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.

This report presents pilot research of archaeological pottery excavated in the Early-Neolithic settlement of Chavdar located in the Pirdop-Zlatitsa field, Bulgaria (first half of VI mill BC). The object of investigation is a red-slipped ceramic fragment decorated on both sides with white paint. A multi-analytical approach including optical microscopy, laser-induced breakdown spectroscopy, X-ray fluorescence spectroscopy, and Fourier-transform infrared spectroscopy was undertaken to obtain comprehensive information contributing to the archaeological interpretation. The observations identified the qualitative chemical composition of the ceramic body and the pigment used for the decoration and gave implications on the temperature and the atmospheric conditions at which the vessel has been fired.

In the presented work, a total of 60 bronze artefacts from the prehistoric settlement of Baley, Bulgaria were analyzed by means of laser-induced breakdown spectroscopy (LIBS) and X-ray fluorescence spectroscopy (XRF). The archaeological finds were excavated from three levels, with a time span from the 15th century BC to the first half of the 11th century BC. The obtained analytical information was used for quantitative estimation of the amount of tin, lead and arsenic, which determine the mechanical properties of the alloy and the manufacturing technology. Based on the estimated quantities of these elements, a chemometric statistical analysis (principal component analysis—PCA) was performed to classify and divide the samples into separate groups according to the production dating. The data obtained in this study can be used for comparison with the elemental content in deposits from other settlements of this period.

In this work, laser-induced breakdown spectroscopy was applied to determining the elemental composition of a set of ancient bronze artefacts dated from the Late Bronze Age and Early Iron Age (14^th – 10^th century BC). We used a Nd:YAG laser at 1064 nm with pulse duration of 10 ns and energy of 10 mJ and determined the elemental composition of the bronze alloy that was used in manufacturing the samples under study. The concentrations of tin and lead in the bulk of the examined materials was estimated after generating calibration curves for a set of four standard samples. The preliminary results of the analysis will provide information on the artefacts provenance and on the production process.