In the environment, plants and animals in vivo, pesticides can be degraded or metabolized to form transformation products (TPs) or metabolites, which are even more toxic than parent pesticides. Hence, it was necessary to evaluate residue and risk of pesticides and their TPs (or metabolites). Here, a rapid, simple, and reliable method using QuEChERS and LC-MS/MS had been developed for simultaneous analysis of prothioconazole and its toxic metabolite, prothioconazole-desthio, in soil, wheat plant, straw, and grain. The average recoveries of prothioconazole and prothioconazole-desthio in four matrices ranged from 86 to 108% with relative standard deviations (RSDs) of 0.53-11.87% at three spiking levels. The method was successfully applied to investigate the dissipation and terminal residues of the two compounds in wheat field. It was shown that prothioconazole was rapidly degraded to prothioconazole-desthio, with half-lives below 5.82 days. Prothioconazole-desthio was slowly dissipated in soil and plant. The terminal residues of prothioconazole in wheat grain with a pre-harvest interval (PHI) of 21 or 28 days were below the maximum residue limits (MRLs) (0.1 mg/kg, Codex Alimentarius Commission (CAC)). We also evaluated the intake risk of prothioconazole-desthio residues in wheat grain in China. For long-term intake assessment, the hazard quotients (HQ) ranged from 1.30 to 5.95%. For short-term intake assessment, the acute hazard indexes (aHI) ranged from 1.94 to 18.2%. It indicated that the intake risk of prothioconazole-desthio in wheat consumption was acceptable. Thus, the prothioconazole application on wheat with the scientific practices would not pose public health risk.
The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO3 (-)), Fe (III) ions, and titanium dioxide (TiO2) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO3 (-), Fe (III), and TiO2 slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L(-1) Fe (III) and 500 mg L(-1) TiO2 were about 7-fold and 13-fold faster than that without Fe (III) and TiO2 under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.
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