Localization and chemical forms of cadmium in plant samples by combining analytical electron microscopy and X-ray spectromicroscopy

International audienceCadmium (Cd) is a metal of high toxicity for plants. Resolving its distribution and speciation in plants is essential for understanding the mechanisms involved in Cd tolerance, trafficking and accumulation. The model plant Arabidopsis thaliana was exposed to cadmium under controlled conditions. Elemental distributions in the roots and in the leaves were determined using scanning electron microscopy coupled with energy dispersive X-ray microanalysis (SEM-EDX), and synchrotron-based micro X-ray fluorescence (μ-XRF), which offers a better sensitivity. The chemical form(s) of cadmium was investigated using Cd LIII-edge (3538 eV) micro X-ray absorption near edge structure (μ-XANES) spectroscopy. Plant μ-XANES spectra were fitted by linear combination of Cd reference spectra. Biological sample preparation and conditioning is a critical point because of possible artifacts. In this work we compared freeze-dried samples analyzed at ambient temperature and frozen hydrated samples analyzed at −170 °C. Our results suggest that in the roots Cd is localized in vascular bundles, and coordinated to S ligands. In the leaves, trichomes (epidermal hairs) represent the main compartment of Cd accumulation. In these specialized cells, μ-XANES results show that the majority of Cd is bound to O/N ligands likely provided by the cell wall, and a minor fraction could be bound to S-containing ligands. No significant difference in Cd speciation was observed between freeze-dried and frozen hydrated samples. This work illustrates the interest and the sensitivity of Cd LIII-edge XANES spectroscopy, which is applied here for the first time to plant samples. Combining μ-XRF and Cd LIII-edge μ-XANES spectroscopy offers promising tools to study Cd storage and trafficking mechanisms in plants and other biological samples

Ni-Mn-Ga films in the austenite and the martensite structures at room temperature: Uniaxial texturation and epitaxial growth

Ni-Mn-Ga films in the austenite and the martensite structures at room temperature have been obtained using the DC magnetron sputtering technique. Two elaboration processes were studied. A first batch of samples was deposited using a resist sacrificial layer in order to release the film from the substrate before vacuum annealing. This process leads to polycrystalline films with a strong (022) fiber texture. The martensitic phase transformation of such polycrystalline freestanding films has been studied by optical and scanning electron microscopy. A second batch of samples was grown epitaxially on (100)MgO substrates using different deposition temperatures. The texture has been analyzed with four-circle X-ray diffraction. Epitaxial films crystallized both in the austenite and the martensite structures at room temperature have been studied

Martensite structures and twinning in substrate-constrained epitaxial Ni-Mn-Ga films deposited by a magnetron co-sputtering process

In order to obtain Ni-Mn-Ga epitaxial films crystallized in martensite structures showing Magnetic-Induced Rearrangement (MIR) of martensite variants, a fine control of the composition is required. Here we present how the co-sputtering process might be helpful in the development of Ni-Mn-Ga epitaxial films. A batch of epitaxial Ni-Mn-Ga films deposited by co-sputtering of a Ni-Mn-Ga ternary target and a pure manganese target has been studied. The co-sputtering process allows a precise control of the film compositions and enables keeping the epitaxial growth of Ni-Mn-Ga austenite during deposition at high temperature. It gives rise to tune the content of the MIR-active 14-modulated martensite in the film at room temperature, as well as micro and macro-twinned domains sizes

Metallic coatings of MEMS at low temperatures: stress, elasticity and non-linear dissipation

International audienceWe present mechanical measurements performed at low temperatures on cantilever-based microelectro-mechanicalstructures(MEMS) coated with a metallic layer. Two very different coatings are presented in order to illustrate the capabilities of the present approach, namely (soft) aluminum and (hard) niobium oxide. The temperature is used as a control parameter to access materials properties. We benefit from low temperature techniques to extract a phase-resolved measurement of the first mechanical resonance mode in cryogenic vacuum. By repeating the experiment on the same samples, after multiple metallic depositions, we can determine accurately the contribution of the coating layers to the mechanical properties in terms of surface stress, additional mass, additional elasticity and damping. Analytic theoretical expressions are derived and used to fit the data. Taking advantage of the extremely broad dynamic range provided by the technique, we can measure the anelasticity of the thin metallic film. The key parameters describing the metals' dynamics are analyzed in an original way in order to provide new experimental grounds for future theoretical modelings of the underlying mechanisms

Tuning macro-twinned domain sizes and the b-variants content of the adaptive 14-modulated martensite in epitaxial Ni-Mn-Ga films by co-sputtering

