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Expensive and time-consuming preparation procedures for radiocarbon and stable isotope analyses can be conducted on archaeological bone samples even if no collagen is preserved. Such unsuccessful preparation can lead to the partial destruction of valuable archaeological material. Establishing a rapid prescreening method for evaluating the amount of bone collagen while minimizing the impact of sampling constitutes a challenge for the preservation of archaeological collections. This study proposes and discusses a new methodology to detect and quantify collagen content in archaeological bone samples by attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. A total of 42 Pleistocene to modern bone samples were selected according to their nitrogen content measured using an elemental analyzer. Comparison of collagen content estimation using ATR-FTIR and mass spectrometry reveals that some of the studied samples are contaminated by a nitrogen source coming from the burial environment. Two different FTIR calibration approaches were tested on the uncontaminated samples: peak-to-peak ratio and multivariate regression (PLS). The two approaches yield similar results with a good correlation of ATR-FTIR analyses and N wt% from 0.7 to 4wt% (R²=0.97–0.99; standard error of estimation ±0.22 to 0.25wt%). While collagen content remains difficult to detect in poorly preserved bones (less than ~3wt%), ATR-FTIR analysis can be a fast alternative for sample screening to optimize the sampling strategy and avoid partial destruction of valuable samples that do not contain enough collagen for further analysis.

The first in situ micro-Raman spectroscopic study of prehistoric drawings found in the cave of Rouffignac-Saint-Cernin (Dordogne, France) was carried out. Rouffignac cave art, assigned to the upper Magdalenian Paleolithic period (13500-12000 BP), is constituted of more than 250 drawings and engraving including 158 mammoths. There are about a hundred drawings, all made of black pigments. Until now, destructive chemical analyses performed on one sample, as well as recent micro X-ray fluorescence (m-XRF) in situ analyses have shown that the drawings contain manganese oxides. Because no carbon has yet been found, no direct dating of the drawings could be performed. This new study of the Rouffignac cave using non-destructive in situ micro-analyses aims at confirming or not the absence of carbon-based drawings and at understanding the apparent homogeneity of the parietal representations by the identification of the crystalline phases constituting the black pigments. The adaptability of portable equipment as well as the feasibility of in situ micro-Raman analyses in a cave environment was tested. The results obtained are compared with in situ XRF, and X-ray diffraction microanalysis is performed at the same time in the cave. We demonstrate that a portable Raman instrument is very useful to analyze non-destructively drawings in the following difficult conditions: high humidity, various wall geometries, and small amounts of material studied. These results show that the black manganese oxides romanechite and pyrolusite were used as pigments by prehistorical artists. Carbon and carotenoids have been found locally. Differences between the various figures are highlighted and hypotheses about the drawings production are proposed.

ABSTRACT. Radiocarbon dating of the carbonate remaining in calcined bones is widely regarded as a viable alternative to date skeletal remains in situations where collagen is no longer present. However, anomalously low ô 13 C values measured in calcined bones prompted questions about the origin of the carbon used for dating. The goal of this study was to quantify the magnitude of carbon isotope exchange between bone carbonate and environmental C0 2 for bones calcined under natural conditions. Four archaeological bones ranging in age between the Neolithic and the Medieval period were combusted on a separate open fire for up to 4 hr and subsamples of calcined bones were taken every hour. All the bones experienced a significant increase in IRSF values and decrease in carbonate content and 5 13 C values. 14 C ages measured in the carbonate fraction of well-calcined bones indicate that 67 ± 3% to 91 ± 8% of the carbon present in bone carbonate was replaced by carbon from the atmosphere of combustion. This finding confirms previous results obtained under laboratory conditions and has serious implications for 14 C dating of calcined bones found in archaeological contexts. The 14 C age obtained on a calcined bone will only reflect the true age of the bone sample if the age difference between the bone and the charcoal can be neglected. Our results show also that ô 13 C values of calcined bones can be used to estimate the degree of C exchange and control for postburial diagenetic alteration.

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Neanderthals are often considered as less technologically advanced than modern humans. However, we typically only find faunal remains or stone tools at Paleolithic sites. Perishable materials, comprising the vast majority of material culture items, are typically missing. Individual twisted fibres on stone tools from the Abri du Maras led to the hypothesis of Neanderthal string production in the past, but conclusive evidence was lacking. Here we show direct evidence of fibre technology in the form of a 3-ply cord fragment made from inner bark fibres on a stone tool recovered in situ from the same site. Twisted fibres provide the basis for clothing, rope, bags, nets, mats, boats, etc. which, once discovered, would have become an indispensable part of daily life. Understanding and use of twisted fibres implies the use of complex multi-component technology as well as a mathematical understanding of pairs, sets, and numbers. Added to recent evidence of birch bark tar, art, and shell beads, the idea that Neanderthals were cognitively inferior to modern humans is becoming increasingly untenable.

Derivative Fourier transform infrared (FTIR) spectroscopy and curve fitting have been used to investigate the effect of a thermal treatment on the nu(1)nu(3) PO(4) domain of modern bones. This method was efficient for identifying mineral matter modifications during heating. In particular, the 961, 1022, 1061, and 1092 cm(-1) components show an important wavenumber shift between 120 and 700 degrees C, attributed to the decrease of the distortions induced by the removal of CO(3)(2-) and HPO(4)(2-) ions from the mineral lattice. The so-called 1030/1020 ratio was used to evaluate crystalline growth above 600 degrees C. The same analytical protocol was applied on Magdalenian fossil bones from the Bize-Tournal Cave (France). Although the band positions seem to have been affected by diagenetic processes, a wavenumber index--established by summing of the 961, 1022, and 1061 cm(-1) peak positions--discriminated heated bones better than the 1030/1020 ratio, and the splitting factor frequently used to identify burnt bones in an archaeological context. This study suggest that the combination of derivative and curve-fitting analysis may afford a sensitive evaluation of the maximum temperature reached, and thus contribute to the fossil-derived knowledge of human activities related to the use of fire.

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