The suitability and mechanism of polyaluminum-titanium chloride composite coagulant (PATC) for polystyrene microplastic removal: Structural characterization and theoretical calculation

Abstract

Microplastics (MPs) particles bring potential threats to the aqueous environment, and the coexistence of natural organic matter (NOM) enhances their toxicity. Coagulation is an efficient method for particle removal and exploring the binding sites and modes of the coagulant hydrolysates with MPs in the presence of NOM is essential to understand the coagulation mechanism. In this study, a novel polymerized polyaluminum-titanium chloride composite coagulant (PATC) was prepared and used to remove polystyrene (PS). It was found that PATC could compress or even destroy the surface layer of the negatively charged PS. In comparison to PAC and PTC, PATC was more efficient in decreasing the energy barrier of the PS particles and increasing their aggregation rate over a wider pH range. The results of the Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) calculation revealed that the interaction between the hydrolysates of PATC and PS was mainly polar interaction (VAB), such as hydrogen bonding. The peak intensity and peak shift in Fourier-transformed infrared (FTIR) and X-ray photoelectron spectra (XPS) were analyzed to further explore the interaction between the hydrolysates of PATC and PS. It was found that hydrogen bonding existed between the -OH group of PATC and the aliphatic C-H and C=O groups of PS. And the main interaction between HA and PS was the π-π* conjugation and hydrogen bonding between the -COOH, -OH, and C=O groups of HA and the C=O and aliphatic C-H groups of PS. Therefore, in the HA@PS system, the active sites of HA (e.g. -COOH and -OH) and PS (e.g., C=O and aliphatic C-H) binding with the coagulants were occupied, which accordingly led to the dramatic decline in the removal efficiency of both HA and PS. In actual lake water treatment, although the removal efficiency of PS was significantly poor, PATC performed better for PS removal than PAC and PTC. Besides, the effluent pH was maintained at 6.81±0.08, which met the requirements of the subsequent water treatment process. This study provides systematic knowledge for understanding the interaction between PS, NOM, and coagulant hydrolysates, and further confirms the application potential of PATC for MPs removal.