Speciation Change of Uranyl in Lithium Borate Glasses.

Determining the uranyl(VI) UO22+ reactivity in crystalline and amorphous oxides is necessary to control its mobility. The intrinsic versatility of borate structural units containing both triangular BO3 and tetrahedral BO4 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 % Li2O using a combined structural and spectroscopic approach based on X-ray absorption spectroscopy (XAS). M4- and L3-edge high-resolution XAS demonstrates the speciation of U(VI) as uranyl in both glasses. Comparison of uranyl bond distances obtained by EXAFS with distances found in borate crystals reveals that in the low alkali borate glass, uranyl is present as hexagonal bipyramids with six equatorial oxygen ligands. This local environment was never observed in any other oxide glass. We show that the increase of the lithium content induces the decrease of the equatorial coordination number. The associated uranyl bond elongation suggests the influence of the alkali cations in relation with drastic changes in the structure of the borate network. The spectroscopic evidence of this speciation change is discussed in terms of change in the uranyl electronic structure and covalency.

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 13th century, underwent several restoration works during the 20th 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. We found six distinct colour groups, each containing both medieval and modern glasses, with colouring processes specific to each colour. This illustrates medieval glassmakers' mastering of glass colouring and modern glassmakers' management to reproduce medieval glasses colours. Full UV-visible-NIR energy range is necessary for determining the contribution of colouring elements as Fe2+ and Cu2+. Systematic thickness measurements reveal an average glass thickness of 3 mm and demonstrate the major control of chromophore concentration on glass colour. Yellow, red and purple colours arise from a single chromophore each, suggesting the use of well-defined glassmaking techniques leading to robust colour reproducibility. By contrast, blue and green glasses show different chromophore combinations depending on production time, which suggests more diversity in glassmaking techniques.

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. The migration of uranium and other contaminants depends on (i) the chemical stability of secondary phases and sorbed species (dissolution and desorption processes), and (ii) the mechanical transport of fine particles bearing these elements. Uranium is stabilized after formation of secondary uranyl sulfates and phosphates, and adsorbed complexes on mineral surfaces (e.g. clay minerals). In particular, the stock of insoluble uranyl phosphates increases with time, thus contributing to the long-term stabilization of uranium. At the surface, a sulfate-cemented duricrust is formed after evaporation of pore water. This duricrust limits water infiltration and dust aerial dispersion, though it is enriched in uranium and many other elements, because of pore water rising from underlying levels by capillary action. Satellite images provided a detailed description of the tailings pile over time and allow monitoring of the chronology of successive tailings deposits. Satellite images suggest that uranium anomalies that occur at deep levels in the pile are most likely former surface duricrusts that have been buried under more recent tailings.

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. The spectral resolution enables to observe fine resonances arising in the absorption bands of Cr(3+), and the complementary information obtained in the NIR enables to determine the contribution of Fe(2+), a key indicator of glassmaking conditions.

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. A microthermometric stage has been adapted on the microscope for measuring optical absorption spectra up to 900 K with application to the thermochromism of minute natural spinel crystals (MgAl2O4:Fe(2+),Cr(3+)). This experimental setup provides an easy and fast way to follow the evolution of spectral properties and color of glasses or crystals with temperature as well as the possibility of measuring spatially resolved optical absorption spectra.

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. This comparison indicates that gamma-ray absorption by such geological samples does not cause significant deviations. This work shows the feasibility of using portable HPGe detector in the field as a preliminary method to observe variations of radionuclides concentration with the aim of identifying samples of interest. The HPGe is particularly useful for samples with strong secular disequilibrium such as mill tailings.