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

Published online by Cambridge University Press:  21 February 2017

Laura W. Adlington*
Affiliation:
UCL Institute of Archaeology, 31-34 Gordon Square, London, WC1H 0PY
Ian C. Freestone
Affiliation:
UCL Institute of Archaeology, 31-34 Gordon Square, London, WC1H 0PY
*
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Abstract

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.

Type
Articles
Copyright
Copyright © Materials Research Society 2017 

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References

REFERENCES

Adlington, L. W. (in press) ‘The Corning Archaeological Reference Glasses: New Values for “Old” Compositions’, Papers from the Institute of Archaeology.Google Scholar
Bamford, C. R. (1977) Colour generation and control in glass. Amsterdam: Elsevier.Google Scholar
Brill, R. H. (1999) Chemical analyses of early glasses. Corning, NY: Corning Museum of Glass.Google Scholar
Dungworth, D. (2011) ‘The value of historic window glass’, The Historic Environment, 2(1), pp. 2148. doi: 10.1179/175675011X12943261434567.Google Scholar
Dungworth, D. (2012) ‘Historic windows: Investigation of composition groups with nondestructive pXRF’, Glass Technology: European Journal of Glass Science and Technology Part A, 53(5), pp. 192197.Google Scholar
Fernández-Navarro, J.-M. and Villegas, M.-Á. (2013) ‘What is Glass? An Introduction to the Physics and Chemistry of Silicate Glasses’, in Janssens, K. (ed.) Modern Methods for Analysing Archaeological and Historical Glass. Chichester, UK: John Wiley & Sons, pp. 122. Available at: http://onlinelibrary.wiley.com/book/10.1002/9781118314234.Google Scholar
Freestone, I. C., Kunicki-Goldfinger, J. J., Gilderdale-Scott, H. and Ayers, T. (2010) ‘Multidisciplinary Investigation of the Windows of John Thornton, Focusing on the Great East Window of York Minster’, in Shepherd, M. B., Pilosi, L., and Strobl, S. (eds) The Art of Collaboration: Stained-Glass Conservation in the Twenty-First Century. London: The International Committee of the Corpus Vitrearum for the Conservation of Stained Glass, pp. 151158.Google Scholar
French, T. (2003) York Minster: The Great East Window. Oxford: Oxford University Press (Corpus Vitrearum Medii Aevi: Great Britain, Summary Catalogue 2).Google Scholar
Gratuze, B., Soulier, I., Barrandon, J.-N. and Foy, D. (1995) ‘The origin of cobalt blue pigment in French glass from the thirteenth to the eighteenth centuries’, in Hook, D. R. and Gaimster, D. R. M. (eds) Trade and Discovery: Scientific Study of Artefacts from Post-medieval Europe and Beyond. London: British Museum (British Museum Occasional Paper), pp. 123133.Google Scholar
Kaiser, B. and Shugar, A. N. (2012) ‘Glass analysis utilizing handheld X-ray fluorescence’, in Shugar, A. N. and Mass, J. L. (eds) Handheld XRF for Art and Archaeology. Leuven, Belgium: Leuven University Press (Studies in Archaeological Sciences), pp. 449470.Google Scholar
Kunicki-Goldfinger, J. J., Freestone, I. C., McDonald, I., Hobot, J. A., Gilderdale-Scott, H. and Ayers, T. (2014) ‘Technology, production and chronology of red window glass in the medieval period - rediscovery of a lost technology’, Journal of Archaeological Science, 41, pp. 89105. doi: 10.1016/j.jas.2013.07.029.Google Scholar
Marks, R. (1993) Stained Glass in England during the Middle Ages. London: Routledge.Google Scholar
Melcher, M. and Schreiner, M. (2006) ‘Leaching studies on naturally weathered potash-lime-silica glasses’, Journal of Non-Crystalline Solids, 352(5), pp. 368379. doi: 10.1016/j.jnoncrysol.2006.01.017.CrossRefGoogle Scholar
Newton, R. G. (1982) The deterioration and conservation of painted glass: A critical bibliography. Oxford: Oxford University Press (Corpus Vitrearum Medii Aevi Great Britain Occasional Papers II).Google Scholar
Pollard, A. M. and Heron, C. (1996) ‘The chemistry and corrosion of archaeological glass’, in Pollard, A. M. and Heron, C. (eds) Archaeological chemistry. Cambridge: Royal Society of Chemistry, pp. 149195.Google Scholar
Potts, P. J., Williams-Thorpe, O. and Webb, P. C. (1997) ‘The bulk analysis of silicate rocks by portable X-ray fluorescence: Effect of sample mineralogy in relation to the size of the excited volume’, Geostandards Newsletter, 21(1), pp. 2941. doi: 10.1111/j.1751-908X.1997.tb00529.x.CrossRefGoogle Scholar
Ringwood, A. E. (1955) ‘The principles governing trace element distribution during magmatic crystallization: Part I. The influence of electronegativity’, Geochimica et Cosmochimica Acta, 7(3–4), pp. 189202. doi: 10.1016/0016-7037(55)90029-6.CrossRefGoogle Scholar
Schreiner, M., Woisetschläger, G., Schmitz, I. and Wadsak, M. (1999) ‘Characterisation of surface layers formed under natural environmental conditions on medieval stained glass and ancient copper alloys using SEM, SIMS and atomic force microscopy’, Journal of Analytical Atomic Spectrometry, 14, pp. 395403. doi: 10.1039/a807305h.CrossRefGoogle Scholar
Scott, R. B., Shortland, A. J., Degryse, P., Power, M., Domoney, K., Boyen, S. and Braekmans, D. (2012) ‘In situ analysis of ancient glass: 17th century painted glass from Christ Church Cathedral, Oxford and Roman glass vessels’, Glass Technology: European Journal of Glass Science and Technology Part A, 53(2), pp. 6573.Google Scholar
Shannon, R. D. (1976) ‘Revised Effective Ionic Radii and Systematic Studies of Interatomic Distances in Halides and Chaleogenides’, Acta Crystallographica, A 32, pp. 751767.Google Scholar
Van der Snickt, G., Legrand, S., Caen, J., Vanmeert, F., Alfeld, M. and Janssens, K. (2016) ‘Chemical imaging of stained-glass windows by means of macro X-ray fluorescence (MA-XRF) scanning’, Microchemical Journal, 124(JANUARY), pp. 615622. doi: 10.1016/j.microc.2015.10.010.Google Scholar
Wedepohl, K. H. (2003) Glas in Antike und Mittelalter: Geschichte eines Werkstoffs. Stuttgart: Schweizerbart’sche Verlagsbucchandlung.Google Scholar
Weyl, W. A. (1951) Coloured Glasses. Sheffield, UK: The Society of Glass Technology.Google Scholar