Microcosmic mechanism analysis of the combined pollution of aged polystyrene with humic acid and its efficient removal by a composite coagulant

The composite pollutants formed by aged polystyrene (APS) and natural organic matter are complex and harmful, which lead to the deterioration of water quality. In this work, the interaction mechanism between humic acid (HA) and APS was discussed by investigating the changes in their functional groups. Besides, a novel polyaluminum-titanium chloride composite coagulant (PATC) was prepared, and its binding behaviors with HA@APS under different pH conditions were analyzed from a microscopic perspective. It was found that at pH 4, pi-pi conjugation was the dominant interaction between HA and APS. And the main removal mechanism of HA@APS by PATC was surface complexation. With the increase of pH, pi-pi conjugation, n-pi electron donoracceptor interaction (EDA), and hydrogen bonding gradually dominated the interaction between APS and HA. At pH 7, PATC hydrolyzed to form various polynuclear Al-Ti species, which could meet the demand for different binding sites of HA@APS. Under alkaline conditions, HB and n-pi EDA in HA@APS were weakened, while pi-pi conjugation held a dominant position again. At this time, the main coagulation mechanism of PATC changed from charge neutralization to sweeping action, accompanied by hydrogen bonding. Environmental Implication: Microplastics (MPs) have attracted the public's attention due to their potential toxicity to humans. The combined pollution of aged microplastics and humic acid (HA) will bring great harm to aquatic environment. The development of novel composite coagulants is hopeful to efficiently remove MPs and their combined pollutants. Elucidating the interactions between HA and aged MPs is helpful to understand the transformation and fate of MPs in actual environments, and to reveal the removal mechanism of composite