Quantification of two-site kinetic transport parameters of polystyrene nanoplastics in porous media.

In this study, a combination of column experiments, interface chemistry theory and transport model with two-site kinetics was used to systematically investigate the effect of pH on the transport of polystyrene nanoparticles (PSNPs) in porous media. The porous media containing quartz sand (QS) and three kinds of clay minerals (CMs)-kaolinite (KL), illite (IL) and montmorillonite (MT), was used in column experiments to simulate the porous media in the soil-groundwater systems. Experimental results showed that the inhibitory effect of CMs on the transport of PSNPs is weakened as pH increases. The two-dimensional (2D) surface of the DLVO interaction energy (2D-pH-DLVO) was built to calculate the interactions between PSNPs and CMs under different conditions of pH. Results suggested the inflection point of PSNP-QS, PSNP-KL, PSNP-IL and PSNP-MT are 2.42, 3.30, 2.84 and 3.69, respectively. Most importantly, there was a significant correlation between the two-site kinetic parameters related to PSNPs transport and the DLVO energy barrier (DB). The contributions of the interactions of PSNPs-PSNPs and PSNPs-minerals were determined for PSNPs transport in porous media. The critical values of pH related to the migration ability of PSNPs in porous media could be determined by a combination of column experiments, 2D-pH-DLVO and PSNPs transport model. The critical values of pH were 2.95-3.01, 3.22-3.51, 2.98-3.02, 3.31-3.33 for the migration ability of PSNPs in QS, QS + KL, QS + IL and QS + MT porous media, respectively. The stronger migration ability of PSNPs under high pH conditions is attributed to the enhanced deprotonation of the media surface and increased negative surface charge, which increases the electrostatic repulsion between PSNPs and porous media (QS, CMs). Moreover, the agglomeration of PSNPs usually is weaker and the average particle size of agglomerates is smaller under the condition of high pH, thus leading to the stronger migration ability of PSNPs under high pH conditions.