Abstract: Stained glass windows incorporating dark blue and purple enamel paint layers are in some cases subject to severe degradation while others from the same period survived the ravages of time. A series of dark blue, greenblue and purple enamel glass paints from the same region (Northwestern Europe) and from the same period (16early 20th centuries) has been studied by means of a combination of microscopic X-ray fluorescence analysis, electron probe micro analysis and transmission electron microscopy with the aim of better understanding the causes of the degradation. The chemical composition of the enamels diverges from the average chemical composition of window glass. Some of the compositions appear to be unstable, for example those with a high concentration of K2O and a low content of CaO and PbO. In other cases, the deterioration of the paint layers was caused by the less than optimal vitrification of the enamel during the firing process. Recipes and chemical compositions indicate that glassmakers of the 1617th century had full control over the color of the enamel glass paints they made. They mainly used three types of coloring agents, based on Co (dark blue), Mn (purple) and Cu (light-blue or greenblue) as coloring elements. Bluepurple enamel paints were obtained by mixing two different coloring agents. The coloring agent for redpurple enamel, introduced during the 19th century, was colloidal gold embedded in grains of lead glass.

Abstract: Sensitive multi-element analysis techniques together with major-element and isotopic analyses were applied to spring, mine and surface waters in the vicinity of an important known zinclead deposit in a carbonate environment, in the Les Malines area (Gard, France). Both the dissolved and suspended phases were investigated, and concretions and sediments were also considered in some cases. This methodological test shows that the ore body leaves various clear fingerprints, such as the Zn, As, Sb, Pb and U levels in the dissolved phase, the sulfate increment and the δ 34S. Some of the elements in solution are controlled by slightly soluble compounds, e.g. Zn by smithsonite and hydrozincite, Ba by barite, and Pb by hydrocerussite. Mapping the saturation indices for these elements appears useful for displaying the hydrogeochemical anomaly.

Abstract: Non-destructive 14-MeV neutron activation analysis for silicon in steel has been applied with 56Mn as internal standard.56Mn is formed from the iron matrix via the 56Fe(n,p)56Mn reaction. Several methods of internal standardisation via56Mn are discussed. The 0.84-MeV photopeak of 56Mn is recommended if steel samples of about the same composition are to be analysed. Chemically analysed steel samples are used as silicon standards. A precision of 0.7% was obtained for an analysis plus standardisation time of 13 min. Special attention was paid to interferences produced by concentration changes of impurity elements. Several possible sources of errors were investigated.

Abstract: Urban atmospheres in modern cities carry characteristic mixtures of particulate pollution which are potentially aggravating for chronic respiratory patients (CRP). Although air quality surveys can be detailed, the obtained information is not always useful to evaluate human health effects. This paper presents a novel approach to estimate particle deposition rates in airways of CRP, based on real air pollution data. By combining computational fluid dynamics with physical-chemical characteristics of particulate pollution, deposition rates are estimated for particles of different toxicological relevance, that is, minerals, iron oxides, sea salts, ammonium salts, and carbonaceous particles. Also, it enables some qualitative evaluation of the spatial, temporal, and patient specific effects on the particle dose upon exposure to the urban atmosphere. Results show how heavy traffic conditions increases the deposition of anthropogenic particles in the trachea and lungs of respiratory patients (here, +0.28 and +1.5 μg·h1, respectively). In addition, local and synoptic meteorological conditions were found to have a strong effect on the overall dose. However, the pathology and age of the patient was found to be more crucial, with highest deposition rates for toxic particles in adults with a mild anomaly, followed by mild asthmatic children and adults with severe respiratory dysfunctions (7, 5, and 3 μg·h1, respectively).

Abstract: Sensitive multi‐element analytical techniques were applied to determine 24 dissolved trace components in 25 different water samples from a 10 km2 zone in Brittany, France. Correspondence factor and multiple regression analyses showed that the elements considered are influenced mainly by the presence of: Fe‐Mn oxide accumulations, a local poly‐metallic sulfide mineralization, and non‐mineralized host rocks, agricultural activity and abundant organic material in local swamps. Via these numerical techniques the location of the poly‐metallic ore body can be derived from the data set.

Abstract: A general standardization method is described for the determination of oxygen in solid samples via the 16O(n,p)16N reaction. Two systems of flux monitoring are considered: the sample versus standard comparator method and BF3 monitoring. The average flux in sample and standard, fast neutron shielding, fast neutron scattering, absorption of fast neutrons, absorption of 16N γ-rays and counting efficiency of sample and standard are considered. The influence of the target diameter on the obtained correction factors has also been studied. Total achievable accuracy is believed to be about 1%.

Abstract: Sensitive multi-element analysis techniques were applied to water samples collected in the vicinity of a small Zn-Pb-Cu sulfide mineralization in the region of Menez-Albot (Finistère, France). The variation of the trace-element content along a local stream shows the presence of the mineralization, mainly through a simultaneous positive anomaly in solution for a group of about 10 elements (e.g. Ni, Cu, Zn, As, Sb) which are connected with this type of mineralization. The anomaly decreases steeply due to the influx of swamp water rich in Fe, Mn and organic matter. The precipitation barrier is reflected in the stream sediment composition. Contamination from fertilizers was observed in some samples.

Abstract: Chrome yellow refers to a group of synthetic inorganic pigments that became popular as an artists material from the second quarter of the 19th century. The color of the pigment, in which the chromate ion acts as a chromophore, is related to its chemical composition (PbCr1-xSxO4, with 0≤x≤0.8) and crystalline structure (monoclinic/orthorhombic). Their shades range from the yellow-orange to the paler yellow tones with increasing sulfate amount. These pigments show remarkable signs of degradation after limited time periods. Pure PbCrO4 (crocoite in its natural form) has a deep yellow color and is relatively stable, while the co-precipitate with lead sulfate (PbCr1-xSxO4) has a paler shade and seems to degrade faster. This degradation is assumed to be related to the reduction of Cr(VI) to Cr(III). We show that on increasing the sulfur(S)-content in chrome yellow, the band gap increases. Typically, when increasing the band gap, one might assume that a decrease in photo activity is the result. However, the photo activity relative to the Cr content, and thus Cr reduction, of sulfur-rich PbCr1-xSxO4 is found to be much higher compared to the sulfur-poor or non-doped lead chromates. This discrepancy can be explained by the evolution of the crystal and electronic structure as function of the sulfur content: first-principles density functional theory calculations show that both the absorption coefficient and reflection coefficients of the lead chromates change as a result of the sulfate doping in such a way that the generation of electron-hole pairs under illumination relative to the total Cr content increases. These changes in the material properties explain why paler shade yellow colors of this pigment are more prone to discoloration. The electronic structure calculations also demonstrate that lead chromate and its co-precipitates are p-type semiconductors, which explains the observed reduction reaction. As understanding this phenomenon is valuable in the field of cultural heritage, this study is the first joint action of photo-electrochemical measurements and first-principles calculations to approve the higher tendency of sulfur-rich lead chromates to darken.