Photodegradation of three antidepressants in natural waters: Important roles of dissolved organic matter and nitrate

Abstract

Antidepressants have become ubiquitous emerging organic pollutants. Therefore, it is essential to investigate photodegradation of the antidepressants in environment waters for their ecological risk assessment. However, photodegradation behavior of antidepressants varied from different structures and photodegradation mechanism was rarely known for most antidepressants. Herein, citalopram (CIT), paroxetine (PAR) and fluvoxamine (FLUVO) were employed to study the photodegradation behavior of antidepressants in lake water. Results show that direct photolysis of CIT decreased when pH increased from 6 to 9 while the pH effect was not obvious on direct photolysis of FLUVO and PAR. Photodegradation of CIT occurred from its triplet-state and can undergo self-photosensitization through reaction with the generated hydroxyl radical (·OH). In lake water, PAR and FLUVO are degraded mainly via direct photolysis, while CIT is transformed mainly via indirect photolysis. Dissolved organic matter (DOM) and NO3- was proved to be the main factors affecting antidepressants photodegradation in lake water. DOM and NO3- showed inhibition effect on photodegradation of FLUVO and PAR, while promoted CIT degradation. The promotion effect of CIT was mainly through reaction with ·OH and excited triplet-state of DOM while singlet oxygen played a minor role. Based on the photodegradation products identified by MS/MS, the photodegradation pathways were proposed for CIT and PAR, respectively. For FLUVO, one (Z)-isomer degradation product was also found. Understanding the photodegradation behavior of antidepressants is vital for providing data to do ecological risk assessment.