期刊
CHEMOSPHERE
卷 293, 期 -, 页码 -出版社
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.chemosphere.2022.133573
关键词
Pyridine herbicides; Triclopyr; UV photolysis; Laser flash photolysis photodegradation; Heterolytic C -Cl bond cleavage
资金
- Russian Science Foundation [RSF-NSFC N? 21-43-00004]
- Ministry of Science and Higher Education of the RF
The mechanism of direct UV photolysis of the pyridine herbicide triclopyr was investigated using nanosecond laser flash photolysis, steady-state photolysis coupled with high resolution LC-MS, and DFT quantum chemical calculations. Short-lived intermediates and final products were detected and identified for the first time. The results provide insights into the fate of pyridine herbicides in UVC disinfection and natural waters under sunlight.
Mechanism of direct UV photolysis of pyridine herbicide triclopyr (TRI) was revealed by the combination of nanosecond laser flash photolysis, steady-state photolysis coupled with high resolution LC-MS and DFT quantum chemical calculations. Both the detection of short-lived intermediates and the detailed identification of final products were done for the first time. The quantum yield of TRI photodegradation is about 4% at both UVC (254 nm) and UVB (308 nm) excitation. The primary stage is the heterolytic cleavage of C-Cl bond in dissociative triplet state of TRI with the formation of phenyl cation followed by a fast nucleophilic attack by a solvent molecule. The minor channel is the photohydrolysis leading to the formation of 3,5,6-trichloropyridin-2-ol. Primary photoproducts undergo secondary photolysis by the mechanism similar to initial TRI with the formation of products of acetic group elimination, sequential substitution of chlorine atoms to hydroxyl groups and, finally, oxidation and opening of the pyridine ring. Obtained results can be important for understanding the fate of pyridine herbicides in the processes of UVC disinfection and in natural waters under action of the sunlight.
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