Skip to main content
SpringerLink
Log in

A study of degradation of historic parchment using small-angle X-ray scattering, synchrotron-IR and multivariate data analysis

  • Original Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Parchment has been in use for thousands of years and has been used as the writing or drawing support for many important historic works. A variety of analytical techniques is currently used for routine assessment of the degree of denaturation of historic parchment; however, because parchment has a heterogeneous nature, analytical methods with high spatial resolution are desirable. In this work, the use of small-angle X-ray scattering (SAXS) and synchrotron-IR (SR-IR) was examined in conjunction with multivariate data analysis to study degradation of an extended set of historic parchment samples, and particularly to investigate the effect of lipids and the presence of iron gall ink on the degradation processes. In the data analysis, shrinkage temperature, lipid content, sample age, presence of ink and accelerated degradation were included. The analysis of loading factors in partial least-squares regression and principal component analyses based on SAXS, SR-IR and other analytical and descriptive data reveals the effect of lipid removal on diffraction patterns, and lipids are found to cause the degradation process in parchment to accelerate. The effect of iron gall ink is also evident, although the mechanism of ageing is different to that of natural ageing in the absence of ink. In addition, a historic parchment score from ca. 1750 is examined, demonstrating the significant effect of iron gall ink, and lipids and inorganic soiling on its increased degradation.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Ryder ML (1964) Parchment—its history, manufacture and composition. J Soc Archiv 2:391–399

    Article  Google Scholar 

  2. Budrugeac P, Miu L, Bocu V, Wortman FJ, Popescu C (2003) Thermal degradation of collagen-based materials that are supports of cultural and historical objects. J Therm Anal Calorim 72:1057–1064

    Article  CAS  Google Scholar 

  3. Kolar J, Strlič M (2006) Iron gall inks: on manufacture, characterization, degradation and stabilization. National and University Library, Ljubljana

    Google Scholar 

  4. Bailey AJ, Paul RG (1998) Collagen: a not so simple protein. J Soc Leath Technol Chem 82:104–110

    CAS  Google Scholar 

  5. Kennedy CJ, Hiller JC, Lammie D, Drakopoulos M, Vest M, Cooper M, Adderley WP, Wess TJ (2004) Microfocus X-ray diffraction of historical parchment reveals variations in structural features through parchment cross sections. Nano Letters 4:1373–1380

    Article  CAS  Google Scholar 

  6. Ghioni C, Hiller JC, Kennedy CJ, Aliev AE, Odlyha M, Boulton M, Wess TJ (2005) Evidence of a distinct lipid fraction in historical parchments: a potential role in degradation? J Lip Res 46:2726–2734

    Article  CAS  Google Scholar 

  7. Strlič M, Kralj Cigić I, Rabin I, Kolar J, Pihlar B, Cassar M (2009) Autoxidation of lipids in parchment. Polym Degrad Stab 94:886–890

    Article  Google Scholar 

  8. Možir A, Strlič M, Trafela T, Kralj Cigić I, Kolar J, Deselnicu V, de Bruin G (2011) On oxidative degradation of parchment and its non-destructive characterisation and dating. Appl Phys A 104:211–217

  9. Popescu C, Budrugeac P, Wortmann FJ, Miu L, Demco DE, Baias M (2008) Assessment of collagen-based materials which are supports of cultural and historical objects. Polym Degrad Stab 93:976–982

    Article  CAS  Google Scholar 

  10. Gonzalez L, Wess T (2008) Use of attenuated total reflection–Fourier transform infrared spectroscopy to measure collagen degradation in historical parchment. Appl Spectr 62:1108–1114

    Article  CAS  Google Scholar 

  11. Mannucci E, Pastorelli R, Zerbi G, Bottani CE, Facchini A (2000) Recovery of ancient parchment: characterization by vibrational spectroscopy. J Ram Spectr 31:1089–1097

    Article  CAS  Google Scholar 

  12. Edwards HGM, Farwell DW, Newton EM, Rull Perez F, Jorge Villar S (2001) Application of FT-Raman spectroscopy to the characterisation of parchment and vellum, I; novel information for paleographic and historiated manuscript studies. Spectrochim Acta A 57:1223–1234

    Article  CAS  Google Scholar 

  13. Larsen R (2002) Microanalysis of parchment. Archetype, London

    Google Scholar 

  14. Larsen R, Vest M, Nielsen KJ (1993) Determination of hydrothermal stability (shrinkage temperature) of historical leather by the micro hot table technique. J Soc Leath Technol Chem 77:151–156

    CAS  Google Scholar 

  15. Cohen SN, Odlyha M, Foster GM (2000) Measurement of shrinkage behaviour in leather and parchment by dynamic mechanical thermal analysis. Thermochim Acta 365:111–117

