Modifications structurales et défauts ponctuels paramagnétiques induits par irradiation électronique externe de la hollandite Ba1.16Al2.32Ti5.68O16

Des matrices BaxCsy (M,Ti)8O16 (x+y<2, M cation trivalent) de type hollandite, sont envisagées pour confiner spécifiquement le césium radioactif. Afin de simuler l'effet des rayonnements b, les modifications structurales et les défauts ponctuels paramagnétiques produits par irradiation électronique externe à température proche de l'ambiante d'une hollandite de composition simplifiée sans césium Ba1,16Al2,32Ti5,68O16 ont été étudiés par RPE et RMN. Des modifications ont été observées au niveau de l'environnement des cations Al3+ et Ti4+, résultant de la formation de lacunes d'oxygène et d'une augmentation du désordre dans les tunnels associée à des déplacements d'ions baryum. Des centres à électrons (Ti3+) et à trous électroniques (O2-) ont été observés. Ceux-ci sont relativement stables à température ambiante mais des recuits (traitements isochrones entre 50 et 800°C, traitements isothermes à 300°C) engendrent la formation d'autres défauts issus des défauts précédents correspondant à des ions Ti3+ de surface de type titanyl et des agrégats d'oxygène

Effet de la nature des ions alcalins et alcalino-terreux sur la structure d'un verre riche en terre

Dans le cadre d'une étude structurale d'un verre de confinement de déchets nucléaires de type aluminoborosilicate et riche en terres rares, l'influence de la nature des ions alcalins ou alcalino-terreux est analysée. Pour cela deux séries de verres ont été élaborées dans lesquelles l'ion Na+ (respectivement l'ion Ca2+) présent dans la composition de référence, est totalement substitué par un autre ion alcalin Li+, K+, Rb+ ou Cs+ (respectivement un autre ion alcalino-terreux Mg2+, Sr2+ ou Ba2+). Ces verres, analysés par spectroscopie d'absorption optique, Raman et RMN 27Al et 11B, ont permis de montrer le fort impact de la nature de l'ion modificateur aussi bien sur la structure du réseau vitreux ( variation du rapport BO3/BO4 et variations locales du degré de polymérisation) que de l'environnement local de la terre rare (diminution du degré de covalence de la liaison Nd-O avec l'augmentation de la force de champ de l'ion modificateur)

Interlayer Magnetic Frustration in Quasi-stoichiometric Li1-xNi1+xO2

Susceptibility, high-field magnetization and submillimeter wave electron spin resonance measurements of layered quasi-stoichiometric Li1-xNi1+xO2 are reported and compared to isomorphic NaNiO2. A new mechanism of magnetic frustration induced by the excess Ni ions always present in the Li layers is proposed. We finally comment on the possible realization of an orbital liquid state in this controversial compound.Comment: 4 pages, 5 figures, submitted to Phys.Rev.B, Rapid Com

Combined Quantitative X-ray Diffraction, Scanning Electron Microscopy, and Transmission Electron Microscopy Investigations of Crystal Evolution in CaO–Al2O3–SiO2–TiO2–ZrO2–Nd2O3–Na2O System

Glass-ceramics, with a specific crystalline phase assembly, can combine the advantages of glass and ceramic and avoid their disadvantages. In this study, both cubic-zirconia and zirconolite-based glass-ceramics were obtained by the crystallization of SiO2-CaO-Al2O3-TiO2-ZrO2-Nd2O3-Na2O glass. Results show that all samples underwent a phase transformation from cubic-zirconia to zirconolite when crystallized at 900, 950, and 1000 °C. The size of the cubic-zirconia crystal could be controlled by temperature and dwelling time. Both cubic-zirconia and zirconolite crystals/particles show dendrite shapes, but with different dendrite branching. The dendrite cubic-zirconia showed highly oriented growth. Scanning electron microscopy images show that the branches of the cubic-zirconia crystal had a snowflake-like appearance, while those in zirconolite were composed of many individual crystals. Rietveld quantitative analysis revealed that the maximum amount of zirconolite was ∼19 wt %. A two-stage crystallization method was used to obtain different microstructures of zirconolite-based glass-ceramic. The amount of zirconolite remained approximately 19 wt %, but the individual crystals were smaller and more homogeneously dispersed in the dendrite structure than those obtained from one-stage crystallization. This process-control feature can result in different sizes and morphologies of cubic-zirconia and zirconolite crystals to facilitate the design of glass-ceramic waste forms for nuclear wastes

Biotransfer possibilities of selenium from plants used in phytoremediation

We are investigating the biotransfer of accumulated Se by the plant in several phytoremediation systems. In study I, we evaluated the biotransfer of Se from Indian mustard, a Brassica species, to the insect-cabbage looper (Trichoplusia ni); mortality, deterrence, and biomagnification of Se were examined. We determined that feeding behavior of food chain consumers was affected not only by the plant concentration of Se, but also by the mobility of the insects and choice of feed available. In study II, we examined the survival and development of beet armyworm (Spodoptera exigua) fed Se-enriched plant tissues from different lines of saltbush (Atriplex spp.) After feeding on lines of saltbush that produced high biomass and accumulated high concentrations of Se, insect growth and survival was reduced. In studies III, IV, and V, lambs, dairy cows, and rabbits were fed Se-enriched Brassica and Medicago (alfalfa) plants as part of their feed ration. None of the tested animals exhibited any Se toxicity symptoms, but they had increased levels of Se in most tissues sampled (e.g., organs, blood, urine, feces), excluding milk. In study VI, we evaluated biotransfer of Se from broccoli to rats to determine efficacy of Se for reducing colon cancer. We found that Se-enriched plant material was more effective than inorganic sources of Se for preventing precancerous colon lesions. Results from all studies clearly show that Se absorbed by plants can be transferred biologically in an intentional or unintentional manner to insects and animals

Hormonal signaling in cnidarians : do we understand the pathways well enough to know whether they are being disrupted?

Author Posting. © The Author, 2006. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Ecotoxicology 16 (2007): 5-13, doi:10.1007/s10646-006-0121-1.Cnidarians occupy a key evolutionary position as basal metazoans and are ecologically important as predators, prey and structure-builders. Bioregulatory molecules (e.g., amines, peptides and steroids) have been identified in cnidarians, but cnidarian signaling pathways remain poorly characterized. Cnidarians, especially hydras, are regularly used in toxicity testing, but few studies have used cnidarians in explicit testing for signal disruption. Sublethal endpoints developed in cnidarians include budding, regeneration, gametogenesis, mucus production and larval metamorphosis. Cnidarian genomic databases, microarrays and other molecular tools are increasingly facilitating mechanistic investigation of signaling pathways and signal disruption. Elucidation of cnidarian signaling processes in a comparative context can provide insight into the evolution and diversification of metazoan bioregulation. Characterizing signaling and signal disruption in cnidarians may also provide unique opportunities for evaluating risk to valuable marine resources, such as coral reefs