M. Guerra

Performance of three different Si X-ray detectors for portable XRF spectrometers in cultural heritage applications

In this work, a study of detection systems in portable X-ray fluorescence (PXRF) spectrometry was performed. An assessment of various detectors and their influence on the measurement of trace elements in different bulk materials, from light to heavy matrices, was done. Four reference materials were analyzed: Orchard Leaves (NBS-1571); Bone Meal (NIST-1486); River Sediment (NBS-1645) and Free-Cutting Brass (NBS-1105). Detection limits were calculated for the elements present in the reference materials, quantitative calculations were performed for three known samples and a comparison was made for each detector. Three case studies were also performed in order to appraise the behavior of the detection systems: A paper document from 1909, a potassium alum/calcite mixture and a Portuguese coin.

Spectroscopic characterization of a masterpiece: The Manueline foral charter of Sintra

The foral charter attributed by D. Manuel I of Portugal, in 1514, to the village of Sintra was studied using Energy Dispersive X-ray Fluorescence spectrometry, Raman and Infrared micro-spectroscopies. A complete characterization of the pictorial materials used in the production of this masterpiece allowed the identification of iron gall inks used in the written text; pigments such as malachite, azurite, lead white, cinnabar, yellow ochre, gold, silver and carbon black in the illuminations and letterings; filler and binder used in the production of coloring materials and inks. Gum and calcium carbonate were the most recurrent binder and filler identified in this study. Silvering and gilding were mostly obtained by applying ground silver and gold on parchment.

Modified binary encounter Bethe model for electron-impact ionization

Theoretical expressions for ionization cross sections by electron impact based on the binary encounter Bethe (BEB) model, valid from ionization threshold up to relativistic energies, are proposed. The new modified BEB (MBEB) and its relativistic counterpart (MRBEB) expressions are simpler than the BEB (nonrelativistic and relativistic) expressions because they require only one atomic parameter, namely the binding energy of the electrons to be ionized, and use only one scaling term for the ionization of all sub-shells. The new models are used to calculate the K-, L- and M-shell ionization cross sections by electron impact for several atoms with Z from 6 to 83. Comparisons with all, to the best of our knowledge, available experimental data show that this model is as good or better than other models, with less complexity.

New development on materials and techniques used in the heraldic designs of illuminated Manueline foral charters by multi-analytical methods.

In the illuminated foral charters commissioned by D. Manuel I, King of Portugal (1495-1521), heraldry played a prominent role. In this work, royal emblems corresponding to the third heraldic design, applied to the Charter of Couto de Teixedo, are studied by means of EDXRF, SEM-EDS, micro-Raman, micro-FTIR and HPLC-DAD to characterize the materials and techniques used to produce this masterpiece of Portuguese Renaissance. By comparing this data with the results previously obtained in other three charters, this research allows for the first time an accurate insight into the reformed manuscripts production, especially since the illuminated charters under consideration were all investigated on the basis of similar micro-spectroscopic techniques. Inks, metal coatings, pigments, organic dyes, fillers or extenders, and binding media are discussed, and their use enlightened by the politic and legal messages the foral charters had to convey. Parchment analysis allowed us to identify the animal species, and all undertaken processes along its preparation. HPLC-DAD allowed us to differentiate the gums used. CaSO4 was observed in the parchment as a degradation product of CaCO3 used in parchment production in the presence of metal sulfates coming from the ink. Pigments used in the different colors as well as some specific phases for some colors were identified. Silvering and gilding processes, metal caratage and silver oxidation compounds were also objects of the present study.

Development of a combined portable x-ray fluorescence and Raman spectrometer for in situ analysis

In this work, we have built a portable X-ray fluorescence (XRF) spectrometer in a planar configuration coupled to a Raman head and a digital optical microscope, for in situ analysis. Several geometries for the XRF apparatus and digital microscope are possible in order to overcome spatial constraints and provide better measurement conditions. With this combined spectrometer, we are now able to perform XRF and Raman measurements in the same point without the need for sample collection, which can be crucial when dealing with cultural heritage objects, as well as forensic analysis. We show the capabilities of the spectrometer by measuring several standard reference materials, as well as other samples usually encountered in cultural heritage, geological, as well as biomedical studies.

Single differential electron impact ionization cross sections in the binary-encounter-Bethe approximation for the low binding energy regime

An analytical expression based on the binary-encounter-Bethe model for energy differential cross sections in the low binding energy regime is presented. Both the binary-encounter-Bethe model and its modified counterpart are extended to shells with very low binding energy by removing the constraints in the interference term of the Mott cross section, originally introduced by Kim et al. The influence of the ionic factor is also studied for such targets. All the binary-encounter-Bethe based models presented here are checked against experimental results of low binding energy targets, such as the total ionization cross sections of alkali metals. The energy differential cross sections for H and He, at several incident energies, are also compared to available experimental and theoretical values.

