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Electron energy loss spectroscopy elucidates the elusive darkening of zinc potassium chromate in Georges Seurat’s A Sunday on La Grande Jatte—1884

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Abstract

The color darkening of selected brushstrokes of Georges Seurat’s A Sunday on La Grande Jatte—1884 was noted as early as 1892. Artificial aging of model systems containing zinc yellow (K2O·4ZnCrO4·3H2O) mixed with linseed oil successfully replicated the phenomena observed on La Grande Jatte. Electron energy loss spectroscopy measurements performed on the uppermost few microns of thin sections of the paint layers (obtained with focused ion beam milling) determined that samples which turned olive green (aged at 90% RH, with SO2 and light) contain mostly the altered species Cr(III) and that the ochre-yellow coloration of specimens aged at 50% RH with SO2 and light is due to the presence of dichromate ions (Cr (VI)). The altered species are only present in the first few microns of paint and are likely poorly crystalline, so that they eluded other types of bulk and surface measurements, but they create a substantial color alteration at the surface of the paint films. A similar phenomenon was confirmed on a sample from La Grande Jatte, where Cr(III) and Cr(VI) dichromate ions were detected in the ochre-colored, altered brushstrokes of zinc yellow. Laboratory simulations demonstrated that the equilibrium between chromate and dichromate ions is reversible within the paint film and that the orange dichromate ions can be transformed back into bright yellow chromates by exposure to highly alkaline gases.

Georges Seurat, A Sunday on La Grande Jatte—1884, The Art Institute of Chicago. In the inset: Electron Energy Loss spectra of Cr rich pigment particles on a sample of paint from a darkened dot of La Grande Jatte, documenting Cr (III) and Cr(VI) dichromate alteration species

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Acknowledgments

The authors would like to thank Gonghu Li, Luciana Zanella and Jean-Francois Gaillard for their valuable experimental and intellectual contributions to this work. Conservation Science research at the Art Institute of Chicago is generously funded by the Andrew W. Mellon Foundation. The FT-Raman instrument is funded through the National Science Foundation, Division of Materials Research, Major Research Instrumentation Program, grant DMR-0723053. The RET program at Northwestern University, sponsored by the Materials Research Science and Engineering Center under NSF grant DMR 0520513, and its director, Prof. Monica Olvera de la Cruz are also gratefully acknowledged. The TEM/EELS work was performed in the EPIC and Keck-II facility of NUANCE Center at Northwestern University. NUANCE Center is supported by NSF-NSEC, NSF-MRSEC, Keck Foundation, the State of Illinois, and Northwestern University. Gloria Groom, Douglas Druick and Frank Zuccari at the Art Institute of Chicago are also thanked for their support of this project.

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Authors and Affiliations

  1. Conservation Department, The Art Institute of Chicago, Chicago, IL, 60603, USA

    F. Casadio & I. Fiedler

  2. CAMCOR, University of Oregon, Eugene, OR, 97403, USA

    S. Xie

  3. Libertyville High School, Libertyville, IL, 60048, USA

    S. C. Rukes

  4. McCormick School of Engineering, Northwestern University, Evanston, IL, 60208, USA

    B. Myers, K. A. Gray & R. Warta

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  1. F. Casadio
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  2. S. Xie
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  3. S. C. Rukes
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  5. K. A. Gray
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  6. R. Warta
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  7. I. Fiedler
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Correspondence to F. Casadio.

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Published in the special issue Analytical Chemistry for Cultural Heritage with Guest Editors Rocco Mazzeo, Silvia Prati, and Aldo Roda.

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Casadio, F., Xie, S., Rukes, S.C. et al. Electron energy loss spectroscopy elucidates the elusive darkening of zinc potassium chromate in Georges Seurat’s A Sunday on La Grande Jatte—1884 . Anal Bioanal Chem 399, 2909–2920 (2011). https://doi.org/10.1007/s00216-010-4264-9

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