The characterization of archaeological ceramics according to their chemical composition provides essential information about the production and distribution of specific pottery wares. If a correlation between compositional patterns and local production centers is assumed, pottery manufacturing and trade and, more generally, economic, political, as well as cultural relations between communities and regions can be investigated. In the present paper, the combined application of portable XRF and statistical analysis to the investigation of a large repertory of ceramic fragments allowed us to group the assemblage by identifying geochemical clusters. The results from the chemical and statistical analysis were then compared with reference ceramic samples from the same area, as well as with macroscopic and petrographic observations to confirm, coalesce or sub-divide putative sub-divisions. The study of 141 samples from different sites located within a wide area spanning across the Colline Metallifere and the coast (Monterotondo Marittimo, Roccastrada, Donoratico, and Vetricella) provided new clues for a new interpretive archaeological framework that suggests that there was a well-defined organization of pottery manufacturing and circulation across southern Tuscany during the early medieval period.
suggested the application of a lead oxide flux to an unfired non-calcareous ceramic body, in accordance with late Antique and early-Medieval traditions. The isotopic investigation of the glazes also suggested different sources for PbO, which was frequently applied as a mix of different metal batches. The Pb isotopic record identified the Southern Tuscany districts (Campiglia Marittima and Colline Metallifere) and a source controlled by the Carolingian kings in the northern districts of Central Europe (either in Aquitaine or in the Middle German ore districts) as the most reliable sources. SEM-EDS showed the presence of tin impurities in the form of secondary cassiterite agglomerates in most of the glazes obtained by the use of local lead. The presence of cassiterite veins in Southern Tuscany lead sulphide deposits was considered as the main cause for tin impurities in the glazing mixture and, thus, an important marker for the exploitation of local lead.
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