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Characterization and Identification of Colorants in a Japanese Pillar Print
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By Cyntia Karnes and Gwenanne Edwards
Introduction
Traditional colorants used in Japanese woodblock printing may be visually and chemically altered by exposure to light, pollutants, pH extremes, humidity, water, and other solvents. It is helpful, therefore, to identify colorants in Japanese prints when considering the potential impact of conservation treatment, storage, and exhibition on their long-term preservation.
Method
Five colored inks, including black, were used to create "Two Beauties under a Cherry Tree" (Ouka no nibijin), printed by Torii Kiyonaga in 1782-83. The inks were identified by close visual inspection and non-destructive instrumental analysis. First, a stereomicroscope at high magnification was used to visually determine if the inks appeared to be composed of dyes, pigments, or a mixture of the two. When pigment particles were present, physical characteristics such as relative particle size, edge definition, surface reflectance (matte or shiny), and transparency or opacity were noted. These observations were compared to known samples of traditional Japanese colorants to make a tentative identification. For example, the green robe on the figure at the right is a mixture of blue and yellow pigments. The yellow pigment is semi-opaque, irregularly shaped, and -- compared with the blue pigment particles, which were small enough to sink into the interstices of the paper -- much larger and variable in size. The yellow pigment correlated well with known samples of orpiment, an arsenic sulfide pigment, and the blue appeared similar to indigo, a plant based dye.
Imaging under discrete bands of ultraviolet, visible, and infrared radiation using a multispectral digital camera was used to further characterize the colorants. Because each colorant is a different chemical compound, each selectively absorbs, fluoresces, transmits, or reflects characteristic wavelengths when exposed to specific bands of the electromagnetic spectrum. These characteristic responses are captured by the digital camera and are compared to the spectral responses of known colorant samples. Because different materials may have similar responses to all wavelengths and therefore cannot be readily distinguished by imaging alone, additional analytical tools are often used to solidify a preliminary identification.
Conclusions
Comparison of the spectral responses obtained from the print with known samples, supported by instrumental analyses provided by the Preservation Research and Testing Division, indicated that the printing inks are composed of:
Red lead: an orange-red mineral pigment known in Japan as tan. Red lead absorbs ultraviolet radiation (appears dark in the ultraviolet images), is transparent to infrared (disappears in the infrared images), and appears yellow in false-color infrared. The chemical compound of red lead, lead tetroxide, degrades to a black product, lead sulfide, upon exposure to sulfurous compounds. In false-color infrared, the black corrosion product, lead sulfide, appears dark. (While the presence of lead sulfide could be the result of exposure to sulfur dioxide, an omnipresent environmental pollutant produced by burning fossil fuels, Japanese printmakers sometimes deliberately induced conversion of red lead tetroxide to silver lead sulfide, which also degrades to a black color. For more information about both environmentally-induced and deliberate alteration of red lead in Japanese prints, see Conservation Treatment of a Japanese Pillar Print.) X-ray fluorescence (XRF) analysis confirmed the presence of lead in the red colorant of the Kiyonaga print and Raman spectroscopic analysis positively identified the colorant as red lead.
Safflower: a pink colorant extracted from safflower petals, known in Japan as beni. The most characteristic feature of beni is its bright orange-pink fluorescence when exposed to ultraviolet radiation. Beni fades quickly upon exposure to light and may be easily solubilized in water. XRF and Raman analyses indicated only that the pink colorant in the Kiyonaga print is organic. A definitive identification of the colorant would require further analysis. The presence of safflower was indicated primarily through its bright, orange-pink fluorescence in ultraviolet light.
Indigo: a dark blue plant-based dye precipitated onto an inorganic substrate such as a metallic salt, known in Japan as bero-ai. In the image by Kiyonaga, indigo was used to print the textile pattern in the kimono worn by the left figure and was mixed with yellow to create green, seen in the kimono worn by the right figure. The colorant has altered over time so that it appears a dull green-gray. The most characteristic feature of indigo is its bright pink appearance in false-color infrared. Indigo is sensitive to high pH. Raman spectroscopy positively identified the gray colorant in the Kiyonaga print as indigo.
