Applied Physics A

, Volume 83, Issue 2, pp 213–218 | Cite as

Minerals discovered in paleolithic black pigments by transmission electron microscopy and micro-X-ray absorption near-edge structure

  • E. Chalmin
  • C. Vignaud
  • H. Salomon
  • F. Farges
  • J. Susini
  • M. Menu
Article

Abstract

Analysis of archeological materials aims to rediscover the know-how of prehistoric men by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. The preparation mode of the painting matter of the paleolithic rock art apparently consisted of mixing, grinding, and also heat-treatment.

In this study, we focus on black pigments and more particularly manganese oxides. Using the combined approach of transmission electron microscopy (TEM) and Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy, we analyzed a variety of archeological black painted samples. The studied pigments arise from the caves of Ekain (Basque country, Spain), Labastide and Gargas (Hautes-Pyrénées, France). In addition, a black “crayon” (i.e., a “pen”) from the cave of Combe Saunière (Dordogne, France) was also investigated. From the analysis of these painting matters, several unusual minerals have been identified as black pigment, such as manganite, groutite, todorokite and birnessite. These conclusions enable us to estimate the technical level of paleolithic artists: they didn’t use heat-treatment to prepare black painting matter. Consequently, the unusual mineralogy found in some of these pigments suggests that some of the manganese ores are coming from geological settings that are sometimes relatively far away from the Dordogne and Basque region such as in Ariège (central-oriental Pyrénées).

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References

  1. 1.
    E. Carthailhac, L’Anthropologie 16, 41 (1902)Google Scholar
  2. 2.
    H. Moissan, Compte-rendu de l’Académie des Sciences 134, 1536 (1902)Google Scholar
  3. 3.
    H. Moissan, Compte-rendu de l’Académie des Sciences 136, 144 (1903)Google Scholar
  4. 4.
    C. Couraud, A. Laming-Emperaire, Lascaux inconnu, Ed. par Leroi-Gourhan, A. Allain, J. Paris: CNRS (1979) p. 153Google Scholar
  5. 5.
    J. Clottes, M. Menu, P. Walter, Bulletin de la Société Préhistorique Française 87, 170 (1990)Google Scholar
  6. 6.
    M.P. Pomiès, M. Menu, C. Vignaud, Archaeometry 41, 185 (1999)CrossRefGoogle Scholar
  7. 7.
    A. Clot, M. Menu, P. Walter, L’Anthropologie 99, 221 (1995)Google Scholar
  8. 8.
    R. Simonnet, Congrès National des Sociétés Historiques et Scientifiques, 118th, Pau, 341 (1993)Google Scholar
  9. 9.
    J.M. Geneste, H. Plisson, Gallia Préhistoire 29, 9 (1986)Google Scholar
  10. 10.
    J.E. Post, Catena Suppl. 21, 51 (1992)MathSciNetGoogle Scholar
  11. 11.
    E. Chalmin, phD, University of Marne la Vallée (2003) Free PDF version at http://pelleas.univ-mlv.fr/document/UMLV-2004-000148-PDF (in French)Google Scholar
  12. 12.
    N. Aujoulat, E. Chalmin, C. Vignaud, J.M. Geneste, M. Menu, Actes du colloque des 10èmes journées d’études de la SFIIC, 5 (2002)Google Scholar
  13. 13.
    E. Chalmin, C. Vignaud, M. Menu, Appl. Phys. A 79, 187 (2004)CrossRefADSGoogle Scholar
  14. 14.
    D.C. Smith, M. Bouchard, M. Lorblanchet, J. Raman Spectrosc. 30, 347 (1999)CrossRefGoogle Scholar
  15. 15.
    M. Lorblanchet, La maison des sciences de l’homme (Documents d’archéologie française, Paris 2001)Google Scholar
  16. 16.
    J. Vouvé, J. Brunet, F. Vouvé, Stud. Conserv. 37, 185 (1992)CrossRefGoogle Scholar
  17. 17.
    D. Haskel, www.aps.anl.gov/xfd/people/haskel. (1999)Google Scholar
  18. 18.
    E. Chalmin, F. Farges, G.E. Brown Jr., Am. Mineral. (submitted)Google Scholar
  19. 19.
    F. Farges, E. Chalmin, C. Vignaud, I. Pallot-Frossard, J. Susini, J. Bargar, G.E. Brown Jr., M. Menu, Physica Scripta, T115 (2005)Google Scholar
  20. 20.
    M. Menu, P. Walter, Nucl. Instrum. Methods Phys. Res. B 64, 547 (1992)CrossRefADSGoogle Scholar
  21. 21.
    A. Witter, J.R. Journée, Ein Führer zu über 40 Fundstellen.- Aufschluss 48 (von Loga, Köln, 1997) p. 64Google Scholar
  22. 22.
    D.A. Mc Keown, J.E. Post, Am. Mineral. 86, 701 (2001)Google Scholar
  23. 23.
    J.R. Bargar, B.M. Tebo, J.E. Villinski, Geochim. Cosmochim. Acta 64, 2775 (2000)CrossRefADSGoogle Scholar

Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • E. Chalmin
    • 1
    • 2
  • C. Vignaud
    • 1
    • 3
  • H. Salomon
    • 1
  • F. Farges
    • 2
    • 4
  • J. Susini
    • 5
  • M. Menu
    • 1
  1. 1.Centre de Recherche et de Restauration des Musées de France, UMR 151 (CNRS)ParisFrance
  2. 2.Laboratoire des GéomatériauxUniversité de Marne la ValléeMarne la Vallée Cedex 2France
  3. 3.Laboratoire Interfaces et Systèmes ElectrochimiquesParis Cedex 05France
  4. 4.Department of Geological and Environmental SciencesStanford UniversityStanfordUSA
  5. 5.ESRFGrenobleFrance

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