In order to obtain modulated-martensite in our epitaxial Ni-Mn-Ga films, we have tuned the composition by using a co-sputtering process. Here we present how the composition affects the variant distribution of the 14-modulated martensite at room temperature. The nature of such modulated-martensites is still strongly debated for magnetic shape memory alloys. It has been very recently demonstrated that the modulated-martensites in Ni-Mn-Ga are adaptive phases. The results presented here corroborate this theory for the first time, for three different compositions. Moreover, we demonstrate with the help of the adaptive modulations theory that b-variants of the 14-modulated martensite form close to the free-surface of the film to release the stress induced by branching of macro-twinned domains during the martensitic transformation on a rigid substrate. At room temperature, the content of such b-variants is found to strongly decrease when the macro-twinned domain sizes increase

Fabrication and characterization of a Ni-Mn-Ga uniaxially textured freestanding film deposited by DC magnetron sputtering

Homogeneous freestanding films have been obtained by the direct current (DC) magnetron sputtering technique using a sacrificial layer. After annealing, the films are crystallized with a strong out-of-plane texture along the (022) direction. The stoichiometry of the annealed films is close to the target composition and leads to a martensitic transformation around 255K. The annealed films demonstrate ferromagnetic behavior with a Curie temperature of about 362K. The magnetization process has been studied on the both states and during the martensitic transition. The saturation magnetizations have been determined by fitting the experimental data with a saturation approach law in the range 1-5T. Results show the saturation magnetization of the martensite is around 10% higher than that of the austenite. A model based on intrinsic magnetic properties of each state allowing the description of the magnetization M=f (H, T) of such polycrystalline films during the martensitic transformation is presented. The mass fraction of martensite inside the austenite phase can be determined using this model. The shape memory effect is analyzed both by scanning electron microscopy and by optical microscopy with in-situ measurement of the resistance temperature dependence

Light in the cave: Opal coating detection by UV-light illumination and fluorescence in a rock art context

The formation of silica coatings on the cave walls of the Points cave raises questions about the analytical access to the specificities of the pictorial material (geochemistry and petrography); and about the state of conservation of the rock art. Conventional in situ spectroscopic techniques (pXRF, pRaman) are ineffective to identify and characterize these coatings. In this study, we propose to use a UV fluorescence method for the detection and recognition of opaline coatings, based on the fluorescence specificities of the uranyl-silica complexes composing these deposits. Spectral identification using UV laser-induced fluorescence spectroscopy coupled with UV illumination was performed on samples, µ-samples and on the walls of the Grotte aux Points rock art site. The well-defined peaks observed in the fluorescence emission spectra due to uranyl ions validate the detection of the complex opal-uranyl and its correspondence with the green fluorescence observed under UV light at micro and macroscopic scales. In situ optical measurements under UV illumination reveal the presence of an opal layer, in particular on the rock art walls of the cave. Observations on the occurrence and distribution of opal provide the first insights into the evolution of the walls and the chronological constraints on the development of the opal layer. regarding the interactions between the silica coating and the pigment suggested by the multi-scale observations of the µ-samples, it opens the question of rock art conservation. Thus, by developing a specific method of non-destructive characterization of opal coatings, this study starts a new approach for the study of the taphonomy of decorated walls and proposes to use siliceous mineralization both as a marker of the natural history of caves and as an index of their use by ancient human groups

Template-growth of periodically domain-structured KTiOPO4

International audienceWe performed the first growth, from a high temperature solution, of a 38.86 μm-periodicity PPKTP crystal of good optical quality over a thickness of more than 800 μm onto each of the two faces perpendicular to the c direction of a PPKTP substrate previously obtained by electric field poling. The quasi-phase matched second harmonic generation properties in the grown layer and substrate are similar and in accordance with calculation

Zinc distribution and speciation in Arabidopsis halleri x Arabidopsis lyrata progenies presenting various zinc accumulation capacities

The definitive version is available at http://www.blackwell-synergy.com/loi/nphInternational audienceThe purpose of this study was to investigate the relationship between the chemical form and localization of zinc (Zn) in plant leaves and their Zn accumulation capacity. * An interspecific cross between Arabidopsis halleri sp. halleri and Arabidopsis lyrata sp. petrea segregating for Zn accumulation was used. Zinc (Zn) speciation and Zn distribution in the leaves of the parent plants and of selected F1 and F2 progenies were investigated by spectroscopic and microscopic techniques and chemical analyses. * A correlation was observed between the proportion of Zn being in octahedral coordination complexed to organic acids and free in solution (Zn-OAs + Znaq) and Zn content in the leaves. This pool varied between 40% and 80% of total leaf Zn depending on the plant studied. Elemental mapping of the leaves revealed different Zn partitioning between the veins and the leaf tissue. The vein : tissue fluorescence ratio was negatively correlated with Zn accumulation. * The higher proportion of Zn-OAs + Znaq and the depletion of the veins in the stronger accumulators are attributed to a higher xylem unloading and vacuolar sequestration in the leaf cells. Elemental distributions in the trichomes were also investigated, and results support the role of carboxyl and ⁄ or hydroxyl groups as major Zn ligands in these cells