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Abstract
Fluopyram, a typical phenylamide fungicide, was widely applied to protect fruit vegetables from fungal pathogens-responsible yield loss. Highly linked to the ecological and dietary risks, its residual and metabolic profiles in the fruit vegetable ecosystem still remained obscure. Here, an approach using modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) extraction combined with GC-MS/MS analysis was developed to investigate fluopyram fate in the typical fruit vegetables including tomato, cucumber, pepper under the greenhouse environment. Fluopyram dissipated in accordance with the first-order rate dynamics equation with the maximum half-life of 5.7 d. Cleveage of fluopyram into 2-trifluoromethyl benzamide and subsequent formation of 3-chloro-5-(trifluoromethyl) pyridine-2-acetic acid and 3-chloro-5-(trifluoromethyl) picolinic acid was elucidated to be its ubiquitous metabolic pathway. Moreover, the incurrence of fluopyram at the pre-harvest interval (PHI) of 7–21 d was between 0.0108 and 0.1603 mg/kg, and the Hazard Quotients (HQs) were calculated to be less than 1, indicating temporary safety on consumption of the fruit vegetables incurred with fluopyram, irrespective of the uncertain toxicity of the metabolites. Taken together, our findings reveal the residual essential of fluopyram in the typical agricultural ecosystem, and would advance the further insight into ecological risk posed by this fungicide associated with its metabolites.
Highlights
Fluopyram, a typical phenylamide fungicide, was widely applied to protect fruit vegetables from fungal pathogens-responsible yield loss
Method, authentic fluopyram detected at tR 7.5 min with the parent ion m/z 396.6 was monitored in the full scan mode in the range m/z 50–500 (Fig. 2A,B), and ion 173.4 was selected as the first-order parent ion fragments (Fig. 2B)
After the single application at 62.4 g a.i. ha−1, fluopyram dissipated rapidly in the vegetable greenhouse ecosystem in accordance with the first-order rate dynamics with the maximum half-life as 5.7 d, in trifluoromethyl benzamide (TMB), TPA and TPAA were simultaneously analyzed in tomato (A), cucumber (B), pepper (C), tomato soil (D), cucumber soil (E) and pepper soil (F)
Summary
A typical phenylamide fungicide, was widely applied to protect fruit vegetables from fungal pathogens-responsible yield loss. Linked to the ecological and dietary risks, its residual and metabolic profiles in the fruit vegetable ecosystem still remained obscure. Our findings reveal the residual essential of fluopyram in the typical agricultural ecosystem, and would advance the further insight into ecological risk posed by this fungicide associated with its metabolites. A typical pyridinyl moiety-contained phenylamide fungicide (Fig. 1) with the broad-spectrum activity, was developed by Bayer Crop Science in 20103,4, and has been widely applied to eliminate fungal pathogens from fruit vegetables since its full registration in 2012 in China[5]. It was found that this fungicide was capable of altering the microbial diversity in soil ecosystem, leading to depraved soil health[13] It seems that constant and excessive application of fluopyram may pose a risk towards human health through the imbalance of the associated agricultural ecosystem. A reliable, unified and compatible methodology remained to be developed for rapid qualitative and quantitative analysis of fluopyram and the related metabolism in such vegetable ecosystems
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