Use of in situ and confocal Raman spectroscopy to study the nature and distribution of carotenoids in brown patinas from a deteriorated wall painting in Marcus Lucretius House (Pompeii).

Colonisation of wall paintings by microorganisms and other organisms is a well-known problematic phenomenon. Besides taxonomic identification of the biodeteriogen, it is essential to evaluate the consequences of the colonisation, e.g., unsightly coloured patinas. This work proposes new methodology for characterisation of the nature of the main carotenoids and their distribution in brown stains or patinas of a deteriorated wall painting on the north wall of the atrium of Marcus Lucretius House (Pompeii, Italy). Characterisation of the brown patinas and surrounding areas (plaster and polychromy) from the wall painting started with in situ screening using, mainly, a portable Raman instrument with a handheld FTIR (DRIFTS sampling interface) in order to select the sampling areas suitable for further analysis in the laboratory. Two wall painting fragments were then analysed in the laboratory in two steps. First, microscopic observations (SEM and phase-contrast microscopy) were used to determine whether biodeteriogens were present in the samples. In a second step, confocal Raman microscopy (785 and 514 nm excitation lasers) was used to characterise the main biogenic compounds of the brown stains. Because of the resonance Raman effect (514 nm excitation laser), it was possible to obtain reliable Raman features to assign not only the nature of the main biogenic pigments (carotenoids) present in the stains, but also their spatial conformation. Moreover, Raman confocal applications, for example, Raman imaging and depth profiling were also used in a first attempt to determine the distribution of biosynthesised carotenoids in the stains, and to determine the thickness of the brown patinas.

In-situ multianalytical approach to analyze and compare the degradation pathways jeopardizing two murals exposed to different environments (Ariadne House, Pompeii, Italy).

This study aimed at using portable analytical techniques to characterize original and decayed materials from two murals paintings of Ariadne House (archaeological site of Pompeii, Italy) and define the degradation pathways threatening their conservation. The first wall, located in an outdoor environment, has been directly exposed to degradation processes triggered by weathering and atmospheric pollution. The second wall, placed in a basement under the ground floor, has been constantly sheltered from sunlight exposure and drastic temperature fluctuations. The analytical data obtained in-situ by using Raman spectroscopy and Laser Induced Breakdown Spectroscopy (LIBS) correlates the degradation patterns affecting the two surfaces to their environmental context. The deterioration processes detected on the outdoor wall, which entailed the complete loss of the paint layer, were mostly related to leaching and thermal fluctuation phenomena. The mural painting from the basement instead, showed deep degradation issues due to soluble salt infiltration and biological colonization. The results obtained from this unique case of study highlight the indispensable role of in-situ spectroscopic analysis to understand and predict the degradation pathways jeopardizing the cultural heritage and provide to the Archaeological Park of Pompeii important inference to consider in future conservation projects.