Adsorption behavior of azole fungicides on polystyrene and polyethylene microplastics

Agricultural plastic films and triazole fungicides are widely used in agricultural production process. Exposure to natural environment, agricultural plastic films will degrade into micron plastic particles, which will adsorb pesticide molecules and may affect their toxicity, biological activity and persistence. The long-term coexistence of microplastics (MPs) and triazole fungicides will bring potential harms to the agricultural ecological environment. Therefore, two kinds of triazole fungicides flusilazole (FLU) and epoxiconazole (EPO) were selected as cases and the adsorption behaviors of them on polystyrene and polyethylene were investigated. A series of factors which could affect the adsorption behavior were evaluated. Specifically, the particle size of MPs could affect its adsorption capacity, and the smaller the particle size, the stronger the adsorption capacity. Moreover, with the increase of pH value from 6.0 to 9.0, the adsorption capacity of MPs to target compounds gradually increased. The effect of ionic strength was evaluated by NaCl, and 0.05% of NaCl was beneficial to the adsorption process, while the continuous increase of NaCl concentration inhibited the adsorption. Oxalic acid and humic acid decreased the adsorption capacity of flusilazole on PE by 15.99-32.00% and PS by 35.02-48.67%, respectively. In addition, compared with the single pesticide system, the adsorption capacity of MPs for flusilazole and epoxiconazole in the binary pesticides system decreased by 36.13-37.93% and 44.36-51.35%, respectively, indicating that competitive adsorption occurred between the two pesticides. Meanwhile, the adsorption process was evaluated by adsorption kinetics and adsorption isotherms and were consistent with pseudo-second-order kinetic model and Freundlich isotherm model, respectively. Finally, several characterization analyses were conducted to investigated the adsorption mechanism, and hydrogen, halogen bonding and hydrophobic interaction proved to play an important role. The study on the adsorption behavior and mechanism of pesticide on MPs was the basis of assessing the risk of joint exposure.