Archaeological excavation at the San Giusto site (Lucera, Italy) has unearthed a Late Antique kiln that was most certainly dedicated to the production of cooking ware. An archaeometric study of numerous specimens of cooking and painted ware found at this site was carried out using optical microscopy, scanning electron microscopy, micro-Raman spectroscopy, X-ray diffraction, X-ray fluorescence, inductively coupled plasma mass and optical emission spectrometry and instrumental neutron activation analysis. The integration of historicalarchaeological data with archaeometric data has revealed that these specimens can be attributed to the San Giusto site. Furthermore, the production cycle of this ware can thus be reconstructed: from the diversified supply of raw materials (fluvial and marine sediments), to the relatively complex preparation of the paste, to firing at variable temperatures (600-750 ° C for cooking ware; 850 -1050 ° C for painted ware).

The aim of the present study is to reconstruct the production technology of Sienese ‘archaic’ majolica in the early decades of the 14th century ad. The integration of archaeological data with archived data revealed the presence of numerous workshops, suggesting that the Sienese tradition of majolica production was well developed up until the end of the 16th century. Sixty‐seven uncoated and coated waste products were analysed. The ceramic bodies were examined by OM, XRDp, SEM–EDS, XRF, ICP–OES, ICP–MS and INAA. The coatings (enamels and glazes) were analysed by SEM–EDS and Raman microspectroscopy. The results showed that ceramics were rejected due to poor control of the firing temperature (technological wastes), faulty production technology (wastes of uncertain classification) and accidents (post‐firing wastes). Finally, the analyses revealed extreme homogeneity of the ceramic bodies, indicating the continued use of the same raw material over the whole period studied.

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Archaeometric investigation allowed the characterization of two important classes of ceramics: 'vetrina sparsa' and 'invetriata grezza'. Their archaeological peculiarity makes them particularly suited for tracing the evolution of glaze manufacturing in southern Tuscany throughout the medieval period (10th-14th centuries). These ceramics were found in different sites of historical importance, and also from a mining perspective. Local copper, lead, zinc and iron mineralizations supported the growth of several settlements in the vicinity of the mines. The many castles and different archaeological finds (ceramics, glazed ceramic, slag etc.) attest to the intense mineral exploitation of the area from at least the first millennium BC up to the modern period. In light of these geological and archaeological characteristics, archaeometric investigation was intended to provide insight into ancient technical knowledge of ceramic glazing and to determine the source area for raw materials in the medieval period (10th-14th centuries). Ceramic bodies were analysed through OM, XRDp, SEM-EDS and XRF, while coatings were investigated through SEM-EDS. Mineralogical, petrographic and chemical analyses revealed slightly different preparation and firing processes for the two classes of ceramics. These data suggest the continuity through the centuries of the 'vetrina sparsa ' and 'invetriata grezza' production technology. The mineralogical phases, such as monazite, xenotime, zircon, barite, Ti oxide, ilmenite, titanite, tourmaline and ilvaite, and the lithic (intrusive and volcanic) fragments detected within the ceramic bodies suggest a source area in the vicinity of the Campiglia mining district. Lastly, the presence of Cu-Zn-Pb (Ag) and Fe sulphide mineralizations (materials used to produce glaze) in the area supports the hypothesis of local manufacture.