Speciation Change of Uranyl in Lithium Borate Glasses.

Determining the uranyl(VI) UO reactivity in crystalline and amorphous oxides is necessary to control its mobility. The intrinsic versatility of borate structural units containing both triangular BO and tetrahedral BO makes them original and rich hosts for uranyl. As part of the effort to determine the uranium stability in borate oxides, we have determined the speciation of uranium(VI) in two lithium borate glasses containing, respectively, 10 mol % and 30 mol % LiO using a combined structural and spectroscopic approach based on X-ray absorption spectroscopy (XAS).

The Grande Rose of the Reims Cathedral: an eight-century perspective on the colour management of medieval stained glass.

The Grande Rose of Reims Cathedral (France), a UNESCO Cultural Heritage Monument from the 13 century, underwent several restoration works during the 20 century. Its colours result from centuries of colour management from which little information remain. We used non-destructive and portable optical absorption spectroscopy to quantify glass colour and determine the colouring species on a large-scale study of this monumental window.

Influence of crystallographic environment on scandium K-edge X-ray absorption near-edge structure spectra.

The absence of an extensive series of Sc K-edge X-ray absorption near-edge structure spectroscopy (XANES) reference spectra and the scarcity of direct structural data on Sc are major hurdles to develop our understanding of Sc chemistry. However, this first step is essential to develop new Sc-based applications and to better understand the formation of Sc deposits. Here, we present a detailed comparative study of Sc K-edge XANES spectra of three Sc-bearing compounds: a garnet (CaScSiO), an oxide (ScO) and a phosphate (ScPO·2HO).

Nondestructive Redox Quantification Reveals Glassmaking of Rare French Gothic Stained Glasses.

The sophisticated colors of medieval glasses arise from their transition metal (TM) impurities and capture information about ancient glassmaking techniques. Beyond the glass chemical composition, the TM redox is also a key factor in the glass color, but its quantification without any sampling is a challenge. We report a combination of nondestructive and noninvasive quantitative analyses of the chemical composition by particle-induced X-ray emission-particle-induced γ-ray emission mappings and of the color and TM element speciation by optical absorption spectroscopy performed on a red-blue-purple striped glass from the stained glass windows of the Sainte-Chapelle in Paris, France, during its restoration.

Assessment of Transition Element Speciation in Glasses Using a Portable Transmission Ultraviolet-Visible-Near-Infrared (UV-Vis-NIR) Spectrometer.

A new low-cost experimental setup based on two compact dispersive optical spectrometers has been developed to measure optical absorption transmission spectra over the 350-2500 nm energy range. We demonstrate how near-infrared (NIR) data are essential to identify the coloring species in addition to ultraviolet visible data. After calibration with reference glasses, the use of an original sample stage that maintains the window panel in the vertical position enables the comparison of ancient and modern glasses embedded in a panel from the Sainte-Chapelle of Paris, without any sampling.

Evolution of uranium distribution and speciation in mill tailings, COMINAK Mine, Niger.

This study investigated the evolution of uranium distribution and speciation in mill tailings from the COMINAK mine (Niger), in production since 1978. A multi-scale approach was used, which combined high resolution remote sensing imagery, ICP-MS bulk rock analyses, powder X-ray diffraction, Scanning Electron Microscopy, Focused Ion Beam--Transmission Electron Microscopy and X-ray Absorption Near Edge Spectroscopy. Mineralogical analyses showed that some ore minerals, including residual uraninite and coffinite, undergo alteration and dissolution during tailings storage.

Optical Absorption Microspectroscopy (μ-OAS) Based on Schwarzschild-Type Cassegrain Optics.

A new experimental setup, combining a custom-designed Schwarzschild-type Cassegrain-based microscope and an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer, has been developed, focusing the light beam down to 20 μm diameter. Optical absorption spectra (in the 300-2500 nm range) have been measured on micrometer-sized natural glass inclusions providing information on iron speciation in magmatic melts. The absence of contribution from the host crystal matrix provides a test of the efficiency of micro-focusing.

Field analyses of (238)U and (226)Ra in two uranium mill tailings piles from Niger using portable HPGe detector.

The radioactivities of (238)U and (226)Ra in mill tailings from the U mines of COMINAK and SOMAÏR in Niger were measured and quantified using a portable High-Purity Germanium (HPGe) detector. The (238)U and (226)Ra activities were measured under field conditions on drilling cores with 600s measurements and without any sample preparation. Field results were compared with those obtained by Inductive Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) and emanometry techniques.

Uranium association with iron-bearing phases in mill tailings from Gunnar, Canada.

The speciation of uranium was studied in the mill tailings of the Gunnar uranium mine (Saskatchewan, Canada), which operated in the 1950s and 1960s. The nature, quantification, and spatial distribution of uranium-bearing phases were investigated by chemical and mineralogical analyses, fission track mapping, electron microscopy, and X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies at the U LIII-edge and Fe K-edge. In addition to uranium-containing phases from the ore, uranium is mostly associated with iron-bearing minerals in all tailing sites.

