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.
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