A multi-technique approach to unveil the composition and fabrication of a pre-Roman glass masterpiece: a double-faced human-head shape polychrome glass pendant (2nd -1st c. BC)

Abstract

Pre-Roman glass craftsmanship reached its summit with the development of complex polychrome glass beads, being the Phoenician glass pendants the most exquisite and elaborate example. The uniqueness and complexity of such findings could reveal key information for the understanding of the production and trade of glass pieces at that age. However, these findings have practically never been studied from a physic-chemical perspective. In this work, a remarkable polychrome glass pendant (2nd -1st c. BC) found at the archaeological site of Pintia (Padilla de Duero, Valladolid, Spain) is studied by a multi-analytical non-destructive approach, employing X-ray tomography to understand its fabrication procedure, as well as X-ray fluorescence (XRF) and Raman spectroscopy, both employed in microscopic mode, to determine the composition of each glass employed in its fabrication. The outstanding preservation state and well-defined archaeological context of this glass pendant offered a unique opportunity to expand the understanding of pre-Roman glass pieces, while the combination of the experimental techniques employed provided the first complete and detailed study of a Phoenician glass pendant. The fabrication procedure of the pendant has been identified step-by-step, showing evidence of the use of pre-made pieces for the eyes, as well as hints of its fabrication in a secondary workshop. Moreover, the microchemical analysis of the vividly colored glasses by XRF and Raman spectroscopy revealed a composition compatible with the use of natron as fluxing agent, typical of Phoenician glass, the presence of surface alterations corresponding to carbonatation processes, as well as the nature of the employed chromophores or pigments: Mn, Cu, and Co for the blue, Fe-S for the black, CaSb₂O₇ and CaSb₂O₇ + TiO₂ for two diverse white glasses, and a pyrochloric triple oxide (Pb₂Sb_2 − xSn_xO_7−x/2) and lead oxides for the yellow. Remarkably, the use of pyrochloric triple oxides as yellow pigments has scarcely been previously reported at that age. Finally, the identification by Raman spectroscopy of CaSb₂O₇ and the β-phase of CaSiO₃, as well as the Raman spectra features of the glass matrix corresponding to the blue glass, indicated maximum firing temperatures below 1100 °C.