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Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment

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Abstract

Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical–physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T 1, indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, 13C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the 13C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

The state of deterioration of a Dead Sea scroll fragment was studied by means of 1H and 13C solid state NMR and proton T 1 relaxation measurements

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References

  1. Temple scroll columns II-V, Report on the treatment in the laboratory of the Israel Antiquities Authority (2005). The Shrine of the Book

  2. Boyd-Alkalay E, Libman E (1998) Preserving the Dead Sea Scrolls and Qumran Artifacts. In: Peter WF, Vanderkam JC (eds) The Dead Sea Scrolls after fifty years. Brill, Leiden, pp 535–544

    Google Scholar 

  3. Poole JB, Reed R (1962) The preparation of leather and parchment by the Dead Sea Scrolls community. Technol Cult 3:1–36

    Google Scholar 

  4. Kennedy CJ, Wess TJ (2003) The structure of collagen within parchment—a review. Restaur-Int J Preserv Libr Arch Mater 24(2):61–80

    CAS  Google Scholar 

  5. Kronick PL, Buechler PR (1986) Fiber orientation in calfskin by laser light scattering of X-ray diffraction and quantitative relation to mechanical properties. J Am Leather Chem Assoc 81:221–231

    CAS  Google Scholar 

  6. Purlslow PP, Wess TJ, Hukins DWL (1998) J Exp Biol 201:135–142

    Google Scholar 

  7. Fratzl P, Fratzl-Zelman N, Klaushofer K (1993) Biophys J 63:260

    Google Scholar 

  8. Prockop DJ, Fertala A (1998) J Struct Biol 122:111

    CAS  Google Scholar 

  9. Price RI, Lees S, Kirschner DA (1997) Int J Biol Macromol 20:23

    CAS  Google Scholar 

  10. Gutsmann T, Fantner GE, Venturoni M, Ekani-Nkodo A, Thompson JB, Kindt JH, Morse DE, Kuchnir Fygenson D, Hansma PK (2003) Biophys J 84:2593

    CAS  Google Scholar 

  11. Ottani V, Raspanti M, Ruggeri A (2001) Collagen structure and functional impications. Micron 32:251–260

    CAS  Google Scholar 

  12. Strlic M, Cigic IK, Rabin I, Kolar J, Pihlar B, Cassar M (2009) Autoxidation of lipids in parchment. Polym Degrad Stab 94(6):886–890

    CAS  Google Scholar 

  13. Larsen R, et al. (2005) Improved Damage Assessment of Parchment (IDAP), European project EVK4-CT-2001-00061. Available at: http://www.idap-parchment.dk.

  14. Kennedy CJ, Hiller J, Odlyha M, Nielsen K, Drakopoulos M, Wess TJ (2002) Degradation in historical parchments: structural, biochemical and thermal studies. Pap Restaur 3(4):23–30

    Google Scholar 

  15. Della Gatta G, Badea E, Ceccarelli R, Usacheva T, Masic A, Coluccia S (2005) Assessment of damage in old parchments by DSC and SEM. J Therm Anal Calorim 82(3):637–649

    CAS  Google Scholar 

  16. Larsen R (ed) (2002) Microanalysis of parchment. European project SMT4-CT96-2106. Archetype Publications, Copenhagen

  17. 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 Lett 4(8):1373–1380

    CAS  Google Scholar 

  18. Larsen R, Poulsen DV, Juchauld F, Jerosch H, Odlyha M, de Groot J, Wess T, Hiller J, Kennedy C, Della Gatta G, Badea E, Masic A, Boghosian S, Fessas D (2005) Damage assessment of parchment: complexity and relations at different structural levels. In: 14th ICOM-CC Meeting, Hague, pp 1–10

  19. Giustetto R, Llabrès I, Xamena FX, Richiardi G, Bordiga F, Damin A, Gobetto R, Chierotti MR (2005) J Phys Chem B 109(41):19360–19368

    CAS  Google Scholar 

  20. Borgia GC, Camaiti M, Cerri F, Fantazzini P, Piacenti F (2003) Hydrophobic treatments for stone conservation: influence of application method on penetration, distribution and efficiency. Stud Conserv 48(4):217–226

    CAS  Google Scholar 

  21. Appolonia L, Borgia GC, Bortolotti V, Brown RJS, Fantazzini P, Rezzaro G (2001) Effects of hydrophobic treatments of stone on pore water studied by continuous distribution analysis of NMR relaxation times. Magn Reson Imaging 19:509–512

    CAS  Google Scholar 

  22. Casieri C, Bubici S, Viola I, De Luca F (2004) A low-resolution non-invasive NMR characterization of ancient paper. Solid State Nucl Magn Reson 26:65–73

    CAS  Google Scholar 

  23. Viola I, Bubici S, Casieri C, De Luca F (2004) The Codex Major of the Collectio Altaempsiana: a non-invasive NMR study of paper. J Cult Herit 5:257–261

    Google Scholar 

  24. Blümich B, Anferova S, Sharma S, Segre AL, Federici C (2003) Degradation of historical paper: nondestructive analysis by the NMR-MOUSE. J Magn Reson 161:204–209

    Google Scholar 

  25. Proietti N, Capitani D, Pedemonte E, Blumich B, Segre AL (2004) Monitoring degradation in paper: non-invasive analysis by unilateral NMR. Part II. J Magn Reson 170:113–120

    CAS  Google Scholar 

  26. Sharma S, Casanova F, Wache W, Segre A, Blumich B (2003) Analysis of historical porous building materials by the NMR-MOUSE. Magn Reson Imag 21:245–255

    Google Scholar 

  27. Proietti N, Capitani D, Lamanna R, Presciutti F, Rossi E, Segre AL (2005) Fresco paintings studied by unilateral NMR. J Magn Reson 177(1):111–117

