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International audience; Synchrotrons have provided significant methods and instruments to study ancient materials from cultural and natural heritages. New ways to visualise (surfacic or volumic) morphologies are developed on the basis of elemental, density and refraction contrasts. They now apply to a wide range of materials, from historic artefacts to paleontological specimens. The tunability of synchrotron beams owing to the high flux and high spectral resolution of photon sources is at the origin of the main chemical speciation capabilities of synchrotron-based techniques. Although, until recently, photon-based speciation was mainly applicable to inorganic materials, novel developments based, for instance, on STXM and deep UV photoluminescence bring new opportunities to study speciation in organic and hybrid materials, such as soaps and organometallics, at a submicrometric spatial resolution over large fields of view. Structural methods are also continuously improved and increasingly applied to hierarchically structured materials for which organisation results either from biological or manufacturing processes. High-definition (spectral) imaging appears as the main driving force of the current trend for new synchrotron techniques for research on cultural and natural heritage materials.

Les particularités du rayonnement synchrotron, notamment sa très grande brillance et son spectre blanc des rayons X à l’infrarouge lointain, en font une source de plus en plus employée pour l’étude de la composition chimique, des propriétés et de la réactivité des matériaux patrimoniaux. La construction de l’Institut photonique d’analyse non destructive européen des matériaux anciens, attenant au synchrotron SOLEIL, par l’État français et la Région Île-de-France permet un soutien fortement accru des équipes françaises et internationales travaillant à l’étude des matériaux anciens. Les allers-retours entre développement de méthodes et applications encouragent à la fois l’apparition de nouveaux instruments et un usage optimisé de techniques de spectroscopie et d’imagerie de pointe. Le développement d’IPANEMA sur le territoire de Paris-Saclay s’inscrit dans le cadre plus global de la mise en place de l’infrastructure européenne E-RIHS, dédiée à l’étude du patrimoine culturel et naturel. The specific features of synchrotron radiation, namely its very high brightness and its white spectrum from X-rays to far infrared light, make it an increasingly used source in the study of the chemical composition, properties and reactivity of ancient materials. Constructed by the French government and the Île-de-France region, adjacent to the SOLEIL synchrotron, IPANEMA (Institut photonique d’analyse non-destructive européen des matériaux anciens/European Institute of Non-Destructive Photonic Analysis of Ancient Materials), provides extensive additional support to French and international teams involved in research into ancient materials. Interaction between the development of methods and applications encourage both the emergence of new instruments and an optimized use of spectroscopic techniques and cutting-edge imaging. The building of IPANEMA on the Paris-Saclay site is part of a more global strategy within E-RIHS, the European Research Infrastructure for Heritage Science.

International audience; The identification of the chemical nature of varnish is essential for art restorers in order to choose a suitable solvent during its removal. Until today, such identification has been performed using chemical analysis after sampling. An innovative technique is presented here, using ultraviolet (UV) fluorescence spectroscopy. The method is nondestructive, workable in situ, and leads to results in real time. It is based on the comparison between the emission spectrum of an unknown varnish with those of fresh, artificially aged, or old reference resins and varnishes, for different monochromatic excitation wavelengths. The resin and the nature of the varnish as spirit, oil, or mixed can thus be identified. Various examples are presented on home-made samples applied on fluorescent backgrounds and on real works of art.

High-flux synchrotron techniques allow microspectroscopic analyses of artworks that were not feasible even a few years ago, allowing for a more detailed characterization of their constituent materials and a better understanding of their chemistry. However, interaction between high-flux photons and matter at the sub-microscale can generate damages which are not visually detectable. We show here different methodologies allowing to evidence the damages induced by microscopic X-ray absorption near-edge structure spectroscopy analysis ( $$\mu$$ XANES) at the Fe and Zn K-edges of a painting dating from the turn of the twentieth century containing Prussian blue and zinc white. No significant degradation of the pigments was noticed, in agreement with the excellent condition of the painting. However, synchrotron radiation damages occurred at several levels, from chemical changes of the binder, modification of crystal defects in zinc oxide, to Prussian blue photoreduction. They could be identified by using both the $$\mu$$ XANES signal during analysis and with photoluminescence imaging in the deep ultraviolet and visible ranges after analysis. We show that recording accurately damaged areas is a key step to prevent misinterpretation of results during future re-examination of the sample. We conclude by proposing good practices that could help in integrating radiation damage avoidance into the analytical pathway.

