This study presents the results of the examination and characterisation of the wall paintings that decorate the rupestrian church named Grotta del Crocifisso, which is located in the territory of Lentini (eastern Sicily, few tens of kilometres from Catania and Syracuse). The earliest mural paintings in the church date back to the twelfth century AD. A multi-analytical approach was adopted for the characterisation of stone materials, secondary degradation products, and pigments. For this purpose, the following techniques were used: reflected light microscopy (RLM), polarised light microscopy on thin sections (PLM), X-ray powder diffraction (XRPD), mercury intrusion porosimetry (MIP), portable X-ray fluorescence (p-XRF), scanning electron microscopy (SEM-EDS), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy (RS). The lithic substrate and the plaster’s coating layers were thoroughly characterised from compositional and textural points of view, and the use of locally available raw materials was established. Similarly, the newly formed crystalline phases produced by alteration processes of the original materials were recognised. The red, yellow, brown, and green pigments were easily identified by p-XRF and SEM-EDS. The use of “earth pigments” widely available in the surrounding area (various types of ochre) was thus highlighted. The recognition of the dark blue pigment created some additional issues in its identification, making further diagnostic methods necessary. In fact, the use of the most common mineral pigments was categorically excluded by both p-XRF and SEM-EDS, since no chromophore metallic elements were highlighted with the exception of trace amounts of iron. A combination of detailed microscopic observations together with the application of FTIR and RS supported the use of an organic pigment obtained from the maceration of woad (Isatis tinctoria). The green pigment is the result of a mixture between woad and yellow ochre. Woad is even today easily available in Sicily, and some additional experimental tests were carried out on Isatis tinctoria that had been freshly collected in the area (treated with traditional procedures). Over the past centuries, woad was widely used for dyeing fabrics, but its practice for wall paintings has only been sporadically proven. The identification reported in this case study could be considered a novelty at least in the Sicilian panorama.
Interpreting depositional settings of cave sites is generally problematic, especially in absence of palaeontological/archaeological evidence. This is the case of some deposits at San Teodoro Cave (Sicily), a key site for the Mediterranean Palaeolithic. In a stratigraphic level interrupted by a carbonatic concretion, phosphatic nodules are present only in the part enclosed between the concretion and the cave wall. The discovery of these nodules combined with the punctual lack of fossils had initially suggested an erosion phenomenon and subsequent formation of nodules at a vadose level. Here we show the usefulness of an integrated, geochemical-palaeoecological approach in defining stratigraphy and palaeoenvironmental reconstructions. XRD, ICP-OES, ATR-FTIR and EDS analyses allowed the formulation of a new hypothesis regarding the origin of the nodules, the depositional dynamics, and the role played by the guano produced by an extensive colony of bats. The role of barium and rubidium in detecting taphonomical processes has been highlighted.
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