Photochemical behavior of constructed wetlands-derived dissolved organic matter and its effects on Bisphenol A...

Free water surface flow (FWS) constructed wetlands (CWs) have been broadly applied for polishing secondary treated effluents. Dissolved organic matter derived from FWS CWs (WDOM) plays key roles in contaminants transformations. Conversely, photodegradation could shape the quantity and quality of WDOM, thereby affecting its roles in the photolysis of organic micropollutants (OMPs). Nevertheless, whether and how solar irradiation-induced photodegradation modify the properties of WDOM, and the effects of WDOM on the photodegradation of OMPs remain unclear. This study elucidates the photochemical behavior of two WDOM isolated from field-scale FWS CWs for effluent polishing under simulated sunlight irradiation using spectroscopic tools and high-resolution mass spectra. Furthermore, the roles of WDOM in the photodegradation of Bisphenol A (BPA), as a representative endocrine-disrupting compound (EDC), were comprehensively investigated. Solar irradiation was demonstrated to lower the molecular weight and aromaticity of WDOM, as well as weaken its light absorption. Ultrahigh-resolution mass spectra further confirmed that aromatic and unsaturated structures were susceptible to solar irradiation-induced photodegradation reactions. Subsequently, less aromatic and more saturated structures eventually formed under sunlight irradiation, consistent with the result from spectroscopic characterization. The reactive species produced from WDOM significantly enhanced the photodegradation of BPA with the k_obs noticeably increasing 4-fold compared with the k_obs for direct photolysis. Additionally, ³WDOM* was identified as the dominant reactive species leading to the photolysis of BPA in the presence of WDOM. These findings improve understanding of the phototransformation behavior of WDOM under sunlight irradiation and the roles that WDOM plays in the photochemical fate of coexisting OMPs in CWs treatment systems.