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Developing FTIR Microspectroscopy for the Analysis of Animal-Tissue Residues on Stone Tools

  • Gilliane Monnier
  • Ellery Frahm
  • Bing Luo
  • Kele Missal
Article

Abstract

The analysis of microscopic residues on stone tools provides one of the most direct ways to reconstruct the functions of such artifacts. However, new methods are needed to strengthen residue identifications based upon visible-light microscopy. In this work, we establish that reflectance Fourier-transform infrared microspectroscopy (FTIRM) can be used to document IR spectra of animal-tissue residues on experimental stone tools. First, we present a set of reflectance FTIRM standards for the most commonly identified animal-tissue residues on stone tools: skin, meat, fat, hair, blood, feather barbules, fish scales, and bone. We provide spectral peak assignments for each residue and demonstrate that high-quality reflectance FTIRM spectra can be generated under ideal circumstances. Second, we document the spectra for these residues when they are located on a stone substrate such as flint or obsidian. We discuss procedures for correcting spectra that are affected by specular reflection and explain the effects of spectral interference from the stone. Our results show that reflectance FTIRM is sensitive to small intra-sample differences in composition. This means that it will record the effects of decomposition in ancient residues. The methodological developments we present here will help lithic residue analysts incorporate in situ reflectance FTIRM into their analysis protocols to strengthen identifications.

Keywords

FTIR microspectroscopy residue analysis lithic analysis 

Notes

Acknowledgements

This work was funded by NSF grant # BCS-1420702. It was carried out at the University of Minnesota in the Evolutionary Anthropology Laboratories and in the Characterization Facility, which receives partial support from the NSF through the MRSEC program. Many thanks to Matt Edling, Greg Haugstad, Keith Manthie, Colin McFadden, Marjorie Schalles, Nora Last, Kara Kersteter, and Gil Tostevin. Thanks also to the three anonymous reviewers whose comments and suggestions helped improve the final manuscript.

Supplementary material

10816_2017_9325_MOESM1_ESM.pdf (265 kb)
Figure S1 FTIRM spectra of feather calamus residues obtained in reflectance mode (on a mirrored slide) and in transmission mode (on a NaCl plate), compared with an FTIR standard for keratin (prepared using the KBr pellet method) from the Kimmel Center for Archeological Science, Weizmann Institute of Science. Peak assignments are in Table 4. The reflectance spectrum (red line) is similar to the transmission spectrum (green line); both clearly exhibit the protein peaks seen in the keratin standard (blue line). The upside-down peaks on the reflectance spectrum (red line) at ~2350 cm−1 are due to atmospheric CO2 and should be ignored. Note: all spectra are graphed in calculated absorbance mode (log(1/R)). (PDF 264 kb)
10816_2017_9325_MOESM2_ESM.pdf (217 kb)
Figure S2 The FTIRM spectrum for skin residue on obsidian with the Kramers-Kronig transform applied (blue line), compared with the skin reflectance standard (purple line, graphed in calculated absorbance mode [log(1/R)]). Above 1250 cm−1, the residue on obsidian spectrum exhibits peaks at the same locations as on the standard, although relative peak heights and the baseline are distorted. Peaks in the range of 1750–1200 cm−1 are also shifted to lower wavenumbers. Below 1250 cm−1, (to the right of the dashed line), however, the spectrum exhibits severe derivative peaks. Peak assignments are in Table 1. (PDF 217 kb)
10816_2017_9325_MOESM3_ESM.pdf (324 kb)
Figure S3 The FTIRM spectra for feather calamus residue on English flint and obsidian compared with the feather calamus reflectance standard. Between 4000 and 1350 cm−1, the residue on flint is consistent with the calamus reference spectrum, although the latter exhibits a small carbonyl peak (7) and more absorbance in the CH3 stretching regions (peaks 4 and 6), which indicates compositional differences between the two. Below 1350 cm−1, as with almost all other spectra of animal residues on stone, the peaks no longer match, and derivative features are seen. The spectrum of the residue on obsidian differs because it exhibits very low reflectance, thereby resulting in low resolution. Finally, for both flint and obsidian spectra, many of the peaks are shifted to higher wavenumbers, relative to the standard, an important effect which needs to be taken into account (see peak assignments in Table 4). Note: all spectra are graphed in calculated absorbance mode (log(1/R)). (PDF 324 kb)

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© Springer Science+Business Media New York 2017

Authors and Affiliations

  1. 1.Department of AnthropologyUniversity of MinnesotaMinneapolisUSA
  2. 2.Yale Initiative for the Study of Ancient Pyrotechnology, Department of AnthropologyYale UniversityNew HavenUSA
  3. 3.Characterization FacilityUniversity of MinnesotaMinneapolisUSA

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