Phototransformation and photoreactivity of MPs-DOM in aqueous environment: Key role of MPs structure decoded by optical and molecular signatures.

The dissolved organic matter (DOM) derived from microplastics (MPs-DOM) can be one of the photoactive components in DOM. However, information on the properties and photoreactivity of MPs-DOM during phototransformation is limited. Here, we investigated the properties and photoreactivity of MPs-DOM from polyolefins (MPs-DOM-POs), MPs-DOM derived from benzene-containing polymers (MPs-DOM-BCPs), and Suwannee River natural organic matter (SR-NOM), during a 168-hour phototransformation. After phototransformation, all examined types of DOM exhibit a decrease in concentration and molecular weight. Notably, MPs-DOM-POs display increased aromaticity and saturation, while MPs-DOM-BCPs and SR-NOM show reduced aromaticity and saturation. MPs-DOM-POs present higher steady-state concentrations of •OH but much lower steady-state concentrations of ¹O₂ than those of MPs-DOM-BCPs. In comparison, MPs-DOM produce more •OH but less ¹O₂ than SR-NOM. This study proposes that the diversification of aliphatic C─H bonds (arylation and carbonylation) by reactive intermediates (especially •OH) is the main pathway for MPs-DOM-POs phototransformation for the first time. On the other hand, the cleavage on the aromatic carboxylic acids by reactive intermediates (especially ¹O₂) is the main mechanism for MPs-DOM-BCPs and SR-NOM phototransformation. Our findings provide new insights into the phototransformation and photoreactivity of MPs-DOM and help to understand the potential risks of MPs in aqueous environment.