Silver nanomaterials (AgNMs) are broadly used and among the most studied nanomaterials. The underlying molecular mechanisms (e.g. protein and metabolite response) that precede phenotypical effects have been assessed to a much lesser extent. In this paper, we assess differentially expressed proteins (DEPs) and metabolites (DEMs) by high-throughput (HTP) techniques (HPLC-MS/MS with tandem mass tags, reversed-phase (RP) and hydrophilic interaction liquid chromatography (HILIC) with mass spectrometric detection). In a time series (0, 7, 14 days), the standard soil model Enchytraeus crypticus was exposed to AgNM300K and AgNO₃ at the reproduction EC20 and EC50. The impact on proteins/metabolites was clearly larger after 14 days. NM300K caused more upregulated DEPs/DEMs, more so at the EC20, whereas AgNO₃ caused a dose response increase of DEPs/DEMs. Similar pathways were activated, although often via opposite regulation (up vs down) of DEPs, hence, dissimilar mechanisms underlie the apical observed impact. Affected pathways included e.g. energy and lipid metabolism and oxidative stress. Uniquely affected by AgNO₃ was catalase, malate dehydrogenase and ATP-citrate synthase, and heat shock proteins (HSP70) and ferritin were affected by AgNM300K. The gene expression-based data in Adverse Outcome Pathway was confirmed and additional key events added, e.g. regulation of catalase and heat shock proteins were confirmed to be included. Finally, we observed (as we have seen before) that lower concentration of the NM caused higher biological impact. Data was deposited to ProteomeXchange, identifier PXD024444.

Whether toxicity of silver nanoparticles (AgNPs) to organisms originates from the nanoparticles themselves or from the dissolved Ag-ions is still debated, with the majority of studies claiming that extracellular release of Ag-ions is the main cause of toxicity. The objective of this study was to determine the contributions of both particles and dissolved ions to toxic responses, and to better understand the underlying mechanisms of toxicity. In addition, the pathways of AgNPs exposure to plants might play an important role and therefore are explicitly studied as well. We systematically assessed the phytotoxicity, internalization, biodistribution, and antioxidant responses in lettuce (Lactuca sativa) following root or foliar exposure to AgNPs and ionic Ag at various concentrations. For each endpoint the relative contribution of the particle-specific versus the ionic form was quantified. The results reveal particle-specific toxicity and uptake of AgNPs in lettuce as the relative contribution of particulate Ag accounted for more than 65% to the overall toxicity and the Ag accumulation in whole plant tissues. In addition, particle toxicity is shown to originate from the accumulation of Ag in plants by blocking nutrient transport, while ion toxicity is likely due to the induction of excess ROS production. Root exposure induced higher toxicity than foliar exposure at comparable exposure levels. Ag was found to be taken up and subsequently translocated from the exposed parts of plants to other portions regardless of the exposure pathway. These findings suggest particle related toxicity, and demonstrate that the accumulation and translocation of silver nanoparticles need to be considered in assessment of environmental risks and of food safety following consumption of plants exposed to AgNPs by humans.

Silver (Ag) is amongst the most well studied nanomaterials (NMs), although most studies have only dealt with a single AgNM at a time and one biological endpoint. We here integrate the results of various testing-tools (endpoints) using a terrestrial worm, the standard ecotoxicological model organism Enchytraeus crypticus. Exposure spanned both water and soil exposure, it covered all life stages (cocoons, juveniles and adults), varying exposure durations (1-2-3-4-5-21 days), and covered 5 biological endpoints: hatching success, survival, reproduction, avoidance and gene expression (qPCR target genes GABA and Acetyl cholinesterase). We tested 4 Ag materials: PVP coated (PVP-AgNM), non-coated (NC-AgNM), the JRC reference Ag NM300K and AgNO₃. Results showed that short-term exposure via water to assess impact on cocoons’ hatching predicted longer term effects such as survival and reproduction. Moreover, if we extended the exposure from 11 to 17 day this allowed discrimination between hatch delay and impairment. Exposure of juveniles and adults via water showed that juveniles were most sensitive with survival affected. Across materials the following toxic ranking was observed: AgNO₃ ≥ Ag NM300K ≫ NC-AgNM ≥ PVP-AgNM. E. crypticus avoided AgNO₃ in a dose-response manner, avoiding most during the first 24 h. Avoidance of Ag NM300K and NC-AgNM only occurred during the first 24 h and the PVP coated AgNM were not avoided at all. The up-regulation of the GABA triggering anesthetic effects, indicated the high ecological impact of Ag materials in soil: Ag affects the GABAergic system hence organisms were not able to efficiently avoid and became intoxicated, this caused impacts in terms of survival and reproduction.

