During prehistory, on the Balkans various pigments have been used for decoration of ceramics - white, yellow, red, brown, black. During the long period of its use (VI - I mill BC), only the white pigment undergoes development in the technology of decoration. At the beginning of the Neolithic age, on the Balkan Peninsula, it appears as the prime coloring agent for decorative applications on ceramics. A paint (homogenized thick or diluted solution) was used, which was applied with an instrument over a flattened, smoothed or polished surface, probably before the baking of the vessel. Gradually, close to the end of the epoch, a radically different technique of decoration appears, white paste was inlaid on the outer or inner surface of the vessels. The pigment comprises of materials with different consistency (a paste of components with a variety of gauges), which implies another way of fixing and applying it, most probably after the baking, thus indicating a completely new technology. Incrusted decoration persist up to the beginning of the Early Iron age, whereas the painting with white coloring agent disappears much earlier, at the beginning of the Chalcolite.

The archeometric analysis of white pigment, used for decoration of the ceramics from all over Europe, presents a great variety in the mineral composition: anatase, talc, kaolin, apatite or hydroxylapatite, calcium oxide, calcium carbonate, dolomite. These raw materials have a different base composition and structure, leading to different properties. Whether the raw material, the composition of the white pigment or only the way of preparation depending on the way of decoration (paint or inlay) has changed, is a question that can be answered through archeometric investigations. In this paper, we focus on the archaeometric characterisation of pigments used for different kind of decoration on pottery – incrustation or painting. The fragments are from different archaeological sites located in Western, Central and Eastern Bulgaria, dated to a long period of time - VI-IV millennium BC (Neolithic and Chalcolithic period). We made analyses on more than 50 ceramic pieces from 13 archaeological sites. In order to identify the inorganic ingredients of the pigments we used a multi-analytical approach, including various techniques. Leading analysis is XRD (X-ray diffraction), considering that the white paste is made up of inorganic materials as various minerals.