Alkyl halide formation from degradation of carboxylic acids in the presence of Fe(III) and halides under light irradiation

Advanced oxidation processes (AOPs) have been widely used in water and wastewater treatment and have shown excellent performance in remediating contaminated water. However, their oxidation byproducts, including halogenated organics, have recently attracted increasing attention. Alkyl halides are among the most important environmental pollutants in nature. Here, we report a Fenton-like reaction in which alkyl halides can form during the photodegradation of aliphatic carboxylic acids in the presence of Fe(III) and halides. Chloromethane, chloroethane, and 1-chloropropane were produced from the degradation of acetic acid, propionic acid and nbutyric acid, respectively. CH3Cl, CH2Cl2 and CHCl3 were all identified as the products of acetic acid with the yields of approximately 5.1%, 0.2% and 0.005%, respectively. It was demonstrated that hydroxyl radicals, halogen radicals and alkyl radicals were involved in the formation of alkyl halides. A possible mechanism of chloromethane formation was proposed based on the results. In real samples of saline water, the addition of carboxylic acid and Fe(III) significantly promoted the generation of CH3Cl under xenon lamp irradiation. The results indicated that the coexistence of Fe(III), halides and carboxylic acids enhanced the photochemical release of alkyl halides. The reactions described in this paper may contribute to knowledge on the mechanism of halogenated byproduct formation during AOPs.