Comparing the adsorption of methyl orange and malachite green on similar yet distinct polyamide microplastics: Uncovering hydrogen bond interactions

Microplastics (MPs) and dye pollutants are widespread in aquatic environments. Here, the adsorption characteristics of anionic dye methyl orange (MO) and cationic dye malachite green (MG) on polyamide 6 (PA6) and polyamide 66 (PA66) MPs were investigated, including kinetics, isotherm equilibrium and thermodynamics. The co-adsorption of MO and MG under different pH was also evaluated. The results reveal that the adsorption process of MO and MG is suitably expounded by a pseudo-second-order kinetic model. The process can be characterized by two stages: internal diffusion and external diffusion. The isothermal adsorption equilibrium of MO and MG can be effectively described using the Langmuir model, signifying monolayer adsorption. Furthermore, the thermodynamic results indicated that the adsorption was spontaneous with exothermic and endothermic properties, respectively. The results of binary systems reveal that MO dominates the adsorption at low pH (2-5), while MG dominates at high pH (8-10). Strong competitive adsorption was observed between MO and MG in neutral conditions (pH 6-8). The desorption experiments confirm that PA6 and PA66 could serve as potential carriers of MO and MG. The interaction between dyes and polyamide MPs is primarily mediated through hydrogen bonds and electrostatic attraction. The results reveal that PA6 formed more hydrogen bonds with the dyes, resulting in higher adsorption capacity than that of PA66. This difference can be attributed to the disparities in the synthesis process and polymerization method. Our study uncovered the adsorption mechanism of dye pollutants on PA6 and PA66, and provided a more comprehensive theoretical basis for the risk assessment concerning different types of polyamide MPs in aquatic environments.