Micro- and nanoplastics retention in porous media exhibits different dependence on grain surface roughness and clay coating with particle size.

The presence and/or coating of natural colloids (e.g., clays and metal oxides or hydroxides) on collector surfaces has frequently been demonstrated to enhance the retention of engineered colloids that are negatively charged due to favorable electrostatic interactions. However, this work demonstrates that the presence of natural clay coating can lead to reduced or nonmonotonic retention of micro- and nanoplastics (MNPs). Column experiments were carried out to systematically investigate the transport of MNPs with different sizes in relatively smooth and rough sands that had various clay coating fractions. These coating fractions on the collector were found to significantly influence MNP retention in a complex manner that changed with the colloid size and the roughness properties of the sand. This observation was attributed to the impact of clay coatings on the roughness and morphology properties of collector surfaces that were dominant over surface charge. Scanning electron microscopy and interaction energy calculations on surfaces with pillars or valleys indicate that mechanisms that contributed to MNP retention changed with the colloid size. In particular, retention of nanosized plastics was mainly controlled by interactions on convex/concave locations that changed with the solution chemistry, whereas microsized plastics were also strongly influenced by the applied hydrodynamic torque and straining processes. Additionally, the significant sensitivity of MNP retention under a low-level ionic strength also reflects the importance of roughness and charge heterogeneities. These observations are important for investigating the mechanisms of colloid transport in natural systems that ubiquitously exhibit clay coating on their surfaces.