Abiotic transformation of kresoxim-methyl in aquatic environments: Structure elucidation of transformation products by LC-HRMS and toxicity assessment

In this study, abiotic transformation of an important strobilurin fungicide, kresoxim-methyl, was investigated under controlled laboratory conditions for the first time by studying its kinetics of hydrolysis and photolysis, degradation pathways and toxicity of possibly formed transformation products (TPs). The results indicated that kresoxim-methyl showed a fast degradation in pH9 solutions with DT50 of 0.5 d but relatively stable under neutral or acidic environments in the dark. It was prone to photochemical reactions under simulated sunlight, and the photolysis behavior was easily affected by different natural substances such as humic acid (HA), Fe3+ and NO3- which are ubiquitous in natural water, showing the complexity of degradation mechanisms and pathways of this chemical compound. The potential multiple photo-transformation pathways via photoisomerization, hydrolyzation of methyl ester, hydroxylation, cleavage of oxime ether and cleavage of benzyl ether were observed. 18 TPs generated from these transformations were structurally elucidated based on an integrated workflow combining suspect and nontarget screening by high resolution mass spectrum (HRMS), and two of them were confirmed with reference standards. Most of TPs, as far as we know, have never been described before. The in-silico toxicity assessment showed that some of TPs were still toxic or very toxic to aquatic organisms, although they exhibit lower aquatic toxicity compared to the parent compound. Therefore, the potential hazards of the TPs of kresoxim-methyl merits further evaluation.

Automated summary

In this study, the abiotic transformation of kresoxim-methyl was investigated. The results showed that kresoxim-methyl degraded quickly in pH9 solutions but remained stable in neutral or acidic environments in the dark. Photolysis of kresoxim-methyl was influenced by natural substances and multiple transformation pathways were observed. Eighteen transformation products (TPs) were identified, most of which have not been previously described. The TPs showed lower aquatic toxicity compared to the parent compound, but further evaluation of their potential hazards is warranted.