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: Both energy- and wavelength-dispersive systems were used to obtain Malpha/Lalpha intensity ratios for Ta, W, Pt, Au, Pb and Bi at various overvoltages. A table of these ratios corrected for matrix absorption and detector efficiency is presented, in addition to an interpolatory function of Malpha/Lalpha generated ratios vs. overvoltage, for each element. In addition, three different ZAF correction models were used to predict both detected and generated ratios. Finally, experimental Mbeta/Malpha ratios measured at different overvoltages are presented for the six elements considered.

Abstract: The paintings by edouard Manet in The Courtauld Gallery Dejeuner sur l'herbe (1863-68), Marguerite de Conflans en Toilette de Bal (1870-1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies-Bergere (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV-Vis-NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Dejeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies-Bergere Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.

Abstract: A current method for the protection of cretaceous limestone present in various monuments consists of performing a passivating treatment with ammonium oxalate (AmOx). A calcium oxalate protective layer is formed on the surface and enhances the acid resistance of the stone. The in-depth formation of the calcium oxalate layer was investigated on cross sections by using combined micro X-ray fluorescence and micro X-ray powder diffraction (mu XRF/mu XRPD). XRPD showed the presence of both whewellite and weddellite in the calcite stone matrix. A correction was made for sample misalignment, which was visible in both the fluorescence and the diffraction line measurements. A semi-quantitative analysis was performed on the basis of Klug's equation for a two-phase mixture (the presence of weddellite was neglected) without the need for a known reference sample. By assuming two extreme compositions for a reference weight fraction (1 and 99wt%), it was possible to obtain whewellite concentration profiles, which can be used for comparing the effectiveness of different methods for the application of AmOx to the stone surface and the effect of treatment time and AmOx concentration used. It is shown that for the relative amounts of whewellite formed, the differences due to the assumed weight fractions are smaller than the errors due to sample heterogeneity and preferred orientation. Copyright (c) 2013 John Wiley & Sons, Ltd.

Abstract: The research of soil contamination by heavy metal is an important field due to its environmental and health implications. The goal was to study the elemental mobility as a function of depth. For this reason, the distribution of heavy metals (V, Cr, Co, Ni, Cu, Zn, As, Sn, and Pb) was investigated along soil profiles up to a depth of 15m at 9 sampling sites in the Nilufer industrial district (Bursa, Turkey). Elemental analyses were done with the Epsilon 5 energy dispersive X-ray fluorescence and inductively coupled plasma mass spectrometry equipment. Particle analysis was performed with a JEOL scanning electron microscope equipped with a Si(Li) X-ray detector. The crystallographic compositions of oxide compounds in soil samples were identified by a Rigaku X-ray diffraction instrument. Different parameters such as the soil's chemical (mineralogical structure, pH, and electrical conductivity) and physical properties (the number of blows, the stiffness index, the liquidity index, the plasticity index, and the water content) were analyzed. To assess the mobility of the heavy metals, diffusion (D) and convection coefficients (?) were calculated with the finite difference method. Convection was determined to dominate the studied region. In addition, the mobility coefficient was determined for each metal. High mobilities were determined for Zn and V, moderate mobilities for Cr, Ni, Cu, and As, and low mobilities were determined for Co and Pb. The results revealed that elements had reached depths of up to 15m, causing irreversible soil contamination that may lead to environmental health issues.

Abstract: Elemental composition of aerosols is important to source apportionment studies and to understand atmospheric processes that influence aerosol composition. Energy dispersive X-ray fluorescence spectroscopy was applied for measuring the elemental composition of Amazonian atmospheric aerosols. The instrument used was a spectrometer Epsilon 5, PANalytical B. V., with tridimensional geometry that reduces the background signal with a polarized X-ray detection. The measurement conditions were optimized for low-Z elements, e. g. Mg, Al, Si, that are present at very low concentrations in the Amazon. From Na to K, our detection limits are about 50% to 75% lower than previously published results for similar instrument. Calibration was performed using Micromatter standards, except for P whose standard was produced by nebulization of an aqueous solution of KH2PO4 at our laboratory. The multi-element reference material National Institute of Standards and Technology-2783 (air particulate filter) was used for evaluating the accuracy of the calibration procedure of the 22 elements in our standard analysis routine, and the uncertainty associated with calibration procedures was evaluated. The overall performance of the instrument and validation of our measurements were assessed by comparison with results obtained from parallel analysis using particle-induced X-ray emission and another Epsilon 5 spectrometer. The elemental composition in 660 samples collected at a pristine site in the Amazon Basin and of 1416 samples collected at a site perturbed by land use change was determined. Our measurements show trace elements associated with biogenic aerosols, soil dust, biomass burning, and sea-salt, even for the very low concentrations as observed in Amazonia. Copyright (C) 2014 John Wiley & Sons, Ltd.