Photophysics and photochemistry of carminic acid and related natural pigments.

Carminic acid (CA) and other related compounds have been widely used as dyes in cultural heritage, cosmetics and the food industry. Therefore, the study of their properties upon photoexcitation is particularly important. In this work, the photophysical and photochemical properties of CA, carminic lake and other related pigments in aqueous solutions are revisited. Novel quantitative information regarding the fate of the photoexcited states is provided including the efficiency of reactive oxygen species (ROS) photosensitized production (i.e., singlet oxygen and hydrogen peroxide) as well as the efficiency of nonradiative deactivation pathways. Laser-induced optoacoustic spectroscopy (LIOAS) data revealed that for all the investigated compounds, almost all the absorbed energy is released as prompt heat to the media. This is in agreement with the fact that other deactivation pathways, including fluorescence (ΦF ∼ 10-3-10-5), photochemical degradation (ΦR ∼ 10-4) and/or photosensitized ROS formation (ΦH2O2 < 10-5 and ΦΔ âˆ¼ 0), are negligible or null. In addition, a comprehensive investigation of the photodegradation of CA and lake is herein reported. The influence of different experimental parameters such as irradiation wavelength and oxygen partial pressure was evaluated. UV-vis absorption and fluorescence emission spectroscopy in combination with chemometric data analysis were used to elucidate the relevant aspects of the photodegradation mechanism involved and the spectroscopic features of the photoproducts generated. In aqueous media, CA follows an O2-dependent photochemical degradation when subject to elapsed photoexcitation in the UVB, UVA and visible regions. The photoproduct profile depends on the excitation wavelength giving rise to quite distinctive spectroscopic profiles. With respect to lake, our data suggest that upon photoexcitation, this pigment releases a CA-like chromophore that follows a similar fate to CA.

A multi-analytical approach for the characterization of modern white paints used for Argentine concrete art paintings during 1940-1960.

Modern art has challenged many aspects of the analytical approaches that are typically used for traditional paint characterization and ageing studies. The paint industry has changed significantly throughout the twentieth century, frequently altering its manufacturing techniques in order to achieve paints with improved appearance, application and performance for a range of diverse household, industrial and artistic uses. This has led to the appearance and use of a multitude of new binding media, pigments and additives, most of which require new analytical methods for their identification. Concrete art is the name given to a significant art movement that took place in Argentina (and other nearby countries) during the 1940s and 1950s, at the exact same time as a flourishing paint industry was utilizing many of these new products and diversifying formulas. This paper reports on some initial findings from a long-term study to develop and apply analytical methodologies on paint samples from a number of Concrete artworks, that will help to better understand art history and advance the conservation field by shedding light on these artist's painting techniques, and the ageing behavior of their materials. Specifically, samples of white paints manufactured by local paint companies in Argentina from that time period were purchased and studied with a multi-analytical approach, which will serve as a reference collection for the field. The analytical techniques used were X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray analysis (SEM-EDX) and gas chromatography coupled with mass spectrometry (GC/MS) with previous derivatization. Artworks samples were studied with a similar multi-analytical approach, and utilized micro-Raman spectroscopy instead of XRD, for its non-destructive application. A wide range of possible compounds was identified due to the complementarity use of analytical techniques, representing a significant first step in Argentinian modern art research.

Virtuous colours for Mary. Identification of lapis lazuli, smalt and cochineal in the Andean colonial image of Our Lady of Copacabana (Bolivia).

The image of Our Lady of Copacabana, a gilded polychrome sculpture carved in maguey wood in 1583, is one of the most important devotions in the Americas. In former research, we have identified the use of gypsum, Armenian bole, cerussite and atacamite in its polychromy. In this study, a red sample taken from the Virgin's tunic and a blue sample extracted from the cloak have been analysed with the aim to identify both pigments and offer insights into the painting technique. Analysis by micro-Raman spectroscopy complemented with scanning electron microscopy-energy dispersive spectroscopy and high-performance liquid chromatography allowed the identification of carmine lake in the red sample. Analysis by micro-Raman spectroscopy of the surface of the blue sample and its cross section showed the presence of smalt-the blue-glass pigment-over a cerussite layer, bathed by a very thin ultramarine layer-from a probable native origin-following a pictorial tradition that would last even until the eighteenth century. This is the first time that lapis lazuli has been scientifically identified in a Spanish American colonial painted layer.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.