Oil-in-water emulsions as suitable working media for the direct polarographic determination of aziprotryne and desmetryne from its organic extracts in water samples

The electroanalytical behavior of the reduction of the herbicides aziprotryne (2-azido-4-isopropylamino-6-methylthio-1,3,5-triazine) and desmetryne (4-isopropylamino-6-methylamino-2-methylthio-1,3,5-triazine) in oil-in-water emulsions is reported. This medium allows the differential pulse polarographic determination of these s-triazines directly from their sample extracts in an appropriate organic solvent. Sodium pentanesulfonate was chosen as the most suitable surfactant to be used as emulsifying agent, whereas ethyl acetate was selected as the organic solvent to form the emulsions. The peak current was maximum in a 0.3 mol L^–1 HClO₄ medium of the continuous aqueous phase for aziprotryne, and at pH 3.0 for desmetryne, and the potential became more negative as the pH increased for both herbicides. The limiting current is diffusion controlled and the electrode process is irreversible. Four electrons are involved in the overall electrochemical reduction process as determined by controlled potential coulometry, whereas the αn_a values suggested that two electrons are involved in the rate-determining step. Using differential pulse polarography, aziprotryne and desmetryne can be determined in the emulsified medium over the concentration ranges 1.0 · 10^–7–1.0 · 10^–4 mol L^–1, with limits of detection of 4.5 · 10^–8 mol L^–1 and 6.6 · 10^–8 mol L^–1, respectively. The method was applied to the determination of aziprotryne and desmetryne in spiked irrigation water. At concentration levels of 6.0 · 10^–7 mol L^–1 aziprotryne and 4.0 · 10^–7 mol L^–1 desmetryne, recoveries of 94 ± 3% and 94 ± 4%, respectively, were obtained after preconcentration on Sep-Pack C₁₈ cartridges. Finally, partial least-squares regression (PLSR) has been used for treatment of the polarographic data obtained from mixtures of aziprotryne, desmetryne and simazine in oil-in-water emulsions. The size of the calibration set was of 29 samples by ninety two current measurements at different potentials. Prediction of the herbicides concentration within the range 1.0 · 10^–6 –1.0 · 10^–5 mol L^–1 was possible.