Nitrate-induced photodegradation of atenolol in aqueous solution: kinetics, toxicity and degradation pathways
Yuefei Ji1, Chao Zeng, Corinne Ferronato
1State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, PR China.
Abstract:
The extensive utilization of β-blockers worldwide led to frequent detection in natural water. In this study the photolysis behavior of atenolol (ATL) and toxicity of its photodegradation products were investigated in the presence of nitrate ions. The results showed that ATL photodegradation followed pseudo-first-order kinetics upon simulated solar irradiation. The photodegradation was found to be dependent on nitrate concentration and increasing the nitrate from 0.5 mML(-1) to 10 mML(-1) led to the enhancement of rate constant from 0.00101 min(-1) to 0.00716 min(-1). Hydroxyl radical was determined to play a key role in the photolysis process by using isopropanol as molecular probe. Increasing the solution pH from 4.8 to 10.4, the photodegradation rate slightly decreased from 0.00246 min(-1) to 0.00195 min(-1), probably due to pH-dependent effect of nitrate-induced .OH formation. Bicarbonate decreased the photodegradation of ATL in the presence of nitrate ions mainly through pH effect, while humic substance inhibited the photodegradation via both attenuating light and competing radicals. Upon irradiation for 240 min, only 10% reduction of total organic carbon (TOC) can be achieved in spite of 72% transformation rate of ATL, implying a majority of ATL transformed into intermediate products rather than complete mineralization. The main photoproducts of ATL were identified by using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS) techniques and possible nitrate-induced photodegradation pathways were proposed. The toxicity of the phototransformation products was evaluated using aquatic species Daphnia magna, and the results revealed that photodegradation was an effective mechanism for ATL toxicity reduction in natural waters.
Insights
The photodegradation of atenolol (ATL) in natural waters is enhanced by nitrate ions, with hydroxyl radicals playing a key role. This process effectively reduces ATL toxicity, although complete mineralization is not achieved.
Area of Science:
- Environmental Chemistry
- Photochemistry
- Ecotoxicology
Background:
- Beta-blockers like atenolol (ATL) are frequently detected in natural waters due to widespread use.
- Understanding the environmental fate and transformation of pharmaceuticals is crucial for water quality assessment.
Purpose of the Study:
- To investigate the photolysis behavior of atenolol (ATL) in the presence of nitrate ions.
- To identify the photodegradation products of ATL and evaluate their toxicity.
- To elucidate the role of nitrate ions and other water constituents in ATL photodegradation.
Main Methods:
- Simulated solar irradiation experiments were conducted to study ATL photodegradation kinetics.
- Hydroxyl radical's role was assessed using isopropanol as a molecular probe.
- Photodegradation products were identified using solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC-MS).
- Toxicity of phototransformation products was evaluated using Daphnia magna.
Main Results:
- ATL photodegradation followed pseudo-first-order kinetics and was significantly enhanced by increasing nitrate concentrations.
- Hydroxyl radical was identified as the primary reactive species in the photolysis process.
- Bicarbonate and humic substances influenced ATL photodegradation rates through pH effects and light attenuation/radical scavenging.
- While ATL transformation reached 72% in 240 min, total organic carbon (TOC) reduction was only 10%, indicating intermediate product formation.
- Identified photoproducts showed reduced toxicity to Daphnia magna compared to the parent compound.
Conclusions:
- Nitrate-induced photodegradation is an effective pathway for atenolol removal and toxicity reduction in natural waters.
- The photodegradation process leads to the formation of intermediate products rather than complete mineralization.
- Environmental factors such as pH, bicarbonate, and humic substances modulate the efficiency of ATL photodegradation.
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