Probing some organic ukiyo-e Japanese pigments and mixtures using non-invasive and mobile infrared spectroscopies.

Non-invasive identification of organic colourants in paintings still remains a challenging issue, especially in the case of extremely thin layers of paint on printed paper such as Japanese ukiyo-e prints. Because prints are fragile artworks, various non-invasive analytical methods need to be employed. The present work focuses on results obtained by combining fibre optic reflectance spectroscopy in the near-infrared range (FORS NIR) with mid-infrared (MIR) spectroscopy. The first step consists of identifying spectroscopic marker bands typical of some organic pigments (indigo, gamboge, cochineal, turmeric, safflower, dragon's blood). Some reference printouts involving paper substrate, binder and pigments (seldom used or as mixtures) were then investigated in order to establish a straightforward way to extract the marker bands of the pigments. Some data post-treatments were applied to the spectra, such as spectral subtraction, in order to abstract the signal from overlapping bands originating from both substrate and binder, and second derivative calculation to emphasise the pigment marker bands' frequency positions. These data treatments turned out to be relevant to extract information on the organic pigments of interest, even within complex mixtures.

Comparison between non-invasive methods used on paintings by Goya and his contemporaries: hyperspectral imaging vs. point-by-point spectroscopic analysis.

The development of non-invasive techniques for the characterization of pigments is crucial in order to preserve the integrity of the artwork. In this sense, the usefulness of hyperspectral imaging was demonstrated. It allows pigment characterization of the whole painting. However, it also sometimes requires the complementation of other point-by-point techniques. In the present article, the advantages of hyperspectral imaging over point-by-point spectroscopic analysis were evaluated. For that purpose, three paintings were analysed by hyperspectral imaging, handheld X-ray fluorescence and handheld Raman spectroscopy in order to determine the best non-invasive technique for pigment identifications. Thanks to this work, the main pigments used in Aragonese artworks, and especially in Goya's paintings, were identified and mapped by imaging reflection spectroscopy. All the analysed pigments corresponded to those used at the time of Goya. Regarding the techniques used, the information obtained by the hyperspectral imaging and point-by-point analysis has been, in general, different and complementary. Given this fact, selecting only one technique is not recommended, and the present work demonstrates the usefulness of the combination of all the techniques used as the best non-invasive methodology for the pigments' characterization. Moreover, the proposed methodology is a relatively quick procedure that allows a larger number of Goya's paintings in the museum to be surveyed, increasing the possibility of obtaining significant results and providing a chance for extensive comparisons, which are relevant from the point of view of art history issues.

Symbolic use of marine shells and mineral pigments by Iberian Neandertals.

Two sites of the Neandertal-associated Middle Paleolithic of Iberia, dated to as early as approximately 50,000 years ago, yielded perforated and pigment-stained marine shells. At Cueva de los Aviones, three umbo-perforated valves of Acanthocardia and Glycymeris were found alongside lumps of yellow and red colorants, and residues preserved inside a Spondylus shell consist of a red lepidocrocite base mixed with ground, dark red-to-black fragments of hematite and pyrite. A perforated Pecten shell, painted on its external, white side with an orange mix of goethite and hematite, was abandoned after breakage at Cueva Antón, 60 km inland. Comparable early modern human-associated material from Africa and the Near East is widely accepted as evidence for body ornamentation, implying behavioral modernity. The Iberian finds show that European Neandertals were no different from coeval Africans in this regard, countering genetic/cognitive explanations for the emergence of symbolism and strengthening demographic/social ones.

Spectrofluorimetric study of the ageing of mixtions used in the gildings of mediaeval wall paintings.

INTRODUCTION: In the Middle Ages, we could find gildings on mural paintings. Gold, silver or tin leaves were applied according to distemper or mixtion technique. For the first one, a binder as glue is necessary, and for the second, a lipidic binder is used to stick the metallic leaf. Studies of gildings materials characterization show that the mixtion technique, with a mordant, is the most common. Linseed oil seems to be the binder used. It is always mixed with a siccative agent as lead. Because of bad conditions of conservation, the gildings do not resist anymore, only remain traces of metal or the adhesive under-layer. Thanks to the binder fluorescence, we can nowadays detect ancient gildings. OBJECTIVE: The purpose of this paper is to study the degradation of the linseed oil, generally mixed with lead white to give a mordant for the metallic leaf, by spectrofluorimetry. MATERIALS AND METHODS: To understand in situ fluorescence, gildings recreations, linseed oil and lead white are aged in hydro-thermal and ultraviolet (UV) light (313 nm) climatic rooms and under UV irradiation. Irradiation wavelengths are chosen according to the maximum of absorption of linseed oil and the bibliography (296, 313 and 366 nm = mercury bands). RESULTS: In comparison with results (in situ UV lamp, spectrofluorimetry), excitation wavelength chosen is 366 nm. Irradiations at 366 nm of linseed oil and linseed oil mixed with lead white show the most degrading effect in the fluorescence to the big wavelength. Lead white plays an important siccative role; it increases the intensity fluorescence and accelerates the drying of linseed oil. This study also allows to show that 366 nm wavelength is good for the in situ observation.