Study of some UV filters stability in chlorinated water and identification of halogenated by-products by gas chromatography–mass spectrometry

This work studies the stability of three UV filters: 2-ethylhexyl salicylate (ES), 2-ethylhexyl 4-(dimethylamino) benzoate (EHPABA) and 2-hydroxy-4-methoxybenzophenone (BP-3), in water samples containing low concentrations of free chlorine. Moreover, 2,4-dihydroxybenzophenone (2,4-DHBP), a metabolite of BP-3, was also included in some of the performed assays. Experiments were carried out considering free chlorine and analytes concentrations at the μg mL−1 and ng mL−1 level, respectively. Gas chromatography with mass spectrometry was used to follow the time course of target compounds and to identify their halogenated by-products. Concentration of water samples with solid-phase extraction cartridges and derivatization (silylation) of some species were also employed to improve their detectability. Under the experimental conditions explored in this work, ES showed an acceptable stability whereas the rest of species reacted with free chlorine at significant rates following pseudo-first-order kinetics. Their half-lives ranged from 0.4 to 25 min depending on the UV filter, chlorine concentration, water pH and presence of bromide traces. For EHPABA a relatively simple degradation pathway was established. It consisted of aromatic substitution of one atom of hydrogen per chlorine or bromide. The same reaction pattern was observed for BP-3 leading, in this case, to mono- and di-halogenated by-products. In addition, several halogenated forms of 3-methoxyphenol were identified as BP-3 cleavage by-products.