Elemental analysis, and in particular stratigraphic distribution of elements themselves, is a fundamental method to address the composition of materials, but its nature, often invasive, crashes with the necessity of avoiding artefacts' damage when dealing with Cultural Heritage objects. In fact, when work of art are involved, sampling is often forbidden, and transferring an artistic artefact to equipped laboratories is a not negligible issue. The skill to employ in situ non‐destructive and non‐invasive analytical method is essential. In this scenario, portable X‐ray fluorescence (p‐XRF) has become one of the most employed techniques due to the development of adaptable and open architecture instruments. In this paper, we show a new data analysis protocol and its application to XRF data acquired from a work by Giotto never studied before: ‘God the Father with Angels’ (ca. 1330, San Diego Museum of Art). The measurements have been performed in situ during the closing time of the exhibition ‘Giotto, l'Italia’ (Milano Palazzo Reale – 2 September 2015/10 January 2016). Combining the effectiveness of scanning p‐XRF with the responsive of image spectroscopic analysis, we move step by step toward the discovery of Giotto's palette for the flesh tones in God the Father with Angels; our method allows to argue the stratigraphy of the painting without complementary measurements and, at the same time, provides a sequential and smart representation of complex data. Copyright © 2017 John Wiley & Sons, Ltd.

This paper describes the physico-chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy-dispersive X-ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro-Fourier-transforminfrared (micro-FTIR) and a Fourier-transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography -mass spectrometry (GC-MS) and micro-FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X-ray diffraction (XRD) and scanning electron microscopy -energy-dispersive X-ray (SEM-EDX) in addition to the above-cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.

In this paper, we report a few examples showing how energy dispersive XRF analysis (EDXRF) coupled with visible reflectance spectroscopy (vis‐RS) can be successfully applied for the investigation of wood or canvas paintings by performing stratigraphic analyses with non‐invasive techniques. The specific aim is to reconstruct layers and their thicknesses. The method has been tested in the laboratory on paint layers similar to traditional Renaissance ones. In situ analyses of a famous wood painting by Andrea Mantegna—‘Madonna col bambino e un coro di cherubini’, Pinacoteca di Brera, Milan—were also carried out. While illustrating the results concerning the identification of pigments and the discrimination of layer stratigraphy, advantages and limitation of this method are pointed out. Copyright © 2007 John Wiley & Sons, Ltd.

Ceramics provenance studies based on minor and trace elements are widely used to help in gathering knowledge of local furnace presence and commercial trades. Most of the times, destructive analyses are allowed because of the high amount of material, but sometimes (integer vessels, architectural decorations, etc.), a nondestructive examination is required. In both cases, X-ray fluorescence (XRF) analysis can be a useful tool.In this work, we compare the classification results obtained on a set of bricks from the medieval Chartusian monastery Certosa di Pavia in the Po valley, northern Italy, exploiting XRF, portable XRF, and total reflection XRF (TXRF) spectrometers.The XRF nondestructive analyses were performed both in situ before sampling and in the laboratory without preparing the shards. Grounded samples were instead used to obtain semi-quantitative TXRF analysis without dissolving the samples but using a suspension in high-purified water. The project aimed at verifying if a correct classification was possible even if a quantitative determination of minor and trace elements is abandoned, allowing a faster response when a large amount of data is concerned. For this reason, weight concentration was determined from laboratory XRF measurements only, whereas semiquantitative results and entire spectra were considered for TXRF and the in situ campaign, respectively. Data were then submitted to different statistical data treatments to obtain provenance classification.

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