[Chlorination of ethynyl estradiol: a kinetic and mechanistic study]

The objective of this research is to explore the fundamentals of reactions between chlorine and ethynyl estradiol (EE2), which is expected to occur during the drinking water treatment. The first step of EE2 chlorination was shown to follow the second-order kinetics with the first order to concentrations of both target compound and chlorine, respectively. Apparent rate constants of EE2 chlorination exhibit the pH-dependent profile which indicates that the phenolic ring is the preferred site of attack by Cl. The transformation of EE2 is governed by 3 elementary reactions between different species of EE2 and HClO. The deprotonated EE2 anion is significantly more reactive than its neutral conjugate. HPLC/MS analysis revealed that several Cl atoms can be incorporated into this site via complex multi-step pathways, resulting in the formation of mono and di-chlorine substituted EE2. The incorporation of the third Cl is accompanied by immediate broken down of the ring via hydrolysis. The results of this study are helpful to fully understand the behavior of EE2 in chlorinated drinking water disinfection, provide the basis for evaluating the potential exposure of this contaminant to human. The data of this work also give insights to the formation of chlorinated drinking water disinfection by-products (DBPs).