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Chlorination amplifies source-dependent photochemical divergence between microplastic-derived and fulvic-acid dissolved organic matter
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Water treatment plants use chlorine to disinfect wastewater, but this study finds that chlorine reacts differently with organic matter that comes from microplastics compared to natural sources. This matters because chlorinated microplastic byproducts can change how quickly antibiotics and other contaminants break down in rivers, potentially affecting water quality in ways standard treatment wasn't designed to handle.
Chlorination is widely applied before the discharge of wastewater effluent into receiving waters, yet the distinct response of artificial and non-plastic dissolved organic matter (DOM) to chlorination remains unclear. Here, fulvic-acid (FA), expanded polystyrene-derived DOM (EPS-DOM) and poly(butylene adipate-co-terephthalate)-derived DOM (PBAT-DOM) were compared to determine how chlorination-induced optical and molecular transformations regulate sulfamethazine (SMT) photodegradation. Chlorination caused pronounced source-dependent DOM restructuring. The E/E ratio increased from 4.60 to 42.92 for EPS-DOM and from 3.09 to 41.50 for PBAT-DOM, but fluorescence intensities decreased by 81.0% and 97.2%, respectively. By comparison, FA showed positive responses after chlorination. FT-ICR-MS identified PBAT-DOM as the most extensively altered molecular structures. Additionally, chlorination increased the SMT photodegradation rate (k) from 0.0079 to 0.0111 h for EPS-DOM and from 0.0073 to 0.0085 h for PBAT-DOM; however, chlorinated PBAT-DOM displayed decreased k from 0.0089 to 0.0079 h in river water, indicating greater matrix sensitivity. Mechanism analysis shows that chlorination affected the contributions of DOM*, O, •OH, and O, reduced electron-donating capacity, and altered the light-shielding effects of DOM, particularly MP-DOM. Overall, chlorination amplifies the photochemical divergence between MP-DOM and FA, making MP-DOM a more sensitive regulator of contaminant phototransformation in receiving water.
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