进一步全面评估富硫蔬菜及相关食品中百菌清的安全性提供了有价值的信息。
