Abstract: A flow injection hydride generation graphite furnace atomic absorption spectrometric (FI-HG-GFAAS) method was applied to the determination of Se in Se-doped and undoped cereals and bakery products. For the purpose of doping, the soils used for the cultivation of the cereals were dosed with Se- doped foliar fertilizers. The samples were dissolved in a mixture of HNO(3) and H(2)O(2) solutions using micro-waveassisted digestion. The decomposition of H(2)Se generated from the sample solutions and the trapping of elemental Se were performed at a temperature of 300 degrees C on an Ir-pretreated integrated graphite platform of a transversally heated graphite atomizer(THGA). For release of the trapped Se within a fairly short atomization time (5s), an atomization temperature of 2200 degrees C was observed to be optimal. The overall efficiency of hydride generation, transport and trapping was similar to 86%. The upper limit of the linear dynamic range of calibration was 10 mu gL(-1), which corresponds to 0.5 mu g g(-1) for solid samples. Recovery of the samples spiked with Se(VI) solutions was found to be 93 +/- 6% on average. The relative standard deviation of the determinations was less than 8%. The limit of detection was found to be 0.06 mu gL(-1), corresponding to 3 ng g(-1) for solid samples. The accuracy of the method was verified with the use of IAEA-155 ( whey powder) certified reference material. End-capped THGA tubes resulted in an extension of the linear calibration range compared to that of standard THGAs. The Se content in bakery products made of undoped cereals ranged from 7.7 to 68 ng g(-1) ( wet weight) in 18 samples, whereas the Se content of the corresponding cereals was found to be below 100 ng g(-1) ( wet weight). The Se level of cereals grown on soils treated with Se- doped fertilizers ranged from 128 to 1046 ng g(-1) ( wet weight), and it depended linearly on the Se concentration of the corresponding foliar fertilizer.

Abstract: As part of its conservation-restoration, the 13th century stained-glass panel ‘the Annunciation’, was examined at the micro- and macro level. This window, since 1898 in the collection of the Museum Mayer Van den Bergh (Antwerp, B), was formerly a part of the southern Rose window of the Notre Dame Cathedral (Paris, F). The insigths emerging from a first phase of the analysis, comprising non-invasive analysis techniques such as optical microscopy combined with macroscopic X-ray fluorescence (MA-XRF) and X-ray diffraction (MA-XRPD) mapping, were used to select sampling positions for the second phase of investigation that involved micro-invasive analysis, namely scanning-electron microscopy coupled to energy-dispersive X-ray analysis (SEM-EDX). The aim of the investigation was fourfold: (1) to assess the applicability of MA-XRF scanning for the characterisation of stained glass windows prior to any conservation or restoration procedure, (2) to assess the applicability of MA-XRPD scanning to identify the degradation products formed on the surface of stained glass windows, (3) to establish a method to limit the set of sampled glass fragments taken from a glass panel for quantititive analysis while maintaining sufficient representativeness and (4) to distinguish the original glass panes and grisaille paint from non-original glass panes that were inserted during various past interventions. Most of the panes in this window proved to consist of medieval potash glass, consistent with the 13th c. origin of the window while a limited number of panes were identified as non-original infills, with divergent glass compositional types and/or colorants. Most panes derive their color from the pot metal glass (i.e. homogenously colored) they were made of. Some of the panes that originally had a red flashed layer on their surface, completely or partially lost this layer due to weathering. Three main compositional glass families with similar color could be defined. With the exception of the yellow and orange panes, the chromophoric elements responsible for the dark(er) and light(er) blue (Co), green (Cu), purple (Mn) and red colors (Cu) were identified. Two different grisaille paints were encountered, part of which were restored during the 19th century. On the basis of this information, all missing pieces were replaced by glass panes with appropriate colors and the panel could be successfully conserved to its former glory. On the surface of several panes, typical glass degradation products such as calcite, syngenite and gypsum were identified, together with lead based degradation products such as anglesite and palmierite. In addition, the presence of hematite and melanotekite in the grisailles was observed; also the presence of Zn, uncorrelated to Cu, in the grissailes on the right side of the window became apparent.

