Phototransformation of methabenthiazuron in the presence of nitrate and nitrite ions

The influence of nitrate and nitrite ions on the degradation of methabenzthiazuron upon irradiation using artificial solar light has been investigated. The rate of degradation of methabenzthiazuron (1 microM) was accelerated by NO3- (0.1 mM) by a factor of 10. The irradiation of methabenzthiazuron (0.1 mM) in the presence of NO3- (1 mM) or NO2- (0.1 mM) yielded numerous intermediary photoproducts. Mineralization was achieved after prolonged exposure. Some were identified with the help of LC-ESI-MS and flow injection APCI-MS techniques. Both oxidations of the aromatic ring and of the urea chain were observed. The former started by hydroxylation of the ring. Further oxidation of the ring led to cleavage of the benzenic ring with formation of dialdehydic, diacidic and anhydric compounds. Complete removal of the lateral urea chain took place subsequently to demethylation of the terminal methyl group and loss of the CO-NH2 group. Nitration was a minor process. This work shows that the photodegradation of methabenzthiazuron in the presence of nitrate or nitrite ions is highly non-specific.     

Photolysis of Enrofloxacin in aqueous systems under simulated sunlight irradiation: Kinetics, mechanism and toxicity of photolysis products

Photolysis of Enro in water was investigated under simulated sunlight irradiation using a Xenon lamp. The results showed that Enro photolysis followed apparent first-order kinetics. Increasing Enro concentration from 5.0 to 40.0 mg L⁻¹ led to the decrease of the photolysis rate constant from 1.6 × 10⁻² to 3.0 × 10⁻³ min⁻¹. Compared with the acidic and basic conditions, the photolysis rate was faster at neutral condition. Both of nitrate and humic acid can markedly decrease the photolysis rate of Enro because they can competitively absorb photons with Enro. The electron spin resonance and reactive oxygen species scavenging experiments indicated that Enro underwent self-sensitized photooxidation via OH and ¹O₂. After irradiation for 90 min, only 13.1% reduction of TOC occurred in spite of fast photolysis of 58.9% of Enro, indicating that Enro was transformed into intermediates without complete mineralization. The photolysis of Enro involved three main pathways: decarboxylation, defluorination, and piperazinyl N⁴-dealkylation. The bioluminescence inhibition rate using Vibrio fischeri increased to 67.2% at 60 min and then decreased to 56.9% at 90 min, indicative of the generation of some more toxic intermediates than Enro and then the degradation of the intermediates. The results will help us understand fundamental mechanisms of Enro photolysis and provide insight into the potential fate and transformation of Enro in surface waters.