Transformation of atenolol by a laccase-mediator system: Efficiencies, effect of water constituents, and transformation pathways.

In this study, we investigated the transformation of atenolol (ATL) by the naturally occurring laccase from Trametes versicolor in aqueous solution. Removal efficiency of ATL via laccase-catalyzed reaction in the presence of various laccase mediators was examined, and found that only the mediator 2, 2, 6, 6-tetramethyl-1-piperidinyloxy (TEMPO) was able to greatly promote ATL transformation. The influences of TEMPO concentration, laccase dosage, as well as solution pH and temperature on ATL transformation efficiency were tested. As TEMPO concentrations was increased from 0 to 2000 µM, ATL transformation efficiency first increased and then decreased, and the optimal TEMPO concentration was determined as 500 µM. ATL transformation efficiency was gradually increased with increasing laccase dosage. ATL transformation was highly pH-dependent with an optimum pH of 7.0, and it was almost constant over a temperature range of 25-50 °C. Humic acid inhibited ATL transformation through competition reaction with laccase. The presence of anions HCO3- and CO32- reduced ATL transformation due to both anions enhanced solution pHs, while Cl-, SO42-, and NO3- at 10 mM showed no obvious influence. The main transformation products were identified, and the potential transformation pathways were proposed. After enzymatic treatment, the toxicity of ATL and TEMPO mixtures was greatly reduced. The results of this study might present an alternative clean strategy for the remediation of ATL contaminated water matrix.

Photochemical transformation of C3N4 under UV irradiation: Implications for environmental fate and photocatalytic activity.

In this study, the photo-transformations of bulk C3N4 (CN) and oxidized C3N4 (OCN) under UV-irradiation were examined. Through NO3- release measurements, we found that the photo-transformation rate of OCN is higher than that of CN. Various characterization results revealed the structural and chemical properties changes of CN and OCN after photo-transformation. We proposed that under reactive oxygen species attack, CN and OCN were gradually broken into smaller fragments and finally mineralized into NO3-, CO2, and H2O through the circular reactions of deamination-hydroxylation-decarboxylation. Through the zeta potential measurements and sedimentation experiments, the influence of photo-transformation on the water stabilities of CN and OCN were assessed. The stability of CN in water increased while the water stability of OCN decreased after photo-transformation, implying that the changes to C3N4-based materials caused by photo-transformation may significantly impact their environmental behaviors. Moreover, the photocatalytic activities of the photo-transformed OCN and CN substantially decreased, indicating that the structural changes might be the main reason for their photocatalytic activity loss. These findings highlight the non-negligible influence of photo-transformation on the fate of C3N4 in aquatic environments, as well as on the photochemical stability during its use.