Spectroscopic Study of White Pigments in the Decoration of Neolithic Pottery in the Region of the Thracian Valley, Bulgaria

Abstract

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.