Degradation of herbicides (ametryn and isoproturon) during water disinfection by means of two oxidants (hypochlorite and chlorine dioxide)

Abstract

The paper reports the results of an investigation aimed to find out the number and the chemical structures of byproducts which form during the reactions occurring in aqueous solution between two very common disinfectants, sodium hypochlorite (NaClO) and chlorine dioxide (ClO2), and two herbicides widely used in agriculture and frequently found in groundwaters: ametryn and isoproturon. Under controlled experimental conditions [T=20°C, pH=7, reaction-time =48h, herbicide/disinfectant molar ratios: 0.05 and 0.05xlO-2], ametryn reactions with chlorine dioxide much slower than with sodium hypochlorite, whereas the opposite trend has been observed for isoproturon. In any case, however, the higher the reagents concentration the faster the reactions. As for reaction byproducts, they have been detected by HPLC and identified by HPLC-MS. In particular, ametryn (R-S-CH3) reaction with NaClO gives rise to the consecutive formation of four derivatives: the sulphoxide (R-SO-CH3), the sulphone (R-SO2-CH3), the sulphonate ester (R-SO2-CH3) and its hydrolysis product (R-OH). Within the fixed reaction time (48h), ametryn reaction with ClO2 forms only the sulphoxide derivative (R-SO-CH3). As for isoproturon, it reacts with both oxidants forming aromatic-ring substituted derivatives. In particular, during the reactions with NaClO and ClO2, four and two (chlorinated and/or hydroxylated) derivatives are respectively formed.