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New criteria for the characterization of traditional East Asian papers

Environmental Science and Pollution Research volume 24, pages 2166–2181 (2017)Cite this article

Abstract

We report a pyrolysis–gas chromatography/mass spectrometry (Py-GC/MS) method capable of analyzing traditional East Asian papers. The method proposed is based on rapid and easy single step Py-GC/MS analysis that can be carried out with a minimum amount of matter, in the few microgram range. Three reference papers manufactured from kozo (Broussonetia kazinoki Siebold & Zucc.), mitsumata (Edgeworthia chrysantha Lindl.), and gampi (Wikstroemia sikokiana Franch. & Sav.) with the traditional hand paper making processes were examined. The method allows discrimination between terpenic and steroid compounds, which were revealed as chemical markers of origin of the plant fibers. Each paper investigated was found to have characteristic pyrolysis fingerprints that were unique to the traditional handmade paper, demonstrating the potential for differentiation of these biochemical components of fiber plants on East Asian papers towards identification and conservation of cultural heritage. The investigation on Py-GC/MS was extended to liquid extraction followed by GC/MS analysis to characterize the biochemical components of fiber plants. The main contribution of this study is to provide molecular criteria for discriminating plant species used for traditional East Asian hand papermaking. Py-GC/MS complements efficiently microscope identification especially for adverse cases. A case study of archaeological Chinese paper painting artefacts was thereafter successfully investigated to address informative potential and efficiency of the criteria of identification on ancient and degraded East Asian paperworks.

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Acknowledgments

Pr Masamitsu Inaba (Conservation Science Laboratory, Graduate School of Conservation Tokyo Geijutsu Daigaku, Japan) and Dr Masazumi Seki (Kochi prefectural paper technology center, Kochi, Japan) are gratefully acknowledged for providing the reference paper samples handmade from kozo, mitsumata, and gampi. The authors acknowledge Pr Bernard Bodo (Muséum National d’Histoire Naturelle, Molécules de Communication et Adaptation des Micro-organismes UMR 7245 du CNRS) for providing us the triterpene standard references. The authors also acknowledge the Musée national des arts asiatiques—Guimet (Paris) for the authorization of sampling on the lining paper of a paper painting showing “Two Bouddha and a Bodhisattva” from the library cave in Mogao-ku, Dunhuang, first half of the Five Dynasties (reference EO 3642). The authors would like to thank M. Leon-Bavi Vilmont who performed the microscopic analysis of fibers on the museum samples EO 3642 to confirm its composition. C. A. would like to warmly acknowledge The Corfui Foundation (Turin) and the Ministère de la Culture et de la Communication for their grants and financial support.

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  1. Centre de recherche sur la conservation (CRC, USR 3224), Sorbonne Universités, Muséum national d’Histoire naturelle, Ministère de la Culture et de la Communication, CNRS; CP21, 36 rue Geoffroy-Saint-Hilaire, 75005, Paris, France

    Chiara Avataneo & Michel Sablier

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  1. Chiara Avataneo
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  2. Michel Sablier
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Correspondence to Michel Sablier.

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Responsible editor: Philippe Garrigues

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ESM 1

Supplementary material. Fig. S1 Total ion current chromatograms obtained in the cellulose degradation region 0.5–35 min (RT) from the pyrolysis of (a) Whatman 1 reference paper, (b) kozo, (c) mitsumata, and (d) gampi reference paper samples. Labeled compounds are reported in Table S1. Due to the vast number of identified products, it is not possible to label all peaks in the chromatogram and therefore, only the most important and major compounds are indicated in the figure. Table S1 Identification of the pyrolysis products resulting from the pyrolysis of the cellulose reporting retention time (RT), most likely attribution of the products, corresponding molecular weights, main fragment ions, and formula. Table S2 Identification of the pyrolysis products detected in the intermediate region 32–52 min (RT) resulting from the pyrolysis of the reference paper samples reporting retention time (RT), most likely attribution of the products, corresponding molecular weights, main fragment ions, and formula. Table S3 Identification of the pyrolysis products detected in the region 52–65 min (RT) resulting from the pyrolysis of the reference paper samples reporting retention time (RT), attribution of the products with formula, corresponding molecular weight, structure with fragmentation routes for identification, and mass spectrum. Fig. S2 Total reconstructed ion current chromatogram for the region 45–65 min (RT) obtained from the pyrolysis of a kozo reference paper sample of 7 μg with a selected ion monitoring (SIM) mode of acquisition. Total ion current, reconstructed total ion current from the SIM signals, selected m/z ions: 95, 189, 218, 468 are reported in the figure. Table S4 Identification of the products detected in the region 52–65 min (RT) resulting from the liquid extraction of the reference paper samples reporting retention time (RT), attribution of the products with formula, corresponding molecular weight, structure with fragmentation routes for identification, and mass spectrum. (PDF 1.29 kb)

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Avataneo, C., Sablier, M. New criteria for the characterization of traditional East Asian papers. Environ Sci Pollut Res 24, 2166–2181 (2017). https://doi.org/10.1007/s11356-016-6545-0

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Keywords

  • East Asian paper
  • Pyrolysis
  • Gas chromatography–mass spectrometry
  • Cultural heritage
  • Triterpenes
  • Phytosterols
  • Broussonetia
  • Wikstroemia
  • Edgeworthia