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A multimodal study of smalt preservation and degradation on the painting “Woman doing a Libation or Artemisia” from an anonymous painter of the Fontainebleau School

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Abstract

The blue pigment smalt, a synthetic potash glass tinted with cobalt, was widely used between the sixteenth and the eighteenth centuries. As part of a study on the alteration of smalt and the reconstitution of its original color, the painting: Woman doing a Libation or Artemisia (Fontainebleau school, 1570) was examined in which the artist used smalt as a blue pigment, which is now degraded. Noninvasive imaging was performed using macro-2D X-ray fluorescence and reflectance imaging spectroscopy to get an overview of the artist’s palette and its distribution. Samples prepared as cross sections were also analyzed by scanning electron microscopy coupled with energy dispersive spectroscopy, micro-X-ray absorption near-edge structure spectroscopy and synchrotron micro-X-ray diffraction imaging to determine the preservation state of the smalt as well as structural information on other pigments adjacent to smalt grains in individual paint layers, which could play a role in the degradation process. On the one hand, the study conducted on the alteration of smalt has shown that it is very weathered and mixed with hydrocerussite, which could be a factor that would facilitate the alteration. On the other hand, these analyses have made it possible to identify and locate the pigments used, which will be the basis for the virtual reconstruction of the color of the painting.

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Data Availability Statement

This manuscript has associated data in a data repository of the ESRF. The 2D-\(\upmu\)XRD datasets generated during and analyzed during the current study are available in the ESRF repository: DOI 10.15151/ESRF-ES-527799901. All the other datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.

References

  1. A. Genty-Vincent, T.P. Van Song, C. Andraud et al., Four-flux model of the light scattering in porous varnish and paint layers: towards understanding the visual appearance of altered blanched easel oil paintings. Appl. Phys. A 123, 473 (2017). https://doi.org/10.1007/s00339-017-1092-1

    Article  ADS  Google Scholar 

  2. L. Monico, K. Janssens, E. Hendriks, F. Vanmeert, G. Van der Snickt, M. Cotte, G. Falkenberg, B. Brunetti, C. Miliani, Evidence for degradation of the chrome yellows in van Gogh’s sunflowers: a study using noninvasive in situ methods and synchrotron-radiation-based X-ray techniques. Angew. Chem. 54, 14129–14133 (2015). https://doi.org/10.1002/anie.201505840

    Article  ADS  Google Scholar 

  3. F. Delamare, Aux origines des bleus de cobalt: les débuts de la fabrication du saffre et du smalt en europe occidentale. Comptes-rendus des séances de l année - Académie des inscriptions et belles-lettres 153(1), 297–315 (2009). https://doi.org/10.3406/crai.2009.92472

    Article  Google Scholar 

  4. H. Stege, Out of the blue ? Zeitschrift für Kunsttechnologie: ZKK 18(1), 121–142

  5. B. Mühlethaler, J. Thissen, SMALT. Studies in Conservation 14(2), 47–61. https://doi.org/10.1179/sic.1969.005. Accessed 2022-07-26

  6. M. Spring, C. Higgitt, D. Saunders, Investigation of pigment-medium interaction processes in oil paint containing degraded smalt. Natl. Gallery Tech. Bull. 26, 56–70 (2005)

    Google Scholar 

  7. J. Hartwig, De la fabrication et de l’utilisation du safre ou zaffera (cobalt) et du smalte , par les verriers durant les XVI ème,XVII ème et XVIII ème siècles. Verre 7

  8. M. van Eikema Hommes, Changing pictures : discoloration in 15th-17th-century oil paintings. In: Changing Pictures, pp. 17–50. Archetype, London (2004)

  9. L. Robinet, M. Spring, S. Pagès-Camagna, Vibrational spectroscopy correlated with elemental analysis for the investigation of smalt pigment and its alteration in paintings. Anal. Methods 5(18), 4628 (2013). https://doi.org/10.1039/c3ay40906f

    Article  Google Scholar 

  10. I. Reiche, C. de Mecquenem, M. Eveno, L’utilisation du smalt et son altération dans les peintures des collections françaises. Les bleus et les verts: couleurs et lumières. eds. M. Menu, A-S. Le Hô, eds. Herman, p. 75–88 (2022)

  11. I. Reiche, M. Eveno, C. de Mecquenem, T. Calligaro, E. Laval, R. Pillay, E. Ravaud, V. Etgens, K. Mösl, M. Alfeld, The original appearance and beauty of ancient paintings virtually reconstructed. Fundation for Heritage Science, Heritage for the Future, Science for Heritage, Symposium proceedings, 164–170 (2022)

  12. V. Gonzalez, T. Calligaro, G. Wallez, M. Eveno, K. Toussaint, M. Menu, Composition and microstructure of the lead white pigment in masters paintings using HR synchrotron XRD. Microchem. J. 125, 43–49 (2016). https://doi.org/10.1016/j.microc.2015.11.005

    Article  Google Scholar 

  13. M. Alfeld, J.A.C. Broekaert, Mobile depth profiling and sub-surface imaging techniques for historical paintings-a review. Spectrochim. Acta, Part B 88, 211–230 (2013). https://doi.org/10.1016/j.sab.2013.07.009

    Article  ADS  Google Scholar 

  14. M. Eveno, E. Ravaud, T. Calligaro, L. Pichon, E. Laval, The Louvre crucifix by Giotto—unveiling the original decoration by 2D-XRF, X-ray radiography, emissiography and SEM-EDX analysis. Herit. Sci. 2, 17 (2014). https://doi.org/10.1186/s40494-014-0017-y

