Hydroxyl radical-mediated degradation of salicylic acid and methyl paraben: an experimental and computational approach to assess the reaction mechanisms

Advanced oxidation processes (AOPs) using various energy sources and oxidants to produce reactive oxygen species are widely used for the destruction of recalcitrant water contaminants. The current study is about the degradation of two emerging pollutants-salicylic acid (SA) and methyl paraben (MP)-by high-frequency ultrasonication followed by identification of the oxidation byproducts and modeling of the reaction mechanisms using the density functional theory (DFT). The study also encompasses prediction of the aquatic toxicity and potential risk of the identified byproducts to some aquatic organisms bussing the ECOSAR (Ecological Structure Activity Relationships) protocol. It was found that the degradation of both compounds was governed by center dot OH attack and the pathways consisted of a cascade of reactions. The rate determining steps were decarboxylation (similar to 60 kcal mol(-1)) and bond breakage reactions (similar to 80 kcal mol(-1)), which were triggered by the stability of the reaction byproducts and overcome by the applied reaction conditions. Estimated values of the acute toxicities showed that only few of the byproducts were harmful to aquatic organisms, implying the environmental friendliness of the experimental method.