A painting bearing the signature “Picasso” was investigated and its components – pigments and binders – were characterised using micro-Raman spectroscopy (mRS) combined with other analytical techniques such as Scanning Electron Microscopy with Energy Dispersive X-ray analysis (SEM/EDX), Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Gas Chromatography-Mass Spectrometry (GC-MS). We identified the pigments in order to assess chronological inconsistency (anachronistic pigments) with the work of the Spanish artist Pablo Picasso (1881–1973) by means of in situ and cross-section analyses by mRS. Using mRS we identified the pigments ‘phthalocyanine blue’, ‘phthalocyanine green’, ‘pyrazolone orange’, ‘anatase’ and ‘rutile’ (titanium dioxide). These results were corroborated by SEM/EDX elemental analysis, which detected Ba, S and Zn among others, so prompting discussion about the use of ready-mixed house paints (Ripolin®). The ground layer was also investigated by mRS, which confirmed the use of rutile (titanium dioxide), calcite and phyllosilicates (Al, Fe). mRS on the white area identified the binding media as beeswax, the most important wax used in art. ATR-FTIR and GC-MS analysis support the presence of a wax and an oil–resin mixture as the binder, described in previous research as being used by Picasso. All the artist materials identified were widely used in art at the beginning of the twentieth century according to the available bibliography and are therefore consistent with the Picasso era. To the best of our knowledge this is the first attempt to investigate a painting related to Picasso using the combination of analytical techniques proposed here.

The main objective of this study is to establish an appropriate method for the characterization of the pigments, materials and structure of the paint layers in a copy of the painting the Transfiguration of Christ by Raffaello Sanzio. A multi-technique approach that combines elemental, molecular and structural analyses and involves optical microscopy (OM), scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM–EDX), μ-Attenuated Total Reflection–Fourier Transform InfraRed (µATR-FTIR), μ-Raman spectrometry (µRS) and non-invasive portable diffractometer (pXRD) was used. Our results revealed that this copy of the Transfiguration was executed with a palette, which includes white lead (cerussite and hydrocerussite), lazurite from lapis lazuli pigment, red and yellow earths (goethite, hematite and lepidocrocite), lead tin yellow, cinnabar, red lake, smalt and bone black, and fillers such as calcite, baryte (an impurity associated to some pigments), and traces of colorless powdered glass. A secondary objective of this research was the application of non-invasive in situ pXRD measurements, which do not require painting sampling and helped to confirm some inconclusive results obtained with other techniques regarding the artist's palette. The results showed the crystalline nature of all the pigments identified, which were known from ancient times and available during the 16th and 17th. Lastly, the used of ¹⁴C accelerator mass spectrometry determined that the canvas date was 1451–1633 AD (with a 95% confidence level). Although the main focus of the work was to improve the analytical methodology to better understand the artist’s palette, our results will further help us to explore the authorship of the copy or the school that executed it. Graphical Abstract

The palette used on a small painting on copper support, with the inscription “Boceto di Pablo Veronese” on the back, was characterized. Non-invasive techniques such as X-ray diffraction (XRD) and hand-held X-ray fluorescence (XRF) were proven to be highly effective for this. The objectives of the proposed work were twofold. On the one hand, the objective was the study, in situ, of the pigments of a painting on a copper support. On the other hand, it was to enrich the literature related to the study of paintings on metal supports, since few related studies are available despite the relatively large number of such 16th and 17th century paintings from Italy and Northern Europe. The results of the analysis showed a copper support with a base layer of gypsum mixed with ochre earths. Atop this layer is a sketch with lead white in the lighter areas and bone black in the darker shadow areas, suggesting that the artist performed a preliminary study of the luminosity of the scene. Finally, the upper or pictorial layer consists of a mix of pigments with some lead white to lower saturation and increase lightness, particularly evident in the flesh tones. The resulting palette thus includes lead white, vermilion, bone black, Naples yellow, and lazurite pigments. These results are compared to Veronese’s other paintings, as well as to those of certain contemporary artists, and the use of the resulting pigments in 16th and 17th century Italian painting techniques is discussed.

Alonso Cano is considered one of the most original and brilliant artists from the Spanish Golden Age (known in Spanish as Siglo de Oro), a period of flourishing in arts and literature. He was also the founder of the Baroque painting school of Granada. This paper focuses on the painting the Visitation painted by Cano in 1652 and housed in the main chapel of Granada Cathedral. This study is part of an ambitious 11-year project aimed at understanding Cano's working technique by considering both the evolution of his painting style and the reconstruction of his color palette. Through this extensive project we intended to provide necessary scientific evidence to help in authorship verification in cases of controversial attribution to Cano of paintings included in the current catalogue of the artist. To this end, the Visitation was included in the project and a series of non-invasive and minimally invasive analytical techniques were applied to gain a wider insight into the artist's technique and the materials used to create his paintings. Macroscopic and microscopic examination of the surface, infrared reflectography, ultraviolet fluorescence, and X-radiography were performed. The underdrawings found reveal some significant changes in the composition of the figures. The results of optical microscopy, UV fluorescence microscopy, and scanning electron microscopy revealed a quasi-sculptural treatment of the figures, where the artist tested different pigment:binder ratios and applied several pictorial layers of different thicknesses. SEM with energy dispersive X-ray spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, and micro-Raman spectrometry were used to identify the pigments present in individual layers. The results showed that pigments generally available in the seventeenth century were used, including white lead, malachite, copper resinate, vermilion, red lake, lapis lazuli, smalt, red lead, bone black, and carbon black. Additionally, gas chromatography-mass spectrometry analysis suggested the use of linseed oil binding medium.

The identification of proteinaceous materials in paint constituents provides very valuable information regarding the techniques used by the painter and the most suitable procedures for conserving and restoring their works. Although the analysis of proteinaceous materials is nowadays a common task when dealing with works of art, the reliable detection and identification of protein traces is still complicated, particularly when very small samples can be taken that may contain a mixture of different organic materials (oils, waxes, resins, gums etc.). We therefore proposed a proteomic approach to investigate protein materials in paintings at trace levels in order to obtain a better understanding of the painter's technique. After trypsin digestion of the paint samples, mass spectra were obtained by matrix-assisted laser desorption and ionization time of flight mass spectrometry (MALDI-TOF-MS) and they were compared with the Mascot database and with theoretical digested proteins. This study contributes to the knowledge about the technique used by Alonso Cano (Granada, Spain, 1601–1667), one of the most original and brilliant artists from the Spanish Golden Age (17th century), in the series called the Life of the Virgin (six paintings), part of the iconographic program about the life of the Virgin Mary, nowadays seen in the main chapel of Granada Cathedral. The objective of the present study was to test the use of proteinaceous material, mainly egg yolk, in the paint used by Cano, as suggested in previous research, although this would have been unusual at that time when most artists used oil paints. Based on the results of the analysis here presented, the use of protein in the binding media can most likely be excluded.