A comprehensive insight into the transformation pathways and products of fluoxetine and venlafaxine in wastewater based on molecular networking nontarget screening

Tianshu Wu,Peng Liu,Xu-Xiang Zhang,Depeng Wang,Jinju Geng,Yiran Chen,Xiwei He,Gang Wu

doi:10.1016/j.scitotenv.2023.167727

Abstract

Fluoxetine (FLX) and venlafaxine (VEN) are widely used antidepressant pharmaceuticals and were frequently detected in wastewater. Despite incomplete mineralization during biological wastewater treatment processes has been revealed, little is known about their transformation products (TPs) formed in the biological systems. To fill this gap, batch reactors and molecular networking nontarget screening were employed to identify the TPs and explore the transformation pathways of FLX and VEN in wastewater. On the basis, the concentrations of the TPs in wastewater treatment plants (WWTPs) were determined and their toxicity was predicted. The removal rate constants per unit of biomass of FLX and VEN were up to 0.3192 and 0.1644 L/(gMLSS*d) in batch experiments, respectively. Subsequently, 11 TPs of VEN and 11 TPs of FLX were tentatively identified, among which 9 TPs of FLX and 5 TPs of VEN were newly reported in this study. The proposed transformation pathways provided new insights into the transformation reactions including dehydrogenation, N-formylation and hydroxylation for FLX, and formylation, epoxidation and methylation for VEN. Particularly, N-succinylation and demethylation were the dominant transformation pathways for FLX and VEN during transformation processes. The results of sampling campaigns revealed that the accumulated concentration of TPs were higher than the concentrations of VEN in effluent of WWTPs. In silico prediction results suggested that certain TPs have higher toxicity, persistence and biodegradability than their corresponding parent compounds of FLX and VEN. In addition, VEN-TP264(a) showed higher ecological risks than VEN. This study revealed the transformation processes and fate of FLX and VEN in wastewater, indicating that greater concerns should be exerted on the toxicity detection and control of the TPs of FLX and VEN in the treated wastewater.

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