To improve catalytic performance and stability of Ag nanoparticles (Ag NPs), a facile ultrasonication-assisted chemical reduction method was developed to fabricate reduced graphene oxide (rGO) aerogels loaded with 1–3 nm Ag NPs under the normal temperature and pressure. The ultrasonication facilitated the dispersion of Ag(I) in the form of silver ammonia and anchored onto GO nanosheets. Ag(I) and GO were simultaneously reduced to Ag(0) immobilizing onto 3D rGO hydrogels within the heterogeneous liquid phase, and ultimately formed 3D rGO-Ag NPs aerogels. The 3D rGO-Ag NPs aerogels displayed superb catalytic performance for the reduction of nitrobenzene (NB), 1,3-dinitrobenzene (DNB) and 4-nitrophenol (NP) into aniline, 1,3-diaminobenzene and 4-aminophenol, respectively. The individual reduction rate Kobs for NB, DNB and NP were 0.168 h−1, 0.109 h−1 and 0.092 h−1, which were much higher than those of other Ag NPs-based materials. Moreover, the immobilization of 1–3 nm Ag NPs in 3D rGO-Ag NPs was stable during the whole reduction reaction without aggregation and leaching. The high stability of Ag NPs in 3D rGO-Ag NPs and superb performance on catalytic reduction of nitroaromatic compounds (NACs) could be concluded into ultrasonication influence in the preparation procedure and synergistic effect of Ag NPs and 3D rGO in the catalytic reduction process. The simple ultrasonication-assisted chemical reduction approach provided a scaled-up application prospect in catalytic reduction of NACs by metal nanoparticle catalysts.

The widespread production and use of silver nanomaterials (AgNMs) in consumer and medical products have been raising environmental concerns. Once in the environment, the soil is one of the major sinks of AgNMs due to e.g. sewage sludge applications, and invertebrates are directly exposed. In this study, we investigate the potential of N-acetylcysteine (NAC) to reduce the toxic effects of Ag NM300 K (and AgNO3) on the soil invertebrate Enchytraeus crypticus. Ag NM300 K induces mortality, reproduction impairment, and avoidance. The addition of NAC to the soil showed a remarkable reduction in the toxicity of Ag, indicating that NAC can act as a detoxifying agent for terrestrial organisms exposed to Ag materials. That the reduction in toxicity likely is caused by thiol groups, was confirmed by GSH and GSSH studies. Identifying the mechanisms and hence alternatives that allow the recovery of contaminated soils is an important mitigation measure to promote environmental safety and reduce the associated risks to human health. Further, it may inform on strategies to implement in safe-by-design industry development.

The genus Artemia sp. has been accepted as a reliable model organism for aquatic toxicity and nanotoxicity experiments, as far as the ISO TS 20787 has recently been published to standardize nanotoxicity test with this organism. Experimental and environmental conditions may affect the toxicity of nanomaterials on aquatic organisms including Artemia sp. nauplii. In this study, acute toxicity effects of silver nanoparticles (AgNPs) on the nauplii of Artemia salina was investigated under various conditions (e.g. different lights, salinities, temperatures, volume and agitation of exposure media and instar stages of nauplii). The EC values were calculated using Probit program and all data were analyzed statistically by SPSS software. At all test conditions, the immobilization rate of Artemia nauplii increased in a concentration-dependent manner (P < 0.05). The sensitivity of instar stage II to different concentrations of AgNPs was significantly higher than instar I (P < 0.05). The toxicity effect of AgNPs was affected by alteration of environmental conditions, so that the effective concentration (EC) values for instar I of A. salina decreased with increasing water temperature, decreasing water salinity and in continuous darkness condition. The EC50 value of AgNPs was significantly lower in 100 mL beakers (21.35 ± 5.67 mg L−1) than 10 mL well plates (42.44 ± 11.30 mg L−1). Agitation of exposure media did not affect the toxicity of AgNPs. The results indicated that the experimental and environmental conditions influence on the toxicity of AgNPs in the nauplii of A. salina.

