Chemistry of cultural glasses: the early medieval glasses of Monselice's hill (Padova, Italy)

To investigate the mechanisms of deterioration of historical glasses, under natural evolution, some early medieval glasses from the archaeological site of the Monselice's hill have been analysed. By an archaeological approach, developed at the Dipartimento di Scienze dell'Antichità, University of Padova, the glasses were dated between the VI and the beginning of the VII century and they were ascribed to the same artist or school. By a geological approach, developed at the Dipartimento di Mineralogia e Petrologia, University of Padova, it was found that some pieces of glasses, from the same archaeological site, were made of silica, rich in sodium and calcium, with iron and manganese. The composition was analogous the one of glasses produced during Roman empire, using `natron' (Na2CO3·NaHCO3·2H2O) as melting agent and glasses produced during medieval age, in the Mediterranean basin, using plant ash like `Salsola Kali' as melting agent. It was also found that there was a surface layer, with a special lamellar structure, easy to remove. The surface layer was found poor in alkali and alkaline-earth elements. By surface and microscopic analyses (optical microscopy, SEM-EDS, microRaman, XPS, SIMS and Mössbauer) it has been found that all the samples have a composition rich in silica, sodium and calcium except one that, unexpectedly, was rich in potassium and poorer in sodium. This sample, as composition, seems just like medieval glasses produced north of the Alps, using plant ash like ferns as melting agent. In all the samples the surface layers have less alkaline elements and the depletion goes to ten ?m of depth. The extreme consequence of this depletion is the formation, in some samples, of an alteration layer, easy to remove, that the XPS analyses tell us it is made of very hydrated silica. The surface layers show a little accumulation of calcium. The calcium ion is also present in some birefringent crystal aggregates immersed in the glass that, in some samples, are around one mm large. These aggregates have a circular shape, with a nucleation centre in them. By microRaman spectroscopy it was found that the crystal aggregates are made of vateritic and calcitic calcium carbonate. By Mössbauer spectroscopy it was found that in the flat yellow coloured glasses, richer in iron, the Fe(III) species predominates. Instead in the pale green ones, poorer in iron, the Fe(II) prevails.