The paper reports on the exploitation of an educated multi-technique analytical approach based on a wide non invasive step followed by a focused micro-destructive step, aimed at the minimally invasive identification of the pigments decorating the ceiling of the Gilded Vault of the Domus Aurea in Rome. The combination of elemental analysis with molecular characterization provided by X-ray fluorescence and UV-vis spectroscopies, respectively, allowed for the in situ non-invasive identification of a remarkable number of pigments, namely Egyptian blue, green earth, cinnabar, red ochre and an anthraquinonic lake. The study was completed with the Raman analysis of two bulk samples, in particular, SERS measurements allowed for the speciation of the anthraquinonic pigment. Elemental mapping by scanning electron microscopy-energy dispersive spectrometer combined with micro-fluorimetry on cross-section gave an insight into both the distribution of different blend of pigments and on the nature of the inorganic support of the red dye.

Limestone basements holding bronzes or other copper alloys artefacts such as sculptures, decorations and dedicatory inscriptions are frequently met both in modern and ancient monuments. In outdoor conditions, such a combination implies the corrosion products of the copper based alloy, directly exposed to rainwater, will be drained off and migrate through the porous surfaces, forming stains of different colours and intensities, finally causing the limestone structures to deteriorate.In this work we have analysed samples from two modern limestone monuments in Rome, the Botticino surfaces of the ‘Vittoriano’ (by G.Sacconi, 1885-1911- Piazza Venezia) and the travertine basement of the ‘Statua dello Studente’ (by A.Cataldi, 1920- University city, La Sapienza), and focussed our investigation on the chemical composition of the copper-stained zones using XPS (X-ray Photoelectron Spectroscopy) as a surface-specific technique.Based on observations reporting on the structure and bonding at the calcite surfaces we have identified copper complexes and mixed calcium/copper carbonates associated with the stains, as well as the chemical state of other elements therein included, and related the compositional changes with differences in chromatic characteristics and sampling locations.

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