Throughout history, ceramics have been the most abundant artifacts in archaeological discoveries. Within the Neolithic period in present-day Bulgaria, skilled artisans applied additional materials to decorate their pottery, evolving in composition and application techniques such as painting or incrustation. This study is focused on the investigation of white pigments used in decorating Early and Late Neolithic pottery from Madzherito, Kaloyanovets, and Hadzhidimitrovo—archaeological sites located in the Thracian Valley, Central South Bulgaria, affiliated with the cultural groups of Karanovo I and IV. Thirteen ceramic sherds were investigated through archaeometric techniques, including Fourier-transformed infrared spectroscopy in attenuated total reflection mode (ATR-FTIR) and laser-induced breakdown spectroscopy (LIBS). LIBS data underwent further analysis using principal component analysis (PCA). The results revealed that calcite, enriched with diverse fillers like quartz, clays, feldspars, and metal oxides, was the primary raw material for white decoration throughout the entire period. Talc emerged as an addition to calcite in the paint of two Early Neolithic sherds. The presence of hydroxyapatite and kaolinite in Late Neolithic pottery was also observed. The inclusion of supplementary ingredients in the primary formula for crafting white decorations signifies either the emergence of novel trends in manufacturing techniques or serves as evidence of vessels imported from adjacent territories.

Identifying the mineral pigments used in the decoration of prehistoric pottery is a significant step for understanding the evolution of the technological practices over time. On the Balkan Peninsula during late prehistory, the techniques used for red and dark-colored decorations underwent a significant transformation. In the Early Neolithic period, pottery was often decorated with dark-toned paints, ranging from deep red to brown. However, this approach declined noticeably during the Chalcolithic period, when red pigment pseudo-incrustation became the predominant decorative method. This study aims to identify the mineral pigments used in red and dark decorations on Neolithic and Chalcolithic pottery from Bulgaria and to trace possible technological, regional, or chronological variations in their composition. A total of 34 ceramic sherds, decorated in shades from red to brown and black, were analyzed using two complementary spectroscopic techniques: laser-induced breakdown spectroscopy (LIBS) and Fourier-transform infrared spectroscopy (FTIR). LIBS data were further evaluated using principal component analysis (PCA) to classify materials based on elemental composition. The results indicate that red decorations are consistently composed of hematite and remain compositionally stable regardless of the region, time period, or application technique. In contrast, dark decorations contain various combinations of iron oxides (magnetite and hematite) and manganese oxides, often including barium-rich manganese compounds—potentially indicating pigment provenance. Additionally, the dark decorations display regional differences.

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.