Synergy mechanisms of algal extracellular organic matter and manganese oxides in 17α-ethinylestradiol photochemical degradation
摘要
17α-ethinylestradiol (EE2) is a persistent endocrine-disrupting chemical that threatens aquatic ecosystems. Algal extracellular organic matter (EOM), widespread manganese oxides (MnOx) and their photochemical interactions can drive the natural degradation of EE2. However, these processes can be regulated by the unique surrounding conditions in eutrophic plateau lakes, including elevated levels of dissolved organic carbon, high pH, and abundant anions. Here, we investigated the enhancement of EE2 photodegradation mediated by EOM and MnOx, with emphasis on the effects of above unique surrounding conditions. Results showed that higher EOM concentrations proceed faster EE2 photodegradation rate by providing sufficient binding sites and more superoxide radicals for Mn(III) generation. In contrast, elevated pH inhibited EE2 degradation due to pH-dependent surface modifications of MnOx, which suppressed Mn(III) formation. Nitrate can enhance EE2 photodegradation without influencing Mn(III) generation. Product identification and density functional theory calculations suggest that EE2 degradation proceeds via free radical attack and Mn(III/IV)-mediated electron transfer, producing both small oxidized products and oligomers such as dimers and trimers. This study clarifies the environmental drivers of organic micropollutants’ degradation in eutrophic lakes, highlighting the environmental significance of surrounding conditions.