The simultaneous degradation of prochloraz and tebuconazole in water with monitoring their degradation products using liquid chromatography-tandem mass spectrometry

Prochloraz and tebuconazole are well-known fungicides for broad applications, including medical, industrial, and agricultural. They are frequently used simultaneously which increases the probability of their co-existing in various water sources. In this study, the analysis of PCZ or TBZ in water was performed by a direct analysis using the liquid chromatography-tandem mass spectrometry technique (LC-MS/MS). The optimized method was fully validated according to the European guidelines, SANTE/11312/2021. The complete degradation of these fungicides (each of 2 mg/L) in their single presence in the water was accomplished just after 15 min using 4.2 mM persulfate at 50 °C, while a lower concentration of persulfate (1.4 mM) leads to a degradation of prochloraz and tebuconazole, in their single existence in water, at percentages of 97 % and 98 %, respectively, after 30 min at 50 °C. On the other hand, it takes a complete hour to degrade a mixture of prochloraz and tebuconazole at percentages of 99 % and 94 %, respectively, using 1.4 mM persulfate at 50 °C. Degradation products (DPds) of prochloraz and tebuconazole, either in their single or simultaneous existing in water, were also identified and monitored during the whole degradation process by LC-MS/MS using at least two mass transitions for each DPd at both positive and negative ionization modes. It was elucidated that the persulfate degradation of prochloraz was conducted by the cleavage of the imidazole ring and the subsequent formation of a trichlorophenol, while persulfate degradation of tebuconazole was mainly accomplished by the formation of a hydroxyl structure, cleavage of the tert-butyl chain, and the subsequent formation of a ketone structure. Furthermore, a new DPd of tebuconazole (m/z = 263 Da) with a diketone structure was identified and confirmed.