    Article  CAS  Google Scholar 

  16. Kennedy CJ, Vest M, Cooper M, Wess TJ (2004) Laser cleaning of parchment: structural, thermal and biochemical studies into the effect of wavelength and fluence. Appl Surf Sci 227:151–163

    Article  CAS  Google Scholar 

  17. Koenig JL (1999) Spectroscopy of polymers. Elsevier, London

    Google Scholar 

  18. Jabs A (2011) Determination of secondary structure in proteins by Fourier transform infrared spectroscopy (FTIR). IMB, Jena. Available at http://www.imb-jena.de/ImgLibDoc/ftir/IMAGE_FTIR.htm. Accessed 1 March 2011

  19. Derrick M (1991) Evaluation of the state of degradation of Dead Sea scroll samples using FT-IR spectroscopy. The Book and Paper Specialty Group Session, AIC 19th Annual Meeting, 3–8 June, Albuquerque, New Mexico

  20. Maxwell CA, Wess TJ, Kennedy CJ (2006) X-ray diffraction study into the effects of liming on the structure of collagen. Biomacromolecules 7:2321–2326

    Article  CAS  Google Scholar 

  21. Wess TJ, Orgel JP (2000) Changes in collagen structure: drying, dehydrothermal treatment and relation to long term deterioration. Thermochim Acta 365:119–128

    Article  CAS  Google Scholar 

  22. Hiller JC, Thompson TJU, Evison MP, Chamberlain AT, Wess TJ (2003) Bone mineral change during experimental heating: an X-ray scattering investigation. Biomaterials 24:5091–5097

    Article  CAS  Google Scholar 

  23. Wess T, Alberts I, Hiller J, Drakopoulos M, Chamberlain AT, Collins M (2001) Microfocus small angle X-ray scattering reveals structural features in archeological bone samples: detection of changes in bone mineral habit and size. Calcif Tissue Int 70:103–110

    Article  Google Scholar 

  24. Karmer R (1998) Chemometric techniques for quantitative analysis. Dekker, New York

    Book  Google Scholar 

  25. Wiedemann SCC, Hansen WG, Snieder M, Wortel VAL (1998) NIR calibration in practice. Analusis 26:M 38–M 43

    Article  CAS  Google Scholar 

  26. Trafela T, Strlič M, Kolar J, Lichtblau DA, Anders M, Pucko Mencigar D, Pihlar B (2007) Nondestructive analysis and dating of historical paper based on IR spectroscopy and chemometric data evaluation. Anal Chem 79:6319–6323

    Article  CAS  Google Scholar 

  27. Persikov AV, Ramshaw JAM, Kirkpatrick A, Brodsky B (2000) Amino acid propensities for the collagen triple-helix. Biochemistry 39:14960–14967

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The work was financially supported by the Slovenian Research Agency (programme P1-0153). We also wish to thank user support of the Diamond Synchrotron, particularly Dr. Jen Hiller, Dr. Marc Malfois and Professor Nick Terrill of I22 Beamline. We also wish to thank Dr. Ulrich Schade of the IRIS Beamline at the BESSY Synchrotron, and Emanuel Kindzorra and Roman Schütz for their help with sample preparation and measurements.

Author information

Authors and Affiliations

  1. Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, 1000, Ljubljana, Slovenia

    Alenka Možir & Irena Kralj Cigić

  2. School of Optometry and Vision Sciences, Cardiff University, Maindy Road, Cardiff, CF24 4LU, UK

    Lee Gonzalez & Tim J. Wess

  3. Federal Institute for Materials Research and Testing, 12200, Berlin, Germany

    Ira Rabin & Oliver Hahn

  4. Centre for Sustainable Heritage, The Bartlett School of Graduate Studies, University College of London, 14 Upper Woburn Place, London, WC1H 0NN, UK

    Matija Strlič

Authors
  1. Alenka Možir
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lee Gonzalez
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Irena Kralj Cigić
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Tim J. Wess
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ira Rabin
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Oliver Hahn
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Matija Strlič
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Matija Strlič.

Additional information

Published in the special issue Analytical Techniques in Art, Archaeology and Conservation Science with guest editor Oliver Hahn.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 594 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Možir, A., Gonzalez, L., Kralj Cigić, I. et al. A study of degradation of historic parchment using small-angle X-ray scattering, synchrotron-IR and multivariate data analysis. Anal Bioanal Chem 402, 1559–1566 (2012). https://doi.org/10.1007/s00216-011-5392-6

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-011-5392-6

Keywords

Search

Navigation