Spectroscopic Identification of Mineral Pigments in White Decorated Prehistoric Pottery from Bulgaria

Abstract

In the prehistoric period on the Balkan Peninsula, the technology of white decoration underwent a drastic change. At the beginning of the Neolithic white pigment was applied as paint on a polished surface. At the end of the epoch, white paste was inlaid in incised channels on the surfaces of vessels. This study is focused on the identification of mineral pigments used for white decoration of Neolithic and Chalcolithic pottery from the territory of Bulgaria. The aim of this work is to answer the question of whether the composition of the white pigment varies according to the technique of decoration (paint and inlay). A set of 41 pottery fragments from 11 archaeological sites on the territory of Bulgaria was analyzed utilizing two spectroscopic techniques: laser-induced breakdown spectroscopy (LIBS) and Fourier-transform infrared spectroscopy (FTIR). Additionally, the experimental data from the LIBS were statistically treated with the multivariate technique, principal component analysis (PCA). The results from the spectral analysis indicated that the main constituent in the white decorated sherds is calcite in various combinations with carrier materials like quartz, feldspars, and metal oxides. The statistical analysis revealed that the primal constituent in the inlaid sherds is calcite while in the painted part, the carrier material is dominant. In some particular sherds, gypsum, hydroxylapatite, kaolinite, and aragonite were also detected.