Electrostatic Interactions Override Surface Area Effects in Size-Dependent Adsorptive Removal of Microplastics by Fe3O4 Nanoparticles

Microplastics (MPs), as an emerging persistent contaminant, pose a potential threat to ecosystems and human health. The adsorptive removal of MPs from aqueous environments using magnetic nanoparticles has become a particularly promising remediation technology. Nevertheless, there remain significant knowledge gaps regarding its adsorption mechanism, especially how the key physical properties of magnetic nanoparticles regulate their adsorption behavior towards MPs. This study first investigated the relationship between the particle size of Fe3O4 nanoparticles and their adsorption efficacy for MPs. The results demonstrated a non-monotonic, size-dependent adsorption of MPs by Fe3O4 nanoparticles, with the adsorption efficiency and capacity following the order: 300 nm > 15 nm > 100 nm. This non-linear relationship suggested that factors other than specific surface area (which would favor smaller particles) are significantly influencing the adsorption process. Isotherm analysis indicated that the adsorption is not an ideal monolayer coverage process. Kinetic studies showed that the adsorption process could be better described by the pseudo-second-order model, while intra-particle diffusion played a critical role throughout the adsorption process. Furthermore, the effect of pH on adsorption efficiency was examined, revealing that the optimal performance occurs under neutral to weak acidic conditions, which is consistent with measurements of surface charges of nanoparticles. These findings suggest that the adsorption is not determined by specific surface area but is dominated by electrostatic interactions. The size-dependent adsorption of MPs by Fe3O4 nanoparticles provides new insights for the modification of magnetic adsorbents and offers a novel perspective for the sustainable and efficient remediation of environmental MPs pollution.