Discovery of Unusual Minerals in Paleolithic Black Pigments from Lascaux (France) and Ekain (Spain)

Analyses of archaeological materials aim to rediscover the know-how of Prehistoric people by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. This study deals with identification of manganese oxides in black pigments by micro-XANES (X-ray absorption near-edge structure) based on previous TEM (transmission electron microscopy) studies. Complex mixtures of the manganese oxides studied are present in some of mankind’s oldest known paintings, namely those from the caves of Lascaux (Dordogne, France) and Ekain (Basque country, Spain). Scarce manganese oxide minerals, including groutite, hausmannite, and manganite, were found for the first time in Paleolithic art at these archaeological sites. Because there are no known deposits of such minerals in these areas, more distant origins and trade routes are inferred. The closest known Mn-rich geological province for Lascaux is the central Pyrénées, which is ≈ 250 km from the Dordogne area.