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Adsorption of three pesticides on polyethylene microplastics in aqueous solutions: Kinetics, isotherms, thermodynamics, and molecular dynamics simulation
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Adsorption experiments showed that polyethylene microplastics bind three pesticides (imidacloprid, buprofezin, difenoconazole) in aqueous solution via physical mechanisms, with adsorption capacity following the order difenoconazole > buprofezin > imidacloprid based on hydrophobicity, and fitting Freundlich isotherm and pseudo-first-order kinetic models.
Microplastics could act as a carrier for pesticides in the water environment and pose a potential risk. This study mainly investigated the effects of reaction time, microplastics dosages, pH, and NaCl salinity on the adsorption characteristics of three pesticides (Imidacloprid, Buprofezin, Difenoconazole) on polyethylene (PE) microplastics in aqueous solution. The results showed that high pH and low NaCl salinity were conducive to the adsorption. The adsorption data were well fitted by the Freundlich isotherm model and the pseudo-first-order kinetics, indicating that it was mainly controlled by physical function. The adsorption capacity of three pesticides on PE microplastics followed the order of Difenoconazole > Buprofezin > Imidacloprid. The thermodynamic study indicated the adsorption of all pesticides as spontaneous and exothermic processes, and the elevated temperature was favorable to the adsorption. SEM-EDS and FTIR results verified that pesticides were adsorbed on the microplastics but the adsorption process was mainly controlled by intermolecular Van Der Waals Force and the microporous filling mechanism. Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation results indicated that surface adsorption was the exclusive mechanism for the adsorption of pesticides on microplastics, and the final adsorption configurations revealed that there were complex interactions between the pesticide molecules and the C, H atoms in PE molecules. The results of this study illustrated that PE microplastics are potential carriers for pesticides in the water environment.
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Researchers assessed the sorption behavior of the insecticide fipronil and its degradation products onto polyethylene microplastics in the presence of natural organic matter (NOM) using combined kinetic experiments and computational modeling. They found that dissolved NOM substantially reduced the sorption capacity of microplastics for fipronil compounds by competing for hydrophobic binding sites on the polymer surface.
Theoretical Studies in Molecular Dynamics and DFT of the Interaction between Imidacloprid in Polyethylene and Polypropylene Surfaces
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Researchers used computational chemistry to model how the pesticide imidacloprid interacts with polyethylene and polypropylene microplastic surfaces. They found that the pesticide can adsorb onto both types of plastic, with polypropylene showing stronger binding in certain conditions. The study suggests that microplastics in agricultural soils could act as carriers for pesticides, potentially altering how these chemicals spread through the environment.
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The sorption behavior of the pesticide fipronil onto biodegradable and conventional non-degradable microplastics was compared through both experiments and molecular dynamics simulations, finding differences in how strongly each plastic type binds the pesticide. Biodegradable plastics, often considered safer alternatives, may carry different pesticide contamination risks than conventional plastics when they fragment into microparticles.
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