Evidence of early amorphous arsenic sulfide production and use in Edo period Japanese woodblock prints by Hokusai and Kunisada (original) (raw)
Related papers
2010
Sublimed (dry process) arsenic sulphide pigments have been of interest since historic and modern samples of yellow, orange or red powders and cakes containing arsenic oxide (As 2 O 3), arsenic sulphide glass (g-As x S x), members of the β-As 4 S 4-As 8 S 9 series, the χ-phase and pararealgar (As 4 S 4) were identified. The X-ray amorphous components occur as irregular masses or spherules, whereas the crystalline components consist of octahedral or tabular crystals or radially grown spherules of up to 30 μm in diameter. Artificial arsenic sulphides produced by sublimation have been found in the paint layers of a sixteenth/seventeenth-century South German polychrome recumbent sculpture in Altomünster and in Domenico Tintoretto's painting Entry of Philip II into Mantua (1579/80), which is part of the famous 'Gonzaga Cycle' (Alte Pinakothek, Munich). The identification required the use of light microscopy, X-ray diffraction and scanning electron microscopy as well as Raman analysis. Raman microspectroscopy proved to be a valuable tool, particularly for differentiation between realgar (As 4 S 4), pararealgar, and members of the β-As 4 S 4-As 8 S 9 series, which includes the χ-phase of almost identical chemical composition, as well as the distinction of X-ray amorphous arsenic sulphide glasses. If pure pararealgar is detected using Raman it is not possible to determine whether it was formed from degradation of natural realgar or from members of the β-As 4 S 4-As 8 S 9 series. Keeping in mind the close relationship between natural realgar, alacranite (As 8 S 9), β-As 4 S 4 and the χ-phase, it is highly likely that many of the arsenic sulphides found on works of art will turn out to be of artificial origin.
Journal of Raman Spectroscopy, 2018
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.
Heritage, 2022
The painting The Descent from the Cross, painted in 1620 by Pedro Nunes (1586–1637), presents two large figures with orange-coloured fabrics with conservation problems. Through the analysis of two samples with several analytical techniques, especially scanning electron microscopy combined with X-ray spectroscopy and Raman microscopy, it was possible to conclude that the orange colour is due to a complex artificial pigment made of amorphous arsenic sulphide. It essentially consists of spherical particles obtained by sublimation and condensation, possibly from orpiment, which ended up being joined with irregularly shaped particles resulting from crushing of the residual fraction obtained by solidification and fusion. This is a rare documented case of the extensive use of artificial arsenic sulphides in European easel painting, especially outside Italy. The conservation problems can be explained by the great sensitivity of the arsenic sulphides to photodegradation and the formation of powdery compounds
Pigments-Arsenic-based yellows and reds
Open Access - Archaeological and Anthropological Sciences, 2022
This review offers an update on arsenic-bearing minerals and pigments with the aim of serving as a guide for the study of Cultural Heritage materials in which these materials can be found. The different As-bearing mineral phases (realgar, pararealgar, orpiment, anorpiment, alacranite, dimorphite, bonazziite, uzonite, wakabayashilite, duranusite, arsenolite and claudetite) and some of their light-induced products are examined. The occurrence of As-sulfides and their trade, use, alteration and degradation are also reviewed. Finally, the analytical techniques commonly used for the identification of arsenic-containing pigments are discussed. The manuscript concludes with a good practice guide and a summary of key concepts for use by those working in the field of cultural heritage. This article is part of the Topical Collection on Mortars, plasters and pigments: Research questions and answers
In this study, a combination of elemental analytical techniques (MA-XRF and SEM-EDX) were used to localize arsenic sulfide pigments within a 17 th-century Dutch painting and in the stratigraphy of an 18 th-century Flemish polychrome sculpture. Once located, Raman spectroscopy was used to obtain the vibrational signature of the arsenic sulfide pigments employed. By means of the latter analytical technique and due to the very distinctive Raman scattering signal of the various arsenic sulfide compounds, it was possible to identify the arsenic-based pigments as natural orpiment and amorphous arsenic sulfide. In the latter case, based on the minor bands observed and the good condition of the paint layers, it was possible to identify pararealgar, the orangey-yellow to yellow degradation product of realgar, as the initial arsenic sulfide material used for the synthesis of the amorphous pigment. To the best of our knowledge, this is the first time that combined pararealgar/amorphous arsenic sulfide Raman spectra are reported in historical samples. Therefore, this would be the first identification of pararealgar as the starting material to produce amorphous arsenic sulfide pigments used in artworks.
