The palaeo-Christian glass mosaic of St. Prosdocimus (Padova, Italy): archaeometric characterisation of tesserae with antimony- or phosphorus-based opacifiers

The present paper reports the results of archaeometric characterisation of the opaque tesserae, intentionally coloured with antimony- or phosphorus-based opacifiers, coming from one of the two only palaeo- Christian glass mosaics known in the Veneto region (Italy), i.e., the mosaic which decorated the votive chapel of St. Prosdocimus in Padova. In particular, 55 tesserae belonging to glass types “White”, “Blue”, “Yellow”, “Green” and “Brown” are examined here. The multi-methodological approach (SEM-EDS, EMPA, XRPD, imaging spectroscopy coupled, in some cases, with XAS) gave valuable insights into the complexities of palaeo-Christian glass mosaic production technologies. Two main groups are identified, one characterised by glassy matrixes and opacifiers (calcium or lead antimonate) typical of the Roman period and comprising all “White”, “Blue”, and “Yellow” tesserae and some “Green” ones, and the other characterised by glassy matrixes and an opacifier (calcium phosphate) typical of the 6th century AD, composed of “Green” and “Brown” tesserae. This suggests that, during that century there was a gradual change from older to “new” production technologies: although new opacifiers such as calcium phosphate started to be used, the frequent use of antimony-based ones (43/55 samples) supports the hypothesis that their systematic use was extended until the 6th century, although re-using old tesserae cannot be completely excluded. In addition, comparisons with compositional groups already identified in the “gold” tesserae of the same mosaic and tesserae from Ravenna demonstrate that both the same “base compositions” of the glass were used to produce transparent and opaque glass. This evidence, coupled with the results of the historical-artistic study, suggests technological connections between Padova and Ravenna, the capital of Byzantine mosaics in Italy. Micro-structural observations and chemical analyses of the Paduan antimonybased opacified glass demonstrate that different processes and raw materials were used in their production. Both in situ and ex situ crystallisation can be identified for calcium and lead antimonate in Paduan tesserae, whereas the production of tesserae opacified with calcium phosphate generally appears to be highly standardised. Although the opacifiers used in the Paduan tesserae support technological transitions, the colouring elements identified here, i.e., iron and manganese for white, yellow, brown and some green tesserae, cobalt for blue, and copper for blue and green, suggest continuity, because their use is widely testified in the production of both transparent and opaque glass artefacts dating from the Bronze Age until Medieval times, from whichever archaeological site the samples come. Peculiar relationships among the oxidation states of colouring elements, their contents in the glassy matrix, the types of opacifiers used, and the final colour of tesserae were identified. In addition, the correlations of cobalt and/or copper with other elements, together with identification of relics of colouring and “metallic” droplets, allow us to speculate on possible sources and production technologies. Lastly, identification of newly formed crystalline inclusions in tesserae also yields information on kiln temperatures, which ranged between 900 and 1150°C, a range easily reached in the furnaces of the 6th century AD