Natural organic small molecules promote the aging of plastic wastes and refractory carbon decomposition in water.

Microplastics and nanoplastics are ubiquitous in rivers and undergo environmental aging. However, the molecular mechanisms of plastic aging and the in-depth effects of aging on ecological functions remain unclear in waters. The synergies of microplastics and nanoplastics (polystyrene as an example) with natural organic small molecules (e.g., natural hyaluronic acid and vitamin C related to biological tissue decomposition) are the key to producing radicals (•OH and •C). The radicals promote the formation of bubbles on plastic surfaces and generate derivatives of plastics such as monomer and dimer styrene. Nanoplastics are easier to age than microplastics. Pristine plastics inhibit the microbial Shannon diversity index and evenness, but the opposite results are observed for aging plastics. Pristine plastics curb pectin decomposition (an indicator of plant-originated refractory carbon), but aging plastics promote pectin decomposition. Microplastics and nanoplastics undergoing aging processes enhance the carbon biogeochemical cycle. For example, the increased carbohydrate active enzyme diversity, especially the related glycoside hydrolase and functional species Pseudomonas and Clostridium, contributes to refractory carbon decomposition. Different from the well-studied toxicity and aging of plastic pollutants, this study connects plastic pollutants with biological tissue decomposition, biodiversity and climate change together in rivers.