The first study of triazole fungicide difenoconazole oxidation and its voltammetric and flow amperometric detection on boron doped diamond electrode

Triazole pesticides act as sterol synthesis inhibitors and have been considered as redox-inactive with a variety of electrode materials. In this study, electrochemical oxidation of the fungicide difenoconazole (DFC) was studied in aqueous solutions on oxygen terminated boron doped diamond electrode. It provided a pH-independent irreversible anodic peak at a very positive potential of ca +1.75 V (vs. Ag/AgCl) in acidic media, which could be used for its quantitation in batch voltammetry and flow injection analysis with amperometric detection. The attained detection limits for the determination of DFC in 0.1 mol L-1 HNO3/phosphate buffer pH 2.0 were 0.049 mu mol L-1 for differential pulse voltammetry and 1.58 mu mol L-1 for FIA-ED. The former method did not suffer from any significant matrix interferences or interferences of other fungicides and yielded acceptable percentage recovery values (ranging from 96% to 107%) for DFC determination in model river water samples. Similar results comparing both methods at a 95% confidence level were obtained for DFC determination in pesticide preparations. Further, an oxidation mechanism leading to hydroxylated derivative of DFC and subsequent formation of a quinone was suggested. Results were supported with HOMO spatial distribution calculations and atomic charges calculations for arising radical cations. (c) 2021 Elsevier Ltd. All rights reserved.