Anna Candida Felici

Spectral Behavior of White Pigment Mixtures Using Reflectance, Ultraviolet—Fluorescence Spectroscopy, and Multispectral Imaging

Reflectance spectroscopy, ultraviolet (UV)—fluorescence spectroscopy, and multispectral imaging have been widely employed for pigment identification on paintings. From ancient times to the present, lead white, zinc white, and titanium white have been the most important white pigments used for paintings and they are used as pigment markers for dating a work of art. The spectral behavior of these pigments is reported in several scientific papers and websites, but those of their mixtures are quite unknown. We present a combined nondestructive approach for identifying mixtures of lead white, zinc white, and titanium white as powder and dispersed in two different binder media (egg yolk and linseed oil) by using reflectance spectroscopy, spectrofluorimetry, multispectral reflectance and UV-fluorescence imaging. We propose a novel approach for mapping the presence of white pigments in paintings by false color images obtained from multispectral reflectance and UV-fluorescence images. We found that the presence of lead white mixed with either zinc white or titanium white is highly detectable. Zinc white mixed with lead white or titanium white can be identified due to its UV-fluorescence emission, whereas titanium white in association with lead white or zinc white is distinguishable by its reflectance spectral features. In most cases, the UV-fluorescence analyses also permit the recognition of the binder media in which the pigments are dispersed.

Characterization and Digital Restauration of XIV-XV Centuries Written Parchments by Means of Nondestructive Techniques: Three Case Studies

Parchment is the primary writing medium of the majority of documents with cultural importance. Unfortunately, this material suffers of several mechanisms of degradation that affect its chemical-physical structure and the readability of text. Due to the unique and delicate character of these objects, the use of nondestructive techniques is mandatory. In this work, three partially degraded handwritten parchments dating back to the XIV-XV centuries were analyzed by means of X-ray fluorescence spectroscopy, µ-ATR Fourier transform infrared spectroscopy, and reflectance and UV-induced fluorescence spectroscopy. The elemental and molecular results provided the identification of the inks, pigments, and superficial treatments. In particular, all manuscripts have been written with iron gall inks, while the capital letters have been realized with cinnabar and azurite. Furthermore, multispectral UV fluorescence imaging and multispectral VIS-NIR imaging proved to be a good approach for the digital restoration of manuscripts that suffer from the loss of inked areas or from the presence of brown spotting. Indeed, using ultraviolet radiation and collecting the images at different spectral ranges is possible to enhance the readability of the text, while by illuminating with visible light and by collecting the images at longer wavelengths, the hiding effect of brown spots can be attenuated.

Multi-technique characterisation of commercial alizarin-based lakes

The characterization of ancient and modern alizarin-based lakes is a largely studied topic in the literature. Analytical data on contemporary alizarin-based lakes, however, are still poor, though of primary importance, since these lakes might be indeed present in contemporary and fake paintings as well as in retouchings. In this work we systematically investigate the chemical composition and the optical features of fifteen alizarin-based lakes, by a multi-analytical technique approach combining spectroscopic methods (i.e. Energy Dispersive X-ray Fluorescence Spectroscopy, EDXRF; Attenuated Total Reflectance Fourier-Transform Infrared Spectroscopy, ATR-FTIR; X-ray Powder Diffraction, XRD; UV induced fluorescence and reflectance spectroscopies) and chromatography (i.e. High-performance Liquid Chromatography coupled with a Photodiode Array Detector, HPLC-PDA). Most of the samples contain typical compounds from the natural roots of madder, as occurring in ancient and modern lakes, but in two samples (23600-Kremer-Pigmente and alizarin crimson-Zecchi) any anthraquinonic structures were identified, thus leading to hypothesize the presence of synthetic dyes. The detection of lucidin primeveroside and ruberythrique acid in some lakes suggest the use of Rubia tinctorum. One sample (23610-Kremer-Pigmente) presents alizarin as the sole compound, thereby revealing to be a synthetic dye. Moreover, gibbsite, alunite and kaolinite were found to be used as substrates and/or mordants. Visible absorption spectra of the anthraquinonic lakes show two main absorption bands at about 494-511nm and 537-564nm, along with a shoulder at about 473-479nm in presence of high amounts of purpurin. Finally, from the results obtained by UV induced fluorescence spectroscopy it is possible to figure out that, although it is commonly assumed that the madder lake presents an orange-pink fluorescence, the inorganic compounds, added to the recipe, could induce a quenching phenomenon or an inhibition of the fluorescence, as occurring in some commercial alizarin-based lakes.