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Title: From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES

Abstract

As one of the most desired and expensive artists’ materials throughout history, there has long been interest in studying natural lapis lazuli. The traditional method of extracting the blue component, lazurite, from lapis lazuli, as outlined in Cennini’s Il Libro dell’Arte, involves a lengthy purification process: (1) finely grind the rock; (2) mix with pine rosin, gum mastic, and beeswax; (3) massage in water to collect the lazurite. Repeating the process produces several grades of the pigment, typically referred to as ultramarine blue. Here, we investigate the sulfur environment within the aluminosilicate framework of lazurite during its extraction from lapis lazuli. The sulfur XANES fingerprint from samples taken at the different stages in Cennini’s extraction method were examined. All spectra contain a strong absorption peak at 2483 eV, attributable to sulfate present in the lazurite structure. However, intensity variations appear in the broad envelope of peaks between 2470 and 2475 eV and the pre-peak at 2469.1 eV, indicating a variation in the content of trisulfur (S 3 –˙) radicals. By studying the effect of each step of Cennini’s process, this study elucidates the changes occurring during the extraction and the variability within different grades of the precious coloring material. Themore » increasing application of XANES to the study of artist’s materials and works of art motivated extending the research to assess the possibility of X-ray induced damage. Direct comparison of micro-focused and unfocused beam experiments suggests an increase of the S 3 –˙ radicals with prolonged exposure. Furthermore, analysis indicates that induced damage follows first-order kinetics, providing a first assessment on the acceptable amount of radiation exposure to define the optimal acquisition parameters to allow safe analyses of lapis lazuli and ultramarine pigments.« less

Authors:
 [1];  [2];  [3];  [1];  [2]
  1. The Getty Conservation Institute, Los Angeles, CA (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1437447
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Pure and Applied Chemistry
Additional Journal Information:
Journal Volume: 90; Journal Issue: 3; Journal ID: ISSN 0033-4545
Publisher:
IUPAC
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cennino Cennini; ChemCultHerit; lapis lazuli; radiation damage; ultramarine; XANES

Citation Formats

Ganio, Monica, Pouyet, Emeline S., Webb, Samuel M., Schmidt Patterson, Catherine M., and Walton, Marc S. From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES. United States: N. p., 2017. Web. doi:10.1515/pac-2017-0502.
Ganio, Monica, Pouyet, Emeline S., Webb, Samuel M., Schmidt Patterson, Catherine M., & Walton, Marc S. From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES. United States. doi:10.1515/pac-2017-0502.
Ganio, Monica, Pouyet, Emeline S., Webb, Samuel M., Schmidt Patterson, Catherine M., and Walton, Marc S. Fri . "From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES". United States. doi:10.1515/pac-2017-0502. https://www.osti.gov/servlets/purl/1437447.
@article{osti_1437447,
title = {From lapis lazuli to ultramarine blue: investigating Cennino Cennini’s recipe using sulfur K-edge XANES},
author = {Ganio, Monica and Pouyet, Emeline S. and Webb, Samuel M. and Schmidt Patterson, Catherine M. and Walton, Marc S.},
abstractNote = {As one of the most desired and expensive artists’ materials throughout history, there has long been interest in studying natural lapis lazuli. The traditional method of extracting the blue component, lazurite, from lapis lazuli, as outlined in Cennini’s Il Libro dell’Arte, involves a lengthy purification process: (1) finely grind the rock; (2) mix with pine rosin, gum mastic, and beeswax; (3) massage in water to collect the lazurite. Repeating the process produces several grades of the pigment, typically referred to as ultramarine blue. Here, we investigate the sulfur environment within the aluminosilicate framework of lazurite during its extraction from lapis lazuli. The sulfur XANES fingerprint from samples taken at the different stages in Cennini’s extraction method were examined. All spectra contain a strong absorption peak at 2483 eV, attributable to sulfate present in the lazurite structure. However, intensity variations appear in the broad envelope of peaks between 2470 and 2475 eV and the pre-peak at 2469.1 eV, indicating a variation in the content of trisulfur (S3–˙) radicals. By studying the effect of each step of Cennini’s process, this study elucidates the changes occurring during the extraction and the variability within different grades of the precious coloring material. The increasing application of XANES to the study of artist’s materials and works of art motivated extending the research to assess the possibility of X-ray induced damage. Direct comparison of micro-focused and unfocused beam experiments suggests an increase of the S3–˙ radicals with prolonged exposure. Furthermore, analysis indicates that induced damage follows first-order kinetics, providing a first assessment on the acceptable amount of radiation exposure to define the optimal acquisition parameters to allow safe analyses of lapis lazuli and ultramarine pigments.},
doi = {10.1515/pac-2017-0502},
journal = {Pure and Applied Chemistry},
number = 3,
volume = 90,
place = {United States},
year = {2017},
month = {9}
}

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Figures / Tables:

Fig. 1 Fig. 1: Cennino Cennini’s process for the production of ultramarine blue from lapis lazuli.

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Works referenced in this record:

Analytical Imaging Studies of Cross-Sections of Paintings Affected by Lead Soap Aggregate Formation
journal, September 2007


Thermodynamic and experimental study of the degradation of the red pigment mercury sulfide
journal, January 2015

  • Radepont, Marie; Coquinot, Yvan; Janssens, Koen
  • Journal of Analytical Atomic Spectrometry, Vol. 30, Issue 3
  • DOI: 10.1039/C4JA00372A

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      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.