Modular MA-XRF Scanner Development in the Multi-Analytical Characterisation of a 17th Century Azulejo from Portugal.

A modular X-ray scanning system was developed, to fill in the gap between portable instruments (with a limited analytical area) and mobile instruments (with large analytical areas, and sometimes bulky and difficult to transport). The scanner has been compared to a commercial tabletop instrument, by analysing a Portuguese tile (azulejo) from the 17th century. Complementary techniques were used to achieve a throughout characterisation of the sample in a complete non-destructive approach. The complexity of the acquired X-ray fluorescence (XRF) spectra, due to inherent sample stratigraphy, has been resolved using Monte Carlo simulations, and Raman spectroscopy, as the most suitable technique to complement the analysis of azulejos colours, yielding satisfactory results. The colouring agents were identified as cobalt blue and a Zn-modified Naples-yellow. The stratigraphy of the area under study was partially modelled with Monte Carlo simulations. The scanners performance has been compared by evaluating the images outputs and the global spectrum.

Multi-Spectroscopic Approach for the Non-invasive Characterization of Paintings on Metal Surfaces.

The aim of this study is to propose a non-invasive multi-spectroscopic approach for the characterization of oil painting artworks that use a copper plates as substrate in place of a canvas. Indeed, in the last decade, many studies have been conducted on artworks made of single materials (e.g., paintings, stones, metals). However, the characterization and conservation of composite artifacts has never be fully investigated even though many masterpieces were created using this particular technique. In this work, several spectroscopic techniques such as Infrared Spectroscopy (FTIR), Energy-Dispersive X-Ray Fluorescence spectroscopy (EDXRF), and high spatial resolution Field Emission Scanning Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (EDS), and Optical Microscopy (OM) were performed. The obtained results allowed to fully characterize the micro-chemical and microstructural features of the painted surfaces and of the metal plate. Particularly effective was the use of MA-XRF, resulting in the chemical map of the painted surfaces. Furthermore, traces of the mechanical preparation of the plate were found under the painted layers. Finally, the interface area between the paint film and the metallic support was characterized at a micro scale. This was particularly important in order to identify the degradation products formed by the interaction between the fatty acids of the binder and copper-based substrates.

Differential X-Ray Attenuation in MA-XRF Analysis for a Non-invasive Determination of Gilding Thickness.

When investigating gilded artifacts or works of art, the determination of the gilding thickness plays a significant role in establishing restoration protocols or conservation strategies. Unfortunately, this is done by cross-sectioning the object, a destructive approach not always feasible. A non-destructive alternative, based on the differential attenuation of fluorescence radiation from the sample, has been developed in the past years, but due to the intrinsic random nature of X-rays, the study of single or few spots of an objects surface may yield biased information. Furthermore, considering the effects of both porosity and sample inhomogeneities is a practice commonly overlooked, which may introduce systematic errors. In order to overcome these matters, here we propose the extrapolation of the differential-attenuation method from single-spot X-ray fluorescence (XRF) measurements to macro-XRF (MA-XRF) scanning. In this work, an innovative algorithm was developed for evaluating the large amount of data coming from MA-XRF datasets and evaluate the thickness of a given overlapping layer over an area. This approach was adopted to study a gilded copper-based buckle from the sixteenth to seventeenth century found in Rome. The gilded object under investigation was also studied by other analytical techniques including scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS). Previous results obtained from SEM-EDS were used to confront the data obtained with the proposed methodology and validate it. MA-XRF elemental distribution maps were fundamental in identifying and choosing sampling areas to calculate the thickness of the gilding layer, avoiding lead islands present in the sample that could negatively influence the results. Albeit the large relative standard deviation, the mean thickness values fell within those found in literature and those obtained from previous studies with SEM-EDS. Surface fissure has been found to deeply affect the results obtained, an aspect that is often disregarded.

Rings or daggers, axes or fibulae have a different composition? A multivariate study on Central Italy bronzes from eneolithic to early iron age.

BACKGROUND: One of the main concerns for archaeo-metallurgists and archaeologists is to determine to what extent ancient craftsmen understood the effect of metal alloy composition and were able to control it in order to produce objects with the most suitable features. This problem can be investigated by combining compositional analyses of a high number of ancient artefacts with correlation analyses of the objects' age, production site, destination of usage etc. - and thus chemometric data treatment is carried out. In this study, multivariate analyses were performed on a matrix composed of elemental compositional data from 134 archaeological bronze objects, obtained by XRF analyses. Analysed objects have been dated back from the Eneolithic Period to the end of the Bronze Age including the early Iron Age and were excavated in Central Italy (mainly Abruzzo Region). RESULTS: Chemometric analysis was performed attempting to visualise clouds of objects through PCA. In parallel and independently, object grouping was attempted using several different approaches, based on object characteristics (e.g. shape, weight, type of use - cutting or hitting and age) following indications given by archaeologists (or derived from the archaeological context). Furthermore, case-tailored data pretreatment (logratio-centred scaling) was used, but no homogeneous groups could be identified. CONCLUSIONS: By using chemometric data analysis, homogeneous groups of objects could not be detected, meaning that compositional data of alloys is not correlated with the considered objects' characteristics. This favours the conclusion that - without discussing the ascertained ability of ancient foundry-men - they had also already discovered the convenience of recycling broken objects thus producing a more or less similar bronze alloy each time, depending on materials' availability; necessary mechanical characteristics could then be obtained by post processing. Graphical AbstractScores PCA plot in 3D space with 3 different bronze objects.

Bioinformatics applied to allergy: allergen databases, from collecting sequence information to data integration. The Allergome platform as a model.

Allergens are proteins or glycoproteins that are recognized by IgE produced by the immune system of allergic individuals. Until now around 1,500 allergenic structures have been identified and this number seems not have reached a plateau after 3-4 decades of research and the advent of molecular biology. Several allergen databases are available on Internet. Different aims and philosophies lead to different products. Here we report about main feature of web sites dedicated to allergens and we describe in more details our current work on the Allergome platform. The web server Allergome (www.allergome.org) represent a free independent open resource whose goal is to provide an exhaustive repository of data related to all the IgE-binding compounds. The main purpose of Allergome is to collect a list of allergenic sources and molecules by using the widest selection criteria and sources. A further development of the Allergome platform has been represented by the Real Time Monitoring of IgE sensitization module (ReTiME) that allows uploading of raw data from both in vivo and in vitro testing, thus representing the first attempt to have IT applied to allergy data mining. More recently, a new module (RefArray) representing a tool for literature mining has been released.

New devices for imaging in nuclear medicine.

Pinhole gamma camera imaging offers the ability to obtain high resolution images from single gamma ray emitting radiotracers playing a reasonable tradeoff between very small field of view (FoV) and sensitivity. On the other hand the total spatial resolution of a pinhole imaging device is predominantly affected by the detector intrinsic spatial resolution for reduced magnification factors. To design very compact pinhole SPET scanners with very high intrinsic spatial resolution, authors investigated a miniature gamma camera based on the newly developed Hamamatsu H8500 flat panel photomultiplier. The PSPMT was coupled to the following scintillation arrays: CsI(Tl) array with 0.2-mm, 1-mm, 1.4-mm pixel size and NaI (Tl) with 1-mm pixel size. The imaging performances were evaluated by 57Co spot and flood irradiations. NaI(Tl) array shows a better pixel identification for 1 mm pixel size, proving to be a good candidate to make a large area photodetector based on multi PSPMTs closely packed. Although CsI(Tl) array had the smallest pixel size, the low light output limited the best intrinsic spatial resolution to about 0.5 mm.