Rapid degradation of brominated haloacetaldehydes at elevated temperature: Kinetics and newly discovered mechanisms

As an important class of disinfection byproducts (DBPs) of emerging concern, haloacetaldehydes (HALs) undergo degradation and transformation under environmentally relevant conditions. In this study, the stability of chlorinated and brominated HALs was investigated at different pHs and water temperatures. Results indicated that the degradation of HALs followed second-order kinetics. Surprisingly, rapid degradation of Br-HALs at elevated temperature was newly discovered in this study. At 50 °C and pH 7.5, over 90 % of TBAL degraded in 8 min, while the degradation of TCAL was ∼1 %. Moreover, increasing pH also facilitated the degradation of HALs and the alkaline degradation rate constants ( [Formula: see text] ) were found to be 7-9 orders of magnitude higher than their neutral degradation rate constants ( [Formula: see text] ). Under conditions relevant to environment and DBP measurement, HALs mainly degraded to form corresponding trihalomethanes and formate via decarburization pathway, which accounted for 70-93 % of HALs loss. The remaining 7-30 % of HAL loss was attributed to the dehalogenation pathway newly proposed in this study, successfully closing halogen balance during HAL degradation. In addition, a quantitative structure-activity relationship (QSAR) model was established for HAL degradation and the degradation rate constants for three mono-HALs were predicted at different temperature. The kinetic models and reaction rate constants obtained in this study can be used for quantitative predictions of HAL concentrations in drinking water, which is beneficial for monitoring and control of these emerging DBPs. Furthermore, considering the rapid degradation of Br-HALs into corresponding products, the temperature during sample pre-treatment can have a significant impact on DBP analysis.