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: Various bulk and surface analytical techniques were used to study the chemical deterioration of the 13th-to-15th century limestone cathedral in Mechelen, Belgium. The weathering crust on the walls was found to be rich in sulfate, regardless of the geographic orientation. Nitrate and chloride were only detected in minor amounts in the crust and run-off samples. Attack by gaseous sulfur compounds seems to play a dominant role in the stone deterioration mechanism. Electron microprobe analysis showed predominantly bar-shaped gypsum crystals in the crust, and laser microprobe mass spectrometry showed that carbon seems to be responsible for the blackness of most crust samples. Automated electron microprobe analysis also indicated significant differences in the analytical composition of suspensions in run-off water and in rain-water.

Abstract: Using Laser Microprobe Mass Analysis (LAMMA), we studied the chemical composition of lead-induced intranuclear inclusions in rat kidney tissue prepared by three different wet chemical fixation procedures for transmission electron microscopy. Fixation with glutaraldehyde-Na2S gave the same results as fixation with glutaraldehyde only: a high lead concentration could be detected. Therefore, for lead strongly bound to proteins, precipitation procedures are not essential. Post-fixation with osmium tetroxide drastically changed the composition of the inclusions: the lead concentration decreased substantially, while sodium, calcium, and barium were introduced. The osmium tetroxide fixative was found to be the source of the contamination. It also contained aluminum, and we suggest that other proteins (e.g., in neurofibrillary tangles) might be able to take up Al out of solution and that care must be exercised in interpreting the microanalytical results of osmium-fixed material. For the microanalysis of the lead inclusions, fixation with glutaraldehyde only provides a good compromise between preservation of the ultrastructure and maintenance of the element distribution.

Abstract: Uranyl fluoride particles produced via hydrolysis of uranium hexafluoride have been deposited on different substrates: polished graphite disks, silver foil, stainless steel and gold-coated silicon wafer, and measured with micro-Raman spectroscopy (MRS). All three metallic substrates enhanced the Raman signal delivered by UO2F2 in comparison to graphite. The fundamental stretching of the UO band appeared at 867 cm−1 in case of the graphite substrate, while in case of the others it was shifted to lower frequencies (down to 839 cm−1). All applied metallic substrates showed the expected effect of Raman signal enhancement; however the gold layer appeared to be most effective. Application of new substrates provides more information on the molecular structure of uranyl fluoride precipitation, which is interesting for nuclear safeguards and nuclear environmental analysis.

Abstract: Two groundwater-fed river systems (Nete and Demer, Belgium) carry red suspended material that settles on the river bed forming red sediments. The local aquifer that feeds these river systems is a glauconite-rich sand, which provides most of the dissolved Fe to the rivers. The solid component of these systems, i.e., the red suspended material and sediments, has a simple mineralogy (predominantly ferrihydrite), but shows a complex geochemistry pointing out the different processes contributing to the river chemistry: (1) the red sediments have higher transition metal (excluding Cu) and detrital element (e.g., Si, Al, K, Rb, etc.) concentrations than the red suspended matter because of their longer residence time in the river and higher contribution of the background (aquifer) component, respectively; (2) the red suspended material and sediments have inherited their rare earth element (REE) patterns from the aquifer; (3) the origin of Sr present in the red suspended matter and red sediments is predominantly marine (i.e., Quaternary calcareous rocks), but a small amount is geogenic (i.e., from detrital rocks); (4) Pb in both solids originates mostly from anthropogenic and geogenic sources; (5) all of the anthropogenic Pb in the red suspended material and sediments is hosted by the ferrihydrite; (6) Nd budget of the red riverine samples is controlled by the geogenic source and shows little anthropogenic component; (7) the significant Fe- and Zn-isotope fractionations are in line with the previous studies. Their fractionation patterns do not correlate, suggesting that the processes controlling the isotope geochemistry of Fe and Zn are different: oxidation/reduction most likely governs the Fe-isotope fractionation, whereas adsorption/desorption or admixing of anthropogenic sources controls the isotope fractionation of Zn.

Abstract: Triammonium aurin tricarboxylate (aluminon) has been used to localize aluminum in 2 μm sections of undecalcified, methyl methacrylate embedded bone obtained from patients with terminal chronic renal failure. Aluminum appeared in four cases as bright red lines at the mineralized-bone boundary. In two cases, however, purplish lines were found and one patient showed red as well as purplish lines. Laser microprobe mass analysis (LAMMA) identified aluminum at the location of the red lines and both aluminum and iron at the purplish lines. Furthermore, both iron and aluminum were found in histiocytic bone marrow cells, which showed brownish aluminon staining. It appears that when aluminum and iron occur together, aluminon staining may yield aberrant results. This study shows that LAMMA can be used for the identification of elements sought by histochemical methods and thus permits the evaluation of their staining effects.

