Using handheld pXRF to study medieval stained glass: A methodology using trace elements

The surfaces of 30 pieces of glass from panel 3b of the Great East Window of York Minster (1405-1408 CE) were analyzed by handheld portable X-ray fluorescence (pXRF) and small samples from the same pieces were analyzed by electron microprobe (EPMA). Comparison of the two methods reveals significant divergences which are not systematic, particularly for elements lighter than Ti. Rather than a problem with pXRF calibration or correction software, the non-systematic error is attributable to the presence of a thin surface layer of weathered glass. Analysis of the depths of X-ray generation indicate that virtually all X-rays characteristic of Ca and K are generated within the top 50 µm of the glass. However, for heavier elements such as Rb, Sr and Zr, most emitted X-rays are generated below 100 µm. Using pXRF data for the heavier elements, it is possible to replicate the compositional groupings identified by quantitative EPMA. White glass in the window is likely to have originated in England, while colored glasses were probably obtained from the Continent. The alkali contents of the green and yellow glasses appear to have been manipulated to generate their colors. Glass which is medieval in technology but not original to the panel was identified. In particular, zirconium proved a useful indicator of glassmaking regions, and rubidium and strontium were more sensitive to differences between batches, which has interesting implications for future work

Dating Nathan: The Oldest Stained Glass Window in England?

Relatively little is known about stained glass windows in England predating c. 1170; however, art-historical evaluation by Caviness (1987) argued that four figures from the “Ancestors series” of Canterbury Cathedral, usually dated to the late 12th and early 13th century, in fact date earlier (c. 1130–1160). This would place them amongst the earliest stained glass in England, and the world. Building on our previous work, we address Caviness’s hypothesis using a methodology based upon analysis of a few, well-measured heavy trace elements and a 3D-printed attachment for a pXRF spectrometer that facilitates in situ analysis. The results confirm two major periods of “recycling” or re-using medieval glass. The first is consistent with Caviness’s argument that figures predating the 1174 fire were reused in the early 13th century. The results suggest that in addition to figures, ornamental borders were reused, indicating the presence of more early glass than previously thought. In the second period of recycling (1790s), surviving figures from the Ancestors series were removed and adapted into rectangular panels for insertion into large Perpendicular-style windows elsewhere in the cathedral. The results show that the glasses used to adapt the panels to a rectangular shape were broadly contemporary with the glasses used to glaze the original Ancestors windows, again representing a more extensive presence of medieval glass in the windows

Regional patterns in medieval European glass composition as a provenancing tool

A legacy dataset of 1329 major element analyses of medieval glass (12th-15th centuries) has been compiled and analysed for geographical distribution of compositional characteristics. Three regional compositional types may be distinguished using simple elemental plots, associated with glass production in northwestern France, in the region around the Rhine, and in central Europe. Distribution maps are presented to aid interpretation and use of the data. The application of the approach is illustrated through three case studies. Late thirteenth-early fourteenth century medieval stained glass from York Minster (n = 91), late fourteenth-century stained glass from New College Oxford (n = 79) and a single medieval mirror found in Egypt were analysed using scanning electron microscopy–energy dispersive analysis. The York coloured and white glasses were identical and consistent with an origin in NW France. In the late fourteenth century, the coloured glass samples from Oxford were from the Rhenish region, while the white glass is consistent with an origin in NW France or England. The mirror glass from Egypt is of central European origin, and similar mirror glass is known from Italy. The apparent dominance of German mirror production may reflect an advantage of the glass, which is low in iron. The meta-analysis of the legacy data shows significant potential for developing an understanding of the production and movement of medieval glass