The role of microplastic aging on chlorpyrifos adsorption-desorption and microplastic bioconcentration

Microplastics (MPs) in soil undergo different aging processes such as photoaging, mechanical abrasion and biodegradation, leading to alterations in the surface properties of MPs. In this study, we investigated the adsorption-desorption of chlorpyrifos (CPF) on pristine and UV light-aged low-density polyethylene (LDPE) and biodegradable (Bio) MPs that were derived from plastic mulch films. We also tested the bioconcentration of pristine and aged MPs (LDPE- and Bio-MPs aged under UV light and LDPE-MPs aged in three different soils) associated with CPF by earthworms (Lumbricus terrestris). The results showed that UV-aged MPs showed higher CPF adsorption capacities than pristine MPs, with the adsorption capacities at 184.9 ± 5.3, 200.5 ± 1.8, 193.0 ± 8.7, and 215.9 ± 1.1 μg g^-1 for pristine LDPE-, UV-aged LDPE-, pristine Bio- and UV-aged Bio-MPs, respectively. The desorption rate of CPF from UV-aged LDPE-MPs within 48 h was lower than the desorption from pristine ones (28.8 ± 7.7% vs. 40.0 ± 3.9%), while both pristine and UV-aged Bio-MPs showed very low CPF desorption rates. A 4-day Petri dish experiment showed that UV-aged MPs were significantly less concentrated in earthworm casts than pristine counterparts (52% and 36% lower for UV-aged LDPE- and Bio-MPs), while UV-aged MPs with adsorbed CPF were concentrated significantly more than UV-aged MPs without CPF. Interestingly, LDPE-MPs aged in soil with a high carbon, nitrogen, and carbon-to-nitrogen ratio were significantly more concentrated in earthworm casts than pristine LDPE-MPs. In conclusion, UV-aged MPs acted as stronger vectors for CPF than pristine MPs. The bioconcentration of MPs differed significantly due to microplastic aging, as well as the combined effect with CPF. Moreover, LDPE-MPs aged in soil with enriched carbon and nitrogen were significantly concentrated in earthworm casts. Further studies on the environmental behaviours of aged MPs associated with other pollutants in soil, especially soils high in carbon and nitrogen, are needed.