Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
4429272 | Science of The Total Environment | 2012 | 6 Pages |
It was shown, through a combination of field and laboratory observations, that salicylic acid can undergo photo-bromination reactions in sunlit saline surface waters. Laboratory-scale experiments revealed that the photochemical yields of 5-bromosalicylic acid and 3,5-dibromosalicylic acid from salicylic acid were always low (in the 4% range at most). However, this might be of concern since these compounds are potential inhibitors of the 20α-hydroxysteroid dehydrogenase enzyme, with potential implications in endocrine disruption processes. At least two mechanisms were involved simultaneously to account for the photo-generation of brominated substances. The first one might involve the formation of reactive brominated radical species (Br, Br2−) through hydroxyl radical mediated oxidation of bromide ions. These ions reacted more selectively than hydroxyl radicals with electron-rich organic pollutants such as salicylic acid. The second one might involve the formation of hypobromous acid, through a two electron oxidation of bromine ions by peroxynitrite. This reaction was catalyzed by nitrite, since these ions play a crucial role in the formation of nitric oxide upon photolysis. This nitric oxide further reacts with superoxide radical anions to yield peroxynitrite and by ammonium through the formation of N-bromoamines, probably due to the ability of N-bromoamines to promote the aromatic bromination of phenolic compounds. Field measurements revealed the presence of salicylic acid together with 5-bromosalicylic and 3,5-dibromosalicylic acid in a brackish coastal lagoon, thus confirming the environmental significance of the proposed photochemically induced bromination pathways.
► Brominated derivatives of salicylic acid were detected in a brackish lagoon. ► A photochemical pathway was hypothesized to account for bromination of salicylic acid. ► Radical bromine species are partly responsible for the bromination process. ► Hypobromous acid might be also involved through photo-generation of peroxynitric acid. ► Bromination would mainly occur in saline waters impacted by wastewater discharges.