Monitoring of photocatalytic degradation of selected neonicotinoid insecticides by cathodic voltammetry with a bismuth film electrode

An electroanalytical method has been developed for the determination of two water soluble pyridine based neonicotinoid insecticides (imidacloprid and acetamiprid) by differential pulse voltammetry with a bismuth film electrode in aqueous Britton-Robinson buffer solution as supporting electrolyte. The bismuth film electrode preparation was optimized for cathodic voltammetric application. The reduction peaks of the neonicotionids appeared at potentials more negative than -0.5V (BiFE vs. Ag/AgCl/3.0 M KCl) and the signal characteristics depended on the pH of the supporting electrolyte. The best analysis conditions were found to be pH 8.0 for imidacloprid and pH 3.0 for acetamiprid at the following measurement parameters: pulse amplitude 50 mV, pulse width 50 ms and scan rate 25 mV Calibration curves were linear in the concentration range of 2.43-51.1 mu g/cm(3) for imidacloprid and 2.95-47.3 mu g/cm(3) for acetamiprid, while the detection limits were 0.73 mu g/cm(3) and 0.88 mu g/cm(3) for imidacloprid and acetamiprid, respectively. The electroanalytical method has allowed monitoring the heterogeneous photocatalytic (O-2/TiO2/UV) degradation of the two insecticides via their disappearance. The dynamics and the reaction rate determined on the basis of the electrochemical data were validated with HPLC/DAD and FTIR measurements.