skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues

Abstract

Yellow orpiment (As2S3) and red–orange realgar (As4S4) photo-degrade and the nineteenth-century pigment emerald green (Cu(C2H3O2)2·3Cu(AsO2)2) degrades into arsenic oxides. Because of their solubility in water, arsenic oxides readily migrate and are found throughout the multi-layered paint system. The widespread arsenic migration has consequences for conservation, and this paper provides better insight into the extent of the problem. Five paint samples containing orpiment, realgar or emerald green pigments deriving from paintings by De Heem (17th C), Van Gogh (19th C), Rousseau (19th C), an unknown 17th C northern European artist and an Austrian painted cupboard (19th C) were investigated using SEM/EDX, imaging ATR-FTIR and arsenic (As) K–edge μ-XANES to obtain the spatial distribution and chemical speciation of arsenic in the paint system. In all of the samples investigated arsenic had migrated throughout the multi-layered paint structure of the art object, from support to varnish. Furthermore, As5+-species were found throughout the entire paint sample. We hypothesize that arsenic trioxide is first formed, dissolves in water, further oxidizes to arsenic pentaoxide, and then reacts with lead, calcium and other ions and is deposited in the paint system as insoluble arsenates. Since the degradation of arsenic pigments such as orpiment, realgar and emerald greenmore » occurs through a highly mobile intermediate stage, it not only affects the regions rich in arsenic pigments, but also the entire object, including substrate and top varnish layers. Furthermore, because of this widespread potential for damage, preventing degradation of arsenic pigments should be prioritized and conservators should minimize exposure of objects containing arsenic pigments to strong light, large fluctuations in relative humidity and water-based cleaning agents.« less

Authors:
 [1];  [2];  [3];  [4];  [5]
  1. Rijksmuseum Amsterdam, Amsterdam (The Netherlands); Univ. of Amsterdam, Amsterdam (The Netherlands)
  2. Winterthur Museum, Winterthur, DE (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of Delaware, Newark, DE (United States)
  5. Utrecht Univ., Utrecht (The Netherlands)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1312787
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Heritage Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2050-7445
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; orpiment; realgar; emerald green; migration; painting; arsenic; degradation; XANES; imaging

Citation Formats

Keune, Katrien, Mass, Jennifer, Mehta, Apurva, Church, Jonathan, and Meirer, Florian. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues. United States: N. p., 2016. Web. https://doi.org/10.1186/s40494-016-0078-1.
Keune, Katrien, Mass, Jennifer, Mehta, Apurva, Church, Jonathan, & Meirer, Florian. Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues. United States. https://doi.org/10.1186/s40494-016-0078-1
Keune, Katrien, Mass, Jennifer, Mehta, Apurva, Church, Jonathan, and Meirer, Florian. Thu . "Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues". United States. https://doi.org/10.1186/s40494-016-0078-1. https://www.osti.gov/servlets/purl/1312787.
@article{osti_1312787,
title = {Analytical imaging studies of the migration of degraded orpiment, realgar, and emerald green pigments in historic paintings and related conservation issues},
author = {Keune, Katrien and Mass, Jennifer and Mehta, Apurva and Church, Jonathan and Meirer, Florian},
abstractNote = {Yellow orpiment (As2S3) and red–orange realgar (As4S4) photo-degrade and the nineteenth-century pigment emerald green (Cu(C2H3O2)2·3Cu(AsO2)2) degrades into arsenic oxides. Because of their solubility in water, arsenic oxides readily migrate and are found throughout the multi-layered paint system. The widespread arsenic migration has consequences for conservation, and this paper provides better insight into the extent of the problem. Five paint samples containing orpiment, realgar or emerald green pigments deriving from paintings by De Heem (17th C), Van Gogh (19th C), Rousseau (19th C), an unknown 17th C northern European artist and an Austrian painted cupboard (19th C) were investigated using SEM/EDX, imaging ATR-FTIR and arsenic (As) K–edge μ-XANES to obtain the spatial distribution and chemical speciation of arsenic in the paint system. In all of the samples investigated arsenic had migrated throughout the multi-layered paint structure of the art object, from support to varnish. Furthermore, As5+-species were found throughout the entire paint sample. We hypothesize that arsenic trioxide is first formed, dissolves in water, further oxidizes to arsenic pentaoxide, and then reacts with lead, calcium and other ions and is deposited in the paint system as insoluble arsenates. Since the degradation of arsenic pigments such as orpiment, realgar and emerald green occurs through a highly mobile intermediate stage, it not only affects the regions rich in arsenic pigments, but also the entire object, including substrate and top varnish layers. Furthermore, because of this widespread potential for damage, preventing degradation of arsenic pigments should be prioritized and conservators should minimize exposure of objects containing arsenic pigments to strong light, large fluctuations in relative humidity and water-based cleaning agents.},
doi = {10.1186/s40494-016-0078-1},
journal = {Heritage Science},
number = 1,
volume = 4,
place = {United States},
year = {2016},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: Painting The Dentist (a), light microscopic image of paint sample taken from the orange skirt, normal light (b) and UV (c); backscatter electron image (d) and part of EDX spectrum (e). The black line represents spot analyses in lower part of layer 5 and the green line inmore » the upper part of layer 5, the realgar/orpiment pigmented layer; the red line represents spot analyses in layer 2, the under drawing; the magenta line in wood structure of the panel (layer 0); the blue line in the resin of the embedding medium« less

