Tatiana Andreani

Abstract Lipid nanoparticles (LN) composed of biodegradable lipids and produced by green methods are candidates for the encapsulation of pesticides, potentially contributing to decreasing their release in the environment. From a safety-by-design concept, this work proposes LN for the encapsulation of insecticide active ingredients (AI). However, given the complexity of nanoparticles, ecotoxicological studies are often controversial, and a detailed investigation of their effects on the environment is required. Accordingly, this work aimed to produce and characterize LN containing the insecticide lambda-cyhalothrin (LC) and evaluate their safety to crops (Solanum lycopersicum and Zea mays), soil invertebrates (Folsomia candida and Eisenia fetida), and soil microbial parameters. The average particle size for LN-loaded with LC (LN-LC) was 165.4 +/- 2.34 nm, with narrow size distribution and negative charge (-38.7 +/- 0.954 mV). LN were able to encapsulate LC with an entrapment efficacy of 98.44 +/- 0.04%, maintaining the stability for at least 4 months. The LN-LC showed no risk to the growth of crops and reproduction of the invertebrates. The effect on microbial parameters showed that the activity of certain soil microbial parameters can be inhibited or stimulated by the presence of LN at highest concentrations, probably by changing the pH of soil or by the intrinsic properties of LN.

Abstract The aim of the present study was to investigate the eco-cytotoxicity of several forms of nanomaterials (NM), such as nano-CuO, nano-TiO2, nano-SiO2 and nano-ZnO, on different aquatic species (Raphidocelis subcapitata, Daphnia magna and Lemna minor) following standard protocols and on human cell lines (Caco-2, SV-80, HepG2 and HaCaT). Predicted no-effect concentrations (PNEC) or hazard concentrations for 5% of the species (HC5) were also estimated based on the compilation of data available in the literature. Most of the NM agglomerated strongly in the selected culture media. For the ecotoxicity assays, nano-CuO and nano-ZnO even in particle agglomeration state were the most toxic NM to the freshwater organisms compared to nano-TiO2 and nano-SiO2. Nano-ZnO was the most toxic NM to R. subcapitata and D. magna, while nano-CuO was found to be very toxic to L. minor. Nano-CuO was very toxic to Caco-2 and HepG2 cells, particularly at the highest tested concentrations, while the other NM showed no toxicity to the different cell lines. The HC5 and PNEC values are still highly protective, due to data limitations. However, the present study provides consistent evidence of the potential risks of both nano-CuO and nano-ZnO against aquatic organisms and also their effects on public health.

Abstract This work reports the role of different dispersants, namely, polyethylene glycol (PEG 200 2%), ethylene glycol 5%, ethanol 2%, dimethyl sulfoxide (DMSO 5%), and polyvinyl alcohol (PVA 5%) in the toxicity profile of several commercial nanomaterials (NM), such as hydrophilic and hydrophobic TiO2, hydrophilic SiO2, SiO2 in aqueous suspension (aq), and ZnO towards the bioluminescent bacterium Aliivibrio fischeri. The majority of NM showed tendency to form agglomerates in the different dispersants. Although some particle agglomeration could be detected, DMSO at 5% was the best dispersant for hydrophobic TiO2 NM while PVA at 5% was the most effective dispersant for the other types of NM. Average size was not the most relevant aspect accounting for their toxicity. A remarkable reduction in average size was followed by a decrease in NM toxicity, as demonstrated for SiO2 aq. in PVA 5%. Contrarily, despite of high particle agglomeration, ZnO NM showed a higher toxicity to bacteria when compared with other tested NM. Independently of the average particle size or surface charge, the dispersant either enhanced the toxicity to bacteria or acted as physical barrier decreasing the NM harmful effect to A. fischeri.

Abstract In this study, following a systematic approach, we used aquatic species (bacteria Vibrio fischeri and microalgae Raphidocelis subcapitata) and different human cell lines (Caco-2, HepG2, SV-80 and HaCaT) representing different tissues and exposure pathways, to investigate how two organic stabilizers (PVA and DMSO) used for NMs dispersion influence their physicochemical properties, the persistence of metals in suspension and the toxicity/ecotoxicity of two metallic NMs (nano-Ag and nano-Cu). Although the stabilizers are expected to contribute to improve the dispersion and stability of NMs, the results obtained clearly showed that no similar changes in toxicity and morphological properties of the nano-Ag can be expected after its stabilization with PVA. Thus, regarding human cell lines, the reduction in the average size of the PVA-nano-Ag was followed by a reduction or maintenance of its toxicity, but the opposite was observed for the aquatic species tested since an increase in the average size enhanced its toxicity. As far as nano-Cu is considered DMSO contributed for a better dispersion of this nanomaterial, however this was not translated in a similar toxicity/ecotoxicity modification. In summary, even for nano-Cu, for which few or no data exists regarding its toxicity after stabilization with organic compounds, it was confirmed with consistent data, that the toxicity of metallic NMs is a complex combination of average size, chemical composition, solubilization or persistence in suspension of the metallic forms, interaction with test medium components and sensitivity of test species and cell lines. The combination of all of these factors makes the toxicity of metallic NMs unpredictable and points for the need of an extensive evaluation of each new formulation.

Abstract Cadmium-based quantum dots (QDs) are increasingly applied in existent and emerging technologies, especially in biological applications due to their exceptional photophysical and functionalization properties. However, they are very toxic compounds due to the high reactive and toxic cadmium core. The present study aimed to determine the toxicity of three different QDs (CdS 380, CdS 480 and CdSeS/ZnS) before and after the exposure of suspensions to sunlight, in order to assess the effect of environmentally relevant irradiation levels in their toxicity, which will act after their release to the environment. Therefore, a battery of ecotoxicological tests was performed with organisms that cover different functional and trophic levels, such as Vibrio fischeri, Raphidocelis subcapitata, Chlorella vulgaris and Daphnia magna. The results showed that core-shell type QDs showed lower toxic effects to V. fischeri in comparison to core type QDs before sunlight exposure. However, after sunlight exposure, there was a decrease of CdS 380 and CdS 480 QD toxicity to bacterium. Also, after sunlight exposure, an effective decrease of CdSeS/ZnS and CdS 480 toxicity for D. magna and R. subcapitata, and an evident increase in CdS 380 QD toxicity, at least for D. magna, were observed. The results of this study suggest that sunlight exposure has an effect in the aggregation and precipitation reactions of larger QDs, causing the degradation of functional groups and formation of larger bulks which may be less prone to photo-oxidation due to their diminished surface area. The same aggregation behaviour after sunlight exposure was observed for bare QDs. These results further emphasize that the shell of QDs seems to make them less harmful to aquatic biota, both under standard environmental conditions and after the exposure to a relevant abiotic factor like sunlight.