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Past thermal history of goethite and hematite fragments from Qafzeh Cave deduced from thermal activation characteristics of the 110°C TL peak of enclosed quartz grains

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The first direct evidence for high temperature firing of ochre as early as 100 ka ago is presented. The thermal activation properties of three ochre fragments from archaeological levels at Qafzeh Cave, Israel, and a natural ochre from a geological source near Qiryat Shemona, Israel, were studied. The occupation of Qafzeh Cave is dated to ~100 ka ago. Under some conditions, the past thermal history of quartz can be deduced on the basis of the thermal activation characteristic (TAC) of its 110°C thermoluminescence (TL) peak. The TAC of quartz grains extracted from as-recovered ochres showed wide differences in the onset of sensitization. Annealing the grains in the laboratory for 600 seconds at 390°C shifted the onset of sensitization up by 200° in the geological ochre and the archaeological ochre QS-2, but not at all in the archaeological ochre QS-1 and only by 30° in the archaeological ochre QS-4. This constitutes proof that QS-1 had indeed been heated in antiquity to a temperature in excess of our anneal, while QS-4 had been heated to a temperature equivalent to only slightly less than what we had chosen. We thus conclude that very early modern humans may have utilised deliberate heat treatment for the production of a variety of ochre colours. We also demonstrate that the direct luminescence dating of heated ochre fragments from archaeological sites is feasible, provided that TAC analysis confirms that they had been heat treated in antiquity to a sufficiently high temperature to have reset the TL clock, and that information essential to annual dose rate reconstruction is collected at time of excavation.
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... The study sites, the ST cave and two nearby springs, the Sorgente Ramosa spring (CA), near the village of Caronia, and the Beato Diego di Sinagra spring (SI), in the village of Sinagra, are in the Messina province, on the slopes of the Nebrodi Mountains, in north-eastern Sicily (Fig. 1). This area belongs to the Kabilo-Calabride geo-structural unit (Giunta et al., 2013a(Giunta et al., , 2013b and is characterised by complicated geo-structural processes involving several faults and overthrusts. The ST site (Fig. 1) is a large cave of about 1200 square metres, located at about 1 km from the coastal village of Acquedolci (Messina province) at about 140 m a.s.l. ...
... The area of SI spring is mainly characterised by the occurrence of Holocene sand and gravel, Palaeozoic phyllads and metaarenites, and Caenozoic arenites and conglomerates of the Capo d'Orlando Flysch. This area is remarkably affected by direct faults (Giunta et al., 2013b). ...
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The use of iron pigments is well documented in the archaeological horizons of the different parts of the world since the Middle Pleistocene. The mineralogical and chemical composition of the pigments allowed defining, in most cases, their inorganic origin, which were then used after a limited transformation and manipulation. The use of a biogenic ochraceous pigment and its manipulation has recently been described in a late Holocene archaeological horizon of the American continent. Here we describe the earliest case of archaeological use of ferrous pigment produced by iron-oxidising bacteria (FeOB), the first identified in a European Epigravettian (late Upper Palaeolithic) layer, at the San Teodoro site in Sicily, Italy. Samples of the ochraceous archaeological deposit, overlying a large burial site, were analysed ac- cording to current methods of physical analysis and SEM highlighting a matrix of bacterial structures and a chemical composition coherent with biogenic productions. The physical-chemical analysis of the archaeological material from the Palaeolithic site, and of the modern bacteriogenic iron sediments from two close springs gave consistent results even after heat treatment. In absence of Terra Rossa or other easily available inorganic ferrous materials in the hinterland of their site, the hunter-gatherers identified several possible water sources rich of pigment used for covering a multiple burial. The implications of these results influence interpretations of the ecology of the late-glacial and Epigravettian sites in Europe, especially in relation to problems such as the increasing complexity of behaviours, the need to establish rituals and the search for materials.
... Cette approche précautionneuse nous a donc permis de parvenir à la conclusion que les matières colorantes rouges et noires de la grotte du Renne ont été sélectionnées au niveau de formations géo- Knight et al. 1995, Ambrose 1998, Barham 1998, Watts 1999, d'Errico & Soressi 2002, Soressi & d'Errico 2007, d'Errico et al. 2003a, d'Errico 2003, Henshilwood & Marean 2003, Henshilwood et al. 2002, Hovers et al. 2003, Godfrey-Smith & Ilani 2004, Van Peer et al. 2004, Conard 2005, Barton 2005, Wadley 2005a,b, d'Errico & Vanhaeren 2008, d'Errico 2008, Henshilwood et al. 2009, Wadley et al. 2009 (Masson 1986, Popelka et al. 2005, Edwards et al. 1998, Mortimore et al. 2004 On compte ainsi un grand nombre d'expérimentations destinées à réaliser un tannage à l'ocre rouge ou à l'hématite (Audouin & Plisson 1982, Philibert 1994, Zinnen 2004, par exemple). ...