International audience; Deep ultraviolet (DUV) photoluminescence (PL) microimaging is an emerging approach to characterise materials from historical artefacts (see M. Thoury, J.-P. Echard, M. Réfrégiers, B. H. Berrie, A. Nevin, F. Jamme and L. Bertrand, Anal. Chem., 2011, 83, 1737–1745). Here we further assess the potential of the method to access a deeper understanding of multi-layered varnishes coating wooden violins and lutes. Cross-section micro samples from important 16th- to 18th-century instruments were investigated using synchrotron PL microimaging and microspectroscopy. Excitation was performed in the DUV and the near ultraviolet (NUV) regions, and emission recorded from the DUV to the visible region, at a submicrometric spatial resolution. Intercomparison of microspectroscopy and microimaging was made possible by radiometrically correcting PL spectra both in excitation and emission. Based on an optimised selection of emission and excitation bands, the specific PL features of the organic binding materials allowed a vastly enhanced discrimination between collagen-based sizing layers and oil/resin-based layers compared to epiluminescence microscopy. PL therefore appears to be a very promising analytical tool to provide new insights into the diversity of surface coating techniques used by instrument-makers. More generally, our results demonstrate the potential of synchrotron PL for studying complex heterogeneous materials beyond the core application of the technique to life sciences.

This study, based on diffuse reflectance spectrometry compared with simulations, shows that three parameters influence the visual aspect of a painting when a varnish is applied on it. The difference between the refractive indices of air, varnish and painting induces a negligible effect. The levelling of the painted surface by a varnish is more consequent. It induces a vertical downwards translation of the reflectance spectrum of the painting. Absorption by the varnish occurs for small wavelengths, under 450 nm. It induces a second decrease of the spectrum in this range. The refractive indices, the surface state modification due to levelling and the absorption law as a function of the wavelength have been evaluated. These results lead to a successful agreement between simulated and measured spectra. Different paintings and varnishes have been investigated and an example of application is given for an old painting.

International audience; Cet article vise à exposer les premiers résultats d’un projet de recherche transdisciplinaire dans le domaine des sciences du patrimoine. A partir d’une réflexion sur l’utilisation croissante et les potentialités des méthodes de micro- et nano- caractérisation synchrotron pour l’étude de matériaux anciens (archéologie, paléontologie, patrimoine culturel, environnements anciens), il s’agira de dégager et tester des éléments conceptuels et méthodologiques de convergence entre sciences physico-chimiques et sciences historiques.

This article aims at presenting the first results of a transdisciplinary research programme in heritage sciences. Based on the growing use and on the potentialities of micro- and nano-characterization synchrotron-based methods to study ancient materials (archaeology, palaeontology, cultural heritage, past environments), this contribution will identify and test conceptual and methodological elements of convergence between physicochemical and historical sciences.

International audience; In order to fully characterize the zinc white artists' pigment (ZnO), much used since the mid-nineteenth century, three samples collected in the early 20th century were studied using a combination of synchrotron and macroscopic photoluminescence spectroscopy and imaging. An improved microscope setup based on synchrotron microspectroscopy and microimaging was used to study the powders dispersed onto indium foil. The synchrotron setup offered a diffraction-limited resolution of 153 nm. The PL spectra of individual grains were measured and the distribution of particles' emission spectra was mapped at the nanoscale. The results revealed that while the samples have apparent homogeneous photoluminescence behavior at the macroscale (bulk), their PL signatures are inhomogeneous below 20 μm. At the nanoscale the three powder samples have quite different PL signatures. Different sources, perhaps even different batches, of zinc white might be readily differentiated using this method.

