In this paper, based on our previous expertise on ceramic artifacts, several archaeometric methods applied to some samples collected from the Dudești archaeological site (Oltenia region, Romania) are reported for the first time in the literature. The chemical composition, and microstructural and morphological characterization of these samples offer important conclusions about the processing conditions. Some specific techniques such as X-ray diffraction (XRD), wavelength-dispersive X-ray fluorescence (WDXRF), optical microscopy (OM), stereomicroscopy, environmental scanning electron microscopy (ESEM), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy provide compositional information about composition and the decay processes. Additionally, the Brunauer–Emmett–Teller (BET) method helps to estimate pore sizes and specific surface areas. A thermogravimetric analysis (TGA/TDG) was used to establish details regarding the production technology and also the raw materials source used to make the ceramics. The obtained results indicated that the ceramics are based on a paste of muscovite and feldspar, with high plasticity, together with quartz and hematite/goethite and calcite, the latter in very low concentrations. According to the obtained results, we could assume that clays from the investigated samples had a low concentration of calcium. Gypsum is present as paste in a very low concentration, identified by the presence of a sulphate group in WDXRF. In the same context, iron oxides have a significant impact on the firing atmosphere of iron-rich clay, resulting in blackening under reducing conditions and a reddish coloration under oxidative conditions. The use of hematite and gypsum as pigments further contributes to the color variations in the pottery. The consistent firing temperature range of 200–600 °C in Dudești pottery implies a standardized production process, the variation in color being dependent on the specific reducing/oxidative regime conditions (reducing atmosphere followed by rapid oxidation). This relationship between clay composition and local sources suggests a connection to Neolithic pottery production in the region and their color depending on the reducing/oxidative regime conditions.
