The extent and nature of symbolic behavior among Neandertals are obscure. Although evidence for Neandertal body ornamentation has been proposed, all cave painting has been attributed to modern humans. Here we present dating results for three sites in Spain that show that cave art emerged in Iberia substantially earlier than previously thought. Uranium-thorium (U-Th) dates on carbonate crusts overlying paintings provide minimum ages for a red linear motif in La Pasiega (Cantabria), a hand stencil in Maltravieso (Extremadura), and red-painted speleothems in Ardales (Andalucía). Collectively, these results show that cave art in Iberia is older than 64.8 thousand years (ka). This cave art is the earliest dated so far and predates, by at least 20 ka, the arrival of modern humans in Europe, which implies Neandertal authorship.
Raman microscopy, with its unique versatility and special advantages of no sample preparation and nondestructive analysis of both inorganic and organic materials, is now well established as the best technique for studying pigments and their fillers in ancient or recent paintings. Here this technique was applied for the first time to prehistoric rock art. Microsampling was carried out on red and black parts of Palaeolithic paintings in the three caves Les Fieux, Les Merveilles and Pergouset in limestone of the Quercy District, Lot Department, France. The initial results are: (a) the identification of 'normal' haematite pigment in red microsamples from each cave; (b) the discovery of an additional, but rare, orange-red phase (A) which seems to be a disordered form of goethite; (c) the confirmation of amorphous carbon in some black microsamples; and (d) the recognition of Mn oxide/hydroxide in some other black microsamples. Hence Raman microscopy is sufficiently powerful for distinguishing different red and different black pigments without the use of additional complementary techniques. Hence it is now reasonable to envisage analysis with optical fibres and a remote sensor inside the caves in order to avoid damaging prehistoric rock art by microsampling.
Raman microscopy (RM) was applied to an ongoing study of prehistoric pigments employed in Palaeolithic wall paintings in the Roucadour Cave (France). Micro-samplings were carried out on parts of red or black painted figures representing animals and also negative human hands.These first analyses showed that in all the red micro-samples, the main pigment is haematite. Where the tone was dark red, well-formed crystals of haematite were identified, but magnetite, Mn oxide and carbon grains were also found. An intermediate mineral phase structurally in-between goethite and haematite was also identified. In red samples, the yellowish hydrated species goethite was also detected. A great quantity of white, greyish-white and yellowish-white crystals were present in the pigment, and many of them were identified as calcite or quartz.The black pigments were constituted of well-formed crystals of Mn oxyhydroxide in some black microsamples. Suggestions are made for the identification of some mineral species (bixbyite, hollandite, nsutite) but there is still much uncertainty on this topic. In others, amorphous carbon grains were utilised as the main pigment. This distinction is important for orienting the research towards a subsequent investigation by radiocarbon dating.Traces of anatase were found in black pigments, as were traces of rutile and gypsum in red pigments. It is interesting that haematite occurs in all the black pigments, black because of the great content of C or of Mn oxyhydroxide, and that several red pigments contain minor carbon, such that each pigment is a mixture with at least five different species in most micro-samples. These data are compatible with the possibility that the prehistoric artists used naturally-occurring impure geological materials (e.g. (Fe,Mn)-ochre rocks) and natural biological materials (e.g. wood or oil to make charcoal or soot), but it cannot exclude the fact that they may have treated the raw materials and/or manufactured mixtures of purer materials.
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