Abstract: This study shows the first Raman microscopy (RM) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) characterization of two 14th and 15th century lead-glazed and luster ceramics from the Manises and Paterna workshops (Valencia, Spain) produced after the Aragon Christian conquest of the Iberian Peninsula (14th century). According to experts, these coetaneous ceramics were most probably involved in a process of technological transfer from the Islamic area of Southeast Spain to the Christian area of Valencia (East Spain) at the beginning of the 14th century; later on, the celebrated Manises and Paterna workshops were formed. Although these ceramics have been studied widely in terms of production technology (ceramic body, glazes and luster) using an array of diverse analytical techniques, until now, an RM study has not been carried out. This paper presents results regarding the complex chemical composition of the glaze and luster coloring agents, and the quality of color manufacturing processes, elucidating firing conditions via spectral components analysis (i.e., Q(n) for stretching/bending components) and polymerization index (Ip), emphasizing chronology and pigment technology changes between both Valencian workshops. Coloring agents identified in glazes and lusters were cobalt present in blue glazes, copper in greenish glazes, copper and cobalt in the turquoise glaze, and pyrolusite in black glazes. Tin oxyde was used as an opacifier in white glazes. Two luster manufacture recipes were recognized mainly based on copper and silver compounds. Calculated firing temperatures were up to 1000 degrees C for white glazes and up to 600 degrees C for luster and color glazes. Copyright (c) 2015 John Wiley & Sons, Ltd.

Abstract: Serum bromine levels in psoriatic Danes increased 2- to 3-fold during a 4-week bathing course in the Dead Sea. This increase correlated well with the improvement in their clinical and psychic condition. Serum bromine levels in psoriatic Danes were somewhat lower than those in healthy subjects residing in Denmark, but the difference was not significant. Israelis working in the open air in the Dead Sea area (air bromine 20-fold higher than in Jerusalem) had higher bromine levels than psoriatic or healthy Israelis residing in Jerusalem or healthy Israelis working in air-conditioned rooms in the Dead Sea area (p < 0.05), but those levels were still within the normal range. As our animal experimentation indicates that the skin is a major target organ for 82Br, applied either by bathing or as an aerosol, we conclude that the higher bromine levels noticed in the psoriatic Danes after their 4-week stay at the Dead Sea may be equally due to their contact with the bromine-containing aerosol and the high bromine level of the Dead Sea waters.

Abstract: Penetration of electrolytes through the human skin was measured in healthy volunteers and in psoriatic patients after bathing in the Dead-Sea or in simulated bath-salt solutions. Significant increases in the levels of serum Br, Rb, Ca and Zn were noticed only in the psoriatic patients after daily bathing in the Dead-Sea for a 4-week regimen. Guinea-pigs bathed in simulated Dead-Sea bath-salt solutions containing radionuclides of Ca, Mg, K and Br. Traces of each radionuclide were detected in the blood and in some internal organs after 60 minutes of bathing. The radionuclides showed a physiological pattern in their organ distribution. Even though the whole investigation was carried out in hypertonic solutions, there is a definite penetration of salts through healthy (human and guinea-pigs) and damaged (psoriatic) epidermis. This finding suggests that improvement of the psoriatic condition after bathing in the Dead-Sea, may be partly attributed (in addition to ultraviolet irradiation) to the minerals' effect on the psoriatic skin.

Abstract: Accuracy and precision of silicon determination in biological matrices (serum, urine, water, beer and spinach) by spectrometric techniques (when necessary after acid destruction) were assessed by means of a collaborative interlaboratory trial. The trial was set up in accordance with ISO 5725-2 (1994). The relative overall repeatability standard deviation was acceptable. It varied between 4% for spinach powder (mean content: 176 mg kg(-1)) and 11% for serum (mean content: 5.33 mg L-1). On the other hand, the relative overall between-laboratory standard deviation was found to vary from a satisfactorily 15% for spinach after destruction (mean content: 3.32 mg L-1) to an unacceptable 107% for spinach powder (mean content: 176 mg kg(-1)). The overall conclusion of the trial was that silicon determination in biological matrices can properly be performed by spectrometric techniques. However, when sample pretreatment (i.e., acid destruction) is needed prior to silicon determination problems still remain.

