Binding between Cu²⁺/Zn²⁺ and aged polyethylene and polyethylene terephthalate microplastics in swine wastewaters:...

Microplastics (MPs) have aroused growing environmental concerns due to their biotoxicity and vital roles in accelerating the spread of toxic elements. Illuminating the interactions between MPs and heavy metals (HMs) is crucial for understanding the transport and fate of HM-loaded MPs in specific environmentally relevant scenarios. Herein, the adsorption of copper (Cu²⁺) and zinc (Zn²⁺) ions over polyethylene (PE) and polyethylene terephthalate (PET) particulates before and after heat persulfate oxidation (HPO) treatment was comprehensively evaluated in simulated and real swine wastewaters. The effects of intrinsic properties (i.e., degree of weathering, size, type) of MPs and environmental factors (i.e., pH, ionic strength, and co-occurring species) on adsorption were investigated thoroughly. It was observed that HPO treatment expedites the fragmentation of pristine MPs, and renders MPs with a variety of oxygen-rich functional groups, which are likely to act as new active sites for binding both HMs. The adsorption of both HMs is pH- and ionic strength-dependent at a pH of 4-6. Co-occurring species such as humic acid (HA) and tetracycline (TC) appear to enhance the affinity of both aged MPs for Cu²⁺ and Zn²⁺ ions via bridging complexation. However, co-occurring nutrient species (e.g., phosphate and ammonia) demonstrate different impacts on the adsorption, improving uptake of Cu²⁺ by precipitation while lowering affinity for Zn²⁺ owing to the formation of soluble zinc-ammonia complex. Spectroscopic analysis indicates that the dominant adsorption mechanism mainly involves electrostatic interactions and surface complexation. These findings provided fundamental insights into the interactions between aged MPs and HMs in swine wastewaters and might be extended to other nutrient-rich wastewaters.