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. ChalminEmail author
  • C. Vignaud
  • H. Salomon
  • F. Farges
  • J. Susini
  • M. Menu


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).


Manganite Manganese Oxide Basque Country Black Pigment Pyrolusite 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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Copyright information

© Springer-Verlag 2006

Authors and Affiliations

  • E. Chalmin
    • 1
    • 2
    Email author
  • 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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