Abstract: Shelf sediments of the southern North Sea, were studied with a microanalytical [electron probe X-ray microanalysis (EPXMA)] and two bulk [X-ray diffraction (XRD) and X-ray fluorescence (XRF)] techniques. The investigation proved that the promptness of the microanalytical method is combined with a reasonable analytical reliability. XRD studies of such a type of sediments with monotonous mineral composition are not able to provide mineralogical information beyond the main well-crystalline minerals and the mineralogical quantitative characteristic of the sediment based on XRD estimations are incorrect. The EPXMA mineralogical interpretations are based on the statistical evaluation of a huge data set (thousands of mineral particles) and provide a rather correct quantitative determination of the main minerals. The comparative EPXMAXRF study revealed that the Al, Si, K, Ca, Fe and to some extent Ti contents estimated by EPXMA are fairly reliable. In this respect the accuracy of the EPXMA-based mineral identification of the pure silicates, pure aluminosilicates, and Al-, Ca-, Fe- and Ti-containing minerals with simple composition is very high. Mg-calcite, augite and apatite determinations are assessed to be correct. The supposed accuracy of the clay mineral determinations is slightly lower (7080%) than that of the other main minerals due to the complex and varying composition of the clays. The identification of XRD-invisible accessory minerals and quantification of their presence in the sediments is an essential advantage of the EPXMA, which makes it a useful approach in tracing the origin of the sediments, the pathways of their transport and the geochemical processes they have undergone. However, the EPXMA has several flaws, which need to be solved in the future sediment investigations: (1) calibration with natural standards is needed in order to provide a higher accuracy of the mineral determinations; (2) any EPXMA study of sediments needs to be secured with XRF examinations of selected samples since EPXMA gives only semi-quantitative information about the abundance of the elements; (3) ultra-thin window EPXMA of low-Z elements has to be used since some of them (O, C) are always present in the main sediment components: silicates, aluminosilicates, carbonates and metal oxyhydroxides; (4) the interpretations of the clay fraction have to be supported with detailed XRD investigations of selected samples, while the mineralogy of the silt and sand fractions needs to be backed up with optical microscopy studies. The information from different analytical techniques (EPXMA with XRFXRD-optical microscopy of selected samples) combined with the knowledge about the most possible minerals in a given environment, would give the most reliable results in studying mineralogical composition of shelf sediments.

Abstract: We used SEM/EDX and micro-Raman spectroscopy to investigate the chemical changes (both on the level of elementary and molecular composition) of mice bones when strontium is incorporated in their microstructure after being administered in the form of two salts: chloride and ranelate. Strontium accumulated mainly in vicinity of bone edges, both cortical and close to bone marrow. The distribution of other elements comprising bone samples (Ca, P, Mg, K etc.) was also determined by energy-dispersive X-ray analysis (EDX). The area adjacent to a cortical bone edge with accumulated strontium has presented modified Raman spectral profiles. Besides most of the Raman bands typical for both mineral (hydroxyapatite with carbonate substitution type B) and organic phases of a bone, we observed a Raman band at 811 cm− 1. It was detected regularly in the sample with high strontium concentration.

Abstract: Two sampling campaigns in suburban places in the north zone of Santa Clara city, Cuba, have been carried out on a weekly base with the use of Radiello passive diffusion tubes in order to monitor the tropospheric ozone (O3) levels in 2010. The first campaign was scheduled from February to April (cold season) and the second one in August and October (warm season), both of them at two sampling sites, i.e., Farm and School of Art Instructors. After aqueous extraction, the samples were analyzed by UVVIS spectrophotometry. A seasonal trend was observed with the maximum O3 concentrations in the cold season and the minimum levels in the warm season. Samples collected during the cold season showed the highest O3 levels. Higher levels were reached at the Farm site with average values of about 58 ± 12 μg/m3, which exceeded the limit of the Cuban Standard 99:1999. In the warm season, the O3 concentrations were similar for both sites, but lower than those observed in the cold season. The overall, seasonal average value was found to be 24 μg/m3. Despite the higher weekly average temperatures in August, the O3 concentrations during this month showed the lowest values of the whole sampling period, which finding is in agreement with that reported by the Meteorological Institute of Cuba. Mathematical models, based on the Cochrane-Orcutt algorithm, were fitted to the acquired data set to explain the change in the tropospheric ozone concentrations under various meteorological conditions during the two campaigns. The correlation coefficients for both the cold and the warm seasons demonstrated a strong correlation, i.e., 0.779 and 0.951, respectively. The high correlation of wind speed in the model from the first sampling campaign explains the sharp decrease in O3 concentrations at the SAI sampling site from the sixth week of sampling.

Abstract: Most of the marine precipitation of CaCO3 is due to the biological activities of planktonic and benthic organisms in waters largely oversaturated with respect to calcium carbonates. This saturation state is expected to decrease as CO2 increases in seawater. A conventional view in oceanography suggests that calcium carbonates organisms are preserved in oversaturated waters and dissolve only below the lysocline. However, it has be postulated that a fraction of the CaCO3 precipitated biogenically could dissolve in oversaturated waters due to the formation of microenvironments in which respired CO2 decreases the saturation state of seawater (Ù) in the vicinity of CaCO3 crystals. In the present study, cells of the coccolithophore Emiliania huxleyi obtained from laboratory cultures and field samples collected in the Gulf of Biscay, were examined using variable-energy electron-probe microanalysis, to determine the presence and thickness of their organic coating. In addition, a new approach for transferring micrometer-sized particles from a filter onto transmission electron microscope grids using manipulators was used to investigate individual coccolithophores. The dry thickness of an organic coating over the coccolithophore surface was found to range between 280 and 350 nm. The resemblance of this coating to the carbohydrates produced and released by the cell is discussed as well as their potential for constituting a microenvironment that hosts bacteria. The properties of this organic coating and its role in the preservation/dissolution and export of biogenic carbonates in the water column are one of the major issues of carbonate geochemistry.

