Advertisement

Analytical and Bioanalytical Chemistry

, Volume 402, Issue 4, pp 1433–1441 | Cite as

Laser-induced fluorescence and FT-Raman spectroscopy for characterizing patinas on stone substrates

  • M. Oujja
  • C. Vázquez-Calvo
  • M. Sanz
  • M. Álvarez de Buergo
  • R. Fort
  • M. Castillejo
Original Paper

Abstract

This article reports on a compositional investigation of stone patinas: thin colored layers applied for protective and/or aesthetic purposes on architectural or sculptural substrates of cultural heritage. The analysis and classification of patinas provide important information of historic and artistic interest, as their composition reflects local practices, the availabilities of different materials, and the development of technological knowledge during specific historical periods. Model patinas fabricated according to traditional procedures and applied onto limestone, and a historic patina sample from the main façade of the San Blas Monastery in Lerma (a village in the province of Burgos, Spain), were analyzed by laser-induced fluorescence and Fourier transform Raman spectroscopy. The results obtained demonstrate the ability of these two analytical techniques to identify the key components of each formulation and those of the reaction products which result from the chemical and mineralogical transformations that occur during aging, as well as to provide information that can aid the classification of different types of patinas.

Figure

Cross section of model patina (left) and FT-Raman spectrum of historic patina from the façade of San Blas Monastery, Lerma, Burgos, Spain (right).

Keywords

Laser-induced fluorescence FT-Raman spectroscopy Patinas Stone substrates 

Notes

Acknowledgements

This work has been funded by the Madrid Regional Government project Geomateriales (S2009/Mat-1629) and by the Ministerio de Ciencia e Innovación under projects CTQ2010-15680 and CONSOLIDER CSD2007-00058. The authors also thank the research group from Universidad Complutense de Madrid: “Alteración y Conservación de los Materiales Pétreos del Patrimonio.”

