Those That Remain Caught in the "Organic Matter Trap": Sorption/Desorption Study for Levelling the Fate of Selected Neonicotinoids.

With projections suggesting an increase in the global use of neonicotinoids, contemporary farmers can get caught on the "pesticide treadmill", thus creating ecosystem side effects. The aim of this study was to investigate the sorption/desorption behavior of acetamiprid, imidacloprid, and thiacloprid that controls their availability to other fate-determining processes and thus could be useful in leveling the risk these insecticides or their structural analogues pose to the environment, animals, and human health. Sorption/desorption isotherms in four soils with different organic matter (OC) content were modelled by nonlinear equilibrium models: Freundlich's, Langmuir's, and Temkin's. Sorption/desorption parameters obtained by Freundlich's model were correlated to soil physico-chemical characteristics. Even though the OC content had the dominant role in the sorption of the three insecticides, the role of its nature as well as the chemical structure of neonicotinoids cannot be discarded. Insecticides sorbed in the glassy OC phase will be poorly available unlike those in the rubbery regions. Imidacloprid will fill the sorption sites equally in the rubbery and glassy phases irrespective of its concentration. The sorption of thiacloprid at low concentrations and acetamiprid at high concentrations is controlled by hydrophilic aromatic structures, "trapping" the insecticides in the pores of the glassy phase of OC.

Those That Remain: Sorption/Desorption Behaviour and Kinetics of the Neonicotinoids Still in Use.

In January 2023, the derogation loophole was closed on "emergency authorisations" for the use of three out of five neonicotinoids in all EU states. In this study, we analysed the sorption/desorption behaviour and kinetic parameters of acetamiprid and thiacloprid, the two neonicotinoids that are still approved for use, either regularly or under emergency authorisations in the EU, and widely used worldwide. Sorption and desorption curves in four soils with different organic matter content were analysed using four kinetic models, namely, Lagergren's pseudo first-order model, two-site model (TSM), Weber-Morris intraparticle diffusion model and Elovich's model. Kinetic parameters were correlated to soil physico-chemical characteristics. To determine the mutual influence of soil characteristics and sorption/desorption parameters in the analysed soils, a factor analysis based on principal component analysis (PCA) was performed. Even though the two insecticides are very similar in size and chemical structure, the results showed different sorption/desorption kinetics. The model that best fits the experimental data was TSM. Thiacloprid showed a more rapid sorption compared to acetamiprid, and, in all soils, a higher proportion sorbed at equilibrium. Intra-particle diffusion seemed to be a relevant process in acetamiprid sorption, but not for thiacloprid. Desorption results showed that acetamiprid is more easily and more thoroughly desorbed than thiacloprid, in all soils. The kinetic behaviour differences stem from variations in molecular structure, causing disparate water solubility, lipophilicity, and acid-base properties.