Synchrotron photon-based methods are increasingly being used for the physico-chemical study of ancient and historical materials (archaeology, palaeontology, conservation sciences, palaeo-environments). In particular, parameters such as the high photon flux, the small source size and the low divergence attained at the synchrotron make it a very efficient source for a range of advanced spectroscopy and imaging techniques, adapted to the heterogeneity and great complexity of the materials under study. The continuous tunability of the source — its very extended energy distribution over wide energy domains (meV to keV) with a high intensity — is an essential parameter for techniques based on a very fine tuning of the probing energy to reach high chemical sensitivity such as XANES, EXAFS, STXM, UV/VIS spectrometry, etc . The small source size attained (a few micrometres) at least in the vertical plane leads to spatial coherence of the photon beams, giving rise in turn to a series of imaging methods already crucial to the field. This review of the existing literature shows that microfocused hard X-ray spectroscopy (absorption, fluorescence, diffraction), full-field X-ray tomography and infrared spectroscopy are the leading synchrotron techniques in the field, and presents illustrative examples of the study of ancient and historical materials for the various methods. Fast developing analytical modalities in scanning spectroscopy (STXM, macro-XRF scanning) and novel analytical strategies regarding optics, detectors and other instrumental developments are expected to provide major contributions in the years to come. Other energy domains are increasingly being used or considered such as far-infrared and ultraviolet/visible for spectroscopy and imaging. We discuss the main instrumental developments and perspectives, and their impact for the science being made on ancient materials using synchrotron techniques.

The use of synchrotron radiation techniques to study cultural heritage and archaeological materials has undergone a steep increase over the past 10-15 years. The range of materials studied is very broad and encompasses painting materials, stone, glass, ceramics, metals, cellulosic and wooden materials, and a cluster of organic-based materials, in phase with the diversity observed at archaeological sites, museums, historical buildings, etc. Main areas of investigation are: (1) the study of the alteration and corrosion processes, for which the unique non-destructive speciation capabilities of X-ray absorption have proved very beneficial, (2) the understanding of the technologies and identification of the raw materials used to produce archaeological artefacts and art objects and, to a lesser extent, (3) the investigation of current or novel stabilisation, conservation and restoration practices. In terms of the synchrotron methods used, the main focus so far has been on X-ray techniques, primarily X-ray fluorescence, absorption and diffraction, and Fourier-transform infrared spectroscopy. We review here the use of these techniques from recent works published in the field demonstrating the breadth of applications and future potential offered by third generation synchrotron techniques. New developments in imaging and advanced spectroscopy, included in the UV/visible and IR ranges, could even broaden the variety of materials studied, in particular by fostering more studies on organic and complex organic-inorganic mixtures, while new support activities at synchrotron facilities might facilitate transfer of knowledge between synchrotron specialists and users from archaeology and cultural heritage sciences.

A comprehensive study of the luminescence properties of cadmium pigments was undertaken to determine whether these properties could be used for in situ identification and mapping of the pigments in paintings. Cadmium pigments are semiconductors that show band edge luminescence in the visible range and deep trap luminescence in the red/infrared range. Emission maxima, quantum yields, and excitation spectra from the band edge and deep trap emissions were studied for sixty commercial cadmium pigments that span the color range from yellow to red (reflectance transition 470 to 660 nm). For paints containing cadmium pigments, luminescence from deep traps was more readily observable than that from the band edge, although the yield varied widely from zero to around 4.5%. Optimal excitation for emission is found to be in the visible for both pigments in powder form and mixed with a medium. The maxima of the deep trap emission shift with the band gap energy, providing a potentially useful way to assign pigment type even when used in pigment mixtures. The usefulness of the results of the study on mockups was demonstrated by the mapping of cadmium pigments of different hues with the aid of calibrated luminescence imaging spectroscopy in a painting by Edward Steichen, entitled Study for 'Le Tournesol' (1920). Analysis of the luminescence image cube reveals at least six unique spectral components, associated with emission from white pigments, paint binder, and cadmium red and yellow pigments. The results were compared with those from X-ray fluorescence spectrometry (XRF) and fiber-optic reflection spectroscopy (FORS) and the results obtained on paint samples containing cadmium pigments. These results show that, when present, the emission from traps can be used as an analytical tool to identify cadmium pigments, to distinguish among cadmium sulfide, cadmium zinc sulfide, and cadmium sulfoselenide, and to map cadmium pigments, even in mixtures.

International audience

Reflection imaging spectroscopy is a useful technique to remotely identify and map minerals and vegetation. Here we report on the mapping and identification of artists' materials in paintings using this method. Visible and infrared image cubes of Picasso's Harlequin Musician are collected using two hyperspectral cameras and combined into a single cube having 260 bands (441 to 1680 nm) and processed using convex geometry algorithms. The resulting 18 spectral end members are identified by comparison with library spectra, fitting by nonlinear mixing, and using results from luminescence imaging spectroscopy. The results are compared with those from X-ray fluorescence spectrometry, polarized light microscopy, and scanning electron microscopy–energy dispersive spectrometry (SEM/EDS). This work shows the potential of reflection imaging spectroscopy, in particular if the shortwave infrared region is included along with information from luminescence imaging spectroscopy.

Site specific, in situ techniques such as X-ray fluorescence (XRF) and Raman spectroscopy are commonly used to identify pigments on illuminated manuscripts. With both techniques, spectra are usually acquired on visually identified sites thought to be representative of the pigments and mixtures used for the illumination. Such visual inspection may not always ensure an adequate representation of the pigment diversity. Here we report on the application of multispectral (MSI) visible/infrared reflectance and luminescence imaging spectroscopy, along with fiber optics reflectance spectroscopy (FORS) to help determine and map the primary pigments in a late 14th century miniature on vellum, attributed to Niccolo da Bologna and representing the birth of John the Baptist. XRF analyses of visually selected sites found elements consistent with azurite, ultramarine, vermillion, lead white, "mosaic gold" and yellow earth pigments. Visible/infrared FORS analyses confirmed these assignments and showed evidence for the use of organic dyes. The spectral analysis of the MSI-reflectance images gave distribution maps for these pigments (i.e., regions of azurite, ultramarine, vermillion) along with some indication of pigment layering not identified visually. The luminescence image gave a probable map of the organic dye(s). Images acquired in the near- and shortwave-infrared (NIR and SWIR, 750 to 2400 nm) revealed preparatory sketches and illumination techniques. These results show, like those of a prior study carried out on another 14th century Italian miniature, that the combination of low light multi-spectral imaging spectroscopy with FORS provides improved in situ mapping and identification of pigments on illuminated manuscripts.

Reflectance imaging spectroscopy, the collection of images in narrow spectral bands, has been developed for remote sensing of the Earth. In this paper we present findings on the use of imaging spectroscopy to identify and map artist pigments as well as to improve the visualization of preparatory sketches. Two novel hyperspectral cameras, one operating from the visible to near-infrared (VNIR) and the other in the shortwave infrared (SWIR), have been used to collect diffuse reflectance spectral image cubes on a variety of paintings. The resulting image cubes (VNIR 417 to 973 nm, 240 bands, and SWIR 970 to 1650 nm, 85 bands) were calibrated to reflectance and the resulting spectra compared with results from a fiber optics reflectance spectrometer (350 to 2500 nm). The results show good agreement between the spectra acquired with the hyperspectral cameras and those from the fiber reflectance spectrometer. For example, the primary blue pigments and their distribution in Picasso's Harlequin Musician (1924) are identified from the reflectance spectra and agree with results from X-ray fluorescence data and dispersed sample analysis. False color infrared reflectograms, obtained from the SWIR hyperspectral images, of extensively reworked paintings such as Picasso's The Tragedy (1903) are found to give improved visualization of changes made by the artist. These results show that including the NIR and SWIR spectral regions along with the visible provides for a more robust identification and mapping of artist pigments than using visible imaging spectroscopy alone.

The analysis of various varnishes from different origins, which are commonly found on historical musical instruments was carried out for the first time with both fluorescence excitation emission spectroscopy and laser-induced time-resolved fluorescence spectroscopy. Samples studied include varnishes prepared using shellac, and selected diterpenoid and triterpenoid resins from plants, and mixtures of these materials. Fluorescence excitation emission spectra have been collected from films of naturally aged varnishes. In parallel, time-resolved fluorescence spectroscopy of varnishes provides means for discriminating between short- (less than 2.0 ns) and long-lived (greater than 7.5 ns) fluorescence emissions in each of these complex materials. Results suggest that complementary use of the two non destructive techniques allows a better understanding of the main fluorophores responsible for the emission in shellac, and further provides means for distinguishing the main classes of other varnishes based on differences in fluorescence lifetime behaviour. Spectrofluorimetric data and time resolved spectra presented here may form the basis for the interpretation of results from future in situ fluorescence examination and time resolved fluorescence imaging of varnished musical instruments.

