Analytical and Bioanalytical Chemistry

, Volume 399, Issue 10, pp 3589–3600 | Cite as

Degradation product emission from historic and modern books by headspace SPME/GC–MS: evaluation of lipid oxidation and cellulose hydrolysis

  • Andrew J. Clark
  • Jesse L. Calvillo
  • Mark S. Roosa
  • David B. Green
  • Jane A. GanskeEmail author
Original Paper


Volatile organic compounds emitted from a several decade series of bound periodicals (1859–1939) printed on ground wood paper, as well as historical books dating from the 1500s to early 1800s made from cotton/linen rag, were studied using an improved headspace SPME/GC–MS method. The headspace over the naturally aging books, stored upright in glass chambers, was monitored over a 24-h period, enabling the identification of a wide range of organic compounds emanating from the whole of the book. The detection of particular straight chain aldehydes, as well as characteristic alcohols, alkenes and ketones is correlated with oxidative degradation of the C18 fatty acid constituency of paper. The relative importance of hydrolytic and oxidative chemistry involved in paper aging in books published between 1560 and 1939 was examined by comparing the relative abundances of furfural (FUR) a known cellulose hydrolysis product, and straight chain aldehydes (SCA) produced from the oxidation of fatty acids in paper. The relative abundance of furfural is shown to increase across the 379-year publication time span. A comparison of relative SCA peak areas across the series of books examined reveals that SCA emission is more important in the cotton/linen rag books than in the ground wood books.


Paper Cotton/linen rag Fatty acid Lipid Aging Oxidation 



The authors acknowledge financial support from the Dean’s Research Fund of Pepperdine University and the Tooma Undergraduate Research Fellowship. We are grateful for the loan of the historic books from Pepperdine University’s Special Collections and Archives, and for the assistance of Melissa Nykanen, Special Collections librarian. Special thanks are due to Nathan Fuller for conducting some of the experiments and Prof. Jim White for helpful discussions.