Save / Share:

Works referenced in this record:

Tracking the transformation and transport of arsenic sulfide pigments in paints: synchrotron-based X-ray micro-analyses
journal, January 2015

  • Keune, Katrien; Mass, Jennifer; Meirer, Florian
  • Journal of Analytical Atomic Spectrometry, Vol. 30, Issue 3
  • DOI: 10.1039/C4JA00424H

Characterization of Pararealgar and Other Light-Induced Transformation Products from Realgar by Raman Microspectroscopy
journal, January 1996

  • Trentelman, Karen; Stodulski, Leon; Pavlosky, Mark
  • Analytical Chemistry, Vol. 68, Issue 10
  • DOI: 10.1021/ac951097o

Identification of artificial orpiment in the interior decorations of the Japanese tower in Laeken, Brussels, Belgium
journal, April 2015


Vibrational spectroscopy at the service of industrial archaeology: Nineteenth-century wallpaper
journal, May 2007

  • Castro, K.; Sarmiento, A.; Pérez-Alonso, M.
  • TrAC Trends in Analytical Chemistry, Vol. 26, Issue 5
  • DOI: 10.1016/j.trac.2007.02.003

Arsenic and Wallpaper
journal, April 1932


Arsenic in Napoleon's wallpaper
journal, October 1982

  • Jones, David E. H.; Ledingham, Kenneth W. D.
  • Nature, Vol. 299, Issue 5884
  • DOI: 10.1038/299626a0

TXM-Wizard : a program for advanced data collection and evaluation in full-field transmission X-ray microscopy
journal, January 2012

  • Liu, Yijin; Meirer, Florian; Williams, Phillip A.
  • Journal of Synchrotron Radiation, Vol. 19, Issue 2
  • DOI: 10.1107/S0909049511049144

Full-field XANES analysis of Roman ceramics to estimate firing conditions—A novel probe to study hierarchical heterogeneous materials
journal, January 2013

  • Meirer, Florian; Liu, Yijin; Pouyet, Emeline
  • Journal of Analytical Atomic Spectrometry, Vol. 28, Issue 12
  • DOI: 10.1039/c3ja50226k

Mesoscale Phase Distribution in Single Particles of LiFePO 4 following Lithium Deintercalation
journal, April 2013

  • Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400106k

Mesoscale Phase Distribution in Single Particles of $LiFePO_{4}$ following Lithium Deintercalation
text, January 2013

  • Boesenberg, Ulrike; Meirer, Florian; Liu, Yijin
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/desy-2014-01931

    Works referencing / citing this record:

    Study of dry‐ and wet‐process amorphous arsenic sulfides: Synthesis, Raman reference spectra, and identification in historical art materials
    journal, December 2018

    • Vermeulen, Marc; Palka, Karel; Vlček, Miroslav
    • Journal of Raman Spectroscopy, Vol. 50, Issue 3
    • DOI: 10.1002/jrs.5534

    Lammerite as a Degradation Product of Emerald Green: Scientific Studies on a Rural Persian Wall Painting
    journal, January 2018


    On the formation of hörnesite in a Fatimid manuscript folio
    journal, September 2018


    Imaging secondary reaction products at the surface of Vermeer’s Girl with the Pearl Earring by means of macroscopic X-ray powder diffraction scanning
    journal, September 2019


    A Photoluminescence Study of the Changes Induced in the Zinc White Pigment by Formation of Zinc Complexes
    journal, March 2017

    • Artesani, Alessia; Gherardi, Francesca; Nevin, Austin
    • Materials, Vol. 10, Issue 4
    • DOI: 10.3390/ma10040340

    Automated mineralogy based on micro-energy-dispersive X-ray fluorescence microscopy (µ-EDXRF) applied to plutonic rock thin sections in comparison to a mineral liberation analyzer
    journal, January 2017

    • Nikonow, Wilhelm; Rammlmair, Dieter
    • Geoscientific Instrumentation, Methods and Data Systems, Vol. 6, Issue 2
    • DOI: 10.5194/gi-6-429-2017

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