Transcription factors including pregnane X receptor (Pxr) and nuclear factor-erythroid 2-related factor-2 (Nrf2) are important modulators of Adenosine triphosphate-binding cassette (ABC) transporters in mammalian cells. However, whether such modulation is conserved in zebrafish embryos remains largely unknown. In this manuscript, pxr- and nrf2-deficient models were constructed with CRISPR/Cas9 system, to evaluate the individual function of Pxr and Nrf2 in the regulation of ABC transporters and detoxification of heavy metal ions like Cd²⁺ and Ag⁺. As a result, both Cd²⁺ and Ag⁺ conferred extensive interactions with ABC transporters in wild type (WT) embryos: their accumulation and toxicity were affected by the activity of ABC transporters, and they significantly induced the mRNA expressions of ABC transporters. These induction effects were reduced by the mutation of pxr and nrf2, but elevations in the basal expression of ABC transporters compensated for the loss of their inducibility. This could be an explanation for remaining transporter function in both mutant models as well as the unaltered toxicity of metal ions in pxr-deficient embryos. However, mutation of nrf2 disrupted the production of glutathione (GSH), resulting in the enhanced toxicity of Cd²⁺/Ag⁺ in zebrafish embryos. In addition, elevated expressions of other transcription factors like aryl hydrocarbon receptor (ahr) 1b, peroxisome proliferator-activated receptor (ppar)-β, and nrf2 were found in pxr-deficient models without any treatment, while enhanced induction of ahr1b, ppar-β and pxr could only be seen in nrf2-deficient embryos after the treatment of metal ions, indicating different compensation phenomena for the absence of transcription factors. After all, pxr-deficient and nrf2-deficient zebrafish embryos are useful tools in the functional investigation of Pxr and Nrf2 in the early life stages of aquatic organisms. However, the compensatory mechanisms should be taken into consideration when interpreting the results and need in-depth investigations.

Silver nanoparticles (AgNPs) are widely incorporated in many products, partly due to their antimicrobial properties. The subsequent discharge of this form of silver into wastewater leads to an accumulation of silver species (AgNPs and derivatives resulting from their chemical transformation), in sewage sludge. As a result of the land application of sewage sludge for agricultural or remediation purposes, soils are the primary receiver media of silver contamination. Research on the long-term impact of AgNPs on the environment is ongoing, and this paper is the first review that summarizes the existing state of scientific knowledge on the potential impact of silver species introduced into the soil via sewage sludge, from microorganisms to earthworms and plants. Silver species can easily enter cells through biological membranes and affect the physiology of organisms, resulting in toxic effects. In soils, exposure to AgNPs may change microbial biomass and diversity, decrease plant growth and inhibit soil invertebrate reproduction. Physiological, biochemical and molecular effects have been documented in various soil organisms and microorganisms. Negative effects on organisms of the dominant form of silver in sewage sludge, silver sulfide (Ag₂S), have been observed, although these effects are attenuated compared to the effects of metallic AgNPs. However, silver toxicity is complex to evaluate and much remains unknown about the ecotoxicology of silver species in soils, especially with respect to the possibility of transfer along the trophic chain via accumulation in plant and animal tissues. Critical points related to the hazards associated with the presence of silver species in the environment are described, and important issues concerning the ecotoxicity of sewage sludge applied to soil are discussed to highlight gaps in existing scientific knowledge and essential research directions for improving risk assessment.

High performance activated carbon (HPAC) supported nanoscale zerovalent iron (nZVI) was prepared and used for recovery of silver. This composite material was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The removal amount of Ag+ increased with pH values and temperature. The removal process achieved equilibrium within 40 min and the maximum removal capacity was 986.5 mg/g at 298 K. The composite material showed fast adsorption rate and high adsorption capacity because the presence of high surface area activated carbon could effectively inhibit aggregation of nanoscale zerovalent iron, thus enhancing its reactivity. The Ag+ removal followed pseudo-second-order kinetic model and Langmuir isotherm model. XPS and XRD characterizations were performed to elucidate removal mechanism. It could be concluded that both coordination adsorption and reductive precipitation contributed to removal of Ag+ on the nZVI/HPAC.

Marine fish are considered a source of high quality proteins and fatty acids. However, the consumption of fish may pose a health risk as it may have potentially toxic elements in high concentrations. In this study we quantify the multielemental composition of muscle and fins for three species of commercial marine fish from Brazil: Sphyraena guachancho (Barracuda), Priacantus arenatus (Common bigeye) and Genidens genidens (Guri sea catfish). We then assessed the potential risk of fish consumption by means of a Provisional Hazard Indices. Amongst the elements detected in fish tissue were potentially toxic elements such as Ag, Ba, Cd, Cr and Hg. Concentration differences were species-specific, and affected by the species trophic level, morphological characteristics and feeding habits. Results suggest the higher the trophic level of the fish, the higher the risk of consumption. Caution is recommended for the frequent ingestion of high trophic level fish species in Brazil.