No abstract

This study focused on surface waters from three small creeks, within the Seine River watershed, which are characterized by different land-uses, namely forested, agricultural and urban. Silver nanoparticles (Ag-NPs) in these waters were detected and quantified by single-particle ICPMS during one-year of monthly sampling. Their temporal and spatial variations were investigated. Ag-NPs, in the three types of surface water, were found to range from 1.5 x10 7 to 2.3 x 10 9 particles L-1 and from 0.4 to 28.3 ng L-1 at number and mass concentrations, respectively. These values are in consistent with the very few previous studies. In addition, the role of factors driving process and potential sources are discussed with correlations between Ag-NPs concentrations and biogeochemical parameters, like dissolved organic carbon concentration and divalent cations concentrations. For the forested watershed NOM controls the stability (number and mass) of the Ag-NPs as recently observed in the field in lake water in Germany. In the case of the agricultural and urban watersheds major cations such as Ca would control the number and mass of Ag-NPs. Dilution processes are rejected as conductivity and Clions do not show significant correlations with Ag-NPs or other major geochemical parameters. The specific exportation rates of Ag-NPs for artificial, agricultural and forested areas were calculated based on the monthly data for the full year and are equal to 5.5 ± 3.0, 0.5 ± 0.3 and 0.2 ± 0.2 gy-1 km-2 , respectively. These data suggest a constant release of Ag-NPs from consumer products into freshwaters in artificial areas, for instance, from textiles, washing machines, domestic tap-water filters, outdoor paints. These first data of Ag-NPs fluxes in surface waters of France enlarge the very limited database of field measurements. Moreover, for the first time, the influence of time, landuse and aquatic geochemistry parameters on Ag-NPs in real natural water samples is reported. It is also helpful to further understand the fate and the process of Ag-NPs in natural waters, as well as to the ecotoxicity studies in real-world environment.

Background: Oral exposure to titanium dioxide (TiO2) is common since it is widely used in food and pharmaceutical products. Concern on the safety of this substance has been recently raised, due to the presence of an ultrafine fraction in food-grade TiO2. Discrepancy exists among data reported in in vitro and in vivo studies on intestinal acute/chronic toxicity of TiO2. This might be due to the different biological identity of TiO2 in traditional in vitro test by respect in vivo conditions. Methods: One food-grade TiO2 and two nanometric TiO2 samples were treated with a simulated human digestive dystem (SHDS) in order to investigate the bio-transformation occurring to the particles once ingested in term of size distribution (Dynamic Light Scattering—DLS-, Flow Particle Imaging, Asymmetric Flow Field Flow Fractionation-AF4-) and surface modification (Electrophoretic Light Scattering—ELS-, Electron Paramagnetic Resonance Spectroscopy—EPR-). The effect of SHDS on the cyto-, genotoxicity and potential to induce oxidative stress towards human colorectal carcinoma HCT116 cells was also assessed. Results: Aggregation as a consequence of the high ionic strength of the gastric and intestinal simulated fluids was observed, together with the formation of a partially irreversible bio-corona containing phosphate ions and proteins. Such bio-corona led to a partial masking of the TiO2 particles surface and reactivity. Pristine and treated TiO2 nanoparticles showed comparable acute toxicity and genotoxicity toward HCT116 cells, whereas a small decrease of the induction of oxidative stress after treatment was observed. Conclusions: Overall the results underline the importance of SHDS as a tool to improve the predictive power of in vitro tests towards intestinal nanomaterial toxicity.

The European Water Framework Directive 2000/60/EC requires monitoring of organic priority pollutants in so-called whole water samples, i.e. in aqueous nonfiltered samples that contain natural colloidal and suspended particulate matter. Colloids and suspended particles in the liquid phase constitute a challenge for sample homogeneity and stability. Within the joint research project ENV08 ''Traceable measurements for monitoring critical pollutants under the European Water Framework Directive 2000/60/EC'', whole water test materials were developed by spiking defined amounts of aqueous slurries of ultrafinely milled contaminated soil or sediment and aqueous solutions of humic acid into a natural mineral water matrix. This paper presents the results of an European-wide interlaboratory comparison (ILC) using this type of test materials. Target analytes were tributyltin, polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in the ng/L concentration range. Results of the ILC indicate that the produced materials are sufficiently homogeneous and stable to serve as samples for, e.g. proficiency testing or method validation. To our knowledge, this is the first time that ready-to-use water materials with a defined amount of suspended particulate and colloidal matter have been applied as test samples in an interlaboratory exercise. These samples meet the requirements of the European Water Framework Directive. Previous proficiency testing schemes mainly employed filtered water samples fortified with a spike of the target analyte in a water-miscible organic solvent. KeywordsWater Framework Directive Á Interlaboratory comparison Á Whole water sample Á Suspended particulate matter Á Polycyclic aromatic hydrocarbons Á Polybrominated diphenyl ethers Á Tributlyltin Electronic supplementary material The online version of this article (

The coupling of the flow field-flow fractionation (FlFFF) to differential refractive index (DRI) and multiangle laser light scattering (LS) detectors is a powerful tool for characterizing charged polysaccharides such as alginate. However, the correct interpretation of the experimental results and extrapolation of meaningful molecular parameters by using an analytical tool with such a level of complexity requires improvement of the knowledge of the alginate behavior in the channel and careful optimization of the operating conditions. Therefore, the influence of the critical operating parameters, such as crossflow rate, carrier composition and concentration, and sample load, on the alginate retention was carefully evaluated. Combined information obtained simultaneously by DRI and LS detectors over the wide range of the crossflow rate, carrier liquid concentration, and injected amount, allowed to set the appropriate combination of optimal parameters. It was found that the crossflow rate of 0.25 mL/min, carrier solution containing 5x10(-2 )mol/L ammonium or sodium chloride, and 50-100 microg of injected sample mass were necessary to achieve complete separation and determination of the meaningful molecular characteristics. The values of the weight-average hydrodynamic radius (R(Hw)), radius of gyration (R(G)), and molar mass (M), obtained under the optimal conditions were in good agreement to those found for alginates in the literature.