ABSTRACT
Chloramines have long been used to provide a disinfecting residual in distribution systems where it is difficult to maintain a free chlorine residual or where disinfection by-product (DBP) formation is of concern. While chloramines are generally considered less reactive than free chlorine, they are inherently unstable even in the absence of reactive substances. These reactions, often referred to as "auto-decomposition", always occur and hence define the maximum stability of monochloramine in water. The effect of additional reactive material must be measured relative to this basic loss process. A thorough understanding of the auto-decomposition reactions is fundamental to the development of mechanisms that account for reactions with additional substances and to the ultimate formation of DBPs. A kinetic model describing auto-decomposition was recently developed. This model is based on studies of isolated individual reactions and on observations of the reactive ammonia-chlorine system as a whole. The work presented here validates and extends this model for use in waters typical of those encountered in distribution systems and under realistic chloramination conditions. The effect of carbonate and temperature on auto-decomposition is discussed. The influence of bromide and nitrite at representative monochloramine concentrations is also examined, and additional reactions to account for their influence on monochloramine decay are presented to demonstrate the ability of the model to incorporate inorganic demand pathways that occur parallel to auto-decomposition.
