High-Resolution Mass Spectrometry Combined with Reactive Oxygen Species Reveals Differences in Photoreactivity of Dissolved Organic Matter from Microplastic Sources in Aqueous Environments

Microplastics (MPs)-derived dissolved organic matter (MPs-DOM) is becoming a non-negligible source of DOM pools in aquatic systems, but there is limited understanding about the photoreactivity of different MPs-DOM. Herein, MPs-DOM from polystyrene (PS), polyethylene terephthalate (PET), poly(butylene adipate-co-terephthalate) (PBAT), PE, and polypropylene (PP), representing aromatic, biodegradable, and aliphatic plastics, were prepared to examine their photoreactivity. Spectral and high-resolution mass spectrometry analyses revealed that PS/PET/PBAT-DOM contained more unsaturated aromatic components, whereas PE/PP-DOM was richer in saturated aliphatic components. Photodegradation experiments observed that unsaturated aromatic molecules were prone to be degraded compared to saturated aliphatic molecules, leading to a higher degradation of PS/PET/PBAT-DOM than PE/PP-DOM. PS/PET/PBAT-DOM was mainly degraded by hydroxyl (^•OH) via attacking unsaturated aromatic structures, whereas PE/PP-DOM by singlet oxygen (¹O₂) through oxidizing aliphatic side chains. The [^•OH]ss was 1.21-1.60 × 10^-4 M in PS/PET/PBAT-DOM and 0.97-1.14 × 10^-4 M in PE/PP-DOM, while the [¹O₂]ss was 0.90-1.35 × 10^-12 and 0.33-0.44 × 10^-12 M, respectively. This contributes to the stronger photoreactivity of PS/PET/PBAT-DOM with a higher unsaturated aromatic degree than PE/PP-DOM. The photodegradation of MPs-DOM reflected a decreasing tendency from aromatic-unsaturated molecules to aliphatic-saturated molecules. Special attention should be paid to the photoreactivity and environmental impacts associated with MPs-DOM containing highly unsaturated aromatic compounds.