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Vibrational spectroscopy (Raman and FTIR) has played an important role in identifying pigments, substrata and deterioration products in rock art studies worldwide: in the laboratory and on-site. However, the detection of organic binders and carrying agents has so far been scarce and the quality of many spectra recorded on-site inadequate. In this study, possible pigments (charcoal, ochre, raptor faeces, thermally treated ostrich egg shell, etc.), binders (fat, egg, blood) and carrying agents (saliva, gall, egg, water) were selected based on artistic considerations and analysed with FTIR and Raman (514.6 and 785 nm excitation, both available in mobile instruments) spectroscopy in order to determine usable marker bands for each ingredient. The resultant marker bands were then used to analyse five ten year old San replica paints. It was found that FTIR spectroscopy is very efficient to identify organic compounds as there is no fluorescence but the broadness of the bands inhibits the exact assignment of many ingredients. A high fluorescence background experienced for many natural products prevented the recording of Raman spectra for all ingredients, in many instances though the sharp peaks usually associated with Raman spectra make identification easier than with FTIR spectroscopy. Most of the ingredients in the paints could be identified, but it is clear that better results are obtained when more that one technique is used.

Thousands of glass trade beads were excavated over a 75 year period on Mapungubwe Hill and at K2, two archaeological sites in the Limpopo valley, South Africa. An assemblage of 175 beads that appeared to be different in shape, size and colour (red, yellow, green, blue, white, black, pink, plum) was studied with Raman scattering. At least seven different chromophores or pigments (lazurite, lead tin yellow type II, Ca/Pb arsenate, chromate, calcium antimonate, Fe–S “amber” and a spinel) have been identified. Pigment identification allows the recognition of specific productions and indicated that many of the pigments colouring the beads excavated on Mapungubwe hill were manufactured after the 13th century, confirming the presence of modern beads in the archaeological record, some dating from the 19th century. This date is in agreement with the last occupation date for the hill suggested by the earlier excavators and raises questions about the revision of this date to 1290 AD by archaeologists in the 1970’s.

Ancient mosaic tesserae are a range of materials of very varied and complex nature, including pottery, stone and glass. Raman spectroscopy is a powerful tool for the analysis of all these kinds of materials. In the particular case of glasses, this technique can be used both for a study of surface weathering and for the characterization of bulk structure, but it has not yet been extensively used for the characterization of mosaic glass tesserae. We carried out Raman analyses on a set of Roman and Late Antiquity period mosaic glass samples, which allowed a good characterization of both the glass matrix and the crystalline inclusions. All the samples show the typical Raman signatures of soda-lime-silicate glasses. Several crystalline phases were also identified, being relics of raw materials used during the glass manufacturing process, such as quartz and feldspars, or linked to the glass color/opacification, such as bindheimite and cuprite. The analyses also led to the identification in some blue, turquoise and green tesserae of calcium antimonate, whose Raman signature has only recently been recognized in the scientific literature on mosaic glasses. Some emphasis is given to the analysis of red lead-containing tesserae, colored with Cu+ ions or even Cu0 (or Au0) metal nanoparticles. Samples with peculiar compositions, as well as “modern” (and restoration) samples, could quite easily be distinguished from the ancient ones by their Raman spectra.