FT Raman spectroscopy and micro-Raman spectroscopy with lasers of three different wavelengths (1064 nm, 785 nm and 532 nm) were used for analysis of reference samples of natural clay pigments including white clay minerals (kaolinite, illite, montmorillonite), green earths (glauconite and celadonite) and red earths (natural mixtures of white clay minerals with hematite). In addition, eight micro-samples obtained from historical paintings containing clay pigments in ground and colour layers have been examined. Powder X-ray diffraction and micro-diffraction were used as supplementary methods. It was found that laser operating at 1064 nm provided the best quality Raman spectra for distinguishing different white clay minerals, but the spectra of green and red earths were affected by strong fluorescence caused by the presence of iron. Green earth minerals could be easily distinguished by 532 or 785 nm excitation lasers, even in small concentrations in the paint layers. On the other hand, when anatase (TiO 2 ) or iron oxides (such as hematite) were present as admixtures (both are quite common, particularly in red earths), the collection of characteristic spectra of clay minerals which form the main component of the layer was hindered or even prevented. Another complicating factor was the fluorescence produced by organic binders when analysing the micro-samples of artworks. In those cases, it is always necessary to use powder X-ray micro-diffraction to avoid misleading interpretations of the pigment's composition.

Mural paintings of exceptional quality, which can be discerned in spite of their extensive mechanical damage and colour fading, have been uncovered in the church of St. Gallus in Kuřívody, Northern Bohemia, dated to the second half of the 13th century. Materials research with particular use of portable X-ray fluorescence, Raman micro-spectroscopy and powder X-ray micro-diffraction revealed the presence of rare pigments. In Kuřívody, it is only a second identification of intentionally used yellow mineral crocoite (PbCrO 4 ) in European art. Its identification is facilitated by providing a very good Raman scattering, even when present in small amounts in fragmentarily preserved colour layers. Light yellow mimetite (Pb 5 (AsO 4 ) 3 Cl) was never before mentioned as intentionally used pigment in Europe. Its finding in Kuřívody, however, corresponds more likely with undesirable physical-chemical conditions causing its formation by alteration of orpiment (As 2 S 3 ) and minium (Pb 3 O 4 ). Obtained results highlight the importance of Raman spectroscopy for direct identification of mineral pigments in low concentrations, which may be crucial for interpreting cultural heritage objects in historical context. By materials, the almost forgotten paintings in Kuřívody can be seen as outstanding and rare example of ancient artistic tradition that has spread to Europe from Mediterranean in early Middle Ages. After all, mineral crocoite was already used by ancient Egyptians to paint sarcophagi and degraded orpiment decorates the walls of the Nefertari's tomb in Thebes.

No abstract