XPS characterization of (copper-based) coloured stains formed on limestone surfaces of outdoor Roman monuments

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.