    CAS  Google Scholar 

  28. Proietti N, Capitani D, Rossi E, Cozzolino S, Segre AL (2007) Unilateral NMR study of a XVI century wall painted. J Magn Reson 186(2):311–318

    CAS  Google Scholar 

  29. Capitani D, Emanuele MC, Segre A, Fanelli C, Fabbri AA, Attanasio D, Focher B, Capretti G (1998) Nord Pulp Pap Res J 13:95

    CAS  Google Scholar 

  30. Paci M, Federici C, Capitani D, Perenze N, Segre AL (1995) NMR study of paper. Carbohydr Polym 26(4):289–297

    CAS  Google Scholar 

  31. Capitani D, Emanuele MC, Bella J, Segre AL, Attanasio D, Focher B et al (1999) 1H NMR relaxation study of cellulose and water interaction in paper. Tappi J 82(9):117–124

    CAS  Google Scholar 

  32. 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(5):976–982

    CAS  Google Scholar 

  33. Badea E, Miu L, Budrugeac P, Giurginca M, Masic A, Badea N, Della Gatta G (2008) Study of deterioration of historical parchments by various thermal analysis techniques complemented by SEM, FTIR, UV-Vis-NIR and unilateral NMR investigations. J Therm Anal Calorim 91(1):17–27

    CAS  Google Scholar 

  34. Aliev AE (2005) Solid State NMR studies of collagen-based parchments and gelatin. Biopolymers 77:230–245

    CAS  Google Scholar 

  35. Rabin I, Brooke G, Hodgson J, Pantos M, Prag J (2007) The Ronald Reed archive at the John Rylands University Library. e-Preservation Science 4:9–12

  36. Mogilner IG, Ruderman G, Raul Grigera J (2002) Collagen stability, hydration and native state. J Mol Graph Model 21:209–213

    CAS  Google Scholar 

  37. Luescher M, Ruegg MPS (1974) Effect of hydration upon the thermal stability of tropocollagen and its dependence on the presence of neutral salts. Biopolymers 13:2489–2503

    CAS  Google Scholar 

  38. Nomura S, Hiltner A, Lando JB, Baer E (1977) Interaction of water with native collagen. Biopolymers 16:231–246

    CAS  Google Scholar 

  39. Shinyashiki N, Asaka N, Mashimo S, Yagihara S, Hikichi K (1990) Microwave dielectric study on hydration of moist collagen. Biopolymers 29:1185–1191

    CAS  Google Scholar 

  40. Melacini G, Bonvin AMJJ, Goodman M, Boelens R, Kaptein R (2000) Hydration dinamics of the collagen triple helix by NMR. J Mol Biol 300:1041–1048

    CAS  Google Scholar 

  41. Kozlov PV, Burdygina GI (1983) The structure and properties of solid gelatin and the principles of their modification. Polymer 24:651–666

    CAS  Google Scholar 

  42. Fraser RDB, MacRae TP (1973) Conformation in fibrous proteins. Academic, New York

    Google Scholar 

  43. Bella J, Eaton M, Brodsky B, Berman H (1994) Science 266:75

    CAS  Google Scholar 

  44. Bella J, Brodsky B, Berman H (1995) Hydration structure of a collagen peptide. Structure 3:893–906

    CAS  Google Scholar 

  45. Pezron I, Djabourov M, Bosio L, Leblond J (1990) X-ray diffraction of gelatin fibres in the dry and swollen states. J Polym Sci part B-Polym Phys 28(10):1823–1839

    CAS  Google Scholar 

  46. Della Gatta G, Badea E, Masic A, Ceccarelli R (2007) Structural and Thermal Stability of Collagen within Parchment: a Mesoscopic and Molecular Approach. In: Larsen R (ed) Improved Damage Assessment of Parchment (IDAP) Collection and Sharing of Knowledge. Directorate-General for Research, Directorate Environment, European Communities, Brussels. pp 51–60

  47. Della Gatta G, Badea E, Mašic A, Usacheva T, Benedetto S, Braghieri A Coparative study of environmental ageing-related changes in parchments by calorimetry and electron microscopy. In: ICOM-CC 14th Triennal Meeting, Hague, 12–16 September 2005. p 58

  48. Ginell WS (1993) Report on Dead Sea Studies. The Getty Conservation Institute, Marina del Rey, California

  49. 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 Lipid Res 46(12):2726–2734

    CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful to the Piedmont Region for financial support. This work was performed as part of the EU IDAP (Improved Damage Assessment of Parchment, EVK4-2001-00061). We would like to thank Prof. G. Della Gatta, Dr. E. Badea, Dr. M. Odlyha, and Dr. R. Larsen for helpful discussions and support of this research. AM is grateful for the support by the Alexander von Humboldt Foundation and the Max Planck Society in the framework of the Max Planck Research Award funded by the Federal Ministry of Education and Research.

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Authors and Affiliations

  1. Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, 14424, Potsdam, Germany

    A. Masic

  2. Department of Chemistry IFM and NIS Centre of Excellence, University of Torino, Via Pietro Giuria 7, 10125, Torino, Italy

    M. R. Chierotti, R. Gobetto, G. Martra & S. Coluccia

  3. BAM Federal Institute for Materials Research and Testing, Unter den Eichen 44-46, 12203, Berlin, Germany

    I. Rabin

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  1. A. Masic
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  2. M. R. Chierotti
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Correspondence to A. Masic.

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

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Masic, A., Chierotti, M.R., Gobetto, R. et al. Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment. Anal Bioanal Chem 402, 1551–1557 (2012). https://doi.org/10.1007/s00216-011-5265-z

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