Visualization of As(<scp>iii</scp>) and As(<scp>v</scp>) distributions in degraded paint micro-samples from Baroque- and Rococo-era paintings

Vermeulen, Marc; Nuyts, Gert; Sanyova, Jana; Vila, Anna; Buti, David; Suuronen, Jussi‐Petteri; Janssens, Koen

doi:10.1039/c6ja00134c

Cited by 49 publications

(43 citation statements)

References 32 publications

(33 reference statements)

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“…The use of cinnabar/vermillion and arsenic sulfide pigments, which were present in all the corresponding red and yellow areas of the objects investigated, is in agreement with historical records [1,4,5]. Nevertheless, evidence of production of amorphous arsenic sulfide by sublimation of natural orpiment was found [50,51,62], indicating that natural orpiment was not the only arsenic sulfide pigment used. Moreover, green is usually reported to be a mixture of orpiment and indigo (Table 1), but no indigo was found in the green areas of these objects.…”

Section: Discussionsupporting

confidence: 86%

The evolution of the materials used in the yun technique for the decoration of Burmese objects: lacquer, binding media and pigments

et al. 2019

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A series of Burmese lacquered objects decorated with the yun (incised) technique and belonging to the British Museum's collection was analysed with the aim to investigate the decorative materials-lacquer, binding media, additives and pigments-used in the production of these objects, which span chronologically from the eighteenth century to the late twentieth century. As the manufacturing process is supposed to have remained very similar over this time period, especially regarding the use of materials, we were interested in scientifically assessing for the first time the nature of these materials and the correspondence to the written sources in the relation to their specific use. Gas chromatography mass spectrometry (GC-MS) and analytical pyrolysis with in situ silylation coupled with GC-MS (Py(HMDS)GC-MS) were used for the identification of the organic components in several samples taken from the coloured areas of the objects. Fibre optic reflectance (FORS) and Raman spectroscopies were used to identify the pigments after a visual investigation of the samples by digital microscopy. Burmese lacquer was detected in all objects and trends in its degradation were highlighted. Lipids, proteins and saccharide material were found to be mixed with lacquer, and they appeared to be applied with specific pigments, in good agreement with the written records, apart from proteins, which are not mentioned. The use of synthetic pigments, such as phthalocyanines blue and green and chrome yellow, was assessed in the most recent objects, showing an evolution in the use of pigments. Indigo, although expected, was not identified in any of the green samples and Prussian blue appeared to be the main source of blue colour. All this information is of fundamental importance for conservation practices and corrects the general opinion about the production materials of these objects. These results also open the way to future research dedicated to exploring the chemical interaction between Burmese lacquer, proteins, lipids, gums and pigments, with the aim to predict possible differences in degradation pathways.

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Section: Discussionsupporting

confidence: 86%

The evolution of the materials used in the yun technique for the decoration of Burmese objects: lacquer, binding media and pigments

et al. 2019

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“…In Raman spectroscopy, the contributions observed between 100 and 600 cm −1 correspond to natural arsenic sulfide in prints by Hokusai (A-C) and to artificial arsenic sulfide in the print by Kunisada (D); the one at 1573 indicates indigo and the pair of contributions between 2095 and 2155 cm −1 correspond to Prussian blue profile and particular contributions are characteristic for the various bending and stretching bonds found in amorphous arsenic sulfide pigments, as reported in previous arsenic sulfide characterization studies [14,22,23]. While not previously reported as a characteristic for amorphous arsenic sulfide pigments, the increase in the 100-250 cm −1 region has consistently been noted in non-background corrected spectra in identification studies of amorphous arsenic sulfide pigments [8,10,14,20,22]. This can therefore be used along the main Raman contributions as a secondary indication that amorphous arsenic sulfide pigment is present.…”

Section: Resultssupporting

confidence: 77%

“…Nonetheless, all pigments and colorants identified in print D will be reported. All Band assignments for natural orpiment and amorphous arsenic sulfides have been published previously and will therefore not be discussed here [20,21]. It is important to note that inflection points in FORS are not clear identifiers for yellow colorants-including orpiment-as the they can shift depending on the color of the support and change if the yellow is faded.…”

Section: Resultsmentioning

confidence: 99%

Evidence of early amorphous arsenic sulfide production and use in Edo period Japanese woodblock prints by Hokusai and Kunisada

