[Toxicity of nanoparticles on reproduction]. / Reprotoxicité des nanoparticules.

Nanoparticles (NPs) are sized between 1 and 100nm. Their size allows new nanoscale properties of particular interest for industrial and scientific purpose. Over the past twenty years, nanotechnology conquered many areas of use (electronic, cosmetic, textile…). While, human is exposed to an increasing number of nanoparticles sources, health impacts and, particularly on reproductive function, remains poorly evaluated. Indeed, traceability of nanoparticles use is lacking and nanotoxicology follows different rules than classical toxicology. This review focuses on the impact of NPs on health and particularly on fertility and addresses potential risks of chronic exposure to NPs on human fertility.

Synthesis of Ge-imogolite: influence of the hydrolysis ratio on the structure of the nanotubes.

The synthesis protocol for Ge-imogolite (aluminogermanate nanotubes) consists of 3 main steps: base hydrolysis of a solution of aluminum and germanium monomers, stabilization of the suspension and heating at 95 °C. The successful synthesis of these nanotubes was found to be sensitive to the hydrolysis step. The impact of the hydrolysis ratio (from n(OH)/n(Al) = 0.5 to 3) on the final product structure was examined using a combination of characterization tools. Thus, key hydrolysis ratios were identified: n(OH)/n(Al) = 1.5 for the formation of nanotubes with structural defects, n(OH)/n(Al) = 2 for the synthesis of a well crystallized Ge imogolite and n(OH)/n(Al) > 2.5 where nanotube formation is hindered. The capability of controlling the degree of the nanotube's crystallinity opens up interesting opportunities in regard to new potential applications.

Combining size fractionation, scanning electron microscopy, and X-ray absorption spectroscopy to probe zinc speciation in pig slurry.

Zinc occurs in high quantity in pig slurry since it is used as an essential micronutrient at high concentrations in animal feeds despite the low Zn assimilation by pigs. Zinc accumulation was measured in soil surface layers that had been amended with pig slurry, while also determining the phytotoxicity as well as the extent of groundwater quality degradation. To accurately predict the mobility and bioavailability of Zn derived from pig slurry spreading, the speciation of this element has to be assessed since the total concentration is not sufficient. This study involved a combination of techniques to investigate Zn speciation in pig slurry. Size fractionation was first performed to account for the complexity of pig slurry, and 75% of total Zn was detected in the 0.45- to 20-mum particle-size range. Then X-ray diffraction, scanning electron microscopy, coupled with energy dispersive spectrometer, and extended X-ray absorption fine structure analyses were combined to assess Zn speciation. The findings highlighted the presence of 49% Zn bound to organic matter, 37% amorphous Zn hydroxides [Zn(OH)(2)], and 14% sphalerite (ZnS).

Evolution of iron speciation during hydration of C4AF.

It is now well accepted and demonstrated that calcium silicate, calcium aluminate and calcium sulfo aluminate (ettringite, AFm) phases exhibit a good capability to fix metals and metalloids. Unfortunately the role of minor phases and especially calcium-ferric aluminate phase, shorthand C4AF is not well defined. In other systems like in soils or sediments iron phases play a key role in the fixation of pollutant. In cement sorption isotherms, indicated that various metals can be retained by the C4AF hydrated products. Therefore the capabilities of those phase to retain heavy metal should not be neglected. Previous investigations have shown that the minerals formed during the hydration of C4AF are similar to those formed from C3A (pure tri-calcium aluminate) under comparable conditions. Nevertheless no investigation was conducted at the molecular level and there is still a controversy whether Fe substitutes for Al in the hydrated minerals in whole or in part, or if it forms FeOOH clusters scattered throughout the matrix. In this context we have conducted XAS experiments using synchrotron radiation. It was found that the hydration of C4AF forms C3AH6 (hydrogarnet) in which Fe randomly substitutes for Al as well as an amorphous FeOOH phase. Intermediate products like AFm (i.e., an ill organized lamellar phase) are also formed but rapidly evolve to C3AH6; iron does not seem to be incorporated in the AFm structure.

XAS study of iron and arsenic speciation during Fe(II) oxidation in the presence of As(III).

The speciation of As and Fe was studied during the oxidation of Fe(II)-As(III) solutions by combining XAS analysis at both the Fe and As K-edges. Fe(II) and As(III) were first hydrolyzed to pH 7 under anoxic conditions; the precipitate was then allowed to oxidize in ambient air for 33 h under vigorous stirring. EXAFS analysis at the As K-edge shows clear evidence of formation of inner-sphere complexes between As(III) and Fe(II), i.e., before any oxidation. Inner-sphere complexes were also observed when Fe became sufficiently oxidized, in the form of edge-sharing and double-corner linkages between AsIIIO3 pyramids and FeIIIO6 octahedra. XAS analyses at the Fe K-edge reveal that the presence of As(III) in the solution limits the polymerization of Fe(II) and the formation of green rust and inhibits the formation of goethite and lepidocrocite. Indeed, As(III) accelerates the Fe(II) oxidation kinetics and leads to the formation of nanosized Fe-As subunits of amorphous aggregates. These observations, rather than a presumed weaker affinity of As(III) for iron oxyhydroxides, might explain why As(III) is more difficult to remove than As(V) by aerating reducing groundwater.

Isotopic tracing of landfill leachates and pollutant lead mobility in soil and groundwater.

Here we provide evidence of the capability of stable lead isotopes to trace landfill leachate in a shallow groundwater. The municipal landfill we have investigated is located in southeastern France. It has no bottom liner, and wastes are placed directly on the ground. Stable lead isotopes allow the characterization of this landfill leachate signature (206Pb/207Pb = 1.189 +/- 0.004) that is clearly different from that of the local atmosphere (206Pb/207Pb = 1.150 +/- 0.006) and crustal lead (206Pb/207Pb = 1.200 +/- 0.005). Piezometers located in the direct vicinity of the landfill generally display this contaminant imprint. The landfill plume is monitored up to 1000 m downgradient of the landfill, in very good agreement with evaluation from chloride concentration. Meanwhile, 206Pb/207Pb ratios measured at a piezometer located 4600 m downgradient of the landfill suggest a contamination by the landfill plume. This result shows that the complexity of a pollutant plume dispersion in this shallow groundwater system requires several independent tracers to clearly resolve origin and transport pathways for contaminants. Furthermore, seasonal rainfall variation for this Mediterranean mixed Quaternary alluvion reservoir and the use of KCl fertilizers might favor an efficient remobilization of atmospheric lead in plowed soils and its transfer into groundwater as shown by lead isotope systematics.

Analysis of the structure of very large bacterial aggregates by small-angle multiple light scattering and confocal image analysis.

This work aims at developing a more accurate measurement of the physical parameters of fractal dimension and the size distribution of large fractal aggregates by small-angle light scattering. The theory of multiple scattering has been of particular interest in the case of fractal aggregates for which Rayleigh theory is no longer valid. The introduction of multiple scattering theory into the interpretation of scattering by large bacterial aggregates has been used to calculate the fractal dimension and size distribution. The fractal dimension is calculated from the form factor F(q) at large scattering angles. At large angles the fractal dimension can also be computed by considering only the influence of the very local environment on the optical contrast around a subunit. The fractal dimensions of E. coli strains flocculated with two different cationic polymers have been computed by two techniques: static light scattering and confocal image analysis. The fractal dimensions calculated with both techniques at different flocculation times are very similar: between 1.90 and 2.19. The comparison between two completely independent techniques confirms the theoretical approach of multiple scattering of large flocs using the Mie theory. Size distributions have been calculated from light-scattering data taking into account the linear independence of the structure factor S(q) relative to each size class and using the fractal dimension measured from F(q) in the large-angle range or from confocal image analysis. The results are very different from calculations made using hard-sphere particle models. The size distribution is displaced toward the larger sizes when multiple scattering is considered. Using this new approach to the analysis of very large fractal aggregates by static light multiple scattering, the fractal dimension and size distribution can be calculated using two independent parts of the scattering curve.

Application of strontium isotopes for tracing landfill leachate plumes in groundwater.

We are evaluating strontium isotopes as alternative tracers of landfill leachate in groundwater. The municipal landfill studied here is located in southeastern France. This landfill has no bottom liner, and wastes are placed directly on the ground. Based on the evaluation of chloride concentration, the plume extends a maximum of 4,600 m. Strontium isotopic composition characterizes two sources: natural groundwater (87Sr/86Sr = 0.708175) and landfill leachate contamination (87Sr/86Sr = 0.708457). The evolution of mixing ratios obtained with strontium reveals a second source of groundwater contamination: fertilizers (87Sr/ 86Sr = 0.707859). These results suggestthat isotopic signatures can be used to provide useful information on sources of groundwater contamination where conventional water quality parameters may yield ambiguous results.

Removal of nom by coagulation-flocculation: a pyrolysis-GC-MS study

Se realizaron remociones del NOM (Materia orgánica natural) en el Río Sena, usando tres coagulantes: cloruro férrico, sulfato de aluminio y policlorosulfato de aluminio. La eficiencia del proceso dependía del pH. Se obtuvieron menores resultados con un pH de 5,5 con el FC y de 6.0 con los coagulantes a base de aluminio. Se analizó la composición del NOM por medio de pirolisis, cromatografía de gas y espectrometría en masa. Se da los resultados obtenidos en detalle, que fueron confirmados por la PC-GC y MS. Se detallan materiales y métodos, los resultados y los comentarios