Electrochemical bioassay for the investigation of chlorpyrifos-methyl in vine samples

This paper reports the optimization of an electrochemical bioassay for the determination of chlorpyrifos-methyl and its application to the analysis of grape and vine leaf samples treated with that pesticide. The analytical method was based on electrochemical determination of the extent of the inhibition exerted by the pesticide on acetylcholinesterase using the substrate acetylthiocholine. Two similar calibration plots were obtained, in the range of 1-300 ng/mL, respectively, for chlorpyrifos-methyl in pure standard form and in the commercial preparation Reldan, with comparable coefficients of variation (CV) in the range of 10% < CV < 20%. After an insecticide treatment, samples were analyzed to evaluate its persistence both in grapes and in vine leaves. Samples were evaluated using different extraction procedures: one based on solvent extraction of pesticide residue from grapes and the other based on aqueous extraction from vine leaves using phosphate buffer. The grape solvent extracts were analyzed using both gas chromatography and electrochemical bioassay, whereas the vine leaf buffer extracts were analyzed using the electrochemical bioassay. Quantitative analysis of chlorpyrifos-methyl determined in the two samples, with the electrochemical bioassay, showed a comparable decrease profile over the experimental period.