X-ray and Infrared Microanalyses of Mona Lisa's Ground Layer and Significance Regarding Leonardo da Vinci's Palette.

An exceptional microsample from the ground layer of Leonardo da Vinci's Mona Lisa was analyzed by high-angular resolution synchrotron X-ray diffraction and micro Fourier transform infrared spectroscopy, revealing a singular mixture of strongly saponified oil with high lead content and a cerussite (PbCO3)-depleted lead white pigment. The most remarkable signature in the sample is the presence of plumbonacrite (Pb5(CO3)3O(OH)2), a rare compound that is stable only in an alkaline environment. Leonardo probably endeavored to prepare a thick paint suitable for covering the wooden panel of the Mona Lisa by treating the oil with a high load of lead II oxide, PbO. The review of Leonardo's manuscripts (original and latter translation) to track the mention of PbO gives ambiguous information. Conversely, the analysis of fragments from the Last Supper confirms that not only PbO was part of Leonardo's palette, through the detection of both litharge (α-PbO) and massicot (ß-PbO) but also plumbonacrite and shannonite (Pb2OCO3), the latter phase being detected for the first time in a historical painting.

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 Hauron's 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.

Watching Kinetic Studies as Chemical Maps Using Open-Source Software.

A nonproprietary software package, "PyMca", primarily developed for X-ray fluorescence analysis offers an easy-to-use interface for calculating maps, by integrating intensity (of X-ray fluorescence, as well as any spectral data) over Regions Of Interest (ROI), by performing per pixel operations or by applying multivariate analysis. Here we show that, while initially developed to analyze hyperspectral two-dimensional (spatial) maps, this tool can be beneficial as well to anyone interested in measuring spectral variations over one or two dimensions, these dimensions being time, temperature, and so on. Different possibilities offered by the software (preprocessing, simultaneous analysis of replicas, of different conditions, ROI calculation, multivariate analysis, determination of reaction rate constant and of Arrhenius plot) are illustrated with two examples. The first example is the Fourier transform infrared spectroscopy (FTIR) follow-up of the saponification of oil by lead compounds. The disappearance of reagent (oil) and formation of products (lead carboxylates and glycerol) can be easily followed and quantified. The second example is a combined extended X-ray absorption fine structure (EXAFS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and mass spectroscopy (MS) analysis of RhAl2O3 catalyst under NO reduction by CO in the presence of O2. It is possible to appreciate, in a single shot, Rh particles' structure and surface changes and gas release and adsorption in the reaction conditions.