Uranium retention in a Callovo-Oxfordian clay rock formation: From laboratory-based models to in natura conditions.

For the performance assessment of radioactive waste disposal, it is critical to predict the mobility of radionuclides in the geological barrier that hosts it. A key challenge consists of assessing the transferability of current knowledge on the retention properties deduced from model systems to in natura situations. The case of the redox-sensitive element uranium in the Callovo-Oxfordian clay formation (COx) is presented herein. Extensive experimental work was carried out with respect to parameters affecting uranium speciation (pH, PCO2, [Ca] and redox potential) with illite, COx clay fraction and raw COx claystone. The "bottom-up" approach implemented, with illite and montmorillonite as reactive phases, quantitatively explains the adsorption results of U(VI) and U(IV) on COx. While retention is high for U(IV) (Rd∼104 L kg-1), it remains very low for U(VI) (Rd∼4 L kg-1) due to the formation of soluble ternary Ca(Mg)-U(VI)-carbonate complexes. The applicability of the sorption model was then assessed by comparing predictive analyses with data characterizing the behavior of naturally-occurring U (<3 mg kg-1). The COx clay phase is the largest reservoir of naturally-occurring U (∼65%) but only a small fraction appears to be adsorbed (∼1%). Under representative site conditions (especially with respect to reducing conditions), we have concluded that ternary U(VI) complexes control U speciation in solution while U(IV) surface species dominate U adsorption, with Rd values > 70 L kg-1.

A multimodal microcharacterisation of trace-element zonation and crystallographic orientation in natural cassiterite by combining cathodoluminescence, EBSD, EPMA and contribution of confocal Raman-in-SEM imaging.

In cassiterite, tin is associated with metals (titanium, niobium, tantalum, indium, tungsten, iron, manganese, mercury). Knowledge of mineral chemistry and trace-element distribution is essential for: the understanding of ore formation, the exploration phase, the feasibility of ore treatment, and disposal/treatment of tailings after the exploitation phase. However, the availability of analytical methods make these characterisations difficult. We present a multitechnical approach to chemical and structural data that includes scanning electron microscopy (SEM)-based imaging and microanalysis techniques such as: secondary and backscattered electrons, cathodoluminescence (CL), electron probe microanalyser (EPMA), electron backscattered diffraction (EBSD) and confocal Raman-imaging integrated in a SEM (RISE). The presented results show the complementarity of the used analytical techniques. SEM, CL, EBSD, EPMA provide information from the interaction of an electron beam with minerals, leading to atomistic information about their composition, whereas RISE, Raman spectroscopy and imaging completes the studies with information about molecular vibrations, which are sensitive to structural modifications of the minerals. The correlation of Raman bands with the presence/absence of Nb, Ta, Fe (heterovalent substitution) and Ti (homovalent substitution) is established at a submicrometric scale. Combination of the different techniques makes it possible to establish a direct link between chemical and crystallographic data of cassiterite.

Characterization of alunite supergroup minerals by Raman spectroscopy.

Raman spectroscopy has been used to study the molecular structure of different natural minerals of the alunite supergroup (AB(3)(XO(4))(2)(OH)(6)), with A=K(+), Na(+), Ca(2+), Sr(2+), Ba(2+), B=Al(3+), Fe(3+) and X=S(6+), P(5+). The influence of the ions, in A-, B- and X-sites, is highlighted in the Raman spectra by variations in the position of certain vibrations and is discussed in association with published crystallographic data in order to describe the observed differences. It was found that A-site substitutions are characterized by wavenumber shifts of the vibrations involving hydroxyl groups. The positions of these vibrational bands vary linearly with the ionic radius of the ions in this site. B-site substitutions induce shifts of all bands due to structural modifications that lead to differences in the chemical environment around the hydroxyl and XO(4) groups and changes in B-O bond lengths. A correlation showed that these shifts correlate well with the ionic radii of the B-ions. The spectra of compounds containing both sulfate and phosphate groups are described by numerous vibration bands caused by a complex elemental composition and a symmetry change of the XO(4) groups. This study has also made it possible to generalize substitution effects on the wavenumbers of several vibrations and show that Raman spectroscopy could be a powerful tool for identifying and distinguishing minerals of the alunite supergroup.

Evidence of laser-wavelength effect in picosecond ultrasonics: possible connection with interband transitions.

We have studied the effect of wavelength change on picosecond acoustic pulses generated using a femtosecond laser. For the first time, we show that the pulse shape can be strongly influenced by the laser wavelength. The results are in excellent agreement with a calculation based on a thermoelastic model which connects them to significant changes in the piezo-optical constants. There are similarities between the present study and stress modulation spectroscopy, which allows us to ascribe the observations to interband transitions and suggests thus a new potentiality of picosecond ultrasonics.

[Psychiatric hospitalizations after the June 27 1990 Law in a French department]. / Les hospitalisations psychiatriques depuis la loi du 27 juin 1990 dans un département français.

The law, edicted on the 27th june 1990, has introduced in France the without consent hospitalization, to replace the law of 30th june 1838 which was composed of confinements or psychiatric placings. On of the both new types of a without consent admission, called "by a third person request" hospitalization (HDT) containing a procedure called "usual" and another one called "situation emergency", appeared to us more and more used in our practice, particularly the "situation emergency" HDT. Therefore we compared on three periods, one before the law, the two others ones 3 and 6 years after it, the different types of psychiatric admissions in all of the seven psychiatric sectors of a french department. All the hospitalization's forms increase with the chronologic time in Côte d'Or. We notice too in this department an important increase of the HDT, but especially in the "situation emergency" ones, and this, with a statistically revealing way compared to the other types of admission. If this phenomena wasn't purely localized, which only the departmental commissions of psychiatric hospitalization, created by the 1990's law, can reveal by proceeding to an expected assessment of the law consequences, the legislator should fastly take this evolution into account.