... Cependant, en l'absence de témoignage d'utilisation des ces matières colorantes rouges issues du chauffage de la goethite, nous ne pouvons que supposer l'existence de ce chauffage volontaire, qui, manifestement, n'a pas été systématiquement contrôlé, comme peut en témoigner le bloc polychrome Skhul 2.Faute d'avoir procédé aux analyses auxquelles nous nous sommes scrupuleusement et longuement attachée, de nombreux chercheurs se sont lancés dans des hypothèses hâtives que nous pouvons à présent considérer comme non fondées et, en l'occurrence, inexactes. Ce biais méthodologique auquel s'ajoute une nette tendance à conclure trop rapidement à un chauffage délibéré des matières colorantes jaunes dans le but non prouvé d'obtenir des matières colorantes rouges conduisent à des discours développant la théorie du rôle symbolique joué par les matières colorantes rouges, en particulier par la couleur rouge dans les sociétés préhistoriques comme c'est le cas des matières colorantes de Qafzeh auxquelles nous avons eu l'occasion de faire référence (Godfrey-Smith & Ilani 2004, Hovers et al. 2003. Le modèle -dont il sera question ensuite et qui sera précisé -par l'explication symbolique systématiquement appliquée à tous les phénomènes mettant en jeu les matières colorantes donne dans ces travaux l'illustration et la preuve des inconvénients qu'il comporte, en incitant à conclure hâtivement à des activités symboliques sans avoir au préalable mis en évidence, par des moyens analytiques fiables, la nature des matières colorantes et les éventuels traitements thermiques qu'elles auraient pu subir. ...
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Les matières colorantes sont des vestiges encore mal connus de nos jours. L’intérêt qu’elles suscitent tient à ce qu’elles sont susceptibles de révéler des pratiques techniques diverses et complexes, mais il tient aussi à leur forte potentialité à traduire des pratiques symboliques du fait de leur pouvoir colorant intense et des couleurs exploitées : le rouge et le noir qui sont encore aujourd’hui investis d’une forte valeur symbolique. Dans un contexte aussi particulier que celui de la transition entre le Paléolithique moyen et le Paléolithique supérieur, ces vestiges ont été mis au jour en abondance et demandent à être analysés pour restituer les modes de vie des derniers hommes de Neandertal.C’est sur le gisement châtelperronien de la grotte du Renne à Arcy-sur-Cure (Yonne), fouillé de 19491963 par André Leroi-Gourhan, que les nombreuses matières colorantes découvertes ont conduit à échafauder des théories concernant leurs transformations et leurs utilisations qui méritaient d’être éprouvées. En effet, il est supposé, depuis leur découverte, qu’elles ont fait l’objet d’un chauffage contrôlé qui visait à en modifier la couleur, le chauffage permettant de transformer les matières colorantes jaunes (hydroxydes de fer) en orangées, en rouges et en violacés (oxydes de fer). De cette hypothèse découle la théorie selon laquelle les Néandertaliens ont exploité les matières colorantes en tant que pigment pour des réalisations symboliques, voire d’ordre esthétique, ce qui n’a pas encore pu être prouvé.Notre étude, fondée sur le croisement des données issues des analyses de la nature physico-chimiquepétrographique des assemblages de matières colorantes, mais aussi sur leur intégration dans le gisement, en association avec des structures d’habitat dont la conservation est exceptionnelle, et sur une série d’expérimentations visant à caractériser les poudres obtenues par différents moyens (broyage et concassage d’une part, abrasion d’autre part) ont permis de définir les choix techniques qui ont présidé à l’approvisionnement en matières colorantes dans tous les niveaux d’occupation châtelperroniens de la grotte du Renne. Il a ainsi été possible de démontrer qu’aucune des matières colorantes, rouges ou noires, n’a fait l’objet d’un chauffage préalablement à son utilisation, bien au contraire de ce qui avait été supposé jusqu’ici. Ces matières colorantesont fait l’objet d’un approvisionnement raisonné auprès de formations géologiques affleurant ponctuellement à plus de 10 km et à environ 5 km de la grotte. L’exploitation de ces gîtes de matières premières colorantes été la même durant toute la séquence châtelperronienne et s’est orientée préférentiellement vers des matériaux que l’on peut aisément réduire en poudre. Une partie était grossièrement réduite en poudre afin de recouvrirde grandes surfaces (sols, peaux de bêtes) dans le but de les assainir, alors qu’une autre partie des matières colorantes était destinée à des activités plus minutieuses nécessitant leur emploi sous forme d’une poudre fine, régulière et extrêmement colorante. Dans ce dernier cas, les Néandertaliens de la grotte du Renne ont entrepris d’exploiter ces produits en association avec le travail des matières osseuses (os et ivoire de mammouth) maisaussi pour leur couleur. L’assemblage des matières colorantes de la grotte du Renne révèle à la fois une permanence des pratiquestechniques et culturelles qui ont trait à l’emploi de matières colorantes et un profond ancrage des connaissances et de la compréhension des multiples propriétés et qualités de ces matériaux intensément mises à profit dans des activités diverses, domestiques artisanales et manifestement aussi d’ordre symbolique, de telle sorte que le gisement châtelperronien était tout de rouge et noir et la chaîne opératoire qu’il a été possible de restituer relève d’inventions techniques abouties, très élaborées dans leur genre pour l’état des observations ingénieuses, des découvertes et donc de la pensée qu’elles supposent et des capacités dont elles témoignent.
