The chemical composition of medieval wood ash glass from Central Europe

Medieval wood ash glass classified as 6 early medieval wood ash glasses, 17 wood ash glasses, 5 early wood ash lime glasses, 7 wood ash lime glasses and 9 mixed alkali glasses has been analyzed by microprobe and ICP-mass spectrometry on 61 elements. Their calcium oxide to potassium oxide ratio (CaO/K2O) increases from early to late medieval glasses according to an increase of the proportion of twigs in the bulk amount of wood (logs plus twigs). Twigs because of their relatively large proportion of bark contain more calcium than wood logs. The ratio CaO/K2O of the glasses from not yet evaluated excavations can be used for dating. The observation that the 25 minor elements Be, Sc, V, Cr, Ge, V. Nb, REE (La to Lu), Ta, W and Bi occur in almost equal concentrations in the five subtypes of wood ash glass makes it highly probable that these elements were introduced into the starting mixtures of the glasses by means of quartz from quartz-rich sand with heavy minerals. The majorities of the wood ash glasses contain so-called europium anomalies within the group of rare-earth elements (REE). Their Eu concentrations normalized to those of the Continental Earth's Crust are lower than the normalized samarium and gadolinium concentrations. These Eu anomalies are apparently inherited from the granitic source of quartz in the upper Continental Earth's Crust. Soda ash and soda lime glass as the other major types in the history of glass contain no Eu anomaly. Therefore a different source of quartz has caused this important element constellation for these glass types. The elements K, Cu, Rb and S are physiologically separated from Ca, P, Mn, Sr and B during the growth of the wood and bark, respectively, in the trees. Different sources of the metals Cu and Co were used for colouring the glasses of our report. (C) 2009 Elsevier GmbH. All rights reserved.