Abstract: Cellulose powder with 2,2′-diaminodiethylamine (DEN) functional groups exhibits efficient complexation of transition metal cations. Collection yields above 85 % are obtained up to a chelation capacity of 1.5 meq per gram. Since a good collection is obtained for a pH up from 5, no pH adjustments have to be made for natural water samples. The cellulose-DEN powder is insensitive to abundant substances like alkali and alkaline earth ions, and humic matter. Some cations can be eluted efficiently in a small volume of HNO3. Blank concentration levels from the cellulose-DEN powder are reported.

Abstract: Particulate matter with an aerodynamic diameter below 2.5 μm (PM2.5), present in polluted air, has been associated with a large spectrum of health impairments, mainly because of its deep deposition into the lungs. Araraquara City (Southeast Brazil) is surrounded by sugar-cane plantations, which are burned to facilitate the harvesting; this process causes environmental pollution due to the large amounts of soot that are released into the atmosphere. In this work, the elemental composition of PM2.5 was studied in two scenarios, namely in sugar-cane harvesting (HV) and in non-harvesting (NHV) seasons. The sampling strategy included one campaign in each season. PM2.5 was collected using a dichotomous sampler (10 L·min-1, 24 h) with PTFE filters. Information concerning the bulk elemental concentration was provided by energy-dispersive X-ray fluorescence. Enrichment factor analysis indicated that S, Cl, K, Cr, Ni, Cu, Zn, As, Cd and Pb were highly enriched relative to their crustal ratios (to Al). Principal component analysis was used to get some insight about the sources of the elements. Principal component 1 (PC1) explained 30.5% of data variance. The elements that had high loading (>0.7) were: S, Cr, As, and Pb; these are associated with combustion of fossil fuels. In principal component 2 (PC2), Cl, Cu, Zn, and Cd showed high loadings; these elements are associated with biomass burning. The Ni concentration found is three times larger than the threshold of risk for lung cancer, as recommended by the World Health Organization.

Abstract: Erythrocyte selenium-dependent glutathione peroxidase activity was measured in psoriatic Danes, before and after their four-week balneological therapy at the Ein-Bokek International Psoriasis Treatment Center, on the Dead-Sea shore in Israel. The drinking water in Ein-Bokek was found to be rich in selenium, a trace element with anticarcinogenic properties and of great importance in human nutrition and health. The most reliable biological parameter for increase in selenium bioavailability is the erythrocytes' glutathione-peroxidase activity. As psoriasis is a proliferative skin disease, the activity of this enzyme was assayed in 35 psoriatic Danes and in 25 long-term local hotel workers, as well as in 34 volunteers drinking low-selenium water. The glutathione peroxidase activity in the psoriatic patients increased significantly during their four-week stay in Ein-Bokek. Erythrocyte glutathione peroxidase activity in the hotel workers was 50% higher than that in the healthy volunteers consuming low-selenium water. A possible role of selenium in psoriasis is suggested.

Abstract: The zirconium/hafnium ratios of zircons are determined using proton induced X-ray emission. Submilligram samples, imbedded in a starch layer and deposited on a 50 μg/cm2 polystyrene carrier, are irradiated for 1020 min with a 5 nA beam of 3.7 MeV protons, while the Hf-Lβ and Zr-Kα X-rays are counted with a Si(Li) detector. The standard deviation per analysis is in the 36 % range. Only few interferences are possible. To eliminate errors due to absorption effects the zircon layer thickness should be above 40 μm or reproducibly thin samples should be employed. Measuring the Hf-Lβ/Hf-Lα ratio for samples and standards might provide a practical check for the absence of absorption errors. The sensitivity is so favourable that, in practice, the minimal sample size is only limited by the minimal amount that can be handled properly.

Abstract: The penetration of aerosol particles in a Whatman-41 cellulose filter has been studied via the depth profiles of different elements present in the aerosol. Depth profiles were obtained by analyzing both fine and coarse fractions from a dichotomous sampler by secondary ion mass spectrometry. The fine particles had an aerodynamic diameter dae of less than 2.5 μm, whereas the coarse fraction had 2.5 ≤ dae ≤ 15 μm. Elements such as Al, Si, Ca, Ti and Fe were associated with coarse airborne particles, while S, Cl, Zn, and Br were more abundant in the fine fraction. Results showed that particle size plays an important role in the distribution of particulate matter throughout the filter. SiTi-containing particles were mostly deposited near the surface of the filter, and their profiles can be estimated using a polynomial function, whereas the profile of AlCaFe-containing particles can be approached by an exponential decay function. Elements associated with fine fraction aerosols mainly originating from combustion processes, can penetrate up to about 25% of the total filter thickness, and their profiles are better represented by a diffusion function.