Heritage Science, 2015
In this paper, we used a multi-technique approach in order to identify the arsenic sulfide pigment used in the decorative panels of the Japanese tower in Laeken, Belgium. Our attention was drawn to this particular pigment because of its relatively good conservation state, despite its known tendency to fade over time when exposed to light. The pigment was used with different painting techniques, bound with oil and urushi in the lacquers and with an aqueous binder in the mat relief panels. In the latter case it is always applied as an underlayer mixed with ultramarine blue. This quite unusual pigment mixture also shows a good state of preservation. In this study, the orpiment used for the Japanese tower has been identified as an amorphous arsenic sulfide glass (As x S x ) with the aid of light microscopy, PLM, SEM-EDX and Raman microscopy. The pigment features different degrees of As 4 S 4 monomer units in its structure, also known as realgar-like nano-phases. This most likely indicates different synthesis processes as the formation of these As 4 S 4 monomers is dependent of the quenching temperature (Tq) to which the artificial pigment is exposed during the preparation phase.
2009
Two oil paintings in the collection of the Department of Prints and Drawings at the British Museum are catalogued as mechanical paintings on canvas by Francis Eginton after Philip James de Loutherbourg. While the name of de Loutherbourg is familiar, that of Eginton is less so. In the period between 1776 and 1782, Eginton, a glass painter and printmaker, participated in a shortlived partnership with Matthew Boulton, the entrepreneurial owner of the Soho Manufactory in Birmingham, to sell mechanical copies of paintings by prominent late eighteenth century artists, including,
Microchemical Journal, 2018
The study of fragile artworks kept in museums requires mobile devices, short time of analysis and minimal disturbance to insure their good preservation. In situ reflectance spectroscopy and spectrofluorimetric studies are mostly developed for pigment characterization. A recently-designed μspectrofluorimeter (LED μSF) dedicated to in situ measurements, that uses UV-light emission diodes (LED) as excitation sources, was used to verify its potentiality for the identification of pigments and dyes. The colours of five Japanese woodblock prints from the Museum of Zaragoza (Spain) were studied by the combination of UV-VIS-IR spectroscopies and hand-held energy dispersive X-ray fluorescence spectrometer (HHED-XRF), together with Raman Spectroscopy. This study focused on the analysis of red and blue colours in prints by Koryūsai, Utamaro and Eisen (18th-19th centuries). The interpretation of the in situ fluorescence emission spectra could be rather difficult because of the variety of pigment mixtures, natural ageing of colorants and fluorescence of the support (paper), that could lead to spectral changes or band shifts. The combination with diffuse reflectance spectroscopy (DRS), hyperspectral imaging techniques (HSI), and HHED-XRF completed the interpretation of these results. A specific database was built analyzing reference samples made in accordance with Japanese printings techniques and materials. Inorganic and organic red (vermilion, red lead, cochineal, red safflower) and blue (Prussian blue, indigo, dayflower) pigments were used alone or as a mixture to modify the hues. The identification of Prussian blue could be a clue about the relations existing between East and West and, its presence sometimes questioned the dating of some early printings.
Raman spectroscopy of Japanese artists' materials:The Tale of Genji by Tosa Mitsunobu
Journal of Raman Spectroscopy, 2006
Micro-samples from the earliest complete copy of the Japanese masterpiece The Tale of Genji were analyzed by Raman and FTIR spectroscopy to determine the materials used. The album was commissioned in 1509 and consists of 54 illustrations by Tosa Mitsunobu with matching calligraphic pages painted by six different court calligraphers. The pages were originally pasted onto a folding screen but were remounted in an album in the 17th century and a frontispiece and finispiece illustration painted by Tosa Mitsuoki. The illustration for chapter 52 is a replacement of unknown date.The following materials were identified in the illustrations: azurite, indigo, malachite, atacamite, botallackite, chrysocolla, gamboge, vermilion, lead(II,IV) oxide (red lead), red ochre/haematite, calcite and basic lead carbonate (lead white). A smaller range was used on the calligraphic pages: vermilion, lead(II,IV) oxide (red lead), indigo, gamboge, yellow ochre and calcite.Most of the materials identified are part of the traditional Japanese palette, and a wide range of tones was created by mixing pigments from this relatively restricted set. The hydrated copper chlorides, atacamite and botallackite, may be alteration products of original malachite. The chrysocolla, a natural amorphous copper silicate, was probably incorporated accidentally with the malachite, as the two can occur together in nature. Chrysocolla occurs with malachite only on the replacement illustration for chapter 52, which lacks copper chlorides.The lead carbonate and red lead are both discolored in many areas. Lead sulfate was identified in some altered areas of red lead and probably represents a secondary alteration product. The primary alteration product of both lead pigments is assumed to be lead(II) sulfide, as silver in the manuscript has altered to silver sulfide. The alternative alteration product, lead(IV) oxide, is considered less likely. Copyright © 2006 John Wiley & Sons, Ltd.