Abstract: Trace elements can influence dental health, possibly by altering tooth resistance during preeruptive development. Therefore, it was investigated whether lead and fluoride would be incorporated into the calcifying matrices or the cellular parts of tooth germs in vitro. Using laser microprobe mass analysis, the localization of lead and fluoride was studied in the different layers or tooth germs that had been cultured in a medium to which PbCl2 of NaF had been added in different concentrations. Both elements could only be detected in the dentine layer. Hence, the enamel organ in the secretory stage of tooth development excludes lead and fluoride from the enamel, even when enamel formation by the ameloblasts is visibly disturbed. Furthermore, there seemed to be a process of saturation in the accumulation of lead and fluoride in the dentine.

Abstract: Through different research projects on air quality in museums, researcher and conservators try identifying various risks of air pollution on materials. The conclusions may be later translated into specific actions for a maximum preservation of the museum collections, a process known as preventive conservation. Air pollution is a particular problem in historical buildings such as museums, because they were not originally built to exhibit and protect art objects in a sustainable way. This article reports on the data and results that were obtained during 10 sampling campaigns, in the period between November 2008 and February 2012 in a museum in Antwerp (Belgium), i.e. Plantin-Moretus Museum/Print Room. Different pollutants were measured inside and outside the museum such as inorganic gases, particulate matter and black carbon. The report specifically addresses environmental factors that may be responsible for damage to the collections present in museums. Thanks to the knowledge about the current situation in the museum, accurate solutions regarding preventive conservation, in general, are suggested.

Abstract: Thoracic (PM10), fine thoracic (PM2.5) and sub-micrometer (PM1) airborne particulate matter was sampled during day and night. In total, about 100 indoor and outdoor samples were collected for each fraction at ten different office environments. Energy-dispersive X-ray fluorescence spectrometry and ion chromatography were applied for the quantification of some major and minor elements and ions in the collected aerosols. During daytime, mass concentrations were in the ranges: 1129, 8.124, and 6.618 μg m−3, with averages of 20 ± 1, 15.0 ± 0.9, and 11.0 ± 0.8 μg m−3, respectively. At night, mass concentrations were found to be significantly lower for all fractions. Indoor PM1 concentrations exceeded the corresponding outdoor levels during office hours and were thought to be elevated by office printers. Particles with diameters between 1 and 2.5 μm and 2.5 and 10 μm were mainly associated with soil dust elements and were clearly subjected to distinct periods of settling/resuspension. Indoor NO3 − levels were found to follow specific microclimatic conditions at the office environments, while daytime levels of sub-micrometer Cl− were possibly elevated by the use of Cl-containing cleaning products. Indoor carbon black concentrations were sometimes as high as 22 μg m−3 and were strongly correlated with outdoor traffic conditions.

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: This paper presents the results of X-ray fluorescence (XRF) analysis of bricks sampled from historical places in Pernambuco, a state in the northeastern region of Brazil. In this study, twenty bricks found in historical sites were analyzed. Two bricks made in the 17th century, presumably used as ballast in ships coming from Holland, five locally manufactured bricks: one from 18th century, three from 19th century, and one from 20th century, and thirteen bricks collected from a recent Archeological investigation of Alto da Se, in the town of Olinda. Qualitative determination of the chemical elements present in the samples was undertaken using a self-assembled portable XRF system based on a compact X-ray tube and a thermoelectrically cooled Si-PIN photodiode system, both commercially available. X-ray diffraction analysis was also carried out to assess the crystalline mineral phases present in the bricks. The results showed that quartz (SiO2) is the major mineral content in all bricks. Although less expressive in the XRD patterns, mineral phases of illite, kaolinite, anorthite, and rutile are also identified. The trace element distribution patterns of the bricks, determined by the XRF technique, is dominated by Fe and, in decreasing order, by K, Ti, Ca, Mn, Zr, Rb, Sr, Cr, and Y with slight differences among them. Analyses of the chemical compositional features of the bricks, evaluated by principal component analysis of the XRF datasets, allowed the samples to be grouped into five clusters with similar chemical composition. These cluster groups were able to identify both age and manufacturing sites. Dutch bricks prepared with different geological clays compositions were defined.