... (Israel). Some pieces appear to have been heated to modify their colour(d'Errico et al. 2010;Godfrey- Smith et Ilani 2004;Hovers et al. 2003;Salomon et al. 2012). ...
Article
Colour strongly shapes our perception of the world and plays a main role in the emergence of language and in the transmission of information. It has been shown that systematic use of ochre, along with other cultural traits that reflect cognitive complexity, disappear and reappear from the archaeological record, suggesting that cultural transmission follows discontinuous trajectories that to this day are unknown to us. Understanding when humans started using colour and how this feature evolved may therefore be instrumental to understand the evolutionary paths followed by members of our lineage towards cultural complexity. The earliest secure evidence for ochre use is found at 300.000-year-old archaeological sites from Africa and Europe. It usually consists of iron-rich rocks characterized by a red, orange, yellow or brown colour and/or streak, modified by grinding, scraping and knapping to produce red or yellow powder, ochre residues adhering to different types of artefacts or sediment stained with ochre or rich in ochre microfragments. Around 160 ka, ochre use becomes a recurrent feature. Although analyses of ochre collections have become increasingly frequent, there is still very little information on the first instances of ochre use and on how this cultural feature evolved through time. Most cases of early evidence for colour use by different human fossil species were recovered during excavations conducted several decades ago, when ochre was not documented systematically. Excluding a few recently studied cases, there is often a lack of evidence to support the anthropogenic nature of these findings. The aim of this paper is to summarise what we know on ochre use during the Lower Palaeolithic / Early Stone Age (ESA) and Middle Palaeolithic / Middle Stone Age (MSA), review techniques currently used for the analysis of this material and highlight analytical and theoretical issues surrounding this complex cultural feature.
... Such coloration can be a result of heat treatment (intentional) or burning (unintentional) but possibly could result from post-depositional taphonomic processes that have not been identified. Heat treatment of the ornament material is an intentional activity by the ornament makers done to enhance the visual impact of the ornament or to allow the ornament to convey meaning through the special colors produced, and to alter the material's physical properties for workability (e.g., Godfrey-Smith and Ilani, 2004;d'Errico et al., 2010;Salomon et al., 2012). This is supported by examples in modern bead-working (Schoeman, 1983;Wickler and Seibt, 1995). ...
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Forty-one ostrich eggshell (OES) artifacts excavated at five localities of the late Paleolithic Shizitan site, on the North China Loess Plateau, allow the observation of diachronic changes in the utilization of ostrich eggs in the production and use of ornaments considered to be technologies of social signaling, beginning during the Last Glacial Maximum (LGM) and continuing through the Younger Dryas. Based on changes in dimensions, production techniques such as drilling, coloration through heat treatment or the application of ochre, and stringing techniques, the OES pendant and bead use at Shizitan is divided into four phases. Phases 1–3 feature only completed ornaments, usually with heavy usewear. Only in Phase 4, during the Younger Dryas, blanks and drilled preforms are found that indicate local production. While Phase 1 features the use of larger pendants colored grey/black by burning, subsequent phases see beads replacing pendants, no heat coloration, and the use of the ochre pigment. The switch to beads corresponds with the change to microblade technology at Shizitan 29. Phase 3 shows a trend toward a larger relative surface display area and maturation of techniques to produce visual effects of roundedness and weightiness. Phase 4 local production shows technological developments that allowed drilling smaller apertures while also decreasing the bead diameter and increased standardization, implying changing display objectives (stringing beads together with a uniform appearance). The changes observed in the Shizitan diachronic dataset may relate to changing requirements in social signaling—part of the adaptations the hunter–gatherer groups made to survive the challenges of climatic change from the LGM through the Terminal Pleistocene in North China.
