posted on 2012-08-07, 00:00authored byJelena Radjenovic, Maria José Farré, Wolfgang Gernjak
This study evaluates the effect of UV–C and UV–C/H2O2 in the presence of chloramines on the N-nitrosodimethylamine formation potential (NDMA FP) of
tramadol as a model precursor. The experiments were performed at high
initial concentrations of TMDL (i.e., 20 mg/L) in order to elucidate
the structures of TMDL byproducts. Twenty-four byproducts were identified
in UV–C, UV–C/monochloramine, and UV/H2O2/monochloramine oxidation of tramadol using MS3 capabilities of a hybrid quadrupole-linear ion trap mass spectrometer,
combined with online hydrogen/deuterium (H/D) exchange experiments.
Oxidative cleavage of methoxy and methoxybenzene moiety, O-demethylation,
hydroxylation, and cyclohexane ring-opening were identified as major
reaction mechanisms of tramadol in UV oxidation. Addition of monochloramine
decreased the degradation rates of tramadol and its byproducts and
yielded several monochlorinated derivatives. The oxidation rates were
significantly enhanced in the presence of H2O2, and byproducts of oxidative benzene ring-opening were detected.
The majority of the identified byproducts are likely to have a higher
NDMA FP than the parent compound due to a reduced steric hindrance
and/or insertion of electron-donating hydroxyl groups in the N,N-dimethylamine side chain. This was confirmed by the
results of NDMA FP tests, which showed that the formation of NDMA
was enhanced up to four times depending on the process conditions
in UV alone and in UV and UV/H2O2 in the presence
of monochloramine. Prolonged oxidation by hydroxyl radicals in UV/H2O2/monochloramine process mineralized some of the
byproducts and slightly reduced the NDMA FP at the end of the treatment.
The obtained degradation pathway of tramadol allowed the correlation
of changes in NDMA FP during oxidation with its major oxidative transformation
reactions. This manuscript demonstrates the significance of oxidation
byproducts as NDMA precursors and emphasizes the need for their consideration
when evaluating the evolution of NDMA FP during oxidative treatment.