In this paper, we propose an analytical methodology for attributing provenance to natural lapis lazuli pigments employed in works of art, and for distinguishing whether they are of natural or synthetic origin. A multitechnique characterization of lazurite and accessory phases in lapis lazuli stones from Afghan, Siberian and Chilean quarries, on the pigments obtained by their purification, and on synthetic ultramarine pigments was performed. According to the results obtained, infrared spectroscopy is not a suitable technique for distinguishing the provenance of lapis lazuli, but a particular absorbance band makes it relatively easy to determine whether it is of natural or synthetic origin. On the other hand, EDS elemental composition and XRD patterns show the presence of specific mineral phases associated with specific lapis lazuli sources, and can be used to distinguish the provenance of the stones as well as-albeit to a lesser extent-the corresponding purified blue pigments. In contrast, FEG-SEM observations clearly show different stone textures depending on their provenance, although these distinctive features do not persist in the corresponding pigments. PCA analyses of EDS data allow Afghan lapis lazuli stone to be distinguished from Chilean and Siberian ones, and can distinguish between the pigments resulting from their purification as well as synthetic blue ones. Although this methodology was developed using a limited number of samples, it was tested on lapis lazuli pigments collected from three paintings (from the fourteenth to sixteenth centuries) in order to perform a preliminary validation of the technique, and based on the results, the provenance of the blue pigments employed in those artworks is proposed. Finally, upon analytically monitoring the process of purifying lapis lazuli to obtain the corresponding pigments, it was found that ion-exchange reactions occur between the alkali modifiers of silicate/aluminosilicate phases and free carboxylic acids present in the doughy mixture of natural terpenes and ground stone, namely pastello. These reactions favor (i) the retention of silicate phases in the organic mixture and (ii) the selective extraction of lazurite due to the formation of Brønsted acidic sites [Al(OH)Si], which are responsible for its high hydrophilicity in comparison to the one of the other species present in the lapis lazuli stone.
Potential utilization of calcium alkoxides as stone consolidants was considered. Reaction of Ca(OCH 3 ) 2 , Ca(OCH 2 CH 3 ) 2 (CH 3 CH 2 OH) 4 and Ca[OCH(CH 3 ) 2 ] 2 with the atmosphere in different experimental conditions was studied. The reaction produced CaCO 3 and two different pathways seem to be involved, the first taking place through CO 2 insertion into the Ca-O bond of Ca(OR) 2 species with formation of an alkylcarbonate derivative, subsequently transformed into CaCO 3 through ROH elimination; the second takes place through hydrolysis of Ca(OR) 2 to Ca(OH) 2 , which is then carbonated to CaCO 3 . The vaterite/calcite ratios found in the final CaCO 3 vary considerably with the experimental conditions adopted. Investigations demonstrated the potentiality of Ca(OCH 3 ) 2 to act as a stone consolidant. In fact, impregnation of a porous substrate, simulating the deteriorated stone, with a methanol solution of Ca(OCH 3 ) 2 , produced a crystalline vaterite film, which gradually filled all the pores and cavities of substrate and seems to fulfil the necessary requirements for a consolidant.
The Grande Albergo Ausonia & Hungaria (Venice Lido, Italy) has an Art Nouveau polychrome ceramic coating on its façade, which was restored in 2007. Soon after the conservation treatment, many tiles of the façade decoration showed coloured alterations putatively attributed to the presence of microbial communities. To confirm the presence of the biological deposit and the stratigraphy of the Hungaria tiles, stereomicroscope, optical and environmental scanning electron microscope observations were made. The characterisation of the microbial community was performed using a PCR-DGGE approach. This study reported the first use of a culture-independent approach to identify the total community present in biodeteriorated artistic tiles. The case study examined here reveals that the coloured alterations on the tiles were mainly due to the presence of cryptoendolithic cyanobacteria. In addition, we proved that the microflora present on the tiles was generally greatly influenced by the environment of the Hungaria hotel. We found several microorganisms related to the alkaline environment, which is in the range of the tile pH, and related to the aquatic environment, the presence of the acrylic resin Paraloid B72® used during the 2007 treatment and the pollutants of the Venice lagoon.
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