Rapid Communication: oxidative stress induced by mixed exposure to glyphosate and silver nanoparticles.

The aim of this study was to examine oxidative stress induced by the binary mixture of silver nanoparticles (AgNP) and glyphosate (Gly) in Daphnia magna by measurement of reactive oxygen species (ROS) production, glutathione (GSH) levels, enzyme activities of catalase (CAT) and superoxide dismutase (SOD) as well as malondialdehyde (MDA) content. Acute exposure of Daphnia magna to binary mixture of AgNP and Gly resulted in significant biochemical responses indicative of oxidative damage. This response seemed to be related to imbalance in enzymatic/non-enzymatic antioxidant enzymes associated with intracellular overproduction of ROS and significant increase in MDA levels, indicating that the integrity and function of the cell membrane was damaged. These changes adversely affected the fitness and survival of Daphnia magna and negatively influenced offspring growth and reproduction.

Acute and chronic toxicity of amine-functionalized SiO2 nanostructures toward Daphnia magna.

Silicon oxide (SiO2) nanostructures (SiO2NS) are increasingly being incorporated into an array of products, notably in the food, pharmaceutical, medical industries and in water treatment systems. Amorphous SiO2NS have low toxicity, however, due to their great versatility, superficial modifications can be made and these altered structures require toxicological investigation. In this study, SiO2NS were synthetized and amine-functionalized with the molecules (3-aminopropyl)triethoxysilane (APTMS) and 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (AEAEAPTMS), named SiO2NS@1 and SiO2NS@3, respectively. The bare SiO2NS, SiO2NS@1 and SiO2NS@3 samples were characterized and the influence of the culture medium used in the toxicological assays was also evaluated. The effect of amine functionalization of SiO2NS was investigated through acute and chronic toxicity assays with Daphnia magna. Modifications to ultrastructures of the intestine and eggs of these organisms were observed in TEM and SEM analysis. The toxicity was influenced by the surface modifications and a possible Trojan horse effect was highlighted, particularly in the case of chronic exposure. Exposure to all NSs promoted alterations in the microvilli and mitochondria of the D. magna intestine and some damage to egg cells was also observed. The results demonstrate the importance of carrying out a full characterization of these materials, since surface modifications can enhance their toxic potential.

Toxicity of binary mixtures of Al2O3 and ZnO nanoparticles toward fibroblast and bronchial epithelium cells.

The objective of this study was to examine the cytotoxic effects of binary mixtures of Al2O3 and ZnO NPs using mouse fibroblast cells (L929) and human bronchial epithelial cells (BEAS-2B) as biological test systems. The synergistic, additive, or antagonistic behavior of the binary mixture was also investigated. In toxicity experiments, cellular morphology, mitochondrial function (MTT assay), apoptosis, nuclear size and shape, clonogenic assays, and damage based upon oxidative stress parameters were assessed under control and NPs exposure conditions. Although Abbott modeling results provided no clear evidence of the binary mixture of Al2O3 and ZnO NPs exhibiting synergistic toxicity, some specific assays such as apoptosis, nuclear size and shape, clonogenic assay, activities of antioxidant enzymatic enzymes catalase, superoxide dismutase, and levels of glutathione resulted in enhanced toxicity for the mixtures with 1 and 1.75 toxic units (TU) toward both cell types. Data demonstrated that co-presence of Al2O3 and ZnO NPs in the same environment might lead to more realistic environmental conditions. Our findings indicate cytotoxicity of binary mixtures of Al2O3 and ZnO NPs produced greater effects compared to toxicity of either individual compound.

Individual and combined multigenerational effects induced by polystyrene nanoplastic and glyphosate in Daphnia magna (Strauss, 1820).

In this study, the acute and multigenerational effects of the individual and combined toxicity of polystyrene nanoplastic (PSNP - 15.6, 31.2 62.5, 125, 250 and 500 mg/L) and glyphosate (Gly - 6.2, 12.5, 25, 50, 100 and 200 mg/L) on the freshwater crustacean Daphnia magna were investigated. The acute toxicity interactions were predicted mathematically using Abbott's model and multiple toxicological endpoints. In the multigenerational tests, we evaluated the effects in filial (F1 and F2) generations of daphnids after parental (F0) exposure to Gly and PSNP, as individual compounds and as a mixture, during their life history. Based on Abbott's model, the combined individual toxicities of Gly and PSNP are increased when they are present as a mixture. This indicates synergy between the components of the mixture, especially in the case of co-exposure to Gly and PSNP in higher equitoxic proportions. The mixture of PSNP and Gly caused an increase in immobility and ROS production and decrease in swimming activity. Multigenerational responses indicated that the exposure of F0 daphnids to Gly and PSNP as a mixture induced effects in the F1 and F2 reproduction parameters in the recovery tests. Thus, the results reported herein provide important information on the interaction of hydrophilic organic and nanoplastic pollutants in aqueous ecosystems. This will be useful in future studies on the toxicity of mixtures and multigenerational effects and provide a basis for management decisions aimed at the protection of environmental health.

