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

Keune, Katrien; Mass, Jennifer; Mehta, Apurva; Church, Jonathan; Meirer, Florian

doi:10.1186/s40494-016-0078-1

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

Journal Article · Thu Apr 21 00:00:00 EDT 2016 · Heritage Science

DOI:https://doi.org/10.1186/s40494-016-0078-1· OSTI ID:1312787

Keune, Katrien ^[1]; Mass, Jennifer ^[2]; Mehta, Apurva ^[3]; Church, Jonathan ^[4]; Meirer, Florian ^[5]

Rijksmuseum Amsterdam, Amsterdam (The Netherlands); Univ. of Amsterdam, Amsterdam (The Netherlands)
Winterthur Museum, Winterthur, DE (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Univ. of Delaware, Newark, DE (United States)
Utrecht Univ., Utrecht (The Netherlands)

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1312787

Journal Information:: Heritage Science, Vol. 4, Issue 1; ISSN 2050-7445

Publisher:: SpringerCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 33 works

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Lammerite as a Degradation Product of Emerald Green: Scientific Studies on a Rural Persian Wall Painting Holakooei, Parviz; Karimy, Amir-Hossein; Nafisi, Golriz Studies in Conservation, Vol. 63, Issue 7 https://doi.org/10.1080/00393630.2017.1419658	journal	January 2018
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