Archaeometric Research of Boian Pottery Decoration from the Settlement of Hârșova-Tell
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This paper presents the results of archaeometric research on the white and red materials used to decorate some ceramic vessels belonging to the Boian culture, the Vidra and Spanţov phases from the 5th millennium BC, discovered at Hârşova-Tell, on the right bank of the Danube, Romania. Digital microscopy, wavelength-dispersive X-ray fluorescence spectroscopy, X-ray diffraction, and Fourier transform infrared spectroscopy were used to identify the morphology, the crystalline phases, chemical formula, and percentage content of each crystalline phase in the white decoration materials and what type of pigment was used to prepare the red paint. The results obtained reveal that the white decorating material in the pottery is mostly made of calcite. It was added after the pottery was fired. Sometimes, powders from burnt bones were also used. The red pigment is hematite. The work contributes to the completion of a puzzle related to the artistic vision of the members of the Boian communities in decorating ceramics with culture-specific motifs, preserving the pattern, and adapting to the local natural resources.
![View from the south on the master profile in S.C/p.P, on which the Boian levels were marked, researched in the 2016–2017 campaigns [11,12].](https://www.researchgate.net/profile/Anca-Gheboianu/publication/386430060/figure/fig3/AS:11431281371738485@1744388138233/View-from-the-south-on-the-master-profile-in-SC-pP-on-which-the-Boian-levels-were_Q320.jpg)
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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.
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Pottery is a complex archaeological material that is found ubiquitously in various spatial—temporal frameworks from all over the world; therefore, it is of great importance to archaeological research. The current paper aims to present and discuss the results obtained on a batch of Neolithic (ca. 6000–5000 BC) and Chalcolithic (ca. 5000–3900 BC) pottery sherds from Southern Romania through X-ray Computed Tomography, a non-destructive methodology that allows for the 3D reconstruction and precise measurement of inclusions and voids present within ceramic artefacts. Images from several potsherds were subsequently exported and analyzed by means of dedicated software (ImageJ 1.54p and GIMP) to extract quantitative information on the observed features. Grain size and morphometric analyses were performed on the particles, while the contour variability of the examined inclusions was characterized through the application of shape descriptors. Voids were analyzed in order to reveal specific orientation patterns through the examination of the aspect ratio of the holes and of the Rayleigh z test values. These analyses evidenced the general reliance of moderately and poorly sorted clays for ceramic production, accompanied by a gradual transition from organic to grog tempering, while conservative traditions remained prevalent in primary pottery-forming processes.
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The current study aims to present and discuss the results obtained by complementary archaeometric methods applied for the first time on white pigments inlaid on excised pottery of the Boian-Vidra tradition (Early Chalcolithic, c. 4900-4600 BCE). The samples came from three settlements located in Southern Romania (Sultana-Ghețărie, Vidra, and Vlădiceasca). They were selected considering that the pottery was produced in approximately contemporary sites, located relatively close to each other in the same geographical region, namely the Romanian Plain. The experimental part included the analysis of local samples of carbonate concretions and prehistoric animal bone ash as reference materials. Archaeometric investigations consisted in applying "in-air" PIXE and EDX methods for the chemical composition, XRD and FTIR for mineralogical data, SEM for micro-structure observation, and EPR for the characterisation of the paramagnetic centres. Calcite, bone ash, and silica-rich sediments were identified as the primary decorating pigments. The mixtures of calcite and bone-ash observed in 13 samples were specific to the sites at Vidra and Vlădiceasca. Silica-rich sediments from distant sources were the main whitening materials in two samples from Vlădiceasca, while for the samples from Sultana-Ghețărie, calcite was the only whitening mineral. The results show with a high degree of confidence the use of both local (i.e., carbonate neo-formations and bone ash) and exotic (silica-rich sediments) raw materials to obtain the white pigment applied to Boian-Vidra pottery. Thus, the current data show the adaptability of the potters with respect to the surrounding resources and also provide new evidence for a vast trade network of raw materials and/or finished products in the Lower Danube area during the Early Chalcolithic. The deliberate mixing of two whitening materials from different sources could be a technological choice and may highlight complex symbolic behaviours.
In this work, Infrared spectroscopy has been carried out to characterize the composition of the as-prepared samples in magnetite and hematite. The infrared spectra presented in this work were recorded in the range from 400 to 4000 cm-1 with FT-IR spectrometer. Infrared light is guided through an interferometer and then through the sample (or vice versa). A moving mirror inside the apparatus alters the distribution of infrared light that passes through the interferometer. The results obtained showed that the characteristic bands of magnetite and hematite are appeared in the spectra of two samples. Characteristic bands of hematite appeared in spectra of magnetite. Besides other materials appear in spectra of the two samples as, sulphate, water, silica and carbonate. Infrared spectroscopy proved to be easy and fast methods for the identification of characterization composition in hematite, magnetite samples and could be used for other materials.
Rédaction en chef, maquette, PAO - DAO et couverture : Albane BURENS (CNRS)