Phototransformation of Three Psychoactive Drugs in Presence of Sedimental Water Extractable Organic Matter.

Psychoactive drugs are classified as contaminants of emerging concern but there is limited information on their fate in surface waters. Here, we studied the photodegradation of three psychoactive drugs (sertraline, clozapine, and citalopram) in the presence of organic matter (WEOM) extracted under mild conditions from sediment of Lake Pamvotis, Greece. Spectral characterization of WEOM confirmed its humic-like nature. Preliminary experiments using chemical probes showed that WEOM was able to produce oxidant triplet excited state (3WEOM*), singlet oxygen (1O2), and hydroxyl radicals under irradiation with simulated solar light. Then, WEOM at 5 mgC L-1 was irradiated in the presence of the three drugs. It enhanced their phototransformation by a factor of 2, 4.2, and 16 for sertraline, clozapine, and citalopram, respectively. The drastic inhibiting effect of 2-propanol (5 × 10-3 M) on the reactions demonstrated that hydroxyl radical was the key intermediate responsible for drugs photodegradation. A series of photoproducts were identified by ultra-high performance liquid chromatography (UHPLC) coupled to high resolution mass spectrometry (HR-MS). The photodegradation of the three drugs proceeded through several pathways, in particular oxidations of the rings with or without O atom inclusion, N elimination, and substitution of the halogen by OH. The formation of halogenated aromatics was observed for sertraline. To conclude, sedimental natural organic matter can significantly phototransform the studied antidepressant drugs and these reactions need to be more investigated. Finally, ecotoxicity was estimated for the three target analytes and their photoproducts, using the Ecological Structure Activity Relationships (ECOSAR) computer program.

Investigation of the Aquatic Photolytic and Photocatalytic Degradation of Citalopram.

This study investigated the direct and indirect photochemical degradation of citalopram (CIT), a selective serotonin reuptake inhibitor (SSRI), under natural and artificial solar radiation. Experiments were conducted in a variety of different operating conditions including Milli-Q (MQ) water and natural waters (lake water and municipal WWT effluent), as well as in the presence of natural water constituents (organic matter, nitrate and bicarbonate). Results showed that indirect photolysis can be an important degradation process in the aquatic environment since citalopram photo-transformation in the natural waters was accelerated in comparison to MQ water both under natural and simulated solar irradiation. In addition, to investigate the decontamination of water from citalopram, TiO2-mediated photocatalytic degradation was carried out and the attention was given to mineralization and toxicity evaluation together with the identification of by-products. The photocatalytic process gave rise to the formation of transformation products, and 11 of them were identified by HPLC-HRMS, whereas the complete mineralization was almost achieved after 5 h of irradiation. The assessment of toxicity of the treated solutions was performed by Microtox bioassay (Vibrio fischeri) and in silico tests showing that citalopram photo-transformation involved the formation of harmful compounds.

Study of the photoinduced transformations of sertraline in aqueous media.

In the present study, the photoinduced degradation of the antidepressant drug sertraline under artificial solar radiation was examined. Photolysis was studied under different experimental conditions to explore its photolytic fate in the aqueous environment. Photolytic degradation kinetics were carried out in ultrapure water, wastewater effluent, as well as in the presence of dissolved organic matter (humic acids), bicarbonate and nitrate ions which enabled their assessment on sertraline photo-transformation. The reaction of sertraline with photoactive compounds accelerated sertraline transformation in comparison with direct photolysis. Moreover, TiO2-mediated photocatalytic degradation of sertraline was investigated, and focus was placed on the identification of by-products. As expected, photocatalysis was extremely effective for sertraline degradation. Photocatalytic degradation proceeded through the formation of forty-four transformation products identified by HPLC-HRMS and after 240 min of irradiation total mineralization was achieved. Microtox bioassay (Vibrio fischeri) was employed to assess the ecotoxicity of the photocatalysis-treated solutions and results have indicated that sertraline photo-transformation proceeds through the formation of toxic compounds.