Elemental characterization of plants and soils in Panasqueira tungsten mining region

PurposeMining activities represent a current source of pollution due to the large release of trace elements from mineral particles into the soil, atmosphere, and ecosystems. In active or abandoned metal-mining areas, direct discharge from mining deposits is one of the most common processes of contamination.Materials and methodsIn this work, we calculated the elemental concentrations of plants, edible for cattle, which might contain high values of toxic elements, such as As, Cu, Zn, and W, originated from mining exploitation, especially wolframite. Several species of plants originating from the same contaminated place, close to the mine, were the subject of our study in order to compare the uptake of harmful elements, from the contaminated soils, in the different plants. We have used the energy-dispersive X-ray fluorescence technique to perform the analysis and quantification of the elements present in the collected samples. The quantification was based on the fundamental parameters method for plants and on the WinAxil compare mode using a standard reference material, for soils. Calibration against a series of standard samples has been carried out.Results and discussionA comparison between contaminated and control samples, within the same species, was performed. The contamination of the two mining wash sites is assessed by comparing the elemental concentration of several plants in these places. Elemental content in soils was investigated, and a comparison between elemental levels in plants was performed.ConclusionsHigh concentrations of tungsten were found near the new wash site. Arsenic was found throughout the area in concentrations many times higher than those recommended by the World Health Organization.

A novel portable energy dispersive X-ray fluorescence spectrometer with triaxial geometry

The X-ray fluorescence technique is a powerful analytical tool with a broad range of applications such as quality control, environmental contamination by heavy metals, cultural heritage, among others. For the first time, a portable energy dispersive X-ray fluorescence spectrometer was assembled, with orthogonal triaxial geometry between the X-ray tube, the secondary target, the sample and the detector. This geometry reduces the background of the measured spectra by reducing significantly the Bremsstrahlung produced in the tube through polarization in the secondary target and in the sample. Consequently, a practically monochromatic excitation energy is obtained. In this way, a better peak-background ratio is obtained compared to similar devices, improving the detection limits and leading to superior sensitivity. The performance of this setup is compared with the one of a benchtop setup with triaxial geometry and a portable setup with planar geometry. Two case studies are presented concerning the analysis of a 18th century paper document, and the bone remains of an individual buried in the early 19th century.

Biofortification of durum wheat (Triticum turgidum L. ssp. durum (Desf.) Husnot) grains with nutrients

ABSTRACT Durum wheat (Triticum turgidum L. ssp. durum (Desf.) Husnot) was grown under conditions to promote mineral biofortification at the grain level. Along plant development, biomass accumulation and the kinetics of nutrients accumulation were assessed, identifying the nutrient fluxes of roots and shoots, and the timescale constraints of crop biofortification. Plants were grown under environmentally controlled conditions, submitted to four increasing concentrations of nutrient solutions (1-, 2-, 4- and 6-fold) of micro- (Fe, Zn, Cu and Mn) and macronutrients (Ca, K, P and Mg). The threshold of mineral toxicity was not reached as evaluated through plant biomass accumulation, but considering grain yield, the twofold nutrient concentration was the best treatment for biofortification. In the different treatments, the contents and the mineral unrests of roots uptake and shoots translocation varied, at different magnitudes and trends, before the onset of booting and from the physiological maturity onwards. Except for Cu, all mineral nutrients were mainly detected in the bran and embryo of the grains; therefore, the production of biofortified pasta for human consumption requires the use of integral semolina.

Microscopy and X-Ray Spectroscopy Analyses for Assessment of Gilding and Silvering Techniques of Portuguese Illuminated Manuscripts

The objects of this study are various local charters (cartas de foral, in Portuguese) granted by Dom Manuel I, King of Portugal (1495-1521), which substituted for medieval ones and were intended to achieve an administrative unification. These are luxuriously illuminated manuscripts, and our study aims at obtaining a better understanding of the gilding and silvering techniques applied to the parchments, in which the forais were written, between 1500 and 1520. The combined use of microscopy and X-ray spectroscopy analyses allowed us to identify the vestigial materials used for making the parchments, including products such as salt (NaCl), lime (CaO), pumice stone (SiO2+Al2O3), and chalk (CaCO3). Chalk was employed as a whitening agent to give the parchment its final color and opacity. Shell-gold and shell-silver mixed in with animal glue or gum binding media were directly applied on type 1 and 3 forais, while very thin gold leaves (<1 µm) were applied over lead-based tempera grounds (50-180 µm thick) in type 2 forais. Silver was always employed in its finest form without a further protective layer (thus its recursive state of corrosion), while gold was used in various alloy grades.