Physicochemical Transformations of Silver Nanoparticles in the Oro-Gastrointestinal Tract Mildly Affect Their Toxicity to Intestinal Cells In Vitro: An AOP-Oriented Testing Approach.

The widespread use of silver nanoparticles (Ag NPs) in food and consumer products suggests the relevance of human oral exposure to these nanomaterials (NMs) and raises the possibility of adverse effects in the gastrointestinal tract. The aim of this study was to investigate the toxicity of Ag NPs in a human intestinal cell line, either uncoated or coated with polyvinylpyrrolidone (Ag PVP) or hydroxyethylcellulose (Ag HEC) and digested in simulated gastrointestinal fluids. Physicochemical transformations of Ag NPs during the different stages of in vitro digestion were identified prior to toxicity assessment. The strategy for evaluating toxicity was constructed on the basis of adverse outcome pathways (AOPs) showing Ag NPs as stressors. It consisted of assessing Ag NP cytotoxicity, oxidative stress, genotoxicity, perturbation of the cell cycle and apoptosis. Ag NPs caused a concentration-dependent loss of cell viability and increased the intracellular level of reactive oxygen species as well as DNA damage and perturbation of the cell cycle. In vitro digestion of Ag NPs did not significantly modulate their toxicological impact, except for their genotoxicity. Taken together, these results indicate the potential toxicity of ingested Ag NPs, which varied depending on their coating but did not differ from that of non-digested NPs.

Transport of nanoparticulate TiO2 UV-filters through a saturated sand column at environmentally relevant concentrations.

The fate of sunscreen residues released during bathing activities around recreational areas is an emerging concern regarding the potential ecotoxicity of some of their ingredients, including nanoparticulate TiO2 UV-filters. To assess the extent of contamination in the natural medium, sand-packed column experiments were carried out with bare TiO2 engineered nanoparticles (ENPs) and two commercial nano-TiO2 UV-filters coated with either SiO2 (hydrophilic) or a combination of Al2O3 and simethicone (amphiphilic). The high sensitivity of (single particle)ICPMS online monitoring of the breakthrough curves made it possible to inject the ENPs at trace levels (2-100 µg L-1) in eluents composed of 10-3 and 10-2 M NaCl and pHs of 5.7 and 7.8. The deposition of all ENPs in the sand increased with the ionic strength and decreased with the pH of the carrier. Both bare and SiO2-coated ENPs showed a clear control by the electrostatic interactions between the particles and the quartz grains surfaces, in partial agreement with classical DLVO theory. Unexpectedly high rates of transfer were observed with the amphiphilic UV-filter, which could be explained by the addition of a contribution to the DLVO model to account for the steric repulsion between the sand collector and the polysiloxane surface layer of this ENP. These results demonstrate the major role played by the coating of UV-filters regarding their fate in porous media like soils, sediments and aquifers.

Insight into the Crucial Role of Secondary Mineral Phases in the Transfer of Gold Nanoparticles through a Sand Column Using Online ICP-MS/spICP-MS Monitoring.

Investigating the transport of engineered nanoparticles through representative soils is an important issue in assessing their mobility and fate in the environment. In this study, successive injections of gold nanoparticles (AuNPs) were performed in a quartz sand column with an eluent composed of 10-2 M NaCl at a pH of 7.5. After this series of injections, remobilization of the AuNPs was examined by raising the eluent pH to 10. 197Au and the conservative ionic tracer 79Br were monitored simultaneously by online inductively coupled plasma mass spectrometry (ICP-MS), and the particulate nature of gold eluting from the column was confirmed by setting the ICP-MS in the "single particle" mode. The extent of AuNP attachment was greater than predicted by DLVO theory considering quartz as the sole collector, decreased with the number of injections and with particle size. In contrast with the repulsive interaction energy between the particles and the quartz surface, kaolinite, a secondary mineral of the sand, provided favorable conditions for particle attachment. The superimposed signals of 197Au and 27Al in the column effluent after pH increase suggest that gold nanoparticles were essentially remobilized as heteroaggregates with the kaolinite colloids they were attached to when favorable conditions for clay detachment from the sand grains were encountered.

Silver Accumulation in the Green Microalga Coccomyxa actinabiotis: Toxicity, in Situ Speciation, and Localization Investigated Using Synchrotron XAS, XRD, and TEM.

Microalgae are good candidates for toxic metal remediation biotechnologies. This study explores the cellular processes implemented by the green microalga Coccomyxa actinabiotis to take up and cope with silver over the concentration range of 10(-7) to 10(-2) M Ag(+). Understanding these processes enables us to assess the potential of this microalga for applications for bioremediation. Silver in situ speciation and localization were investigated using X-ray absorption spectroscopy, X-ray diffraction, and transmission electron microscopy. Silver toxicity was evaluated by monitoring microalgal growth and photochemical parameters. Different accumulation mechanisms were brought out depending on silver concentration. At low micromolar concentration, microalgae fixed all silver initially present in solution, trapping it inside the cells into the cytosol, mainly as unreduced Ag(I) bound with molecules containing sulfur. Silver was efficiently detoxified. When concentration increased, silver spread throughout the cell and particularly entered the chloroplast, where it damaged the photosystem. Most silver was reduced to Ag(0) and aggregated to form crystalline silver nanoparticles of face-centered cubic structure with a mean size of 10 nm. An additional minor interaction of silver with molecules containing sulfur indicated the concomitant existence of the mechanism observed at low concentration or nanoparticle capping. Nanoparticles were observed in chloroplasts, in mitochondria, on the plasma membrane, on cytosolic membrane structures, and in vacuoles. Above 10(-4) M Ag(+), damages were irreversible, and photosynthesis and growth were definitely inhibited. However, high silver amounts remained confined inside microalgae, showing their potential for the bioremediation of contaminated water.

Review of nanomaterial aging and transformations through the life cycle of nano-enhanced products.

In the context of assessing potential risks of engineered nanoparticles (ENPs), life cycle thinking can represent a holistic view on the impacts of ENPs through the entire value chain of nano-enhanced products from production, through use, and finally to disposal. Exposure to ENPs in consumer or environmental settings may either be to the original, pristine ENPs, or more likely, to ENPs that have been incorporated into products, released, aged and transformed. Here, key product-use related aging and transformation processes affecting ENPs are reviewed. The focus is on processes resulting in ENP release and on the transformation(s) the released particles undergo in the use and disposal phases of its product life cycle for several nanomaterials (Ag, ZnO, TiO2, carbon nanotubes, CeO2, SiO2 etc.). These include photochemical transformations, oxidation and reduction, dissolution, precipitation, adsorption and desorption, combustion, abrasion and biotransformation, among other biogeochemical processes. To date, few studies have tried to establish what changes the ENPs undergo when they are incorporated into, and released from, products. As a result there is major uncertainty as to the state of many ENPs following their release because much of current testing on pristine ENPs may not be fully relevant for risk assessment purposes. The goal of this present review is therefore to use knowledge on the life cycle of nano-products to derive possible transformations common ENPs in nano-products may undergo based on how these products will be used by the consumer and eventually discarded. By determining specific gaps in knowledge of the ENP transformation process, this approach should prove useful in narrowing the number of physical experiments that need to be conducted and illuminate where more focused effort can be placed.