    Article  Google Scholar 

  15. V.A. Solé, E. Papillon, M. Cotte, P. Walter, J. Susini, A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra. Spectrochim. Acta, Part B 62, 63–68 (2007)

    Article  ADS  Google Scholar 

  16. R. Pillay, J.Y. Hardeberg, S. George, Hyperspectral imaging of art: acquisition and calibration workflows. J. Am. Inst. Conserv. 58(1–2), 3–15 (2019). https://doi.org/10.1080/01971360.2018.1549919

    Article  Google Scholar 

  17. C. Riekel, M. Burghammer, R. Davies, Progress in micro- and nano-diffraction at the ESRF ID13 beamline. IOP Conf. Series: Mater. Sci. Eng. 14, 012013 (2010). https://doi.org/10.1088/1757-899X/14/1/012013

    Article  Google Scholar 

  18. M. Cotte, V. Gonzalez, F. Vanmeert, L. Monico, C. Dejoie, M. Burghammer, L. Huder, W. de Nolf, S. Fisher, I. Fazlic, C. Chauffeton, G. Wallez, N. Jiménez, F. Albert-Tortosa, N. Salvadó, E. Possenti, C. Colombo, M. Ghirardello, D. Comelli, E. Avranovich Clerici, R. Vivani, A. Romani, C. Costantino, K. Janssens, Y. Taniguchi, J. McCarthy, H. Reichert, J. Susini, The “historical materials bag”: A new facilitated access to synchrotron x-ray diffraction analyses for cultural heritage materials at the european synchrotron radiation facility. Molecules 27(6) (2022). https://doi.org/10.3390/molecules27061997

  19. L. Robinet, M. Spring, S. Pagés-Camagna, D. Vantelon, N. Trcera, Investigation of the discoloration of smalt pigment in historic paintings by micro-x-ray absorption spectroscopy at the co k-edge. Anal. Chem. 83(13), 5145–52 (2011)

    Article  Google Scholar 

  20. V. Gonzalez, Caractérisation micro-structurale et luminescence des carbonates de plomb: apport à la discrimination des pigments blancs de plomb des œuvres peintes. PhD thesis (2016)

  21. E. Welcomme, Développement de techniques combinées de microanalyse par rayonnement synchrotron pour l’étude des pigments à base de carbonates de plomb. PhD thesis (2007)

  22. V. Gonzalez, T. Calligaro, G. Wallez, M. Eveno, K. Toussaint, M. Menu, Composition and microstructure of the lead white pigment in masters paintings using HR synchrotron XRD. Microchem. J. 125, 43–49 (2016). https://doi.org/10.1016/j.microc.2015.11.005

    Article  Google Scholar 

  23. P. Taylor, V.J. Lopata, Stability and solubility relationships between some solids in the system PbO-CO2-H2O. Can. J. Chem. 62(3), 395–402 (1984)

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the University School of Humanities, Creation, Heritage, Investment of Future ANR-17- EURE-0021 - Fondation des Sciences du Patrimoine through the MARCS project. We would like to thank the SOLEIL synchrotron facility for providing beamtime through the in house proposal 99200118 as well as Sebastian Schoeder and Laurent Tranchant for the help during beamtime at the PUMA beamline. We would also like to thank the European Synchrotron Research Facility (ESRF) for providing beamtime through the Historical Materials BAG (HG172) as well as Manfred Burghammer for the help brought for the use of the beamline ID13 and Marine Cotte, Victor Gonzales, Frederik Vanmeert and Letizia Monico, responsible scientists of the Historical Materials BAG for their support of the programme. Finally, we thank Cécile Scallierez, curator at the Louvre museum and Isabelle Chochod, restorer of the painting, for allowing us study the artwork together and for the fruitful discussions.

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Authors and Affiliations

  1. IPANEMA, Museum National d’Histoire Naturelle, Université Paris-Saclay, Université de Versailles Saint-Quentin-en-Yvelines, Centre National de la Recherche Scientifique (CNRS): USR3461, Ministère de la Culture, 91192, Gif-sur-Yvette, France

    Clément de Mecquenem

  2. PCMTH, Institut de Recherche de Chimie Paris, UMR8247 (CNRS - Chimie ParisTech - C2RMF), 75005, Paris, France

    Clément de Mecquenem, Myriam Eveno, Elisabeth Ravaud & Ina Reiche

  3. Centre de Recherche et de Restauration des Musées de France (C2RMF), Ministère de la Culture, 75001, Paris, France

    Myriam Eveno, Ruven Pillay, Eric Laval & Elisabeth Ravaud

  4. Department of Materials Science, Delft University of Technology, 2628, Delft, CD, The Netherlands

    Matthias Alfeld

  5. FR New AGLAE, CNRS/Ministère de la Culture/Chimie Paristech: FR3506, 75001, Paris, France

    Ina Reiche

Authors
  1. Clément de Mecquenem
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  2. Myriam Eveno
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  3. Matthias Alfeld
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  4. Ruven Pillay
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  5. Eric Laval
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  6. Elisabeth Ravaud
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  7. Ina Reiche
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Corresponding author

Correspondence to Ina Reiche.

Additional information

Focus Point on Scientific Research in Cultural Heritage 2022 Guest editors: L. Bellot-Gurlet, D. Bersani, A.-S. Le Hô, D. Neff, L. Robinet, A. Tournié.

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de Mecquenem, C., Eveno, M., Alfeld, M. et al. A multimodal study of smalt preservation and degradation on the painting “Woman doing a Libation or Artemisia” from an anonymous painter of the Fontainebleau School. Eur. Phys. J. Plus 138, 185 (2023). https://doi.org/10.1140/epjp/s13360-023-03799-4

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