Characterization and sources of Paleolithic–Mesolithic ochre from Coves de Santa Maira (Valencian Region, Spain)

Abstract

The origin of iron‐oxide materials found at Paleolithic and Neolithic sites in the Spanish Mediterranean region is a pivotal issue that has not yet been explored. The aim of this study is to investigate the exploitation of local ochre sources during the different archaeological phases identified at the site of Coves de Santa Maira (Valencian Region, Eastern Spain). A sampling strategy and a methodological approach were developed. Lumps of ochre and raw materials were sampled from the archaeological site and its surroundings. The archaeological materials studied are from the occupational phases dated to between 15 and 6 ka cal BP, whereas the raw materials sampled from the surroundings of the cave are red fine‐grained and earthy‐grained sedimentary materials and Late Triassic (Keuper) clays. Morphological, mineralogical, and chemical analyses of the samples were carried out, and quantitative data on ochre fragments and processing tools recovered at the site were also included. Finally, Fe‐normalized and log10 transformed data and multivariate statistical analysis, using major, trace, and rare earth elements as variables, were applied to compare the mineralogical and chemical profiles of the archaeological materials with those from geological sources. The results obtained have provided interesting data about iron‐based mineral exploitation during Prehistory in the studied region.

Correlated Functional Models with Derivative Information for Modeling Microfading Spectrometry Data on Rock Art Paintings

“…Due to the complexity of materials found in rock art paintings, a combination of analytical techniques is often needed to provide a comprehensive identification of the pigment, substrate systems at a particular site [66]. At the elemental analysis level, the use of scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) and X-ray fluorescence (XRF) spectrometry has been essential for enhancing the current understanding of these materials, as can be seen from various studies conducted on several rock art sites from Valencia, Spain [67][68][69]. In some cases, inductively coupled plasma-mass spectrometry (ICPMS) has been employed for elemental analysis due to its enhanced sensitivity and the possibility of conducting semi-quantitative analysis; this can be seen for example in two separate studies conducted in Spain [67] and Australia [70].…”

“…At the elemental analysis level, the use of scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) and X-ray fluorescence (XRF) spectrometry has been essential for enhancing the current understanding of these materials, as can be seen from various studies conducted on several rock art sites from Valencia, Spain [67][68][69]. In some cases, inductively coupled plasma-mass spectrometry (ICPMS) has been employed for elemental analysis due to its enhanced sensitivity and the possibility of conducting semi-quantitative analysis; this can be seen for example in two separate studies conducted in Spain [67] and Australia [70]. Most researchers agree that to provide a more accurate identification of the mineral content of rock art, molecular techniques must be used in conjunction with elemental analysis.…”

Invasive and Non-Invasive Analyses of Ochre and Iron-Based Pigment Raw Materials: A Methodological Perspective

“…X-ray powder diffraction (XRPD) is invasive but it is global, very accurate thanks to exhaustive international reference database such as the PDF (powder diffraction files) from the ICDD (International Centre for Diffraction Data ®), and also semi-quantitative. Petrography is another destructive method, it requires the preparation of polished thin sections, but its advantage is its high precision in the determination of the arrangement of the minerals and their crystalline nature [16,35,37,42,48,49]. Micro-Raman spectrometry is a point by point method, allowing the analyses of a very small volume, single grains for instance, which makes it ideal for the analyses of ochre powder deposits and coatings, including drawings and paintings [42,[50][51][52][53][54][55].…”

Characterizing the pigments and paints of prehistoric artists

“…Indeed, accurate diagnostic analysis of rock art productions can provide insight into pigments' raw materials and their provenance, offering precious information on the geographic practices and the social networks of prehistoric artists and their counterparts (Chalmin et al 2006;Iriarte et al 2009;Jezequel et al 2011;Mas et al 2013;Pitarch et al 2014), as well as into painters' manufacturing methods for pigment processing, such as grinding, heating, sieving and settling, and pigment application techniques (Menu and Walter 1992;Salomon et al 2008;Bonneau et al 2012;Salomon et al 2015, Hernanz et al 2008López et al 2017;Cuenca-Solana et al 2016;Gay et al 2020). Through these sorts of approaches, we obtain information to reconstruct the different steps of the chaîne operatoire (operative sequence) required to produce an artwork, the behaviours, acts and skills of ancient artists and their changes over space and time, of interest to identify cultural differences, similarities and interactions (Jezequiel et al 2011;Bonneau et al 2012;Pitarch et al 2014;Velliky et al 2020;Tortosa et al 2020). Moreover, the physicochemical analyses of the rock paintings are also important to characterize any alteration mechanisms threatening the preservation of the paintings, due to natural aging and weathering or to anthropic direct or indirect interventions.…”

“…Blombos cave in South Africa 100,000 years ago (Henshilwood et al 2011), Qafzeh Cave in Israel around 92,000 years ago (Hovers et al 2003), Porc-Epic Cave in Ethiopia ca. 40 ka cal BP (Rosso et al 2014), Santa Maira in Spain between 15 and 6 ka cal BP (Tortosa et al 2020), Cova de l'Or in Spain in early Neolithic deposits (Domingo et al 2012), the Early-Middle Holocene site of Takarkori, in Lybia (di Lernia et al 2016), among many others-reveals that the use of colouring raw materials was not accidental but a well-planned activity since prehistoric times, demanding an important investment of time and effort to source and process these materials.…”