Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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 (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 applicationmore » 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.« less

Authors:
 [1];  [2];  [3];  [1];  [2]
+ Show Author Affiliations
  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 Laboratory (SLAC), 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.
Copy to clipboard
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. https://doi.org/10.1515/pac-2017-0502
Copy to clipboard
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. https://doi.org/10.1515/pac-2017-0502. https://www.osti.gov/servlets/purl/1437447.
Copy to clipboard
@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 = {Fri Sep 22 00:00:00 EDT 2017},
month = {Fri Sep 22 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1515/pac-2017-0502
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Cennino Cennini’s process for the production of ultramarine blue from lapis lazuli.
All figures and tables (8 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

On the origin of the blue/green color of blast-furnace slag-based materials: Sulfur K-edge XANES investigation
journal, February 2017

  • Chaouche, Mohend; Gao, Xiao Xiao; Cyr, Martin
  • Journal of the American Ceramic Society, Vol. 100, Issue 4
  • DOI: 10.1111/jace.14670

2D X-ray and FTIR micro-analysis of the degradation of cadmium yellow pigment in paintings of Henri Matisse
journal, June 2015

Sulfur K X-ray absorption near edge structure spectroscopy on the photochrome sodalite variety hackmanite
journal, March 2013

  • Goettlicher, Joerg; Kotelnikov, Alexey; Suk, Natalya
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 228, Issue 3
  • DOI: 10.1524/zkri.2013.1587

Channel CO2 in feldspathoids: New data and new perspectives
journal, July 2008

  • Della Ventura, Giancarlo; Bellatreccia, Fabio; Piccinini, Massimo
  • RENDICONTI LINCEI, Vol. 19, Issue 2
  • DOI: 10.1007/s12210-008-0008-6

Ultramarine, Lazurite and Sodalite Studied by Positron Annihilation and EPR Methods
journal, July 1995

Trapping of inert gases in sodalite and cancrinite crystals
journal, January 1971

Chromium speciation methods and infrared spectroscopy for studying the chemical reactivity of lead chromate-based pigments in oil medium
journal, January 2016

Mineralogical characterization of the blue pigment of Michelangelo's fresco "The Last Judgment"
journal, July 2006

The nature of the chalcogen colour centres in ultramarine-type solids
journal, January 1999

  • Reinen, Dirk; Lindner, Gottlieb-Georg
  • Chemical Society Reviews, Vol. 28, Issue 2
  • DOI: 10.1039/a704920j

Structure and Dynamics of a Brønsted Acid Site in a Zeolite:  An ab Initio Study of Hydrogen Sodalite
journal, May 1998

  • Fois, Ettore; Gamba, Aldo; Tabacchi, Gloria
  • The Journal of Physical Chemistry B, Vol. 102, Issue 20
  • DOI: 10.1021/jp9808274

New Synthesis and Insight into the Structure of Blue Ultramarine Pigments
journal, May 2004

  • Arieli, D.; Vaughan, D. E. W.; Goldfarb, D.
  • Journal of the American Chemical Society, Vol. 126, Issue 18
  • DOI: 10.1021/ja0320121

Hydrolysis of Baltic amber during thermal ageing – An infrared spectroscopic approach
journal, April 2013

  • Pastorelli, Gianluca; Shashoua, Yvonne; Richter, Jane
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 106
  • DOI: 10.1016/j.saa.2012.12.072

The photodegradation of cadmium yellow paints in Henri Matisse’s Le Bonheur de vivre (1905–1906)
journal, November 2012

Understanding the Charging Mechanism of Lithium-Sulfur Batteries Using Spatially Resolved Operando X-Ray Absorption Spectroscopy
journal, January 2016

  • Gorlin, Yelena; Patel, Manu U. M.; Freiberg, Anna
  • Journal of The Electrochemical Society, Vol. 163, Issue 6
  • DOI: 10.1149/2.0631606jes

Ubiquitous trisulfur radical anion: fundamentals and applications in materials science, electrochemistry, analytical chemistry and geochemistry
journal, January 2013

  • Chivers, Tristram; Elder, Philip J. W.
  • Chemical Society Reviews, Vol. 42, Issue 14
  • DOI: 10.1039/c3cs60119f

Chemical State of Sulfur in Natural and Synthetic Lazurite by s K-Edge Xanes and X-Ray Photoelectron Spectroscopy
journal, October 2005

X-ray absorption spectroscopy of ultramarine pigments: A new analytical method for the polysulfide radical anion S3− chromophore
journal, January 2010

  • Fleet, Michael E.; Liu, Xi
  • Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 65, Issue 1
  • DOI: 10.1016/j.sab.2009.11.008

Lapis lazuli usage for blue decoration of polychrome painted glazed pottery: a recurrent technology during the Middle Ages in Apulia (Southern Italy)
journal, April 2007

  • Catalano, I. M.; Genga, A.; Laganara, C.
  • Journal of Archaeological Science, Vol. 34, Issue 4
  • DOI: 10.1016/j.jas.2006.05.010

The resonance Raman spectrum of ultramarine blue
journal, July 1975

X-ray spectroscopy as a probe for lithium polysulfide radicals
journal, January 2015

  • Pascal, Tod A.; Pemmaraju, C. D.; Prendergast, David
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 12
  • DOI: 10.1039/C4CP05316H