Qualitative UV-fluorescence of varnishes is commonly used to locate repaints on paintings or to specify the homogeneousness of a varnish layer. Photographers can now use flash UV-lamps coupled with a CCD camera to obtain colour images of the fluorescence of paintings, unveiling thus both interest and difficulty to interpret these colours. Starting from this point of view, UV-fluorescence spectra appear to be a potential technique to characterize the nature of varnishes and, if possible, their state of degradation. This identification will be non-invasive, without contact, obtained in real time and workable in situ , as the identification of pigments or dyes by reflectance spectrometry which is already done in our group. The last goal will be to realize both identifications with the same device. Emission fluorescence spectra are implemented with the Jobin-Yvon Fluorolog-3, providing an incident wavelength laying between 200 and 850 nm. The emission spectra are implemented with an optical fiber linked to a Jobin-Yvon spectrometer HR460 and a multi-channel CCD detector. In a first step, popular, fresh, raw resins used between the XVI th and the XIX th century, as mastic, dammar and sandarac, have been used to prepare varnishes films with different solvents. The fluorescence spectra of these films have been carried out at different excitation wavelengths to build databases. After having tested the coherence, the limits and the accuracy of the method, we suggest different applications of our method. A synthesis of the results will be presented to characterize each varnish by their fluorescence spectra.

Photoluminescence is one of the processes by which photons are emitted after the absorption of incoming photons at a higher energy. But the yield and spectral band shape of the emission can be altered by the optical properties of the luminophore environment through scattering and absorption. To understand these effects on a photoluminescent turbid layer, the Kubelka–Munk model, which is a two-flux approximation of the radiative transfer equation, can be used. Compared to previous works, this translucent layer can be applied on a colored opaque background. The model takes into account the absorption, scattering, and luminescent properties of the layer and the reflection by the background, for both the light excitation and the light emission. The competition between these different optical interactions is studied; e.g., the model can predict the presence of an emission maximum by increasing the thickness of the luminescent layer on a light background. Moreover, the model is extended to two important cases: the presence of a photoluminescent background and the effect of a refractive index discontinuity.

For centuries, varnishes applied on works of art have been prepared with natural resins. These natural products degrade in the course of time and consequently modify the visual aspect of the work of arts. Thus, restorers must reduce the layer of varnish using solvents chosen according to the nature of varnish and not deteriorating the pictorial layer. The identification of varnishes is thus essential for the choice of the apt solvent. Until now, that identification was obtained by chemical analyses using samples. With UV fluorescence, we developed a technique allowing nondestructive identification of varnishes which can be carried out in-situ and giving results in real time. This method is based on the comparison of the spectrum of fluorescence of an unknown varnish with those of a database of recent, artificially and naturally aged varnishes of reference. Examples of identification of varnishes on several works of art are presented in this work. In parallel, the first step toward the separation and the identification of principal the fluorophores contained within the resins were carried out by liquid chromatography coupled with the electrospray mass spectrometry.; Depuis des siècles, les vernis apposés sur des œuvres anciennes sont constitués de résines naturelles. Ceux-ci se dégradent au cours du temps et modifient l'aspect visuel de l'œuvre. Les restaurateurs doivent donc alléger la couche de vernis à l'aide de solvants choisis selon la nature du vernis et n'altérant pas la couche picturale. L'identification des vernis est donc essentielle pour le choix solvant. Elle était, jusqu'ici obtenue par des analyses chimiques faites à partir de prélèvements. A l'aide de la fluorescence UV, nous avons développé une technique d'identification non-destructive des vernis, réalisable in-situ et donnant des résultats en temps réel. Cette méthode s'appuie sur la comparaison du spectre de fluorescence d'un vernis inconnu avec ceux d'une base de données de vernis de référence récents, vieillis artificiellement ou naturellement. Des exemples de reconnaissance des vernis sur plusieurs œuvres d'art du patrimoine sont présentés. Parallèlement, la séparation et l'identification des principaux fluorophores contenus au sein des résines ont été réalisées par chromatographie liquide couplée à la spectrométrie de masse utilisant l'ionisation par électrospray.