Abstract: This comprehensive study, a first in Flanders, Belgium, aimed at characterizing the residential indoor air quality of subgroups that took part in the European Community Respiratory Health Survey (ECRHS I1991 and ECHRS II1996) questionnaire-based asthma and related illnesses studies. This pilot study aimed at the evaluation of particulate matter and various inorganic gaseous compounds in residences in Antwerp. In addition personal exposure to the gaseous compounds of one individual per residence was assessed. The main objective was to obtain some base-line pollutant levels and compare these with studies performed in other cities, to estimate the indoor air quality in residences in Antwerp. Correlations between the various pollutant levels, indoor:outdoor ratios and the micro-environments of each residence were investigated. This paper presents results on indoor and ambient PM1, PM2.5 and PM10 mass concentrations, its elemental composition in terms of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Br, Pb, Al, Si, S and Cl and the water-soluble ionic concentrations in terms of SO42−, NO32−, Cl−, NH4+ K+, Ca2+. In addition, indoor, ambient and personal exposure levels of the gases NO2, SO2, and O3 were determined. Elevated indoor:outdoor ratios were found for NO2 in residences containing gas stoves. In smoker's houses increased PM concentrations of 58 and 43% were found for the fine and coarse fractions respectively. Contrary to the fact that all I/O ratios of the registered elements in each individual house were significantly correlated to each other, no correlation could be established between the I/O ratios of the different houses, thus indicating a unique micro-environment for each residence. Linear relationships between the particulate matter elemental composition, SO2 and O3 levels indoors and outdoors could be established. No linear relationships between indoor and outdoor NO2 and particulate mass concentrations were found.

Abstract: This article gives an overview of the state-of-the-art of multi-element and single-element preconcentration procedures prior to X-ray fluorescence (XRF) analysis of liquid samples. Many of these preconcentration methods were developed long ago and the purpose of this review is to present some new efficient variations of these methods and new techniques extending the possibilities of XRF for liquid solutions analysis. In addition, trends and future perspectives in this domain are also commented on and discussed in the last section of the review.

Abstract: The world famous Alhambra monument in Granada, Southern Spain, listed as UNESCO world cultural heritage since 1984, represents probably the most beautiful example of Islamic art and architecture from the Middle Ages in Europe. It is visited by ca. 2 million people annually. Granada is situated in a natural basin, surrounded by mountains with altitudes up to 3500 m. Due to this topography and the prevailing low wind speeds, pollution-derived and especially traffic-derived particulate matter often accumulates in the urban air. In order to evaluate the potential conservation risks from the surrounding air, the atmospheric composition in the Alhambra monument was evaluated. Indoor temperature and relative humidity fluctuations were evaluated for their potential degenerative effects. Furthermore, the atmospheric composition in the Alhambra was analyzed in terms of inorganic gases (NO2, SO2, O3, and NH3) and black carbon. It was found that the open architecture protected the indoor environments from developing a potentially harmful microclimate, such as the build-up of humidity resulting from the huge number of daily tourists. On the downside, the strong ventilation made the indoor air hardly different from outdoor air, as characterized by strong diurnal temperature and relative humidity gradients and high traffic-derived pollutant levels.

Abstract: The use of inks containing organic solvents by the offset printing process implies in the release of volatile organic compounds to the work environment. Many of these compounds such as benzene, toluene, ethylbenzene, and the xylene isomers (well known by the acronym BTEX) are extremely toxic. In this study, the BTEX concentrations were determined in two different printing plants that use distinct types of inks: the conventional and the so-called ecological, which is manufactured based on vegetal oil. Concentration ranges were 4384, 153,480, 2133, 5459, and 2236 μg m−3 for benzene, toluene, ethylbenzene, m + p-xylene, and o-xylene, respectively, for the conventional printing plant. At the ecological printing plant, concentration ranges were below limit of detection (<LD)-31, <LD-618, <LD-1,690, <LD-10,500, <LD-3,360 μg m−3 for benzene, toluene, ethylbenzene, m + p-xylene, and o-xylene, respectively. BTEX concentrations are lower at the ecological printing environment than in the conventional, where mineral oil-based inks are used. However, the worker who cleans the printing matrices is exposed to high concentrations of ethylbenzene and xylenes, due probably to the cleaning products composition (containing high amounts of BTEX). Although the BTEX concentrations found in both printing work environments were below the limits considered by the Brazilian Law for Activities and Unhealthy Operations (NR-15), the exposure to such vapors characterizes risk to the workers health for some of the evaluated samples, mainly the personal ones.