  1. 1.
    Carlton AM (1970) In: Britt KW (ed) Handbook of pulp and paper technology, 2nd edn. Van Nostrand Reinhold, New YorkGoogle Scholar
  2. 2.
    Fenech A, Strlič M, Irena KC, Levart A, Gibson LT, de Bruin G, Ntanos K, Kolar J, Cassar M (2010) Volatile aldehydes in libraries and archives. Atmos Environ 44:2067–2073CrossRefGoogle Scholar
  3. 3.
    Bukovsky V (2000) The influence of light on ageing of newsprint paper. Restaurator 21:55–76CrossRefGoogle Scholar
  4. 4.
    Grosch W (1987) In: Chan HW-S (ed) Autoxidation of unsaturated lipids. Academic, OrlandoGoogle Scholar
  5. 5.
    Buchbauer G, Jirovetz L, Wasicky M, Nikiforov A (1995) Research note: on the odour of old books. J Pulp Pap Sci 21:J398–J400Google Scholar
  6. 6.
    Havermans JB, de Feber MA, Genuit WJ, van Velzen GJ (1999) Emission of volatile organic compounds from paper objects affected with iron-gall ink corrosion, In: Bridgland J (ed) Proceedings of the ICOM Committee for Conservation, 12th Triennial meeting, LyonGoogle Scholar
  7. 7.
    Strlič M, Thomas J, Trafela T, Cséfalvayová L, Kralj Cigić I, Kolar J, Cassar M (2009) Material degradomics: on the smell of old books. Anal Chem 81:8617–8622CrossRefGoogle Scholar
  8. 8.
    Lattuati-Derieux A, Bonnasies-Termes S, Lavédrine B (2004) Identification of volatile organic compounds emitted by a naturally aged book using solid-phase microextraction/gas chromatography-mass spectrometry. J Chromatogr A 1026:9–18CrossRefGoogle Scholar
  9. 9.
    Gaspar EM, Santana JC, Lopes JF, Diniz M (2010) Volatile organic compounds in paper-an approach for identification of markers in aged books. Anal Bioanal Chem. doi: 10.1007/s0021601035203 Google Scholar
  10. 10.
    Strlič M, Kralj Cigić I, Kolar J, de Bruin G, Pihlar B (2007) Non-destructive evaluation of historical paper based on pH estimation from VOC emissions. Sensors 7:3136–3145CrossRefGoogle Scholar
  11. 11.
    Łojewski T, Sawoszczuk T, Łagan JM, Zieba K, Barański A, Łojewska J (2010) Furfural as a marker of cellulose degradation. A quantitative approach. Appl Phys A. doi: 10.1007/20033901056637 Google Scholar
  12. 12.
    Lattuati-Derieux A, Bonnassies-Termes S, Lavédrine B (2006) Characterisation of compounds emitted during natural and artificial ageing of a book. Use of headspace-solid-phase microextraction/gas chromatography/mass spectrometry. J Cult Herit 7:123–133CrossRefGoogle Scholar
  13. 13.
    Bülow A, Bégin P, Carter H, Burns T (2000) Migration of volatile compounds through stacked sheets of paper during accelerated ageing. Part II: variable temperature studies. Restaurator 21:187–203CrossRefGoogle Scholar
  14. 14.
    Gutteridge JM (1995) Lipid peroxidation and antioxidants as biomarkers of tissue damage. Clin Chem 41:1819–1829Google Scholar
  15. 15.
    Sjöström E (1993) Wood chemistry: fundamentals and application, 2nd edn. Academic, San DiegoGoogle Scholar
  16. 16.
    Tulloch AP, Hoffman LL (1977) Composition of wax from seed flax straw. J Oil Chem Soc 54:587–588CrossRefGoogle Scholar
  17. 17.
    Lewin M (2007) Cotton fiber chemistry and technology. CRC Press, Boca RatonGoogle Scholar
  18. 18.
    Kolar J (1997) Mechanism of autoxidative degradation of cellulose. Restaurator 18:163–176CrossRefGoogle Scholar
  19. 19.
    Kočar D, Strlič M, Kolar J, Pihlar B (2002) A new method for determination of hydroperoxides in cellulose. Anal Bioanal Chem 374:1218–1222CrossRefGoogle Scholar
  20. 20.
    Swoboda PAT, Lea CH (1965) The flavour volatiles of fats and fat-containing foods. II-A gas chromatographic investigation of volatile autoxidation products from sunflower oil. J Sci Food Agric 16:680–689CrossRefGoogle Scholar
  21. 21.
    Matthews RF, Scanlan RA, Libbey LM (1971) J Sci Food Agric 48:745–747Google Scholar
  22. 22.
    Spiteller G, Kern W, Spiteller P (1999) Investigation of aldehydic lipid peroxidation products by gas chromatography-mass spectrometry. J Chromatogr A 843:23–98CrossRefGoogle Scholar
  23. 23.
    Ziegleder G (1998) Volatile and odorous compounds in unprinted paperboard. Packag Technol Sci 11:231–239CrossRefGoogle Scholar
  24. 24.
    Harmon CW, Mang SA, Greaves J, Finlayson-Pitts BJ (2010) Identification of fatty acids, phospholipids, and their oxidation products using matrix-assisted laser desorption ionization mass spectrometry and electrospray ionization mass spectrometry. J Chem Educ 87:186–189CrossRefGoogle Scholar
  25. 25.
    Druzik JR, Adams MS, Tiller C, Cass GR (1990) The measurement and model predictions of indoor ozone concentrations in museums. Atmos Environ A 24:1813–1823Google Scholar
  26. 26.
    Grzywacz C (2006) Monitoring for gaseous pollutants in museum environments. Getty Publications, Los AngelesGoogle Scholar
  27. 27.
    Dupont AL, Egasse C, Morin A, Vasseur F (2007) Comprehensive characterisation of cellulose- and lignocellulose-degradation products in aged papers: capillary zone electrophoresis of low-molar mass organic acids, carbohydrates, and aromatic lignin derivatives. Carbohydr Polym 68:1–16CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Andrew J. Clark
    • 1
  • Jesse L. Calvillo
    • 1
  • Mark S. Roosa
    • 2
  • David B. Green
    • 1
  • Jane A. Ganske
    • 1
    Email author
  1. 1.Department of ChemistryPepperdine UniversityMalibuUSA
  2. 2.Dean of LibrariesPepperdine UniversityMalibuUSA

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