Transformation
of atenolol (ATN), a micropollutant containing a secondary (2°)
amine moiety, can be significantly enhanced in water treatment with
sequential and combined use of chlorine and UV (chlorine/UV) through
photolysis of the N–Cl bond. This study investigated the transformation
kinetics, products, and mechanisms of the amine moiety of ATN in chlorine/UV
(254 nm). The fluence-based, photolysis rate constant for N–Cl
ATN was 2.0 × 10–3 cm2/mJ. Transformation
products (TPs) with primary (1°) amines were mainly produced,
but TPs with 2° and 3° amines were also formed, on the basis
of liquid chromatography (LC)/quadrupole-time-of-flight/mass spectrometry
and LC/UV analyses. The amine-containing TPs could be further transformed
in chlorine/UV (with residual chlorine in post UV) via formation and
photolysis of new N–Cl bonds. Photolysis of N–Cl 1°
amine TPs produced ammonia as a major product. These data could be
explained by a reaction mechanism in which the N–Cl bond was
cleaved by UV, forming aminyl radicals that were transformed via 1,2-hydrogen
shift, β-scission, intramolecular addition, and 1,2-alkyl shift.
Among these, the 1,2-alkyl shift is newly discovered in this study.
Despite enhanced transformation, only partial mineralization of the
ATN’s amine moiety was expected, even under chlorine/UV advanced
oxidation process conditions. Overall, the kinetic and mechanistic
information from this study can be useful for predicting the transformation
of amine moieties by chlorine/UV water treatment.