Elsevier

Journal of Cultural Heritage

Volume 33, September–October 2018, Pages 18-29
Journal of Cultural Heritage

Original article
Evaluation of the volatile organic compound emissions in modern and naturally aged Japanese paper

https://doi.org/10.1016/j.culher.2018.03.013Get rights and content

Highlights

  • Non-invasive multi-analytical approach for characterizing Japanese papers.

  • SPME-GC/MS provides information on the organic substances emitted by papers and fibers.

  • Acetic acid and 1-butanol emission are related to the papermaking process.

  • N-N dimethyl formammide was emitted exclusively by industrial papers. Ketones, aldehydes and heavier alcohol were preferentially emitted by fibers and homemade papers.

  • Higher furfural emission from fibers place further question about the use of this compound for evaluating degradation of the paper.

Abstract

Volatile organic compounds (VOCs) can have a strong effect on cellulose degradation, contributing in decreasing the lifetime expectancy of the paper materials, widely employed in the field of conservation. In this work, we investigated several industrial and homemade Japanese papers, as well as fibers, evaluating VOCs emission by using solid-phase micro extraction coupled with gas chromatography–mass spectrometry (SPME-GC/MS). Acetic acid and 1-butanol were highly detected in industrial and homemade papers rather than fibers, suggesting that the emission of these compounds is influenced by the production process more than by the raw material itself. Conversely, N-N dimethyl formammide was peculiar of industrial processes. Ketones, aldehydes and heavier alcohols were preferentially emitted by fibers and homemade papers. The higher emission of furfural from fibers rather than on papers place new questions about the use of this compound to evaluate the degradation state of the paper material that should be carefully evaluated.

Introduction

It has been recognized that volatile organic compounds (VOCs) can have a strong effect on degradation of cellulose, in particular for those organic compounds that contain acidic or oxidizable functions, whose removal has been estimated to positively contributing in increasing the lifetime expectancy of the paper [1], [2]. It has also been observed that the main source of VOCs in libraries and archives consists in the paper itself, as a consequence of the degradation process that, in turn, depends on the stability of the paper materials, as well as the environmental conditions [3], [4]. In the perspective of developing a suitable strategy to storage paper-based heritages, a wider understanding of VOCs emission by papers is desirable. However, although a few of studies were recently carried out for evaluating VOC emissions from historical papers in European libraries [3], [5], to the best of our knowledge, VOCs emission from Japanese papers is still unexplored.

Japanese paper is used for conservation and intervention on a wider range of cultural heritage artifacts [6] in force of its high mechanical properties combined with a high stability, mainly due to the length of the fibers and the low presence of lignin [7], [8]. Nowadays, the term ‘Japanese paper’ is rather ambiguous as it includes materials made using oriental fibers, chemical wood pulp as well as non-oriental fibers, such as Manila hemp, that are sometimes used by several producers for containing the production costs [9], [10]. These non-oriental fibers typically contain higher amount of lignin with respect to Japanese fibers. Higher lignin content in papers used for conservation should be avoided because it can accelerate degradation processes of the paper itself as well as the restored artifacts [7].

Traditional Japanese paper, oftentimes indicated with the Japanese word ‘Washi’, uses oriental fibers as Mitsumata (Edgeworthis chrysantha), Kozo (Broussonetia kazinoki) and Gampi (Diplomorpha sikokiana) [11], with low lignin content [12]. Washi paper is traditionally produced following the so-called Nagashi-suki technique that includes the use of an aqueous solution containing a starchy substance (Neri) obtained from Malvaceae plants (Abelmoschus manihot) [13], [14]. Next to the length of the fibers and the low lignin content, as previously stated, the higher mechanical and chemical quality of Japanese paper is also affected by the production process employed. For example, Uyeda et al. [15] demonstrated that the stability of papers produced with Kozo fibers can vary as a function of the type of alkaline solution used in the cooking step (i.e. sodium rather than calcium hydroxide). As a consequence, the production process could also influence the VOCs emitted by the paper materials once employed in conservation interventions. In this work, we aim to investigate several industrial Japanese papers from the VANGEROW Catalogue and two types of homemade papers made by the Washi paper Master Yuko Isozaki, using Mitsumata and Kozo/Gampi fibers. Since paper samples are naturally-aged and, although not declared by the manufacturers, they may differ in the raw material employed and/or in the papermaking process, we preliminarily characterized the papers using microscopy observations, attenuated total reflectance–Fourier transform infra-red spectroscopy (ATR-FTIR), thermogravimetry and differential scanning calorimetry (TG-DSC). Next to the paper samples, we also investigated the declared raw materials employed for their production (i.e. Mitsumata, Gampi and Kozo fibers). Solid-phase micro-extraction–gas chromatography/mass spectrometry (SPME-GC/MS) was also employed for detecting the VOCs emitted from the papers and the fibers considered in this study.

The availability of naturally-aged papers from the VANGEROW Catalogue (1986) and homemade papers (2005), as well as modern (2015) analogues, provides the unique opportunity also to investigate potential differences in the emission of volatile organic compounds in relation to the natural aging, the production processes and/or the raw material employed. Therefore, in view of their over the time stability and related potential conservation issues in particular for paper interventions, we evaluated the potential use of SPME-GC/MS – a totally non-invasive approach–for shedding light on the composition of Japanese paper VOCs emissions.

Section snippets

Paper samples

Samples of naturally-aged industrial Japanese papers were taken from an original catalogue of VANGEROW (Bolzen, Italy) Japanische Handapapiere of the 1986, and kindly provided by Rosanna Chiggiato. From this catalogue, five paper samples were selected in accordance to their use in the field of conservation. New samples, sold with the same code and characteristics, were purchased from Vangerow (2015). The selected papers differentiate not only for their thickness, but also for their composition.

Optic and SEM micrographs

Japanese fibers of Gampi, Mitsumata and Kozo were investigated using optic microscopy and SEM (See Fig. 1A-C). As shown, Mitsumata fibers were shorter than Kozo and Gampi, although they resulted more regular in thickness. Kozo also showed evident markings and knots all along the fiber that were almost absent in Mitsumata. All these fibers presented natural mucilaginous material and/or specific features such as phytolith assemblages (Fig. 1A-2), encrusting matter (Fig. 1B-2) or typical spherical

Conclusion

In this paper, we proposed a non-invasive multi-analytical approach that can be successfully used for characterizing Japanese paper materials. Several papers (industrial and homemade) were analyzed together with the Japanese fibers Kozo, Mitsumata and Gampi. The volatile organic compounds were detected by SPME/GC-MS and information on the structure and the raw materials used in the paper making process were obtained from ATR-FTIR, complemented by TG-DSC analysis and supported by microscopy

Funding

The research did not receive any specific grant from funding agencies in the public, commercial nor not-for-profit sectors.

Acknowledgments

The authors would like to thank the Washi paper Master Yuko Isozaki for the hand-made papers and the professor and paper conservation restorer Rosanna Chiggiato for her interest in the research and for providing samples. Finally, we would like to thank Dr. Natalie M. Kehrwald for grammar checking and comments, which improved the quality of the manuscript.

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