PIXE and PGAA – Complementary methods for studies on ancient glass artefacts (from Byzantine, late medieval to modern Murano glass)

Combined external milli-beam Particle Induced X-ray Emission (PIXE) and Prompt Gamma Activation Analysis (PGAA) analysis was applied to characterize the composition of paste and colorants from some fragments of Byzantine bracelets (10th–12th Centuries AD), late medieval (17th–18th Centuries AD) and modern Murano glass pieces. As fluxes, PGAA revealed the samples are soda-lime glass, except four samples - two medieval vessel white shards and two dark Byzantine fragments of bracelets – which have potash flux. Aluminium was detected in various proportions in all samples indicating different sources for the added sand. The presence of Magnesium is relevant only in one bracelet fragment suggesting the use of plant (wood?) ash and confirming that the Byzantine bracelet is manufactured from the mixture of both types of glass (natron and plant ash based). PGAA also indicated the presence of low quantities of Cadmium, high level of Arsenic and Lead (possibly lead arsenate) in one medieval sample and of ZnO in Murano glass, and of CoO traces (maximum 0.1%) in all blue-colored Byzantine, late medieval to modern Murano glass artefacts. PIXE confirmed the use of small quantities of CoO for blue color, indicated Manganese combined with Iron for dark glass, Copper for green, Lead, Tin and an Arsenic compound (orpiment?) for yellow and in the case of modern Murano glass Selenium and Cadmium to obtain a reddish color. Despite PIXE – PIGE combination is probably the best one for glass analysis, our external milli-PIXE – PGAA methods proved to be adequate complementary tools to determine many chemical elements from glass composition – Si, Na, K, Ca, Al, Mg, various metallic oxides.