... In some cases, particle size is related to color and authors have used this property to identify differences in ochre particle sizes due to their color properties (Dubiel et al., 2011;Marshall et al., 2005). Color may also be an indicator of thermal alteration of yellow ochre to red; however, color analysis alone is not sufficient to detect anthropogenic heat treatment (Cavallo et al., 2018;Cavallo et al., 2021;de Faria and Lopes, 2007;Garilli et al., 2020;Godfrey-Smith and Ilani, 2004;MacDonald et al., 2019;Plutino and Simone, 2021). ...
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This manuscript seeks to facilitate meta-analysis of cross-disciplinary ochre studies by advocating for a common vocabulary and clarifying the definition of “ochre” as used by archaeological scientists across cultural and geographic specialties. This work reviews the current state of ochre archaeometry, spanning the beginning of its major period of growth in the late 20th century through the present. Here, the focus is on the main areas of ochre archaeometry as represented in the published literature, with characteristic example studies and best practices for each. These areas include methodological approaches to characterization and provenience, instrumental data interpretation and its relation to experimental design and sampling, experimental archaeology, and chronometry. A key focus of this manuscript is highlighting emerging areas of research, such as biological processes and phenomena, and extant but understudied applications in the field including isotopic systems, genomic analysis, and experimental archaeology of ochre.
... For example, some authors (e.g., Wadley, 2013) propose that if ochre heat treatment relied on underground processes, similar to those proposed for stone heat treatment in some contexts, it might be another proxy for complex cognition in the MSA. Outside of Africa, the earliest secure evidence of colour enhancement dates to 100 ka in Israel (Salomon et al., 2012;Godfrey-Smith and Ilani, 2004). In the European Upper Palaeolithic, ochre heat treatment is documented in Italy (Cavallo et al., 2018) and France (Salomon et al., 2013;Salomon et al., 2015). ...
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Research into human uniqueness is gaining increasing importance in prehistoric archaeology. The most striking behaviour unique to early and modern humans among other primates is perhaps that they used fire to transform the properties of materials. In Archaeology, these processes are sometimes termed "engineering" or "transformative techniques" because they aim at producing materials with altered properties. Were such transformative techniques cognitively more demanding than other tool making processes? Were they the key factors that separated early humans, such as Neanderthals and early Homo sapiens, from other hominins? Many approaches to investigating these techniques rely on their complexity. The rationale behind this is that some techniques required more steps than others, thus revealing the underlying mechanisms of human uniqueness (e.g., unique human culture). However, it has been argued that the interpretation of process complexity may be prone to arbitrariness (i.e., different researchers have different notions of what is complex). Here I propose an alternative framework for interpreting transformative techniques. Three hypotheses are derived from an analogy with well-understood processes in modern-day cuisine. The hypotheses are about i) the requirement in time and/or raw materials of transformative techniques, ii) the difficulty to succeed in conducting transformative techniques and iii) the necessity to purposefully invent transformative techniques, as opposed to discovering them randomly. All three hypotheses make testable predictions.
... Thermoluminescence (TL) techniques are widely known for their capacity to detect the last heating event of a material and to evaluate the age of this event [138]. The same techniques can be applied to determine if an ochre piece was heated if it contains thermoluminescent crystals such as quartz [76,137]. However, again, clear evidence of an intentional heat treatment may not be found. ...
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Naturally occurring and deeply coloured iron-bearing materials were exploited very early on by human populations. The characterization of these materials has proven useful for addressing several archaeological issues, such as the study of technical behaviors, group mobility, and the reconstruction of cultural dynamics. However, this work poses some critical methodological questions. In this paper, we will review ochre studies by focusing on the analytical methods employed, the limits of non-invasive methods, as well as examples of some quality research addressing specific issues (raw material selection and provenience, heat treatment). We will then present a methodological approach that aims to identify the instrumental limits and the post-depositional alterations that significantly impact the results of the non-invasive analysis of cohesive ochre fragments from Diepkloof rock Shelter, South Africa. We used ochre materials recuperated in both archaeological and geological contexts, and we compared non-invasive surface analyses by XRD, scanning electron microscopy coupled with dispersive X-ray spectrometry (SEM-EDXS), and particle-induced X-ray emission (PIXE) with invasive analysis of powder pellets and sections from the same samples. We conclude that non-invasive SEM-EDXS and PIXE analyses provide non-representative results when the number of measurements is too low and that post-depositional alterations cause significant changes in the mineralogical and major element composition at the surface of archaeological pieces. Such biases, now identified, must be taken into account in future studies in order to propose a rigorous framework for developing archaeological inferences.
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