Neonicotinoids are systemic insecticides commonly used for pest control in agriculture and veterinary applications. Due to their widespread use, neonicotinoid insecticides (neonics) are found in different environmental compartments, including water, soils, and biota, in which their high toxicity towards non-target organisms is a matter of great concern. Given their widespread use and high toxicity, the development of strategies to remove neonics, while avoiding further environmental contamination is of high priority. In this work, ionic-liquid-based materials, comprising silica modified with tetraalkylammonium cations and the chloride anion, were explored as alternative adsorbent materials to remove four neonics insecticides, namely imidacloprid, acetamiprid, thiacloprid, and thiamethoxam, from aqueous media. These materials or supported ionic liquids (SILs) were first synthesized and chemically characterized and further applied in adsorption studies. It was found that the equilibrium concentration of the adsorbate in the solid phase decreases with the decrease in the SIL cation alkyl chain length, reinforcing the relevance of hydrophobic interactions between ionic liquids (ILs) and insecticides. The best-identified SIL for the adsorption of the studied insecticides corresponds to silica modified with propyltrioctylammonium chloride ([Si][N3888]Cl). The saturation of SILs was reached in 5 min or less, showing their fast adsorption rate towards all insecticides, in contrast with activated carbon (benchmark) that requires 40 to 60 min. The best fitting of the experimental kinetic data was achieved with the Pseudo Second-Order model, meaning that the adsorption process is controlled at the solid-liquid interface. On the other hand, the best fitting of the experimental isotherm data is given by the Freundlich isotherm model, revealing that multiple layers of insecticides onto the SIL surface may occur. The continuous removal efficiency of the best SIL ([Si][N3888]Cl) by solid-phase extraction was finally appraised, with the maximum adsorption capacity decreasing in the following sequence: imidacloprid > thiacloprid > thiamethoxam > acetamiprid. Based on real reported values, under ideal conditions, 1 g of [Si][N3888]Cl is able to treat at least 106 m3 of wastewater and water from wetland contaminated with the studied neonics. In summary, the enhanced adsorption capacity of SILs for a broad diversity of neonics was demonstrated, reinforcing the usefulness of these materials for their removal from aqueous matrices and thus contributing to preventing their introduction into the ecosystems and reducing their detrimental effects in the environment and human health.
This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).
Cytostatic drugs are one of the most important therapeutic options for cancer, a disease that is expected to affect 29 million individuals by 2040. After being excreted, cytostatics reach wastewater treatment plants (WWTPs), which are unable to efficiently remove them, and consequently, they will be released into the aquatic environment. Due to the highly toxic properties of cytostatics, it is particularly relevant to evaluate their potential ecological risk. Yet, cytostatics toxicity data is still not available for various species. In this work, the ecotoxicity of two widely consumed cytostatics, cyclophosphamide (CYP-as a model cytostatic) and mycophenolic acid (MPA-as a priority cytostatic), was evaluated on three freshwater species-Raphidocelis subcapitata, Brachionus calyciflorus, and Danio rerio, and the risk quotient (RQ) was assessed. Both drugs significantly affected the yield and growth inhibition of the microalgae, while for rotifers, the least sensitive species, only significant effects were registered for CYP. These drugs also caused significant effects on the mortality and morphological abnormalities on zebrafish. The estimation of the RQ discloses that CYP seems to pose a low risk to aquatic biota while MPA poses a very high risk. Altogether, these results emphasize the need for more complete environmental risk assessments, to properly prioritize and rank cytostatics according to their potentially toxic effects on the environment and aquatic biota.
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