Olivier Proux

Forms of Zinc Accumulated in the Hyperaccumulator Arabidopsis halleri

The chemical forms of zinc (Zn) in the Zn-tolerant and hyperaccumulator Arabidopsis halleri and in the non-tolerant and nonaccumulator Arabidopsis lyrata subsp. petraea were determined at the molecular level by combining chemical analyses, extended x-ray absorption spectroscopy (EXAFS), synchrotron-based x-ray microfluorescence, and μEXAFS. Plants were grown in hydroponics with various Zn concentrations, and A. halleri specimens growing naturally in a contaminated site were also collected. Zn speciation in A. halleri was independent of the origin of the plants (contaminated or non-contaminated) and Zn exposure. In aerial parts, Zn was predominantly octahedrally coordinated and complexed to malate. A secondary organic species was identified in the bases of the trichomes, which contained elevated Zn concentrations, and in which Zn was tetrahedrally coordinated and complexed to carboxyl and/or hydroxyl functional groups. This species was detected thanks to the good resolution and sensitivity of synchrotron-based x-ray microfluorescence and μEXAFS. In the roots of A. halleri grown in hydroponics, Zn phosphate was the only species detected, and is believed to result from chemical precipitation on the root surface. In the roots of A. halleri grown on the contaminated soil, Zn was distributed in Zn malate, Zn citrate, and Zn phosphate. Zn phosphate was present in both the roots and aerial part of A. lyrata subsp. petraea. This study illustrates the complementarity of bulk and spatially resolved techniques, allowing the identification of: (a) the predominant chemical forms of the metal, and (b) the minor forms present in particular cells, both types of information being essential for a better understanding of the bioaccumulation processes.

CeO2 nanoparticles induce DNA damage towards human dermal fibroblasts in vitro

Cerium dioxide nanoparticles have been proposed for an increasing number of applications in biomedicine, cosmetic, as polishing materials and also as byproducts from automotive fuel additives. The aim of this study was to examine the potential in vitro cyto- and genotoxicity of nano-sized CeO2 (7 nm) on human dermal fibroblasts. By combining a physico-chemical and a (geno)toxicological approach, we defined the causal mechanisms linking the physico-chemical properties of nano-CeO2 with their biological effects. Using X-ray absorption spectroscopy, we observed a reduction of 21±4% of the Ce4+ atoms localized at the surface of CeO2 nanoparticles due to the interactions with organic molecules present in biological media. These particles induced strong DNA lesions and chromosome damage related to an oxidative stress. These genotoxic effects occurred at very low doses, which highlighted the importance of a genotoxicological approach during the assessment of the toxicity of nanoparticles.

Feedback system of a liquid-nitrogen-cooled double-crystal monochromator: design and performances

A new set-up is reported of an indirect cryogenic cooling system for a double-crystal monochromator which runs on the BM30b/FAME beamline at the ESRF (Grenoble, France). This device has been conceived to limit the vibrations on the first diffracting crystal and to maintain it at a constant temperature. These points are crucial for maximizing the beamline stability. Moreover, the relative angular position of the second crystal can be dynamically adjusted by a piezoelectric transducer coupled with a feedback system in order to always be at the maximum of the rocking curve during an X-ray absorption spectroscopy scan. The temperature is stabilized to an accuracy of 0.01 degrees , with two principal consequences. The energy resolution is close to the theoretical value [DeltaE/E = 5.6 x 10(-6) for Si(220)] and the precision of the energy positioning is extremely good even if the power load changes. A feedback mechanism allows a permanent and automatic optimization of the angle between the two crystals of the monochromator. The intensity of the monochromatic beam remains optimized (i) when the intensity of the electron beam decreases in the storage ring and (ii) during an energy scan.

