Kinetic modelling of mancozeb hydrolysis and photolysis to ethylenethiourea and other by-products in water

Water Research 102 (2016) 561–571

http://dx.doi.org/10.1016/j.watres.2016.07.006

The aim of this study was to propose kinetic models suitable for reproducing and predicting mancozeb (Mz) conversion to by-products as a function of the operational conditions. The main factors (pH, temperature and light) potentially affecting the mancozeb degradation in aqueous models were studied by a multifactorial screening design. In addition, the response surface methodology (RSM) was applied to evaluate the interactive effects of these factors on ethylenethiourea (ETU) formation. The response surface revealed that the best degradation conditions to minimize mancozeb conversion to ETU were low pH (2), low temperature (25 °C) and darkness. Under these conditions, the percentage of mancozeb remained in the solution at 72 h was approximately 10% of the initial concentration and the percentage of ETU conversion was 5.4%. However, according to the model, in surface waters under typical environmental conditions (pH 8, 25 °C and light) the percentage of mancozeb conversion to ETU would be about 17.5%. The proposed model provides a satisfactory interpretation of the experimental data obtained during the hydrolysis of mancozeb.

Voltammetric analysis of mancozeb and its degradation product ethylenethiourea

Journal of Electroanalytical Chemistry, 758 (2015) 54-58

doi:10.1016/j.jelechem.2015.08.030

The purpose of this work was to develop a reliable alternative method for the determination of the dithiocarbamate pesticide mancozeb (MCZ) in formulations. Furthermore, a method for the analysis of MCZ's major degradation product, ethylenethiourea (ETU), was also proposed. Cyclic voltammetry was used to characterize the electrochemical behavior of MCZ and ETU, and square-wave adsorptive stripping voltammetry (SWAdSV) was employed for MCZ quantification in commercial formulations.

It was found that both MCZ and ETU are irreversibly reduced (− 0.6 V and − 0.5 V vs Ag/AgCl, respectively) at the surface of a glassy carbon electrode in a mainly diffusion-controlled process, presenting maximum peak current intensities at pH 7.0 (in phosphate buffered saline electrolyte).

Several parameters of the SWAdSV technique were optimized and linear relationships between concentration and peak current intensity were established between 10–90 μmol L− 1 and 10–110 μmol L− 1 for MCZ and ETU, respectively. The limits of detection were 7.0 μmol L− 1 for MCZ and 7.8 μmol L− 1 for ETU. The optimized method for MCZ was successfully applied to the quantification of this pesticide in two commercial formulations. The developed procedures provided accurate and precise results and could be interesting alternatives to the established methods for quality control of the studied products, as well as for analysis of MCZ and ETU in environmental samples.

Voltammetric analysis of mancozeb and its degradation product ethylenethiourea

Journal of Electroanalytical Chemistry

doi:10.1016/j.jelechem.2015.08.030

The purpose of this work was to develop a reliable alternative method for the determination of the dithiocarbamate pesticide mancozeb (MCZ) in formulations. Furthermore, a method for the analysis of MCZ's major degradation product, ethylenethiourea (ETU), was also proposed. Cyclic voltammetry was used to characterize the electrochemical behaviour of MCZ and ETU, and square-wave adsorptive stripping voltammetry (SWAdSV) was employed for MCZ quantification in commercial formulations.

It was found that both MCZ and ETU are irreversibly reduced (−0.6 V and −0.5 V vs Ag/AgCl, respectively) at the surface of a glassy carbon electrode in a mainly diffusion-controlled processes, presenting maximum peak current intensities at pH 7.0 (in phosphate buffered saline electrolyte).

Several parameters of the SWAdSV technique were optimized and linear relationships between concentration and peak current intensity were established between 10–90 μmol L-1 and 10–110 μmol L-1 for MCZ and ETU, respectively. The limits of detection were 7.0 μmol L-1 for MCZ and 7.8 μmol L-1 for ETU. The optimized method for MCZ was successfully applied to the quantification of this pesticide in two commercial formulations. The developed procedures provided accurate and precise results and could be interesting alternatives to the established methods for quality control of the studied products, as well as for analysis of MCZ and ETU in environmental samples.