Vermeulen

Leona

2019

Herit Sci

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This study explores the evolution of the manufacturing process of artificial arsenic sulfide pigments in Edo-period Japan through the analysis of three impressions of the same print dated from the 1830s and attributed to Katsushika Hokusai (1760-1849), and one from 1852 and attributed to Utagawa Kunisada (1786-1865). Colorants in the yellow and green areas of the four prints were investigated by means of non-invasive and microanalytical techniques such as optical microscopy, fiber optic reflectance spectroscopy and Raman spectroscopy. While the pigments in the green and yellow areas are similar throughout the set of prints-Prussian blue, indigo (for the Hokusai prints) and orpiment were identified-optical microscopy and Raman spectroscopy highlighted some variations in the orpiment used in the green areas of the prints. Two of the Hokusai prints present bright yellow particles of larger size and lamellar morphology, identified by Raman spectroscopy as natural orpiment. The third print presents an admixture of bright yellow natural orpiment particles with a smaller number of orange-yellow particles shown by Raman to be partially amorphous arsenic sulfide. Small bright yellow particles identified as fully amorphous arsenic sulfide pigments by Raman were found throughout the green areas of the Kunisada print. Although supported by Japanese historical sources, local production of artificial arsenic sulfide in the early nineteenth century was not previously documented. The simultaneous presence of both crystalline and amorphous domains in a single pigment particle in some of the Hokusai prints suggests that natural orpiment was used as primary source of arsenic for the production of a low grade artificial pigment. The pigment found in the Kunisada print, by contrast, was obtained from arsenic oxide (or arsenolite) and sulfur though a dry-process synthesis, as shown by the sulfur excess, signs of heat treatments and fully amorphous nature of the pigment. These findings set the earliest dates for both the ore sublimation process and the arsenolite dry process, and are of foremost importance to understand the evolution of the amorphous arsenic sulfide production in Edo-period Japan and its introduction in the palette of Japanese woodblock prints.

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“…However, it remains difficult to conclude on the nature of arsenic sulfide pigments based on microscopic and elemental analyses only as the simultaneous presence of arsenic and sulfur may correspond to several arsenic sulfide pigments. Therefore, due to the distinctive vibrational signatures of arsenic sulfide pigments, Raman measurements on the arsenic sulfide particles were undertaken (Figure ).…”

Section: Resultsmentioning

confidence: 99%

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

Vermeulen

Pálka

Vlček

et al. 2018

J Raman Spectroscopy

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This paper reports the dry and wet synthetic procedures and characterization by Raman spectroscopy of amorphous arsenic sulfide reference pigments. Reference spectra of two amorphous materials obtained by wet process methods and four dry process references of amorphous arsenic sulfide pigments of known composition are presented and discussed.While all materials present a main band characteristic for the amorphous pigment centered on 341 cm −1 , additional small contributions indicate the presence of sulfur, arsenic oxide, and crystalline nano phases embedded in the amorphous matrix. Although only the broad 341-cm −1 peak is necessary to identify the arsenic sulfide as an amorphous material, the smaller additional features allow for the characterization of the various manufacturing processes and initial materials used. In ideal conditions, these small features also enable to assess the As/S ratio of the studied amorphous arsenic sulfide pigments based on their relative intensity. In this context, the latter reference spectra were used to characterize the amorphous arsenic sulfide pigments and their arsenic to sulfur elemental composition in four 18th-to 20th-century historical samples and compared with scanning electron microscopy with energy dispersive X-ray semiquantitative analyses. The identification of the amorphous arsenic sulfide used in these historical samples was compared with the description of the manufacturing processes reported in historical sources of the time, allowing for a better understanding of the evolution of the amorphous arsenic sulfide pigments manufacturing methods.

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Visualization of As(iii) and As(v) distributions in degraded paint micro-samples from Baroque- and Rococo-era paintings

Abstract: Orpiment and realgar are two artists' pigments that appear not to be stable upon light exposure, quickly degrading to arsenic trioxide and arsenate. Their identification appears challenging but can be overcome by the use of synchrotron based techniques such as μ-XANES.

Cited by 49 publications

References 32 publications

The evolution of the materials used in the yun technique for the decoration of Burmese objects: lacquer, binding media and pigments

The evolution of the materials used in the yun technique for the decoration of Burmese objects: lacquer, binding media and pigments

Evidence of early amorphous arsenic sulfide production and use in Edo period Japanese woodblock prints by Hokusai and Kunisada

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

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