Membrane adsorption with polyacrylonitrile prepared with superfine powder-activated carbon, case study: separation process applied in water treatment containing diclofenac.

Polyacrylonitrile membranes (PAN) have high stability against chemical agents, making them suitable for a wide range of applications as such Ultrafiltration processes. Ultrafiltration membranes composed of PAN/Superfine powder activated carbon (S-PAC) mixtures can be a good research route, aiming the development of a new separation processes for water treatment. The association of materials to form a single product can have technological and economic advantages in separation processes. In this study, S-PAC impregnated into PAN membranes were prepared, characterized and used, as a case study, to remove diclofenac (DCF) from water. The membranes (PAN/S-PAC) were synthesized with different concentrations of S-PAC (0.2, 0.6, 1.0, 3.0 and 5.0 wt%) by a phase inversion process. The results of the TEM characterizations of the S-PAC indicated the presence of micro and nanoparticles (∼10 nm) and tending to form micrometric clusters. The infrared spectra of the membranes were characteristic of PAN; however, vibrational bands attributed to the S-PAC spectrum were also observed, which indicated an interaction between the materials. The case study showed an increase in the water flux and in the DCF rejection efficiency, for composite membranes (PAN/S-PAC) with higher concentration of S-PAC. The results of static adsorption tests indicated that the mechanism of DCF rejection occurred predominantly by adsorption. There were indications that the PAN/S-PAC membranes formed a composite material and the PAN/S-PAC (3.0) presented the best study composition given the results. Although the research is in its initial phase, the results indicated that the composition can improve many water treatment systems.

Multigenerational Toxic Effects on Daphnia magna Induced by Silver Nanoparticles and Glyphosate Mixture.

Multigenerational toxicological effects of a binary mixture of silver nanoparticles (AgNPs) with glyphosate were identified in Daphnia magna using acute and chronic toxicity tests. Acute toxicity interactions were analyzed with the Abbott method. In the chronic tests, the survival, growth, reproduction, and age at first brood were evaluated for the parents and the exposed (F1E) and non-exposed (F1NE) descendants. The scales tested for binary mixture, at the acute level, presented antagonistic and additive interactions, possibly associated with the complexation of the AgNPs by glyphosate. Multigenerational chronic effects related to the parameters, reproduction, and age at first brood were observed in the descendants tested with the individual compounds, with no recovery for F1E and F1NE. In organisms exposed to binary mixture, there was a delay in the age at first brood and also a significant change in the reproduction parameter, with a strong reduction for the parents, F1E, and F1NE, indicating a higher toxicity than the compounds tested individually. Although the results for acute interactions between AgNP and glyphosate did not provide clear evidence, multigenerational chronic binary mixture trials have resulted in unexpected toxicity compared with individual treatments, increasing the concerns associated with this co-exposure in other scenarios. Therefore, the interaction of binary mixture with the organisms merits further investigation and the results reported in the present study will be useful in this regard. Environ Toxicol Chem 2021;40:1123-1131. © 2020 SETAC.

Probabilistic model for assessing occupational risk during the handling of nanomaterials.

Exposure to nanomaterials (NMs) can be considered as human, occupational or environmental. Occupational exposure may be experienced by the workers and/or researchers who develop and produce these products and the hazards inherent to exposure are not yet fully known. Quantitative and qualitative methods are available to estimate the occupational risks associated with the handling of NMs, however, both have limitations. In this context, the objective of this study was to create a Bayesian network (BN) that will allow an assessment of the occupational risk associated with the handling of NMs in research laboratories. The BN was developed considered variables related to exposure, the hazards associated with NMs and also the existing control measures in the work environment, such as collective protection equipment (CPE), administrative measures and personal protection equipment (PPE). In addition to assessing the occupational risk, simulations were carried out by the laboratory manager to obtain information on which actions should be taken to reduce the risk. The development of a BN to assess the occupational risk associated with the handling of NMs is a novel aspect of this study. As a distinctive feature, the BN has measurement control variables in addition to considering CPE, administrative measures and PPE. An advantage of this network in relation to other risk assessment models is that it allows the easy execution of simulations and provides a guide for a decision making by identifying which actions should be taken to minimize the risk.

Can the surface modification and/or morphology affect the ecotoxicity of zinc oxide nanomaterials?