Changes in arsenic speciation through a contaminated soil profile: A XAS based study

An impacted soil located near an industrial waste site in the Massif Central near Auzon, France, where arsenical pesticides were manufactured, has been studied in order to determine the speciation (chemical forms) of arsenic as a function of soil depth. Bulk As concentrations range from 8780 mg kg(-1) in the topsoil horizon to 150 mg kg(-1) at 60 cm depth. As ores (orpiment As2S3, realgar AsS, arsenopyrite FeAsS) and former Pb- and Al-arsenate pesticides have been identified by XRD at the site and are suspected to be the sources of As contamination for this soil. As speciation was found to vary with depth, based on XRD, SEM-EDS, EPMA measurements and selective chemical extractions. Based on oxalate extraction, As is mainly associated with amorphous Fe oxides through the soil profile, except in the topsoil horizons where As is hosted by another phase. SEM-EDS and EPMA analyses led to the identification of arseniosiderite (Ca2Fe3+3(AsVO4)3O2.3H2O), a secondary mineral that forms upon oxidation of primary As-bearing minerals like arsenopyrite, in these topsoil horizons. These mineralogical and chemical results were confirmed by synchrotron-based X-ray absorption spectroscopy. XANES spectra of soil samples indicate that As occurs exclusively as As(V), and EXAFS results yield direct evidence of changes in As speciation with depth. Linear combination fits of EXAFS spectra of soil samples with those of various model compounds indicate that As occurs mainly As-bearing Fe(III)-(hydr)oxides (65%) and arseniosiderite (35%) in the topsoil horizon (0-5 cm depth). Similar analyses also revealed that there is very little arseniosiderite below 15 cm depth and that As(V) is associated primarily with amorphous Fe oxides below this depth. This vertical change of As speciation likely reflects a series of chemical reactions downward in the soil profile. Arseniosiderite, formed most likely by oxidation of arsenopyrite, is progressively dissolved and replaced by less soluble As-bearing poorly ordered Fe oxides, which are the main hosts for As in well aerated soils.

Evidence for the presence of U–Mo–Al ternary compounds in the U–Mo/Al interaction layer grown by thermal annealing: a coupled micro X-ray diffraction and micro X-ray absorption spectroscopy study

The systematic presence of the ternary phases U6Mo4Al43 and UMo2Al20 is reported in a U–Mo/Al interaction layer grown by thermal annealing. This work shows, therefore, the low Mo solubility in UAl3 and UAl4 binary phases; it contradicts the hypothesis of the formation of (U,Mo)Al3 and (U,Mo)Al4 solid solutions often admitted in the literature. Using µ-XAS (micro X-ray absorption spectroscopy) at the Mo K edge and µ-XRD (micro X-ray diffraction), the heterogeneity of the interaction layer obtained on a γ-U0.85Mo0.15/Al diffusion couple has been precisely investigated. The UMo2Al20 phase has been identified at the closest location from the Al side. Moreover, µ-XRD mapping performed on an annealed fuel plate enabled the characterization of the four phases resulting from the γ-U0.85Mo0.15/Al and (U2Mo + α-U)/Al interactions. A strong correlation between the concentrations of UAl4 and UMo2Al20 and those of UAl3 and U6Mo4Al43 has been shown.

High-resolution spectroscopy on an X-ray absorption beamline

A bent-crystal spectrometer based on the Rowland circle geometry has been installed and tested on the BM30b/FAME beamline at the European Synchrotron Radiation Facility to improve its performances. The energy resolution of the spectrometer allows different kinds of measurements to be performed, including X-ray absorption spectroscopy, resonant inelastic X-ray scattering and X-ray Raman scattering experiments. The simplicity of the experimental device makes it easily implemented on a classical X-ray absorption beamline. This improvement in the fluorescence detection is of particular importance when the probed element is embedded in a complex and/or heavy matrix, for example in environmental sciences.

