Carbendazim determination in orange juice samples by electrochemical techniques. A statistical evaluation of performance

Author(s)

Érica Megumi Kataoka

• Document type: Master's Dissertation
• Press: São Carlos.
• Institution: Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT)
• Defense date: 2016-02-18

Examining board members

Sergio Antonio Spinola Machado

• Advisor: Sergio Antonio Spinola Machado

Abstract

A glassy carbon electrode was modified by depositing a layer of multi-walled carbon nanotubes, functionalized and decorated with gold nanoparticles. This electrode was characterized by optical microscopy, showing a evenly coated surface. In addition, the morphology was investigated by transmission electron microscopy, where the distribution and the average size of 20 nm of the gold nanoparticles were observed. These metal nanoparticles were also characterized by absorption spectroscopy in the UV-vis region showing an absorption maximum at approximately 525 nm, which confirms their average size of 20 nm. The modified electrodes were electrochemically characterized by its voltammetric behavior in a 0.1 mol L-1H2SO4 solution, with a scanning rate of 0.100 V s-1. In these experiments, it became clear the formation and reduction of gold oxide peaks at potentials above 0.8 V vs. Ag/AgCl. It was also observed the proper functioning of the electrodes for the voltammetric response of the redox couple [Ru(NH3)6]Cl2/[Ru(NH3)6]Cl3 in a KCl electrolyte. The performance of the modified electrode for the oxidation of the pesticides: carbaryl, ethyl-parathion, malathion and carbendazim was investigated by square wave voltammetry in phosphate buffer, pH 7, but only the insecticide and fungicide carbendazim showed electroactivity. Thus, future studies focused on this pesticide. The cyclic voltammogram of carbendazim in phosphate buffer showed an oxidation peak and in the reverse scan, a much smaller reduction one. It suggested an EC mechanism and an oxidation reaction scheme was proposed. With the voltammetric profile established, square wave voltammetry was used to determine the calibration curve for the pesticide. With all square wave voltammetric parameters optimized, a linear dependence of the oxidation peak current with the concentration of carbendazim was obtained, with equation: Ip = 0.1 ± 4.30 [carbendazim] with r2 = 0, 9911 (n = 5). This calibration curve showed that the method has a detection limit of 17 x 10-8mol L-1. This methodology was used in the determination of carbendazim in orange juice samples artificially contaminated. A t-test of Student showed that the amounts recovered by voltammetry showed no significant difference in relation to those added to the samples. Thus, this methodology has been validated for use in analysis of orange juice contaminated with carbendazim (AU)

• FAPESP's process: 13/01905-7 - Determination of pesticides in food samples by chromatographic and electrochemical techniques: a statistical comparison of performances
• Grantee: Érica Megumi Kataoka
• Support Opportunities: Scholarships in Brazil - Master