Abstract: Spatially resolved X-ray absorption and fluorescence investigation with a micrometer-scale resolution on actinide-containing samples provide information necessary for safety assessment of nuclear waste disposal. In this paper one example of such an experiment is presented. This example entails neptunium speciation in a fractured granite bore core from the Swedish Äspö Hard Rock Laboratory following a radiotracer experiment using µ-XAFS and µ-XRF. In order to probe micro-volumes below the surface in the granite samples and thereby avoid potential changes in the Np speciation during cutting of the bore core, a confocal irradiationdetection geometry is employed. µ-XAFS results for a selected granite bore core cross section with ~ 3 nmol Np/g reveal that Np, originally introduced as Np(V) in the tracer cocktail, is present in the granite in its reduced Np(IV) form. The Np(IV) is often present as particles, tens of µm in size. Elemental distribution maps show the tracer Np to be located in fissures and permeable channels not larger than 100 µm. The Np distribution appears often correlated with Zn also present in some fissures. We observe small granite fissures containing Fe (presumably Fe(II)), where we do not detect any Np. It is feasible that inflowing Np(V) has a shorter residence time in large fractures, while in the smaller fissures migration is slower, leading to longer residence times, i.e., reaction times, where it is reduced to less soluble Np(IV) and becomes thereby immobilized.

Abstract: As swipe samples from enrichment activities typically contain uranium particles with a detectable amount of fluorine, the question was raised whether the analysis of fluorine in particles could complement the information on the uranium isotope ratios. For this, uranium oxyfluoride particles were prepared from the controlled hydrolysis of uranium hexafluoride (UF6). The relative amount of fluorine was characterized by scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDX), as well as ion-microprobe secondary ion mass spectrometry (IM-SIMS). Of particular interest was the assessment of the reduction of the amount of fluorine over time, and after exposure to UV-light and high temperatures. Micro-Raman spectrometry (MRS) was applied to look for differences in molecular structure between these various sample types. Both SEM-EDX and IM-SIMS showed a general reduction of the fluorine-to-uranium ratio after 12 years of storage. The exposure to UV-light and high temperatures was found to have accelerated the loss of fluorine. A distinct peak at 865 cm− 1 Raman shift was detected for the majority of particles analyzed by MRS. For the particles that were heat-treated, the Raman spectra were similar to the spectrum of U3O8. Although often large variations were observed between particles from the same sample, the three particle measurement techniques (IM-SIMS, SEM-EDX and MRS) showed some consistent trends. They therefore appear promising in terms of the ability to place bounds on particle age, as well as shedding light on the complex processes involved in UO2F2 particle ageing.

Abstract: Indoor and outdoor concentrations of atmospheric gaseous pollutants as well as composition, size, and morphology of particulate matter have been investigated at the monastery of San Jerónimo in Granada (Southern Spain). Complementary micro- and nano-analytical techniques were applied; elemental and mineralogical composition and morphological characteristics of particulate matter were investigated combining electron probe microanalysis at the single particle level, and bulk aerosol samples were analyzed using energy-dispersive X-ray fluorescence, X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray analyzer and transmission electron microscopy (TEM). Microclimatic conditions at the monastery were monitored, and gas concentrations were assessed by means of diffusion tubes subsequently analyzed with ion chromatography. Results revealed high abundances of soil dust particles (aluminosilicates, calcite, dolomite, quartz), salt aerosols (chlorides, sulfates and ammonium-rich salts), and NO2 and SO2 both outdoors and indoors. Amorphous black carbon particles had surprisingly high abundances for Granada, a non-industrialized city. The composition of indoor particles corresponds to severe weathering affecting the construction materials and artworks inside the church; moreover their composition promotes a feedback process that intensifies the deterioration. Chemical reactions between chloride-rich salts and pigments from paintings were confirmed by TEM analyses. Indoors, blackening of surface decorative materials is fostered by particle re-suspension due to cleaning habits in the monastery (i.e. dusting). This is the first air quality study performed in a monument in the city of Granada with the aim of developing a strategy for preventive conservation.

Abstract: The origin(s) and role(s) of metal soaps in paints are a worldwide concern today. These hybrid compounds, containing both fatty acid chains and metals associated with a carboxylate function, are increasingly identified in paints. As reviewed in the first part of this work, the presence of metal soaps in paints is differently interpreted in scientific publications: metal soaps are sometimes considered to play a positive role as anchor points, during paint drying processes; they can also be considered as responsible for many degradation processes (protrusions, efflorescences, darkening, etc.). Their origins are also interpreted in various ways. In some paintings (in particular from the twentieth century), they have sometimes introduced on purpose, as additives, to modify the physical properties of the painting materials. In older paintings, metal soaps are usually thought to result from an uncontrolled reaction of oil with lead-based pigments, in particular lead white, red lead, and lead tin yellow. In the second part of this work, the review of historical recipes of lead-based paint shows an important number of recipes based on controlled mixing of oil with lead driers. In the third part, the experimental reproduction of such traditional recipes using walnut oil and litharge (PbO) shows that lead soaps can be formed, both in about one hour at approximate to 100 degrees C, or in about one month at room temperature. It shows as well that after a few years, litharge is no longer detected in the paint medium, while different lead carbonates are. Finally, the micro-infrared spectroscopy and micro-X-ray diffraction re-analysis of protrusions from a nine-year model painting shows together with lead soaps, the presence of Pb-5(CO3)(3)(OH)(2)O ('synthetic plumbonacrite'), an unusual phase recently observed in a protrusion from a painting by Vincent Van Gogh. This work highlights (i) the multiple origins and roles of metal soaps in paints and (ii) the importance of combining the analysis of fragments from historical paintings with the analysis and reproduction of historical recipes. In particular, we show that the components detected today in historical paintings may severely differ from those originally used or prepared by the painter, complicating the assessment of the painter's intentions. More than the presence of metal soaps, the key questions to be tackled should be about their origins and (re)mobilization.

Abstract: The chemical composition, as determined by electron probe X-ray microanalysis of a series of ca. 100 archaeological glass fragments, excavated at the Raversijde site (Belgium) is discussed. In the 15th-16th century, Raversijde was a flourishing fishermen town located on the shore of the North Sea, close to the city of Ostend. As a consequence of several battles that were fought in its vicinity, the site was abandoned in the 16th century and was not occupied since then. It is one of the rare archaeological sites in Europe that contains a significant amount of information on the daily life inside a small but affluent medieval community. A comparison of the chemical composition of fragments of vessels and window glass encountered in Raversijde to those found in urban centres in Belgium and to literature date on German and French archaeological finds shows that glass made with wood ash dominates. Usually, it concerns artifacts with a predominantly utilitarian use. A few objects made with sodic (i.e., Na-rich) glass were also encountered, likely to have been imported from Venice during the 15th century or in later periods from an urban centre such as Antwerp, where Facon-de-Venice glass manufacturing activities were established near the start of the 16th century. (C) 2004 Elsevier B.V. All rights reserved.