Orpiment: an opaque mineral pigment composed of arsenic sulfide, known as shio. The spectral responses of the yellow colorant, used alone and mixed with blue to create green, was similar to known samples of both orpiment and gamboge. However, as noted during examination under the stereomicroscope, the physical characteristics of the pigment appeared more similar to orpiment than to gamboge, a colorant obtained from tree resin that is valued for its brilliant yellow hue and transparency. XRF confirmed the presence of arsenic and sulfur in the yellow colorant of the Kiyonaga print. Raman spectroscopy positively identified the colorant as orpiment.
Results
Identification of the colorants affected decisions about conservation treatment, storage, and exhibition.
Conservation treatment:
- Safflower is known to be sensitive to moisture. Extensive solubility testing on an inconspicuous area was performed and exposure to water minimized during treatment.
- Indigo, which was identified in areas of unintentional red lead blackening, is sensitive to alkalinity. Blackened red lead reversion was carried out by local brush application of a neutral pH oxidizing solution. Oxidizing solutions are usually buffered to an alkaline pH.
Storage:
- Both safflower and indigo are sensitive to alkalinity. The print was matted with an acid-free, 100% cotton rag board with a neutral pH. Preservation mats are usually cut from matboard that has been buffered to an alkaline pH.
Exhibition:
- • Safflower and indigo are very light sensitive. Light levels in the gallery were kept to a visually acceptable minimum during exhibition (4-5 footcandles).
In addition to informing the preservation of Japanese prints, the identification of colorants also provides technical information that enhances our understanding of their history and production, and the artists who created them. (Related article: Conservation Treatment of a Japanese Pillar Print.)
References:
CAMEO: Conservation & Art Material Encyclopedia Online .
Connors, S., P. Whitmore, R. Keyes, and E. Coombs. 2005. The Identification and Light Sensitivity of Japanese Woodblock Print Colorants: the Impact on Art History and Preservation. In Scientific Research on the Pictorial Arts of Asia: Proceedings of the Second Forbes Symposium at the Freer Gallery of Art, ed. P. Jett, et al. London: Archetype Publications. 35-47.
Feller, R., M. Curran, and C. Bailie. 1984. Identification of Traditional Organic Colorants Employed in Japanese Prints and Determination of their Rates of Fading. In Japanese Woodblock Prints: A Catalogue of the Mary A. Ainsworth Collection, R. Keyes. Oberlin: Allen Memorial Art Museum, Oberlin College. 253-266.
Fiske, B. and L. S. Morenus. 2004. Ultraviolet and Infrared Examination of Japanese Woodblock Prints: Identifying Reds and Blues. The Book & Paper Group Annual 23 (2004), 21-32.
Uyemura, R. 1931. Studies on the Ancient Pigments in Japan. Eastern Art Annual 3: 47-50.
Warda, J., ed. 2011. The AIC Guide to Digital Photography and Conservation Documentation. Washington, DC: American Institute for Conservation.
Authors:
Gwenanne Edwards, 2011-2012 Harper-Inglis Fellow in Paper Conservation, Conservation Division
Cyntia Karnes, Senior Paper Conservator, Conservation Division
Editor:
Mary Oey, Preservation Education Specialist, Conservation Division
Acknowledgements:
Dr. Lynn Brostoff, Conservation Scientist, Preservation Research and Testing Division
Dr. Fenella France, Chief, Preservation Research and Testing Division
Betty Fiske, Paper Conservator in Private Practice, Wilmington, Delaware
Holly Krueger, Head of Paper Conservation, Conservation Division
Linda Stiber Morenus, Program Specialist, Office of the Associate Librarian for Library Services
Amelia Steinemann, Graduate Preservation Science Intern, Preservation Research and Testing Division
Diane Vogt-O’Connor, Chief, Conservation Division
Otoyo Yonekura, Paper Conservator, Tokyo National Museum
Colleagues of the Conservation Division