Body fluid analog chlorination: Application to the determination of disinfection byproduct formation kinetics in swimming pool water
Pierre Le Cloirec , Lucie Tsamba , Nicolas Cimetière , Dominique Wolbert , Olivier Correc
DOI:10.1016/j.jes.2019.06.009
Received May 06, 2019,Revised , Accepted June 10, 2019, Available online June 20, 2019
Volume 32,2020,Pages 112-122
Disinfection by-products (DBPs) are formed in swimming pools by the reactions of bather inputs with the disinfectant. Although a wide range of molecules has been identified within DBPs, only few kinetic rates have been reported. This study investigates the kinetics of chlorine consumption, chloroform formation and dichloroacetonitrile formation caused by human releases. Since the flux and main components of human inputs have been determined and formalized through Body Fluid Analogs (BFAs), it is possible to model the DBPs formation kinetics by studying a limited number of precursor molecules. For each parameter the individual contributions of BFA components have been quantified and kinetic rates have been determined, based on reaction mechanisms proposed in the literature. With a molar consumption of 4 mol Cl2/mol, urea is confirmed as the major chlorine consumer in the BFA because of its high concentration in human releases. The higher reactivity of ammonia is however highlighted. Citric acid is responsible for most of the chloroform produced during BFA chlorination. Chloroform formation is relatively slow with a limiting rate constant determined at 5.50 × 10−3 L/mol/sec. L-histidine is the only precursor for dichloroacetonitrile in the BFA. This DBP is rapidly formed and its degradation by hydrolysis and by reaction with hypochlorite shortens its lifetime in the basin. Reaction rates of dichloroacetonitrile formation by L-histidine chlorination have been established based on the latest chlorination mechanisms proposed. Moreover, this study shows that the reactivity toward chlorine differs whether L-histidine is isolated or mixed with BFA components.
