Enhanced sorption of the UV filter 4-methylbenzylidene camphor on aged PET microplastics from both experimental and theoretical perspectives

In this study, the morphology and sorption behavior of polyethylene terephthalate (PET) microplastics during the aging process are investigated. To clarify the sorption mechanism of aged PET microplastics, the common sunblock 4-methylbenzylidene camphor (4-MBC) was chosen as the target contaminant, and UV irradiation was used for the laboratory aging simulation. The results show that oxygen-containing functional groups (carboxylic, carbonyl, ketone and hydroxyl groups) increase on the surface of aged PET microplastics. Based on density functional theory (DFT) simulations, the camphor part of 4-MBC acts as a hydrogen bond acceptor, whereas the carboxylic group on aged PET microplastics acts as a hydrogen bond donor. The formation of hydrogen bonding causes increased sorption of 4-MBC on aged PET microplastics. The sorption capacity increased from 5 to 11 μg g^-1 for 50 ppb 4-MBC with 100 mg PET microplastics after a five-day aging process. Other environmental factors that affect sorption were also identified; a higher pH value and the presence of salinity reduced the amount of sorption. The sorption of virgin PET ranged from 8.0 to 3.4 μg g^-1 and the sorption of aged PET ranged from 22 to 5 μg g^-1 at pH 4 to 10. In the presence of salinity (10% seawater), the virgin PET sorption dropped to 2.1 μg g^-1 while the aged PET sorption dropped to 4 μg g^-1. A similar phenomenon was also observed in the sorption behavior under natural sunlight (the sorption of PET increased from 0.4 to 0.8 μg g^-1 after 6 months of aging). The potential risk to ecosystems of aged PET microplastics under prolonged sunlight exposure in the natural environment could be greater than that predicted for virgin microplastics.