Archeological applications of XAFS: Prehistorical paintings and medieval glasses

High-resolution manganese and iron K-edges XANES spectra were collected on several samples of archeological interest: prehistorical paintings and medieval glasses. XANES spectra were collected at the ID21 facility (ESRF, Grenoble, France) using a micro-beam device and at the 11-2 beamline (SSRL, Stanford, USA) using a submillimetric beam. The medieval glasses studied are from gothic glass windows from Normandy (XIVth century). The aim of this study is to help understand the chemical durability of these materials, exposed to weathering since the XIVth century. They are used as analogues of weathered glasses used to dump metallic wastes. These glasses show surficial enrichment in manganese, due to its oxidation from II (glass) to III/IV (surface), which precipitates as amorphous oxy-hydroxides. Similarly, iron is oxidized on the surface and forms ferrihydrite-type aggregates. The prehistorical paintings are from Lascaux and Ekain (Basque country). We choose in that study the black ones, rich in manganese to search for potential evidences of some "savoir-faire" that the Paleolithic men could have used to realize their paint in rock art, as shown earlier for Fe-bearing pigments. A large number of highly valuable samples, micrometric scaled, were extracted from these frescoes and show large variation in the mineralogical nature of the black pigments used, from an amorphous psilomelane-type to a well-crystallized pyrolusite. Correlation with the crystals morphology helps understanding the know-how of these early artists.