Observation of the ν3 Raman band of S3− inserted into sodalite cages
journal, January 2007

  • Ledé, B.; Demortier, A.; Gobeltz-Hautecœur, N.
  • Journal of Raman Spectroscopy, Vol. 38, Issue 11
  • DOI: 10.1002/jrs.1795

Characterization of a Degraded Cadmium Yellow (CdS) Pigment in an Oil Painting by Means of Synchrotron Radiation Based X-ray Techniques
journal, April 2009

  • Van der Snickt, Geert; Dik, Joris; Cotte, Marine
  • Analytical Chemistry, Vol. 81, Issue 7
  • DOI: 10.1021/ac802518z

The presence of trapped carbon dioxide in lapis lazuli and its potential use in geo-sourcing natural ultramarine pigment
journal, July 2009

Sulfur K-edge XANES of lazurite: Toward determining the provenance of lapis lazuli
journal, March 2016

  • Gambardella, Alessa A.; Schmidt Patterson, Catherine M.; Webb, Samuel M.
  • Microchemical Journal, Vol. 125
  • DOI: 10.1016/j.microc.2015.11.030

The structure of lazurite, ideally Na6Ca2(Al6Si6O24)S2, a member of the sodalite group
journal, June 1985

  • Hassan, I.; Peterson, R. C.; Grundy, H. D.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 41, Issue 6
  • DOI: 10.1107/S0108270185005662

Paramagnetic resonance of sulfur radicals in synthetic sodalites
journal, March 1970

  • McLaughlan, Stuart D.; Marshall, David John
  • The Journal of Physical Chemistry, Vol. 74, Issue 6
  • DOI: 10.1021/j100701a035

Inorganic Polysulfides Sn2- and Radical Anions Sn.-
journal, April 2004

Characterization of lapis lazuli and corresponding purified pigments for a provenance study of ultramarine pigments used in works of art
journal, December 2011

  • Favaro, M.; Guastoni, A.; Marini, F.
  • Analytical and Bioanalytical Chemistry, Vol. 402, Issue 6
  • DOI: 10.1007/s00216-011-5645-4

Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy
journal, September 2013

  • Cuisinier, Marine; Cabelguen, Pierre-Etienne; Evers, Scott
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 19
  • DOI: 10.1021/jz401763d

Lapis Lazuli – the Most Beautiful Rock in the World
journal, December 2015

Encapsulation of the chromophores into the sodalite structure during the synthesis of the blue ultramarine pigment
journal, January 1998

  • Gobeltz, N.; Demortier, A.; Lelieur, J. P.
  • Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 15
  • DOI: 10.1039/a801526k

The invention of blue and purple pigments in ancient times
journal, January 2007

Insight into Framework Destruction in Ultramarine Pigments
journal, February 2006

  • Del Federico, Eleonora; Shöfberger, Wolfgang; Schelvis, Johannes
  • Inorganic Chemistry, Vol. 45, Issue 3
  • DOI: 10.1021/ic050903z

Lapis-Lazuli From Sar-E-Sang, Badakhshan, Afghanistan
journal, January 1981

  • Wyart, Jean; Bariand, Pierre; Filippi, Jean
  • Gems & Gemology, Vol. 17, Issue 4
  • DOI: 10.5741/GEMS.17.4.184

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

X-ray Absorption Spectra of Dissolved Polysulfides in Lithium–Sulfur Batteries from First-Principles
journal, April 2014

  • Pascal, Tod A.; Wujcik, Kevin H.; Velasco-Velez, Juan
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 9
  • DOI: 10.1021/jz500260s

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

The Characterization of Metal Soaps
journal, January 2003

Aluminium X-ray absorption near-edge spectroscopy analysis of discoloured ultramarine blue in 20th century oil paintings
journal, May 2016

The crystal structures of sodalite-group minerals
journal, February 1984

  • Hassan, I.; Grundy, H. D.
  • Acta Crystallographica Section B Structural Science, Vol. 40, Issue 1
  • DOI: 10.1107/S0108768184001683

The Use of Egyptian Blue and Lapis Lazuli in the Middle Ages - The Wall Paintings of the San Saba Church in Rome
journal, March 2004

  • Gaetani, Maria Carolina; Santamaria, Ulderico; Seccaroni, Claudio
  • Studies in Conservation, Vol. 49, Issue 1
  • DOI: 10.1179/sic.2004.49.1.13

Analytical study into El Greco’s baptism of Christ: clues to the genius of his palette
journal, November 2007

Occupancy of the Sodalite Cages in the Blue Ultramarine Pigments
journal, June 2002

  • Gobeltz-Hautecoeur, N.; Demortier, A.; Lede, B.
  • Inorganic Chemistry, Vol. 41, Issue 11
  • DOI: 10.1021/ic010822c
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Supramolecular Organization in Confined Nanospaces
    journal, April 2018

    Supramolecular organization in confined nanospaces
    text, January 2021

    Supramolecular organization in confined nanospaces
    text, January 2021

    Supramolecular organization in confined nanospaces
    text, January 2018

      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Fig. 1 (p. 2)figure
      Fig. 2 (p. 5)figure
      Fig. 3 (p. 6)figure
      Fig. 4 (p. 7)figure
      Fig. 5 (p. 8)figure
      Fig. 6 (p. 8)figure
      Fig. 7 (p. 9)figure
      Table 1 (p. 11)table
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: