Cerium anomalies in riverbanks: Highlight into the role of ferric deposits.

In wetlands, stream riverbanks represent a large redox reactive front. At their surface, ferric deposits promote their capacity to trap nutrients and metals. Given that rare earth elements (REE) are now considered as emerging pollutants, it seems that the riverbank interface is a strategic area between wetlands and streams in terms of controlling the environmental dissemination of REE. Therefore, the evolutions of the REE distribution and cerium (Ce) anomaly (Ce/Ce*, i.e. depleted or enriched Ce concentration compared to the other REE) were studied at various locations on a riverbank. The positive Ce anomaly is related to a high Fe content, a low organic carbon/iron ratio ((OC)/Fe) and newly formed Fe oxyhydroxides independently of their interactions with organic matter. Micro-X ray fluorescence (µ-XRF) mapping confirms Ce accumulation with ferric deposits. The Ce speciation exhibits a mix of Ce(III) and Ce(IV) in the ferric deposits, almost 20% of Ce occurred as Ce(IV) due to oxidation by newly formed Fe oxyhydroxides, while the subsurface horizons only display Ce(III). These results provide evidence that the Ce anomaly variation observed in stream water between low and high flow periods is partly due to the erosion of ferric deposits exhibiting a positive Ce anomaly. Therefore, the Ce anomaly can be considered as a fingerprint of the release of Fe colloids in the rivers and streams connected to the wetland.

Iodine solubility and speciation in glasses.

The study of iodine in glasses and melts is critical in many areas, from geosciences to materials science to waste management. Glasses in the ternary system Na2O-B2O3-SiO2 were studied with the goal of identifying a glass matrix able to dissolve large quantities of this element, and to identify the main parameters affecting the solubility of iodine. Two sets of experiments were carried out: the first one with the aim of determining the solubility limit of iodine, and the second one to identify the structural variations occurring within the glass network upon iodine incorporation, and to identify the parameters influencing the most both iodine solubility and speciation. We demonstrated that there is a strong dependence of iodine incorporation on bulk chemistry and glass physical properties. A solubility limit of ~5 mol% I has been assessed for B2O3-rich glasses and of ~1 mol% for SiO2-rich ones, and this composition dependence has been explained by considering the fragility parameter of the glass network. Structural variations in the iodine local environment and in the glass network were characterized by Raman, X-ray Absorption Spectroscopy, and 11B NMR. Spectroscopy data point out the coexistence of different I species within the glasses, with iodide being the predominant one, surrounded by Na+ ions.

Iron speciation at the riverbank surface in wetland and potential impact on the mobility of trace metals.

Fe oxyhydroxides in riverbanks and their high binding capacity can be used to hypothesize that riverbanks may act as a "biogeochemical filter" between wetlands and rivers and may constitute a major mechanism in the trapping and flux regulation of chemical elements. Until now, the properties of Fe minerals have been very poorly described in riverbanks. The goals of the present work are to identify Fe speciation in riverbanks where ferric deposits are observed and to determine their impact on the metal behavior (As, Co, Cu, Ni, Pb, Zn, etc.). At the surface, Fe speciation is mainly composed of small poorly crystalline Fe phases, i.e. ferrihydrite (~30%), Fe-OM associations (~40%) as well as crystalline Fe phases, i.e. goethite (~35%). At the subsurface, the Fe distribution is dominated by goethite (~35%) and Fe-mica (~35%), the proportion of which increases at the expense of ferrihydrite and the Fe-OM associations. At the riverbank surface, ferrihydrite and the Fe-OM associations are therefore the main Fe hosting phases in response to (i) the fast Fe(II) oxidation induced by the presence of O2 and (ii) the high amount of OM favoring the formation of nano-phases bound to OM (Fe monomers, polymers and nanoparticles) and preventing mineralogical transformation (ferrihydrite into goethite). During the high-water level period (high flow), a strong erosion of the riverbank transfers these ferric deposits into the river. However, the physicochemical parameters of the river (pH 6.6-7.6 and continuous oxic conditions) do not promote the dissolution of Fe oxyhydroxides and OM. Ferric deposits and the associated trace metals are therefore maintained as colloids/particles and are exported to the outlet. All of the results presented here demonstrate that the ferric deposits trap metals on a seasonal basis and are therefore a key factor in the mobilization of metals during riverbank erosion by river flow.

Influence of soil type on TiO2 nanoparticle fate in an agro-ecosystem.

Nanoparticles (NPs) and in particular TiO2-NPs are increasingly included in commercial goods leading to their accumulation in sewage sludge which is spread on agricultural soils as fertilizers in many countries. Crop plants are thus a very likely point of entry for NPs in the food chain up to humans. So far, soil influence on NP fate has been under-investigated. In this article, we studied the partitioning of TiO2-NPs between soil and soil leachate, their uptake and biotransformation in wheat seedlings and their impact on plant development after exposure on 4 different types of soil with different characteristics: soil texture (from sandy to clayey), soil pH, cationic exchange capacity, organic matter content. Results suggest that a NP contamination occurring on agricultural soils will mainly lead to NP accumulation in soil (increase of Ti concentration up to 302% in sand) but to low to negligible transfer to soil leachate and plant shoot. In our experimental conditions, no sign of acute phytotoxicity has been detected (growth, biomass, chlorophyll content). Clay content above 6% together with organic matter content above 1.5% lead to translocation factor from soil to plant leaves below 2.5% (i.e. below 13mgTi·kg-1 dry leaves). Taken together, our results suggest low risk of crop contamination in an agro-ecosystem.

The LUCIA beamline at SOLEIL.

Commissioned in May 2004 on the SLS machine, the LUCIA beamline was moved to the synchrotron SOLEIL during the summer of 2008. To take advantage of this new setting several changes to its design were introduced. Here, a review of the various improvements of the mechanics and, mostly, of the optics is given. Described in detail are the results of a new multilayer grating monochromator implemented on the Kohzu vessel already holding the two-crystal set-up. It consists of a grating grooved onto a multilayer (replacing the first crystal) associated to a multilayer (as a second crystal). It allows a shift of the low-energy limit of the beamline to around 500 eV with an energy resolution and a photon flux comparable with those of the previous couples of crystals (KTP and beryl).

Combining two structural techniques on the micrometer scale: micro-XAS and micro-Raman spectroscopy.

X-ray absorption and Raman spectroscopies are complementary in the sense that both give very precise information about the local structure of a sample, both are not restricted to crystalline materials, and in both cases the volumes of the material probed are similar. The X-ray technique has the advantage of being element- and orbital-selective, and sensitive to orientational effects owing to polarization selection rules. In many cases, however, its analysis can present some ambiguity. Combining the two techniques on a micrometer scale could therefore be a very powerful method structurally. In this paper the experimental set-up developed at the LUCIA beamline and its application to a natural mineral are described.