Juliette Langlois

Molecular criteria for discriminating museum Asian lacquerware from different vegetal origins by pyrolysis gas chromatography/mass spectrometry

This paper focuses on the identification of several chemical markers of vegetal species of Oriental lacquers with the aim at providing a methodology consistent with sampling restrictions necessarily applied in the field of cultural heritage. The method proposed is based on rapid and easy single step thermally assisted hydrolysis-methylation (THM) pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analysis that can be carried out with a minimum amount of matter (typically 10 μg for a sample collected on a museum or an archaeological object). The main contribution of this study is to provide multiple molecular criteria for discriminating the three Asian species used for making lacquers, namely Rhus verniciflua Stokes, Rhus succedanea and Melanorrhoea usitata. Because these trees grow in specific areas, identifying the species involved in ancient lacquer coatings also provides geobotanical data and fruitful information on the exchange networks and trading routes developed by ancient societies. With this purpose, a systematic study of all pyrolysis products of lacquer coatings was carried out on modern dried lacquer films from authentified provenance. It was demonstrated that the whole pyrolysis products play a significant role in identifying the vegetal species. The chemotaxonomic value of homologous series of alkanes, alkenes and benzene derivatives, rarely explored until now, was assessed. It was shown that the combination of data related to five distinct groups of pyrolytic markers (composition and/or distribution of alkanes, alkenes and benzene, alkenyl-, alkylcatechol and phenol derivatives) provided new strong criteria to establish vegetal origin and provenance of Asian artworks, even though they have been largely altered over time. Case studies of archaeological Chinese lacquered artefacts and Japanese Buddhistic altar were thereafter successfully investigated to address informative potential and efficiency of these criteria on ancient and degraded lacquer coatings.

The ID21 X-ray and infrared microscopy beamline at the ESRF: status and recent applications to artistic materials

The ID21 beamline (European Synchrotron Radiation facility, France) is a multi micro-analytical platform combining X-ray and infrared micro-probes, for characterization of elements, species, molecular groups and crystalline structures in complex materials. Applications are mainly in the fields of cultural heritage, life science, environmental and earth sciences, materials sciences. Here, we first present the status of instruments: (i) the scanning micro-spectroscopy end-station, operating from 2.0 to 9.2 keV, under vacuum and offering cryo conditions, for the acquisition of 2D micro X-ray fluorescence (μXRF) maps, single point micro X-ray Absorption Near Edge Structure (μXANES) spectra and speciation maps with sub-micrometric resolution; (ii) the XANES full-field end-station, operating in the same vacuum and energy conditions, for the acquisition of hyper-spectral radiographs of thin concentrated samples, resulting in speciation maps with micrometric resolution and millimetric field of view; (iii) the scanning micro-X-ray diffraction (μXRD)/μXRF end-station, operating at 8.5 keV, in air, for the acquisition of 2D crystalline phase maps, with micrometric resolution; and (iv) the scanning infrared microscope, operating in the mid-infrared range for the acquisition of molecular maps and some structural maps with micrometric resolution. Recent hardware and software developments are presented, as well as new protocols for improved sample preparation of thin sections. Secondly, a review of recent applications for the study of cultural heritage is presented, illustrated by various examples: determination of the origin of the color in blue Chinese porcelains and in brown Sevres porcelains; detection of lead in ink on Herculaneum papyri; identification and degradation of modeling materials used by Auguste Rodin and of chrome yellow pigments used by Vincent van Gogh. Cryo capabilities are illustrated by the analysis of plants exposed to chromate solutions. These examples show the variety of materials analyzed, of questions tackled, and particularly the multiple advantages of the ID21 analytical platform for the analysis of ancient and artistic materials.

Analysis and conservation of modern modeling materials found in Auguste Rodin's sculptures

Prior to the exhibition Portrait-making, Rodin and his models (2009), the Rodin museum wanted to restore two busts of Hanako and Clemenceau. Interestingly, these two sculptures contain pieces of modern modeling materials (MMMs) invented at the end of the nineteenth century as an alternative to clay or waxes. The poor state of conservation of the two portraits made any handling and exhibition impossible. Accordingly, the purpose of this article is twofold: to contribute to technical art history and conservation. Elemental and chemical analyses were done on samples from 12 sculptures (SEM–EDX, FTIR, GC–MS, GC–FID, XRD, synchrotron-based µXRF, µXANES, and µFTIR) aimed at identifying the composition of MMMs used by Rodin on plaster sculptures and establishing hypotheses about the origins of their degradation. This thorough study of their composition and degradation was necessary to implement an appropriate restoration plan. The development of conservation protocols adapted to such materials is rarely documented. Different tests were performed on mock-ups (pH, solubility, adhesion, consolidation, and cleaning). In particular, a protocol based on laser cleaning was developed and successfully applied to remove superficial dust and crusts so that the sculptures regained their original aspect.

Rediscovering Ducos du Hauron's Color Photography through a Review of His Three‐Color Printing Processes and Synchrotron Microanalysis of His Prints

Louis Ducos du Huron (1837-1920) dedicated his entire life to the elaboration of physical-chemical processes for color photography. This study aimed at highlighting his unique contribution to three-color printing through 1) an in-depth review of the many protocols he published and 2) the synchrotron-based IR and X-ray microanalysis of fragments sampled in three artworks. Ducos du Haurons method relied on the preparation and assembly of three monochromes (red, blue, yellow). This study brings to light complex multistep recipes based on photochemistry (carbon print), organic, and inorganic chemistry. The various ingredients involved (e.g., pigments, dichromate gelatin, collodion, resin) were identified and localized through their spectroscopic signature, confirming the relevance of synchrotron spectromicroscopy for the characterization of historical photographs. The impressive correlation between texts and chemical analyses calls for a wider application to the history of photography.

Synchrotron-based micro-analyses of artistic materials at ID21, ESRF

Marine Cotte1, Letizia Monico2, Koen Janssens3, Wout De Nolf1, Murielle Salomé1, Juliette Langlois4 1Id21, Esrf, Grenoble, France, 2Department of Chemistry, Biology and Biotechnologies/ SMAArt Centre and CNR-ISTM, University of Perugia, Perugia, Italy, 33Department of Chemistry, AXES Research Group, University of Antwerp, Antwerp, Belgium, 4Centre de Recherche et de Restauration des Musées de France (C2RMF), Paris, France E-mail: cotte@esrf.fr