Analysis of Lead Carboxylates and Lead-Containing Pigments in Oil Paintings by Solid- State Nuclear Magnetic Resonance

MRS Online Proceedings Library volume 1656, pages371–379(2014)Cite this article

Abstract

Soap formation in traditional oil paintings occurs when heavy-metal-containing pigments, such as lead white, 2Pb(CO3)2·Pb(OH)2, and lead-tin yellow type I, Pb2SnO4, react with fatty acids in the binding medium. These soaps may form aggregates that can be 100-200 μm in diameter, which swell and protrude through the paint surface, resulting in the degradation of the paint film and damage to the integrity of the artwork. In addition, soap formation has been reported to play a role in the increased transparency of paint films that allows the painting support, the preparatory drawing, and the artists’ alterations to become visible to the naked eye. The factors that trigger soap formation and the mechanism(s) of the process are not yet well understood. To elucidate these issues, chemical and structural information is necessary which can be obtained by solid-state 207Pb, 119Sn, and 13C nuclear magnetic resonance (NMR). In the present study, a combination of 207Pb NMR pulse sequences was used to determine accurately the NMR parameters of lead-containing pigments and lead carboxylates known to be involved in soap formation, such as lead palmitate, lead stearate, and lead azelate. These results show that the local coordination environment of lead azelate is different from lead palmitate or lead stearate and therefore it is unlikely that lead azelate would be incorporated into an ordered structure containing lead palmitate and lead stearate. In addition, the chemical shifts of the pigments obtained are different from those of the soaps, demonstrating that 207Pb NMR is useful in characterizing the components when present in a mixture, such as a paint film. The NMR methods discussed can also be applied to other Pb-containing cultural heritage materials, electronic and optoelectronic materials, superconducting materials, and environmentally contaminated materials.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

US$ 39.95

Tax calculation will be finalised during checkout.

References

  1. 1.

    P. Noble, J. J. Boon and J. Wadum, ArtMatters 1, 46–61 (2003).

    Google Scholar 

  2. 2.

    K. Keune, PhD Thesis, University of Amsterdam, 2005.

  3. 3.

    M. Spring, C. Ricci, D. Peggie and S. Kazarian, Analytical and Bioanalytical Chemistry 392 (1), 37–45 (2008).

    CAS  Article  Google Scholar 

  4. 4.

    C. Higgitt, M. Spring and D. Saunders, National Gallery Technical Bulletin 24, 75–95 (2003).

    Google Scholar 

  5. 5.

    S. A. Centeno and D. Mahon, The Metropolitan Museum of Art Bulletin 67 (1), 12–19 (2009).

    Google Scholar 

  6. 6.

    C. Hale, J. Arslanoglu and S. A. Centeno, in Studying Old Master Paintings. Technology and Practice, edited by M. Spring (Archetype Publications and The National Gallery, London, 2011), pp. 59–64.

    Google Scholar 

  7. 7.

    J. Van der Weerd, PhD Thesis, University of Amsterdam, 2002.

  8. 8.

    J. J. Boon, J. van der Weerd, K. Keune, P. Noble and J. Wadum, in ICOM-CC 13th Triennial Meeting (Rio de Janeiro, 2002), Vol. 1, pp. 410–406.

  9. 9.

    A. Eibner, Malmaterialienkunde als Grundlage der Maltechnik. (Verlag von Julius Springer, Berlin, 1909), pp. 121.

    Google Scholar 

  10. 10.

    P. Noble, A. van Loon and J. J. Boon, in ICOM Committee for Conservation 14th Triennnial Meeting (James and James, The Hague, 2005), Vol. 1, pp. 496–503.

    Google Scholar 

  11. 11.

    A. van Loon, PhD Thesis, University of Amsterdam, 2008.

  12. 12.

    F. Fayon, I. Farnan, C. Bessada, J. Coutures, D. Massiot and J. P. Coutures, Journal of the American Chemical Society 119 (29), 6837–6843 (1997).

    CAS  Article  Google Scholar 

  13. 13.