Distinctive arsenic(V) trapping modes by magnetite nanoparticles induced by different sorption processes.

Arsenic sorption onto iron oxide spinels such as magnetite may contribute to arsenic immobilization at redox fronts in soils, sediments, and aquifers, as well as in putative remediation and water treatment technologies. We have investigated As(V) speciation resulting from different sorption processes on magnetite nanoparticles, including both adsorption and precipitation, using X-ray absorption fine structure (XAFS) spectroscopy and transmission electron microscopy (TEM). XAFS results suggest that AsO(4) tetrahedra form predominantly inner-sphere bidentate corner-sharing ((2)C) complexes and outer-sphere complexes on magnetite in the adsorption experiments.

XANES evidence for rapid arsenic(III) oxidation at magnetite and ferrihydrite surfaces by dissolved O(2) via Fe(2+)-mediated reactions.

To reduce the adverse effects of arsenic on humans, various technologies are used to remove arsenic from groundwater, most relying on As adsorption on Fe-(oxyhydr)oxides and concomitant oxidation of As(III) by dissolved O(2). This reaction can be catalyzed by microbial activity or by strongly oxidizing radical species known to form upon oxidation of Fe(II) by dissolved O(2). Such catalyzed oxidation reactions have been invoked to explain the enhanced kinetics of As(III) oxidation in aerated water, in the presence of zerovalent iron or dissolved Fe(II).

Evidence for different surface speciation of arsenite and arsenate on green rust: an EXAFS and XANES study.

The knowledge of arsenic speciation at the surface of green rusts (GRs), [Fe(II)((1-x))Fe(III)(x) (OH)(2)](x+) (CO(3), Cl, SO(4))(x-), is environmentally relevant because arsenic sorption onto GRs could contribute to arsenic retention in anoxic environments (hydromorphic soils, marine sediments, etc.). The nature of arsenic adsorption complexes on hydroxychloride green rust 1 (GR1Cl) at near-neutral pH under anoxic conditions was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at the As K-edge.

Radiation-stability of smectite.

The safety assessment of geological repositories for high-level nuclear waste and spent nuclear fuel requires an understanding of the response of materials to high temperatures and intense radiation fields. Clays, such as smectite, have been proposed as backfill material around waste packages, but their response to intense radiation from short-lived fission products and alpha decay of sorbed actinides remains poorly understood. Cumulative doses may amorphize clays and may alter their properties of sorption, swelling, or water retention.

Boroxol Rings in Liquid and Vitreous B2O3 from First Principles.

We investigate the structural and vibrational properties of glassy B2O3 using first-principles molecular dynamics simulations. In particular, we determine the boroxol rings fraction f for which there is still no consensus in the literature. Two numerical models containing either a low or a high level of boroxol rings are tested against a gamut of experimental probes (static structure factor, Raman, 11B and 17O NMR data).

Extended X-ray absorption fine structure analysis of arsenite and arsenate adsorption on maghemite.

Arsenic sorption onto maghemite potentially contributes to arsenic retention in magnetite-based arsenic removal processes because maghemite is the most common oxidation product of magnetite and may form a coating on magnetite surfaces. Such a sorption reaction could also favor arsenic immobilization at redox boundaries in groundwaters. The nature of arsenic adsorption complexes on maghemite particles, at near-neutral pH under anoxic conditions, was investigated using X-ray absorption fine structure (XAFS) spectroscopy at the As K-edge.

EXAFS analysis of arsenite adsorption onto two-line ferrihydrite, hematite, goethite, and lepidocrocite.

The modes of As(III) sorption onto two-line ferrihydrite (Fh), hematite (Hm), goethite (Gt), and lepidocrocite (Lp) have been investigated under anoxic condition using X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure spectroscopy (XANES) indicates that the absence of oxygen minimized As(III) oxidation due to Fenton reactions. Extended X-ray absorption fine structure spectroscopy (EXAFS) indicates thatAs(III)forms similar inner-sphere surface complexes on two-line ferrihydrite and hematite that differ from those formed on goethite and lepidocrocite.

Bacterial formation of tooeleite and mixed arsenic(III) or arsenic(V)-iron(III) gels in the Carnoulès acid mine drainage, France. A XANES, XRD, and SEM study.

The oxidation of Fe(II) in acid mine drainage (AMD) leads to the precipitation of Fe(III) compounds which may incorporate toxic elements, such as arsenic (As), within their structure or adsorb them at their surface, thus limiting their mobility. The present work provides evidence for spatial and seasonal variations of microbial activity that influence arsenite oxidation and As immobilization in the heavily contaminated AMD from the Carnoulès mine, Gard, France ([As III] = 80 to 280 mg x L(-1) in the acidic spring draining the waste-pile). In the first tens of meters of the AMD, the rapid oxidation of Fe(II) leads to the coprecipitation of large amounts of As with Fe(III) in bacterial mats.