Among nanomaterials, zinc oxide (ZnO) is notable for its excellent biocidal properties. In particular, it can be incorporated in mortars to prevent biofouling. However, the morphology of these nanomaterials (NMs) and their impact on the action against biofouling are still unknown. This study aimed to assess how the morphology and surface modification can affect the ecotoxicology of ZnO NMs. The morphologies evaluated were nanoparticles (NPs) and nanorods (NRs), and the ZnO NMs were tested pure and with surface modification through amine functionalization (@AF). The toxic effects of these NMs were evaluated by acute and chronic ecotoxicity tests with the well-established model microcrustacean Daphnia magna. The ZnO NMs were characterized by transmission electron microscopy, X-ray diffraction and infrared spectroscopy. The EC5048h to D. magna indicated higher acute toxicity of ZnO@AF NRs compared to all tested NMs. Regarding the chronic test with D. magna, high toxic effects on reproduction and longevity were observed with ZnO@AF NRs and effects on growth were observed with ZnO NRs. In general, all tested ZnO NMs presented high toxicity when compared to the positive control, and the NRs presented higher toxicity than NPs in all tested parameters, regardless of the form tested (pure or with surface modification). Additionally, the pathways of ecotoxicity of the tested ZnO NMs was found to be related to combined factors of Zn ion release, effective diameter of particles and NM internalization in the organism.

Investigation of toxicological effects of amorphous silica nanostructures with amine-functionalized surfaces on Vero cells.

Amorphous silica (SiO2) nanostructures are described in the literature as having low toxicity and are widely used in many industrial products. However, surface modifications, such as amine-functionalization, can result in increased cytotoxicity. In this study, amorphous SiO2 nanostructures (SiO2 NS) were synthesized and amine-functionalized with two different amine molecules: primary (SiO2 NS@1) and tri-amine (SiO2 NS@3). The materials were characterized by transmission electron microscopy (TEM), zeta potential (ZP), effective diameter (ED) and surface area measurements, X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The toxicity of the three SiO2 NS samples toward Vero cells was evaluated. According to the methyl thiazolyl tetrazolium (MTT) assay, the IC50,24h was 1.477 ±â€¯0.12 g L-1 for SiO2 NS, 0.254 ±â€¯0.07 g L-1 for SiO2 NS@1 and 0.117 ±â€¯0.05 g L-1 for SiO2 NS@3. The order of cytotoxicity was SiO2 NS@3 > SiO2 NS@1 ¼ SiO2 NS. There was an increase in malondialdehyde (MDA) levels and ROS productions in the cells exposed to all three materials. Also, TEM images showed damage on the mitochondria and rough endoplasmic reticulum.

Toxicological Evaluation and Quantification of Ingested Metal-Core Nanoplastic by Daphnia magna Through Fluorescence and Inductively Coupled Plasma-Mass Spectrometric Methods.

There are few studies on nanoplastic that propose quantification of the amount ingested combined with evaluation of the toxic effects on aquatic organisms. We propose 2 methods to quantify the amount of polystyrene nanoplastic (PSNP) ingested by Daphnia magna: fluorescence intensity, where a fluorescent monomer (F) is added to the PSNP and quantified through fluorescence light microscopy, and total aluminum quantification, where PSNP is synthesized with Al2 O3 metal-core nanoparticles and used for quantification of the nanoplastic ingested by the organism Daphnia magna using inductively coupled plasma-mass spectrometry. In addition, the PSNP was functionalized with palmitic acid to simulate the environmental conditions leading to biological and chemical transformations. Acute and chronic toxicity tests were performed with fluorescent PSNP (PSNP/F) and palmitic acid-functionalized PSNP/F (PSNP/F-PA). The ingestion quantified was higher by factors of 2.8 and 3.0 for PSNP/F-PA and 1.9 and 1.7 for PSNP/F applying the fluorescence intensity and total Al quantifying methods, respectively, when compared to PSNP. These results are consistent with the data obtained in the toxicity tests, which showed an approximately 3 times increase in the adverse effect of PSNP/F-PA on the mobility and reproduction of the organisms. Thus, the strong inhibition of D. magna reproduction caused by PSNP/F-PA in the chronic toxicity tests could be associated with a greater amount of this nanoplastic being ingested by the organisms. Environ Toxicol Chem 2019;38:2101-2110. © 2019 SETAC.

Comparative assessment of toxicity of ZnO and amine-functionalized ZnO nanorods toward Daphnia magna in acute and chronic multigenerational tests.

Zinc oxide nanomaterials (ZnO NM) have been used in a large number of applications due to their interesting physicochemical properties. However, the increasing use of ZnO NM has led to concerns regarding their environmental impacts. In this study, the acute and chronic toxicity of ZnO nanorods (NR) bare (ZnONR) and amine-functionalized (ZnONR@AF) toward the freshwater microcrustacean Daphnia magna was evaluated. The ZnO NR were characterized by transmission electron microscopy (TEM), X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and the zeta potential and hydrodynamic diameter (HD). The acute EC50(48h) values for D. magna revealed that the ZnONR@AF were more toxic than the ZnONR. The generation of reactive oxygen species (ROS) was observed in both NM. Regarding the chronic toxicity, the ZnONR@AF were again found to be more toxic than the ZnONR toward D. magna. An effect on longevity was observed for ZnONR, while ZnONR@AF affected the reproduction, growth and longevity. In the multigenerational recovery test, we observed that maternal exposure can affect the offspring even when these organisms are not directly exposed to the ZnO NR.