Adsorption mechanisms of five bisphenol analogues on PVC microplastics

Polyvinyl chloride (PVC) plastics are easily embrittled and decomposed to microplastics in an aquatic environment. The plasticizers such as bisphenol A (BPA), bisphenol S (BPS) and their analogues might be released and adsorbed by the PVC microplastics causing consequential pollution to the ecosystem. Herein, a systematic study was performed to determine the adsorption mechanisms of five bisphenol analogues (BPA, BPS, BPF, BPB and BPAF) on PVC microplastics. The maximum adsorption efficiency reached 0.19 ± 0.02 mg·g-1 (BPA), 0.15 ± 0.01 mg·g-1 (BPS), 0.16 ± 0.01 mg·g-1 (BPF), 0.22 ± 0.01 mg·g-1 (BPB), and 0.24 ± 0.02 mg·g-1 (BPAF) at PVC dosage of 1.5 g·L-1. The kinetics study shows that the adsorption processes can be divided into three stages including external mass transport, intraparticle diffusion and dynamic equilibrium. The isotherm modeling shows a better fit of the adsorption results to the Freundlich isotherm compared to the Langmuir model. The thermodynamic study indicates the adsorption of all bisphenols as exothermic processes. Furthermore, the adsorption mechanisms of bisphenols were explicated intensively, with respect to hydrophobic interactions, electrostatic forces, and noncovalent bonds. A positive effect of hydrophobic interactions was identified for bisphenols adsorption on PVC microplastics, but an obvious inhibition by electrostatic repulsions was revealed for BPF due to its ionization in the neutral solution. In addition, noncovalent bonds (hydrogen and halogen bonds) may promote the adsorption of bisphenols on PVC microplastics. Finally, the desorption and competitive adsorption of five bisphenol analogues on the microplastics were provided together with a perspective for future works.