Two sites of the Neandertal-associated Middle Paleolithic of Iberia, dated to as early as approximately 50,000 years ago, yielded perforated and pigment-stained marine shells. At Cueva de los Aviones, three umbo-perforated valves of Acanthocardia and Glycymeris were found alongside lumps of yellow and red colorants, and residues preserved inside a Spondylus shell consist of a red lepidocrocite base mixed with ground, dark red-to-black fragments of hematite and pyrite. A perforated Pecten shell, painted on its external, white side with an orange mix of goethite and hematite, was abandoned after breakage at Cueva Antón, 60 km inland. Comparable early modern human-associated material from Africa and the Near East is widely accepted as evidence for body ornamentation, implying behavioral modernity. The Iberian finds show that European Neandertals were no different from coeval Africans in this regard, countering genetic/cognitive explanations for the emergence of symbolism and strengthening demographic/social ones.

The results of the analyses of elemental composition of red and black pigments of Levantine rock art from La Saltadora rock shelters (Valltorta gorge, Castellón, Spain) are presented in this paper. Nondestructive analyses were carried out using a portable energy dispersive X-ray fluorescence (EDXRF) spectrometer developed for in situ analysis. The results revealed the strong presence of calcium in all the analyzed locations due to the contribution of the underlying calcareous bedrock and the overlying crust. Iron is the main element detected in red pigments and manganese in black pigments. Iron and calcium ratios have been found indicative of the degree of preservation of the pictorial layer. Trace elements detected in the pigment composition confirm the use of different raw materials. Therefore, this work illustrates the potential of the portable EDXRF spectrometers for in situ analysis of rock art paintings.

a b s t r a c tSpanish Levantine Rock Art is a unique pictorial expression within the prehistoric European context. Located in shelters in the inland regions of the Iberian Mediterranean basin, this art form, which must be necessarily studied in the frame of the process of neolithization of this territory, still lacks direct dating, and therefore its authorship is still open to debate.In this paper we present the first characterization of black pigments used in the Cova Remigia shelters in the Valltorta-Gassulla area (Castell on, Spain) by means of EDXRF spectrometry combined with SEM-EDS and Raman spectroscopy. Our aim is both to identify the raw material used for the preparation of black pigments and to make a first approach to the cultural choices involved in its use.The results are relevant for several reasons. Firstly, carbon-based black pigments have been identified for the first time in northern regions of Levantine rock art. Secondly, the recurrent use of black pigments in Cova Remigia questions the assumption of its restricted use in Spanish Levantine art. Thirdly, posterior repainting and graphic re-appropriation of black figures have been observed in Cova Remigia, giving rise to the combination of two colours, black and red, fact that is extremely rare in this rock art tradition. Finally, the identification of organic matter in the black pigments opens the possibility of radiocarbon dating.

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We present a new multi-analytical approach to the characterization of black pigments in Spanish Levantine rock art. This new protocol seeks to identify the raw materials that were used, as well as reconstruct the different technical gestures and decision-making processes involved in the obtaining of these black pigments. For the first of these goals, the pictorial matter of the black figurative motifs documented at the Les Dogues rock art shelter (Ares del Maestre, Castellón, Spain) was characterized through the combination of physicochemical and archeobotanical analyses. During the first stage of our research protocol, in situ and non-destructive analyses were carried out by means of portable Energy Dispersive X-Ray Fluorescence spectrometry (EDXRF); during the second stage, samples were analyzed by Optical Microscopy (OM), Raman spectroscopy, and Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (SEM-EDX). Two major conclusions have been drawn from these analyses: first, charred plant matter has been identified as a main component of these prehistoric black pigments; and second, angiosperm and conifer charcoal was a primary raw material for pigment production, identified by means of the archaeobotanical study of plant cells. For the second goal, black charcoal pigments were replicated in the laboratory by using different raw materials and binders and by reproducing two main chaînes opératoires. The comparative study of the structure and preservation of plant tissues of both prehistoric and experimental pigments by means of SEM-EDX underlines both a complex preparation process and the use of likely pigment recipes, mixing raw material with fatty or oily binders. Finally, the formal and stylistic analysis of the motifs portrayed at Les Dogues allowed us to explore the relationship between identified stylistic phases and black charcoal pigment use, raising new archaeological questions concerning the acquisition of know-how and the transfer of traditionally learned chaînes opératoires in Spanish Levantine rock art.

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The results of the first elemental and structural physicochemical analyses (SEM–EDX, TXRF, XRD, FTIR, GC and EDXRF) of Early Neolithic red pigment samples from the region of Valencia confirm one of the earliest uses of cinnabar (HgS) in Spain (5300 to 5000 cal bc). They also inform on the storage of massive quantities of hematite and the development of specific technologies of hematite‐based paint production and use. The samples were recovered at the three most significant Early Neolithic sites of the Mediterranean coast of Spain: Cova de l'Or (Beniarrés, Alacant), Cova de la Sarsa (Bocairent, Valencia) and Cova Fosca (Vall d'Ebo, Valencia), which together have provided the most important European collection of Cardial ceramic ware (chronoculturally diagnostic of the Early Neolithic).