Abstract:Microplastic pollution in aquatic environments has become increasingly severe, and its effective control remains a pressing challenge. Conventional flocculants such as polyaluminum chloride (PAC) exhibit limited removal efficiency for microplastics and often require relatively high dosages, which may pose potential ecological risks. Enteromorpha polysaccharide (EP), an anionic natural polysaccharide, has demonstrated promising flocculation potential. In this study, based on a systematic comparison of the removal performance of PAC for microplastics with different types and particle sizes, polyethylene (PE) microplastics with a particle size of 100 μm, which are relatively difficult to remove, were selected as the target pollutant. The removal efficiency and underlying mechanisms of PE microplastics by PAC combined with EP were systematically investigated, and the effects of environmental factors on the flocculation performance were also elucidated.The results showed that the addition of an appropriate amount of EP significantly enhanced the flocculation efficiency of PAC for PE microplastics. When the dosages of PAC and EP were 300 mg/L and 20 mg/L, respectively, the removal efficiencies of PE microplastics reached 76.3% for PAC alone and 94.0% for the PAC–EP composite system. Multiple characterization techniques, including zeta potential analysis and Fourier transform infrared (FTIR) spectroscopy, revealed that the enhanced removal of PE microplastics was achieved through the synergistic effects of charge neutralization by polymeric aluminum species, adsorption–bridging by the polysaccharide, and the reconstruction of the aluminum coordination environment.In addition, environmental factors such as water pH, the concentrations of coexisting anions, and natural organic matter were found to influence the removal performance of PE microplastics by the PAC–EP composite flocculant. Further evaluations using lake water and aquaculture water demonstrated that the PAC–EP system maintained removal efficiencies exceeding 80% for PE microplastics at dosages of 300 mg/L PAC and 20 mg/L EP. This study provides a theoretical basis for enhancing the removal of microplastics using bio-based polysaccharides in combination with conventional flocculants and offers valuable data to support the expanded application of polysaccharide materials in the control of emerging contaminants in aquatic environments.