Sulfur K-edge micro- And full-field XANES identify marker for preparation method of ultramarine pigment from lapis lazuli in historical paints

Alessa A. Gambardella*, Marine Cotte, Wout de Nolf, Kokkie Schnetz, Rob Erdmann, Roel van Elsas, Victor Gonzalez, Arie Wallert, Piet D. Iedema, Myriam Eveno, Katrien Keune

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Ultramarine blue pigment, one of the most valued natural artist's pigments, historically was prepared from lapis lazuli rock following various treatments; however, little is understood about why or how to distinguish such a posteriori on paintings. X-ray absorption near-edge structure spectroscopy at the sulfur K-edge in microbeam and full-field modes (analyzed with nonnegative matrix factorization) is used to monitor the changes in the sulfur species within lazurite following one such historically relevant treatment: heating of lapis lazuli before extracting lazurite. Sulfur signatures in lazurite show dependence on the heat treatment of lapis lazuli from which it is derived. Peaks attributed to contributions from the trisulfur radical-responsible for the blue color of lazurite-increase in relative intensity with heat treatment paralleled by an intensified blue hue. Matching spectra were identified on lazurite particles from five historical paint samples, providing a marker for artists' pigments that had been extracted from heat-treated lapis lazuli.

Original languageEnglish
Article numbereaay8782
Pages (from-to)1-11
Number of pages11
JournalScience advances
Volume6
Issue number18
DOIs
Publication statusPublished - Apr 2020

Funding

We thank AzkoNobel for funding, of which A.A.G. gives additional thanks to T. Davies for support and B. Rossenaar for TEM analyses. XANES experiments were performed on beamline ID21 at the ESRF, Grenoble, France (experiments HG62, HG94, and HG139); we are grateful to A. Sol? for providing assistance with PyMca, A. Gotz for reviewing Jupyter notebooks and assisting with the DOI, and A. de Maria for editing the DOI. M.C. thanks the KNAW for supporting her stays in The Netherlands through the Descartes Huygens prize. We are indebted to P. P. Pothoven for providing the lapis lazuli rock, and the Louvre (Paris, France) and the Mauritshuis (The Hague, The Netherlands) for the study of their paintings. For providing the embedded cross-sections and corresponding microscope images of historical samples, additional thanks are given to the C2RMF (Paris, France) for the Maelwael and Bellechose samples; the Mauritshuis (The Hague, The Netherlands)-in particular, S. Meloni-for the Steen sample; and the RKD-Netherlands Institute for Art History (The Hague, The Netherlands)-in particular, the archive of J. R. J. van Asperen de Boer-for the Van der Weyden sample. For imaging the Breughel sample, thanks are given to N. de Keyser of the Rijksmuseum. We also give thanks to the Cultural Heritage Agency of The Netherlands (Amersfoort, The Netherlands) for providing Xenotest chambers and the automatic muller (on permanent loan from Old Holland) as well as to I. Kneepkens, E. van Rietschoten, N. Kollard, J. Rosier, S. Matveev, and P. P. Pothoven for assistance with the pastello treatment. We are additionally grateful for support from the following: G. Albertson, N. de Keyser, G. de Vivo, E. Hermens, A. Krekeler, S. Smelt, B. van Driel, and R. van Langh of the Rijksmuseum; S. Meloni, C. Pottasch, A. Vandivere, and L. d'Hont of the Mauritshuis; F. Meirer of Utrecht University; and J. Rosier and N. Bergman of Vrije Universiteit Amsterdam. This work was supported by AkzoNobel (The Netherlands).

FundersFunder number
C2RMF
Cultural Heritage Agency of the Netherlands
Descartes Huygens
R. van Langh of the Rijksmuseum
RKD-Netherlands Institute for Art History
European Synchrotron Radiation FacilityHG94, HG139
European Synchrotron Radiation Facility
Koninklijke Nederlandse Akademie van Wetenschappen
Universiteit Utrecht
AkzoNobel

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