References

  1. 1.
    Álvarez de Buergo M, Fort R (2003) Constr Build Mater 17:83Google Scholar
  2. 2.
    Vázquez-Calvo C, Álvarez de Buergo M, Fort R (2006) In: Fort R, Álvarez de Buergo M, Gómez-Heras M, Vázquez-Calvo C (eds) Heritage weathering and conservation 969–974. Taylor & Francis/Balkema, LeidenGoogle Scholar
  3. 3.
    Vázquez-Calvo C, Álvarez de Buergo M, Fort R (2007) In: Prikryl R, Smith B (eds) Building stone decay: from diagnosis to conservation (Special Publication 271). The Geological Society of London, London, p 295Google Scholar
  4. 4.
    Kouzeli K, Lazari C, Economopoulos A, Pavelis C (1996) In: Realini M, Toniolo L (eds) Proc 2nd Int Symp on The Oxalate Films in the Conservation of Works of Art. EDITEAM s.a.s., Castello d’ArgileGoogle Scholar
  5. 5.
    Polikreti K, Maniatis Y (2003) Sci Total Environ 308(1–3):111Google Scholar
  6. 6.
    Rampazzi L, Andreotti A, Bonaduce I, Colombini MP, Colombo C, Toniolo L (2004) Talanta 63:967Google Scholar
  7. 7.
    Taniguchi Y, Shimadzu Y, Kakoulli I (2003) In: Proc 25th Annu Conf Jpn Soc Conserv Cultural Property, Kyoto, Japan, June 2003Google Scholar
  8. 8.
    Cooper M, Larson J (1996) The Conservator 20:28Google Scholar
  9. 9.
    Vázquez-Calvo C, Gomez Tubio B, Álvarez de Buergo M, Ortega Feliu I, Fort R, Respaldiza MA (2008) X-Ray Spectrom 37:399Google Scholar
  10. 10.
    Vázquez-Calvo C, Álvarez de Buergo M, Fort R, Varas MJ (2007) Mater Charact 58(11–12):1119Google Scholar
  11. 11.
    Vázquez-Calvo C, Giakoumaki A, Anglos D, Álvarez de Buergo M, Fort R (2007) In: Nimmrichter J, Kautek W, Schreiner M (eds) Lasers in the conservation of artworks (Springer Proceedings in Physics 116). Springer, Vienna, pp 415–420Google Scholar
  12. 12.
    Oujja M, García A, Romero C, Vázquez de Aldana JR, Moreno P, Castillejo M (2011) Phys Chem Chem Phys 13:4625Google Scholar
  13. 13.
    Castillejo M, Martín M, Oujja M, Silva D, Torres R, Manousaki A, Zafiropulos V, Van den Brink OF, Heeren RMA, Teule R, Silva A, Gouveia H (2002) Anal Chem 74:4662Google Scholar
  14. 14.
    Gaspard S, Oujja M, Moreno P, Méndez C, García A, Domingo C, Castillejo C (2008) Appl Surf Sci 255:2675Google Scholar
  15. 15.
    Gaspard S, Oujja M, Abrusci C, Catalina F, Lazare S, Desvergne JP, Castillejo M (2008) J Photochem Photobiol A 193:187Google Scholar
  16. 16.
    Wisniewski M, Sionkowska A, Kaczmarek H, Lazare S, Tokarev V, Belin C (2007) J Photochem Photobiol A: Chem 188:192Google Scholar
  17. 17.
    Nevin A, Osticioli I, Anglos D, Burnstock A, Cather S, Castellucci E (2007) Anal Chem 79:6143Google Scholar
  18. 18.
    Oujja M, Pouli P, Fotakis C, Domingo C, Castillejo M (2010) Appl Spectrosc 64:528Google Scholar
  19. 19.
    Weibring P, Johansson T, Edner H, Svanberg S, Sundnér B, Raimondi V, Cecchi G, Pantani L (2001) Appl Opt 40:6111Google Scholar
  20. 20.
    Bell IM, Clark RJH, Gibbs JP (1997) Spectrochim Acta Part A 53:2159Google Scholar
  21. 21.
    Raimondi V, Cecchi G, Lognoli D, Palombi L, Grönlund R, Johansson A, Svanberg S, Barup K, Hällström J (2009) Int Biodet Biodeg 63:823Google Scholar
  22. 22.
    Vázquez-Calvo C, Álvarez de Buergo M, Fort R (2009) Method of preparation of patinas or films for stone surfaces and applications thereof (patent: WO 2009024642). WIPO, GenevaGoogle Scholar
  23. 23.
    Bustillo A (1980) Bol Geol Minero XCI-III:503Google Scholar
  24. 24.
    Wang J, Wu X, Mullins C (1997) Appl Spectrosc 51:1890Google Scholar
  25. 25.
    Bezouska JR, Wang J, Mullins OC (1998) Appl Spectrosc 52:1606Google Scholar
  26. 26.
    Aminzadeh A (1997) Spectrochim Acta Part A 53:693Google Scholar
  27. 27.
    Teale FWJ, Weber G (1957) Biochem J 65:476Google Scholar
  28. 28.
    Palumbo G, Pratesi R (2004) Lasers and current optical techniques in biology (Comprehensive Series in Photochemistry and Photobiology). Royal Society of Chemistry, CambridgeGoogle Scholar
  29. 29.
    Nevin A, Comelli D, Valentini G, Cubeddu R (2009) Anal Chem 81:1784Google Scholar
  30. 30.
    Athanassia A, Hill AE, Fourrier T, Burgio L, Clark RJH (2000) J Cult Herit 1:S209Google Scholar
  31. 31.
    Lu J, Li Y, Zhao K, Xu JQ, Yu JH, Li GH, Zhang X, Bie HY, Wang TG (2004) Inorg Chem Commun 7:1154Google Scholar
  32. 32.
    Taddei P, Tinti A, Gandolfi MG, Rossi PL, Prati C (2009) J Mol Struct 924–926:548Google Scholar
  33. 33.
    Nevin A, Comelli D, Osticioli I, Filippidis G, Melessanaki K, Valentini G, Cubeddu R, Fotakis C (2010) Appl Phys A 100:599Google Scholar
  34. 34.
    Jeziorowski H, Moser B (1985) Chem Phys Lett 120:41Google Scholar
  35. 35.
    Frost RL (2004) Anal Chim Acta 517:207Google Scholar
  36. 36.
    Shippey TA (1980) J Mol Struct 63:157Google Scholar
  37. 37.
    Campos-Suñol MJ, Domínguez-Vidal A, Ayora-Cañada MJ, De la Torre-López MJ (2008) Anal Bioanal Chem 391:1039Google Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • M. Oujja
    • 1
  • C. Vázquez-Calvo
    • 2
  • M. Sanz
    • 1
  • M. Álvarez de Buergo
    • 2
  • R. Fort
    • 2
  • M. Castillejo
    • 1
  1. 1.Instituto de Química Física Rocasolano, CSICMadridSpain
  2. 2.Instituto de Geociencias, CSIC-UCMMadridSpain

Personalised recommendations