Non-Invasive Study of the Pigments of a Painting on Copper with the Inscription “Boceto di Pablo Veronese” on the Back

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 discussedProject FEDER/Junta de Andalucía-Consejería de Economía y Conocimiento/A-HUM-164-UGR18Research group FQM-338Analytical Techniques Unit EQC2018-004952-

A combination of invasive and non-invasive techniques for the study of the palette and painting structure of a copy of Raphael’s Transfguration of Christ

We thank the owner of the painting Mr. F. Fernandez Fábregas and the research group FQM-338 (University of Granada) for letting us use its facilities. We also thank Maria José Campos for the preparation of the cross-section samplesAll the authors belong to the research team Unit of Non-Invasive Analytical Techniques Unit (University of Granada, Spain) funded by EQC2018-004952-P and A‐HUM‐164‐UGR18 Projects, currently active. All the authors read and approved the fnal manuscript. EM: Professor of Analytical Chemistry applied under Cultural heritage at the Department of Analytical chemistry of the University of Granada, Spain. The author contributed to the examination of the Transfguration of Christ, using photography, SEM–EDX, and performed the µRS and µATR-FTIR analyses; and contributed to the interpretation of the datasets, contextualization of data, and writing of the manuscript. RB: Full Professor of Analytical Chemistry at the Department of Analytical chemistry of the University of Granada, Spain. The author contributed to the examination of the painting, sampling, contextualization of the painting, elaboration of tables and fgures, contextualization of data, and participated in the interpretation of the datasets. The author read and approved the fnal manuscript. JDM-R: Professor of Mineralogy at the Department of Mineralogy and Petrology of the University of Granada, Spain. The author provided the interpretation of the mineralogical data. GCh: Professor of Mineralogy Applied under Cultural Herit‑ age at the Department of Earth Sciences of the University of Torino, Italy, Chief Scientist at the Getty Conservation Institute in Los Angeles, CA (director of the Science department for 11 years). The author works now as a freelance con‑ sultant in the feld of Conservation of Cultural heritage. The author read and approved the fnal manuscript. PS: Scientist at the SETI Institute and founder of eXaminart LLC. The author develops miniature X-ray analytical instruments for Space exploration ((e.g. the NASA CheMin XRD instrument inside the Curiosity Mars rover) and portable instruments dedicated to cultural heritage. The author contributed to the examination of the Transfguration of Christ, using pXRD. The author read and approved the fnal manuscript. JLV: Full Profes‑ sor of Analytical Chemistry at the Department of Analytical chemistry of the University of Granada, Spain. The author contributed to the Transfguration of Christ, using photography, SEM–EDX; contributed to the interpretation of the datasets, the contextualization and revision of data. All authors read and approved the fnal manuscript.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), mu-Attenuated Total Reflection-Fourier Transform InfraRed (mu ATR-FTIR), mu-Raman spectrometry (mu RS) 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 C-14 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.Non-Invasive Analytical Techniques Unit EQC2018-004952-PProyecto de investigación FEDER / Junta de Andalucía-Consejería de Economía y Conocimiento / A ‐ HUM ‐ 164 ‐ UGR18

Pottery grave goods from funerary contexts at the argaric site of Peñalosa (Jaén). A methodological approach

The need for interdisciplinary studies is the basis of ambitious research (ARCHEM Project) that is carried out in the argaric settlement of Peñalosa (Baños de la Encina, Jaén), combining organic residues analysis and techno-typological studies of pottery found in funerary contexts. Manufacture and use of pottery could inform us about customs and traditions that remain hidden in time and in the archaeological record. Knowing the implications and decisions of potters as well as the functionality of those vessels deposited inside the graves can approach the idiosyncrasy of a society in the Bronze Age in the southeast of the Iberian Peninsula. The methodology used to identify patterns of functionality is highlighted by the combination of cutting-edge analysis techniques in both fields such as the application of different chromatographic techniques (GC-MS, UPLC-HRMS and GC-CIRMS) that allow to identify the organic compounds in the ceramics and the application of analytical techniques from Earth Sciences (Stereomicroscopic, X-Ray Diffraction and Petrography), which allow us to characterize ceramic pastes and knowing the catchment of raw materials. This study highlights the Peñalosa site as a melting pot of new research and it brings us closer with the use of a complex methodology combined to the societies 4000 years ago.Spanish Ministry of Economy and Competitiveness HAR2015-66009-PJunta de Andalucía HUM 274 FQM 338Spanish Ministry of Economy, Industry and CompetitivinessUniversity of Granad

Spectroscopic study of mixtures of green copper pigments in fresh and aged model samples. Case studies on masterpieces from the Spanish Golden Age

Precise knowledge of the palette employed by historic painters is fundamental to preserving their works of art and can help pinpoint the period in which their paintings were created, their provenance and au- thorship. Raman and IR spectroscopy is successful in identifying pigments via their molecular spectrum, nevertheless, to distinguish the pigments in a binary mixture is challenging, particularly when the mixed pigments are the same colour and Cu-containing. This is precisely the aim of the current research: to evaluate the effectiveness of the molecular spectroscopy techniques μRS and μFTIR-ATR to discriminate binary mixtures of three green pigments, all containing copper, specifically copper resinate, malachite and verdigris. To that end, two sets of model samples were prepared with pure pigments and their bi- nary mixtures in variable weight concentrations from 20% to 80% for each component. The 15 model samples obtained were mixed with linseed oil in the fixed proportion of 3:1 (w/w) of powdered pigment to binder and spread in a homogeneous layer on a support of commercial grade canvas. Five replicates of μFTIR-ATR and μRS spectra, respectively, were recorded after 0 h, 24 h, 48 h, 72 h and 144 h of exposure within the controlled conditions of a climatic chamber. The aim is to establish the minimum percentage of a Cu-containing pigment in a binary mixture that can be detected by μRS and/or μFTIR-ATR spec- troscopy. The product of this ample study is a database of the spectroscopic signature of each pigment in the specific mixtures (in the given proportions and artificial ageing times) for reference purposes in the study of the green areas of selected masterpieces. The oil paintings used in the research ( The Nativity, The Visitation , and The Assumption ) are of Alonso Cano’s work, a well-known artist of the Spanish Golden Age (the Siglo de Oro in Spanish). With this study, the knowledge of the mixture of green pigments em- ployed in Cano’s palette was expanded, making considerable progress in the ambitious National Projects in which our Research Group, ever since 2003, has been attempting to understand Cano’s technique.University of Granada/CBUAresearch group FQM-338research group HUM-83