Co-impacts of cation type and humic acid on migration of polystyrene microplastics in saturated porous media

The aging process of microplastics (MPs) could significantly change their physical and chemical characteristics and impact their migration behavior in soil. However, the complex effects of different cations and humic acids (HA) on the migration of aged MPs through saturated media are not clear. In this research, the migration and retention of pristine/aged PSMPs (polystyrene microplastics) under combined effects of cations (Na+, Ca2+) (ionic strength = 10 mM) and HA (0, 5, 15 mg/L) were investigated and analyzed in conjunction with the two-site kinetic retention model and DLVO theory. The findings showed that the aging process accelerated PSMPs migration under all tested conditions. Aged PSMPs were less susceptible to Ca2+ than pristine PSMPs. Under Ca2+ conditions, pristine/aged PSMPs showed higher retention than under Na+ conditions in the absence of HA. Furthermore, under Na+ conditions, the migration of aged PSMPs significantly increased at higher concentrations of HA. However, under Ca2+ conditions, the migration of aged PSMPs decreased significantly at higher concentrations of HA. In higher HA conditions, HA, Ca2+, and PSMPs interact to cause larger aggregations, resulting in the sedimentation of aged PSMPs. The DLVO calculations and two-site kinetic retention models' results showed the detention of PSMPs was irreversible under higher HA conditions (15 mg/L) with Ca2+, and aged PSMPs were more susceptible to clogging. These findings may help to understand the potential risk of migration behavior of PSMPs in the soil-groundwater environment.