a b s t r a c tThe early occurrence of intentional heat treatment of silica rocks has recently become a key element in the discussion about the cultural modernity of prehistoric populations. Lithic vestiges are the only sources that remain of this process and the understanding of the material's properties and transformations are essential for reconstructing the conditions and parameters applied during heat treatment. Several models of the structural transformations upon heating have been proposed in the current literature. These models are often contradictory and do not account for the most recent structural and mineralogical data on chalcedony. In order to propose a new model, we elaborated an experimental procedure and applied different techniques involving infrared spectroscopy, solid state NMR, X-ray diffraction and electron microscopy. The results show that the major transformation to happen is the loss of silanole (SiOH) and the creation of new SieOeSi bonds according to the reaction: Si-OH HOeSi / Si eOeSi þ H 2 O. This reaction starts between 200 C and 300 C and causes an increase in the hardness of the rocks. The maximal annealing temperature and the ramp rate are the functions of the ability of the structure to evacuate newly created H 2 O and depend on the size of the specimen and the volume of its porosity. These results also show that the annealing duration at maximum temperature can be relatively short (<50 min) for a sufficiently large amount of transformation to be accomplished.

South Africa has in recent years gained increasing importance for our understanding of the evolution of 'modern human behaviour' during the Middle Stone Age (MSA). A key element in the suite of behaviours linked with modern humans is heat treatment of materials such as ochre for ritual purposes and stone prior to tool production. Until now, there has been no direct archaeological evidence for the exact procedure used in the heat treatment of silcrete. Through the analysis of heat-treated artefacts from the Howiesons Poort of Diepkloof Rock Shelter, we identified a hitherto unknown type of organic residue - a tempering-residue - that sheds light on the processes used for heat treatment in the MSA. This black film on the silcrete surface is an organic tar that contains microscopic fragments of charcoal and formed as a residue during the direct contact of the artefacts with hot embers of green wood. Our results suggest that heat treatment of silcrete was conducted directly using an open fire, similar to those likely used for cooking. These findings add to the discussion about the complexity of MSA behaviour and appear to contradict previous studies that had suggested that heat treatment of silcrete was a complex (i.e., requiring a large number of steps for its realization) and resource-consuming procedure.

Birch tar production by Neanderthals—used for hafting tools—has been interpreted as one of the earliest manifestations of modern cultural behavior. This is because birch tar production per se was assumed to require a cognitively demanding setup, in which birch bark is heated in anaerobic conditions, a setup whose inherent complexity was thought to require modern levels of cognition and cultural transmission. Here we demonstrate that recognizable amounts of birch tar were likely a relatively frequent byproduct of burning birch bark (a natural tinder) under common, i.e., aerobic, conditions. We show that when birch bark burns close to a vertical to subvertical hard surface, such as an adjacent stone, birch tar is naturally deposited and can be easily scraped off the surface. The burning of birch bark near suitable surfaces provides useable quantities of birch tar in a single work session (3 h; including birch bark procurement). Chemical analysis of the resulting tar showed typical markers present in archaeological tar. Mechanical tests verify the tar’s suitability for hafting and for hafted tools use. Given that similarly sized stones as in our experiment are frequently found in archaeological contexts associated with Neanderthals, the cognitively undemanding connection between burning birch bark and the production of birch tar would have been readily discoverable multiple times. Thus, the presence of birch tar alone cannot indicate the presence of modern cognition and/or cultural behaviors in Neanderthals.

International audienceIt was recently found that silcrete raw material was heat-treated during the South African Middle Stone Age (MSA) for altering its flaking properties. This finding led to hypotheses about the implications for the MSA hunter-gatherers such as the cost of thermal treatment in terms of investment and firewood. To date, these hypotheses lack a solid basis, for data on the thermal transformations of South African silcrete and, hence, the necessary heating procedure and heating environment, is missing. In order to produce such data, we conducted an experimental study within the framework of the Diepkloof project. This work is based on the petrographic, mineralogical and structural analysis of South African silcrete from the West Coast and its thermal transformations. Our results shed light on the nature of these transformations, the ideal heating temperatures and the tolerated heating speed. The processes occurring in silcrete are comparable to flint, i.e. the loss of chemically bound 'water' and the formation of new SieOeSi bonds, but their intensity is less pronounced. Effective heating temperatures are significantly higher than for flint and the heating speed tolerated by South African silcrete is relatively fast. These findings imply that silcrete heat treatment cannot be directly compared with flint heat treatment. Unlike flint, heating silcrete does not require the setup of a dedicated heating environment and may have been performed in the same time as other fire related activities. This would represent only a minor supplementary investment in time and firewood. These results have broad implications for the discussion about technological evolution and the acquisition of specialised knowledge in the MSA

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Heat treatment of lithic raw material is known from the Middle Stone Age to the Neolithic. These findings require archaeometric techniques and methods for detecting the heat-induced effects within lithic artefacts. However, the existing methods are often cost-intensive and time-consuming, and most of them are destructive. Here, we present a new method using the infrared spectroscopic measurement of the strength of H-bonds formed between surface silanole groups (SiOH) and H 2 O molecules held in open pores of the samples. The reduction of H-bond strength in chalcedony is shown to be strongly correlated with the loss of open pores induced by heat treatment. Hence, the method is based on measuring one of the transformations aimed for by the instigators of the heat treatment: the reduction of porosity that modifies the rock's mechanical properties. A first application to heat-treated material from the Neolithic Chassey culture (southern France) shows that flint was heated to temperatures between 200°C and 250°C in this period. This has important implications for the study of the procedures used and the heating environments. Our new method is non-destructive, rapid, cost-effective and allows for detection of the used annealing temperatures.

Chalcedony is a porous spatial arrangement of hydroxylated nanometre sized α-quartz (SiO(2)) crystallites. Due to micro-structural transformations upon heat treatment, the optical and mechanical properties of the rock are modified. We investigated these transformations in sedimentary length-fast chalcedony through Fourier Transform near- and mid-infrared spectroscopy using direct transmission and the reflectivity. Chemical adsorption potential and absorption of H(2)O by pores was studied after heat treatment. We found that water held in open porosity is reduced upon heat treatment to temperatures above 150°C. Silanole is noticeably lost from 250 to 300°C upwards and new bridging Si-O-Si further reduces the surface of open pores, creating a less porous material. Molecular water, resulting from the reaction Si-OH HO-Si→Si-O-Si+H(2)O creates new isolated pores within the material. At temperatures above 500°C, the samples start internal fracturing, permitting water held in isolated pores to be evacuated. These results shed light on thermal transformations in chalcedony and allow for a better understanding of mechanical transformations after heat treatment.