Use of standard analytical tools to detect small amounts of smalt in the presence of ultramarine as observed in 15th-century Venetian illuminated manuscripts
Dooley, Kathryn A MacLennan, Douglas Bertolotti, Giulia Gabrieli, Francesca Patterson, Catherine Schmidt Delaney, John K
Dooley, Kathryn A
MacLennan, Douglas
Bertolotti, Giulia
Gabrieli, Francesca
Patterson, Catherine Schmidt
Delaney, John K
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2022-03-21
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2021-12-22
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Non-invasive pigment analysis
smalt
ultramarine
Master of the Murano Gradual
Venice
illuminated manuscripts
XRF
reflectance spectroscopy
Raman
FT-IR
smalt
ultramarine
Master of the Murano Gradual
Venice
illuminated manuscripts
XRF
reflectance spectroscopy
Raman
FT-IR
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Abstract
A previous preliminary study of 15th-century Venetian manuscript fragments by the Master of the Murano Gradual identified the presence of cobalt in many ultramarine blue areas, suggesting the presence of smalt. This would represent an early use of this glassy pigment in Venetian illuminated manuscripts. Whereas sampling has been used to identify smalt in 15th century paintings, only non-invasive methods can be used on manuscripts due to their small size and fragile nature. Here we investigated four non-invasive analysis techniques to identify small amounts of smalt in the presence of ultramarine, including single-point and scanning XRF spectroscopy, UV–vis-NIR-SWIR reflectance spectroscopy (FORS), Raman spectroscopy, and external reflection FT-IR spectroscopy. This was done by studying paint mock-ups of ultramarine and smalt mixtures with and without the presence of a white pigment on parchment. The results showed molecular spectroscopy techniques (reflectance, Raman, and FTIR) require at least ~ 30–40% smalt by percent mass when in the presence of ultramarine in order to detect its presence, whereas elemental XRF spectroscopy can detect cobalt (and thus infer the presence of smalt) at the ~ 1% level. To further explore the inference of smalt by XRF, additional XRF analysis was conducted to specifically look for elements associated with cobalt minerals (i.e. nickel, arsenic, bismuth, etc.). High spatial resolution XRF scanning (60–100 μm X-ray spot size) was used to look for cobalt in smalt particles which are typically larger than those of ultramarine. These two XRF analysis approaches worked well with the mock-up paint samples, and were subsequently applied to the manuscripts for which molecular spectroscopy methods yielded no unambiguous evidence for smalt. The data underscore the challenges of conclusively identifying smalt in complex paint systems when samples are not available, but do suggest that the Master of the Murano illuminated manuscript fragments contain smalt, but perhaps not in a form or amount researchers are used to seeing in paintings.
Citation
Ricciardi, P., Dooley, K.A., MacLennan, D. et al. Use of standard analytical tools to detect small amounts of smalt in the presence of ultramarine as observed in 15th-century Venetian illuminated manuscripts. Herit Sci 10, 38 (2022). https://doi.org/10.1186/s40494-022-00671-z
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Copyright © The Author(s) 2022. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data. The linked file is the published version of the article.
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2050-7445
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openAccess