Photodegradation of a new strobilurin fungicide, mandestrobin, was investigated in buffered aqueous solution and synthetic humic water (SHW) under continuous irradiation with artificial sunlight (λ > 290 nm). In both aquatic media, the direct photolysis preferentially proceeded via homolytic bond cleavage at the benzyl phenyl ether, and the subsequent recombination of geminate radicals in a solvent cage gave the photo-Claisen rearrangement products. A radical mechanism in the photochemical rearrangement was strongly supported by a radical-trapping technique using a novel nitroxide spin label combined with electron spin resonance (ESR) and liquid chromatography-mass spectrometry (LC-MS) analyses. Photosensitized generation of hydroxyl radical in SHW might significantly contribute to enhancing the formation of a benzyl alcohol derivative. The series of photolysis products steadily degraded and finally mineralized to carbon dioxide.

The photodegradation behavior of a new anilide fungicide, inpyrfluxam [3-difluoromethyl-N-[(R)-2,3-dihydro-1,1,3trimethyl-1H-inden-4-yl]-1-methylpyrazole-4-carboxamide] (1), was investigated in aqueous buffer and nitrate solutions under irradiation with artificial sunlight (λ > 290 nm). In both media, 1 mainly photodegraded via oxidation at the 3′-position of the Indane ring, cleavage of the C−N bond of the amide linkage and N-phenyl ring bond, and finally mineralization to carbon dioxide. No isomerization of 1 occurred at the 3′-position of the Indane ring. In the presence of nitrate ion, which originates from fertilizer in agricultural fields, the degradation of 1 was significantly accelerated as compared with buffer solution, and the reaction rate was strongly correlated with the concentration of hydroxyl radicals derived from the photolysis of nitrate ions. The reaction rate constant of hydroxyl radicals with 1 was determined to be 3.0 × 10 10 /M/s, which was higher than that of hydroxyl radicals with other pesticides possessing aromatic rings.

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