Abstract: Increasingmass tourismcan generate importantmicroclimatic perturbations and also elevate indoor pollution by the transport of fine particulatematter. The purpose of this researchwas to study the indoor air conditions in the RoyalMuseum ofWawel Castle in Cracow, Poland, displaying amongst other valuable works of art also a unique collection of Flemish tapestries. The investigation involved in the determination of transport and deposition of particulate matter brought in by visitors. The microclimate inside the exhibition rooms was also monitored. Samples of suspended particulateswere collected inside and outside themuseuminwinterand summer2006.On days with intensive tourist visits the concentration of total suspended particulates was significantly higher (i.e., 130 µg/m3 inwinter and 49 µg/m3 in summer) than on those days without tourists (i.e., 73 µg/m3 and 22 µg/m3 in winter and summer, respectively). The concentrations of all investigated elementswere also considerably higher during the tourist flow. This was especially valid for soil dust associated elements (Si, K, Ca, Al, and Ti), with considerably higher levels in summer than winter. This could be linked with much more frequent tourist activity in the summer period. Also, the concentration of Clwasmuch higher inwinter than summer, due to the use of deicing salts on the roads and pavements.

Abstract: The application of micro-Raman spectroscopy is discussed for the analysis of structural features of human tooth tissues affected by high doses of external ionizing radiation (0.51.7 Gy) after the nuclear plant catastrophe in Chernobyl in 1986. The results have shown significant changes in the mineral matrix of dental enamel that lead to the decrease of tooth enamel hardness. Destruction of the collagen chain of the organic matrix has been observed for dentin and cementum.

Abstract: A highly sensitive and portable electrochemical sensor based on molecularly imprinted nanoparticles (nanoMIPs) was developed. NanoMIPs were computationally designed for specific recognition of amphetamine, and then synthetized using solid phase synthesis. NanoMIPs were immobilized onto screen-printed carbon electrodes using a composite film comprising chitosan, nanoMIPs, and graphene oxide.Ferrocenylmethyl methacrylate was incorporated in nanoMIPs allowing electrochemical detection. The signal recorded for the electrochemical oxidation of ferrocene has proven to be dependent on the presence of amphetamine interacting with nanMIPs. The sensor was tested successfully with street samples, with high sensitivity and satisfactory recoveries (from 100.9% to 107.6%). These results were validated with UPL-MS/MS. The present technology is suitable for forensic applications in selective determination of amphetamine in street samples.

Abstract: The increasing illicit production, distribution and abuse of amphetamine (AMP) poses a challenge for law enforcement worldwide. To effectively combat this issue, fast and portable tools for the on-site screening of suspicious samples are required. Electrochemical profile (EP)-based sensing of illicit drugs has proven to be a viable option for this purpose as it allows rapid voltammetric measurements via the use of disposable and low-cost graphite screen-printed electrodes (SPEs). In this work, a highly practical paraformaldehyde (PFA)-coated sensor, which unlocks the detectability of primary amines through derivatization, is developed for the on-site detection of AMP in seized drug samples. A potential interval was defined at the sole AMP peak (which is used for identification of the target analyte) to account for potential shifts due to fluctuations in concentration and temperature, which are relevant factors for on-site use. Importantly, it was found that AMP detection was not hindered by the presence of common diluents and adulterants such as caffeine, even when present in high amounts. When inter-drug differentiation is desired, a simultaneous second test with the same solution on an unmodified electrode is introduced to provide the required additional electrochemical information. Finally, the concept was validated by analyzing 30 seized AMP samples (reaching a sensitivity of 96.7 %) and comparing its performance to that of commercially available Raman and Fourier Transform Infrared (FTIR) devices.

Abstract: Old master drawings and historic prints often feature white highlights, which are typically painted using lead white, one of the most widely used historical white pigments. However, it has been observed that many of these highlights discolour over time, becoming dark brown or black due to unclear degradation processes. This phenomenon not only misrepresents the original artefacts, threatening their suitability for public display, but also diminishes their longevity. To ensure their preservation, it is essential to determine why some lead white highlights in these museum objects retain their light tones while others are prone to darkening. The objective of this study was to identify the relationships between the composition, provenance, and production methods of lead white pigments, and their role in the discolouration observed on drawings, lithographs and early photographs. Selected samples and artefacts were examined using a range of analytical techniques, namely X-ray fluorescence spectroscopy (XRF), X-ray powder diffraction (XRPD), and lead isotope analysis. While XRF analyses confirmed the presence of lead as the primary element in the majority of the highlights, XRPD measurements identified a variety of lead compounds such as the carbonates cerussite and hydrocerussite alongside galena-a black crystalline sulfide-and lead sulfates. Additionally, isotope analyses classified the lead raw materials into five main groups. Through these measurements, the examined lead white pigments were categorised based on their compositional properties in relation to the raw materials used, as well as their geographical and temporal origin. A significant finding is that lead white pigments from different production periods, spanning from older to more modern, may be characterised by varying proneness to discolouration irrespective of their provenance.