LIBS analysis to define the alteration processes on the surface of ancient stones: the case study of Romanesque medieval monuments (Italy)

Weathering and bio-deterioration processes frequently affect the chromatic aspect of the stones used in the monuments. The surface alteration involves both physical modifications (e.g., increase of porosity) and chemical-mineralogical transformations of the rock, with formation of new secondary phases and deposition of the organic substances and inorganic solid phases (amorphous or crystalline particles). This research aims to study the surface films of stones (i.e., basalts, pyroclastic rocks, limestone, marbles) used in some historical-cultural relevant Sardinian Romanesque churches (XI-XIV sec.) using LIBS and XRD analysis. These latter, together with petrographic analysis by polarized light microscopy in thin section, are useful to reconstruct the micro-stratigraphic aspects of different film levels. The results highlight three different cases: i) chromatic alteration of the stone surface, ii) chemical-mineralogical alteration of stone with formation of coatings similar to the stone substrate, iii) chemical-mineralogical processes with the formation on the surface of secondary phases not related to the substrate, with the presence of Ca-oxalate (i.e. weddelite, whevellite). The presence of the Ca-oxalates, as noted in literature, is a testimony of application of organic substances on the surfaces themselves, with aesthetic purposes, to standardize or improve the color of the stone, or conservative, to limit the negative effects of weathering.