Arsenic speciation in fluid inclusions using micro-beam X-ray absorption spectroscopy

Abstract Synchrotron radiation X-ray fluorescence (SR-XRF) was used to characterize As speciation within natural fluid inclusions from three deposits with different hydrogeochemical and geological settings. The studied samples represent different compositions of Au-bearing fluids: typical orogenic Au deposit (low-salinity, ~6 mol% CO2 ± CH4; Brusson, Western Italian Alps); brines from a Proterozoic (Fe)- Cu-Au deposit (Starra, Queensland, Australia); and an As-rich magmatic fluid with a bulk composition similar to that typical of orogenic gold (Muiane pegmatite, Mozambique). Arsenic K-edge X-ray absorption spectra (XAS) were obtained from fluid inclusions at temperatures ranging from 25 to 200°C, and compared with spectra of aqueous As(III) and As(V) solutions and minerals. X-ray absorption near edge structure (XANES) data show that initially the fluid inclusions from all three regions contain some As in reduced form [As(III) at Brusson and Muiane; As-sulfide or possibly As(0) at Starra]. However, this reduced As is readily oxidized under the beam to As(V). Therefore, extended X-ray absorption fine structure (EXAFS) spectra for the As(III) aqueous complex could be collected only on the sample from the Muiane pegmatite containing large fluid inclusions with high As concentrations (>>1000 ppm). Analysis of these EXAFS data shows that As(OH)3(aq) (coordination number of 3.0 ± 0.2 atoms, bond length of 1.76 ± 0.01 Å) is the dominant arsenic aqueous species in the Muiane fluid inclusions at 100 °C, in accordance with predictions based on studies conducted using autoclaves. The As(V) complex resulting from photooxidation in the Muiane inclusions was characterized at 200 °C; the As-O bond distance (1.711 ± 0.025 Å) corresponds to that found in the arsenate group in minerals, and to that measured for the (HAsO4)2- complex at room temperature (1.700 ± 0.023 Å). The extent of the XAS information that could be obtained for As in this study was limited by the rapid photooxidation that occurred in all inclusions, despite the relatively low photon flux density used (~4.4 × 106 photons/s/μm2). Photosensitivity was not observed in autoclave experiments and is the result of a complex interaction between redox-sensitive complexes in solution and the products of water radiolysis generated by the beam. Even under such challenging experimental conditions, the information gathered provides some precious information about As chemistry in ore-forming fluids

Long-term aging of a CeO2 based nanocomposite used for wood protection

A multi-scale methodology was used to characterize the long-term behavior and chemical stability of a CeO2-based nanocomposite used as UV filter in wood stains. ATR-FTIR and (13)C NMR demonstrated that the citrate coated chelates with Ce(IV) through its central carboxyl- and its α-hydroxyl- groups at the surface of the unaged nanocomposite. After 42 days under artificial daylight, the citrate completely disappeared and small amount of degradation products remained attached to the surface even after 112 days. Moreover, the release/desorption of the citrate layer led to a surface reorganization of the nano-sized CeO2 core observed by XANES (Ce L3-edge). Such a surface and structural transformation of the commercialized nanocomposite could have implications in term of fate, transport, and potential impacts towards the environment.

Superparamagnetic iron oxide nanoparticles as novel X-ray enhancer for low-dose radiation therapy.

Superparamagnetic iron oxide nanoparticles (SPIONs) with a mixed phase composition (γ-Fe2O3)(1-x)(Fe3O4)x and sizes between 9 and 20 nm were synthesized via coprecipitation and were either left uncoated or subsequently surface-stabilized with citrate or malate anions. The sizes, morphology, surface chemistry, and magnetic properties of the nanoparticles were characterized using transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, and superconducting quantum interference device measurements, respectively. Cellular uptake and intracellular distribution in normal tissue and tumor cells were verified by TEM images. X-ray-induced changes of the oxidation state and site geometries of surface iron ions of uncoated and citrate-coated SPIONs were explored by collecting Fe K-edge X-ray absorption spectroscopy data. The potential applicability of citrate- and malate-coated SPIONs as an X-ray enhancer for radiation cancer therapy was substantiated by their drastic enhancement of the concentration of reactive oxygen species (ROS) in X-ray irradiated tumor cells.

Zn impacts Cu coordination to amyloid-β, the Alzheimer's peptide, but not the ROS production and the associated cell toxicity

Combined coordination of Zn(II) and Cu(I) or Cu(II) to the amyloid-β peptide has been investigated using XANES, EPR and NMR spectroscopies. While Zn(II) does alter Cu(II) binding to Aβ, this has no effect on (Aβ)Cu induced ROS production and associated cell toxicity.