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Combined Raman spectroscopic and Rietveld analyses as a useful and nondestructive approach to studying flint raw materials at prehistoric archaeological sites

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Abstract

A set of six lithic tools, unearthed along 2011 in two karst sites of the Guadalteba County (Málaga, Spain), has been nondestructively investigated by Raman spectroscopy and laboratory x-ray diffraction. From a chemist’s point of view, our goal is to develop a systematic screening protocol for a quick, easy, low cost and nondestructive characterization of archaeological flints based on Raman spectroscopy, x-ray diffraction and Rietveld refinement. In this paper, we firstly made use of Raman spectroscopy to determine, in a semiquantitative way, but with the generic advantage of a faster data acquisition than x-ray diffraction, the surface content of moganite of each lithic tool, from the ratio between the relative intensities of the two Raman-active symmetric stretching vibrations (A1 modes) of α-quartz (465 cm−1) and moganite (501 cm−1). The precise bulk quartz/moganite weight content was then accurately quantified by means of high-quality x-ray diffraction, followed by Rietveld refinement. We found a general good correlation between Raman and x-ray data. Nonetheless, as recently reported in the scientific literature by other authors, the vibrational spectroscopic quantification of moganite in silica rocks like flint and chert have to be performed very cautiously, to avoid undesired interferences from other Raman features due to the eventual presence of silanol (SiOH) groups, which could finally lead to an overestimation of the surface moganite concentration. As reported in such a recent article, a useful treatment to reduce the interference from silanol-bands is to heat the samples prior to their Raman analysis at a minimum of 600 ºC (but better at 700 or 800 ºC) for silanol “dehydration”. This, in our opinion, may be for sure a satisfactory procedure when studying flint or chert samples of a “geological origin”. But not of practical use when studying lithic tools which were manufactured by men thousands and thousands of years ago.

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Acknowledgments

Research at the Universities of Málaga and Cádiz was supported by Junta de Andalucía, through funding the FQM-159, FQM-113 and HUM-440 scientific groups. We also acknowledge the help by part of the students of the “Escuela Taller de Peñarrubia”, sponsored by the “Guadalteba County Consortium”, both in regards to the on-site works and the subsequent classification of the findings in the archaeology workroom. Financial and technical support from the Stiftung Neanderthal Museum is also acknowledged. We finally thank José Bello for providing us with moganite-rich samples from Mogán (Canary Islands, Spain).

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Authors and Affiliations

  1. Laboratorio de Espectroscopía Vibracional, Servicios Centrales de Apoyo a la Investigación, Universidad de Málaga, Campus de Teatinos, s/n, 29071, Málaga, Spain

    C. Capel Ferrón

  2. Laboratorio de Difracción de rayos-X, Servicios Centrales de Apoyo a la Investigación, Universidad de Málaga, Campus de Teatinos, s/n, 29071, Málaga, Spain

    L. León-Reina

  3. Área de Geodinámica Interna, Facultad de Humanidades y Educación, Universidad de Burgos, C/ Villadiego s/n, 09001, Burgos, Spain

    S. Jorge-Villar

  4. National Research Center on Human Evolution (CENIEH), Burgos, Spain

    S. Jorge-Villar

  5. Departamento de Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos, s/n, 29071, Málaga, Spain

    J. M. Compaña & M. A. G. Aranda

  6. Departamento de Química Física, Facultad de Ciencias, Universidad de Málaga, Campus de Teatinos, s/n, 29071, Málaga, Spain

    J. T. López Navarrete & V. Hernández

  7. Escuela Taller de Peñarrubia, Consorcio Guadalteba, Paseo de Peñarrubia, s/n, 29320, Campillos, Málaga, Spain

    F. J. Medianero

  8. Área de Prehistoria, Facultad de Filosofía y Letras, Universidad de Cádiz, Avda. Gómez Ulla, s/n, 11003, Cádiz, Spain

    J. Ramos

  9. Stiftung Neanderthal Museum, Talstrasse, 300, 40822, Mettman, Germany

    G.-C. Weniger

  10. Departamento de Ciencias de la Tierra, Universidad de Cádiz, Campus Rio San Pedro, 11510, Puerto Real, Cádiz, Spain

    S. Domínguez-Bella

  11. Institute of Prehistoric Archaeology, University of Cologne, Weyertal 125, 50923, Cologne, Germany

    J. Linstaedter

  12. Red Patrimonio Guadalteba, Consorcio Guadalteba, Paseo de Peñarrubia, s/n, 29320, Campillos, Málaga, Spain

    P. Cantalejo & M. Espejo

  13. Instituto Geológico y Minero de España (IGME), C/ Ríos Rosas, 23, 28003, Madrid, Spain

    J. J. Durán Valsero

Authors
  1. C. Capel Ferrón
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  2. L. León-Reina
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  3. S. Jorge-Villar
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  4. J. M. Compaña
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  5. M. A. G. Aranda
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  6. J. T. López Navarrete
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  7. V. Hernández
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  8. F. J. Medianero
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  9. J. Ramos
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  10. G.-C. Weniger
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  11. S. Domínguez-Bella
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  12. J. Linstaedter
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  13. P. Cantalejo
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  14. M. Espejo
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  15. J. J. Durán Valsero
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Corresponding authors

Correspondence to S. Jorge-Villar or V. Hernández.

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Capel Ferrón, C., León-Reina, L., Jorge-Villar, S. et al. Combined Raman spectroscopic and Rietveld analyses as a useful and nondestructive approach to studying flint raw materials at prehistoric archaeological sites. Archaeol Anthropol Sci 7, 235–243 (2015). https://doi.org/10.1007/s12520-014-0189-0

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  • DOI: https://doi.org/10.1007/s12520-014-0189-0

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