    C. Dybowski and G. Neue, Progress in Nuclear Magnetic Resonance Spectroscopy 41 (3–4), 153–170 (2002).

    CAS  Article  Google Scholar 

  14. 14.

    O. Dmitrenko, S. Bai, P. A. Beckmann, S. van Bramer, A. J. Vega and C. Dybowski, Journal of Physical Chemistry A 112 (14), 3046–3052 (2008).

    CAS  Article  Google Scholar 

  15. 15.

    J. Catalano, Y. Yao, A. Murphy, N. Zumbulyadis, S. A. Centeno and C. Dybowski, Applied Spectroscopy 68 (3), 280–286 (2014).

    CAS  Article  Google Scholar 

  16. 16.

    G. Neue, C. Dybowski, M. L. Smith, M. A. Hepp and D. L. Perry, Solid State Nuclear Magnetic Resonance 6 (3), 241–250 (1996).

    CAS  Article  Google Scholar 

  17. 17.

    A. W. MacGregor, L. A. O’Dell and R. W. Schurko, Journal of Magnetic Resonance 208 (1), 103–113 (2011).

    CAS  Article  Google Scholar 

  18. 18.

    K. Eichele, HBA 3.1 and WSOLIDS, University of Tubingen, 2013.

  19. 19.

    K. Keune and J. J. Boon, Stud. Conserv. 52 (3), 161–176 (2007).

    CAS  Article  Google Scholar 

  20. 20.

    M. J. Plater, B. De Silva, T. Gelbrich, M. B. Hursthouse, C. L. Higgitt and D. R. Saunders, Polyhedron 22 (24), 3171–3179 (2003).

    CAS  Article  Google Scholar 

  21. 21.

    P. Martinetto, M. Anne, E. Dooryhée, P. Walter and G. Tsoucaris, Acta Crystallographica Section C 58 (6), i82–i84 (2002).

    Google Scholar 

  22. 22.

    M. A. Verhoeven, Carlyle, L., Reedijk, J., Haasnoot, J.G., in Reporting Higlights of the De mayerne Programme., edited by J. J. a. F. Boon, E.S.B. (The Hague: Netherlands Organisation for Scientific Reserach (NWO). 2006), pp. 33–42.

  23. 23.

    B. Keisch, in Studies in the History of Art (1971–1972), Vol. 4, pp. 121–133.

  24. 24.

    J. R. Gavarri, J. P. Vigouroux, G. Calvarin and A. W. Hewat, Journal of Solid State Chemistry 36 (1), 81–90 (1981).

    CAS  Article  Google Scholar 

  25. 25.

    S. P. Gabuda, S. G. Kozlova, V. V. Terskikh, C. Dybowski, G. Neue and D. L. Perry, Solid State Nuclear Magnetic Resonance 15 (2), 103–107 (1999).

    CAS  Article  Google Scholar 

  26. 26.

    R. J. H. Clark, L. Cridland, B. M. Kariuki, K. D. M. Harris and R. Withnall, Journal of the Chemical Society. Dalton Transactions. (16), 2577–2582 (1995).

Download references

Author information

Affiliations

  1. Department of Scientific Research, The Metropolitan Museum of Art, New York, NY, 10028, U.S.A.

    Jaclyn Catalano & Silvia A. Centeno

  2. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE, 19716, U.S.A.

    Jaclyn Catalano, Yao Yao, Anna Murphy & Cecil Dybowski

  3. Independent Researcher, USA

    Nicholas Zumbulyadis

Authors
  1. Jaclyn Catalano
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yao Yao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Anna Murphy
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nicholas Zumbulyadis
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Silvia A. Centeno
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Cecil Dybowski
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jaclyn Catalano.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Catalano, J., Yao, Y., Murphy, A. et al. Analysis of Lead Carboxylates and Lead-Containing Pigments in Oil Paintings by Solid- State Nuclear Magnetic Resonance. MRS Online Proceedings Library 1656, 371–379 (2014). https://doi.org/10.1557/opl.2014.707

Download citation