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Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain)

  • AREA 6 • HERITAGE CONSERVATION • RESEARCH ARTICLE
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Abstract

Background, aim, and scope

The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed.

Materials and methods

Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR).

Results

XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite.

Discussion

Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.).

Conclusions

In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas.

Recommendations and perspectives

The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.

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References

  • Andreotti A, Colombini MP, Nevin A, Melessanaki K, Pouli P, Fotakis C (2006) Multianalytical study of laser pulse duration effects in the IR laser cleaning of wall paintings from the Monumental Cemetery of Pisa. Hindawi Publishing Corporation Laser Chemistry. Article ID 39046, p 11, doi:10.1155/2006/39046

  • Blazquez F, Garcia-Valles M, Krumbein WE, Sterflinger K, Vendrell-Saz M (1997) Microstromatolitic deposits on granitic monuments: development and decay. Eur J Mineral 9:889–901

    CAS  Google Scholar 

  • Bosch Reig F, Gimeno Adelantado JV, Moya Moreno MCM (2002) FTIR quantitative analysis of calcium carbonate (calcite) and silica (quartz) mixtures using the constant ratio method. Application to geological samples. Yalanta 58:811–821

    Article  Google Scholar 

  • Bralia A, Matteini M, Moles A, Sabatini G (1989) La sintesi degli ossalati di calcio nella interpretazione delle patine presenti suimarmi esposti all aperto Risultati preliminari.In: Proceedings of the 1st International Syposium ‘The Oxalate Films. Originand Significance in the Conservation of Works of Art’. Centro ‘Gino Bozza’, Milan, pp 75–84

  • Callot G, Maurette M, Portier L, Dubois A (1987) Biogenic etching of microfractures in amorphous and crystalline silicates. Nature 328:147–149

    Article  CAS  Google Scholar 

  • Cappitelli F, Nosachuk JD, Casadevall A, Toniolo L, Brusetti L, Florio S, Principi P, Borin S, Sorlini C (2007) Synthetic consolidants attacked by melani-producing fungi: case study of the biodeterioration of Milan (Italy) Catedral Marble Treated with acrylics. Appl Environ Microbiol 73(1):271–277

    Article  CAS  Google Scholar 

  • Cariati F, Rampazzi R, Toniolo L, Pozzi A (2000) Calcium oxalate films on stone surfaces: experimental assessment of the chemical formation. Stud Conserv 45:180–188

    Article  CAS  Google Scholar 

  • Cervantes-Uc JM, Cauich-Rodriguez JV, Vázquez-Torres H, Garfias-Mesias LF, Paul DR (2007) Thermal degradation of commercially available organoclays studied by TGA-FTIR. Thermochim Acta 457:92–102

    Article  CAS  Google Scholar 

  • Cox GA, Ford BA (1993) The long-term corrosion of glass by groundwater. J Mater Sci 28:5637–5647

    Article  CAS  Google Scholar 

  • Doménech-Carbo MT, Doménech-Carbó A, Osete-Cortina L, Saurí-Peris MC (2006) A study on corrosion processes of archaeological glass from the Valencian region (Spain) and its consolidation treatment. Microchim Acta 154:123–142

    Article  CAS  Google Scholar 

  • Douglas RW, Isard MA (1949) The action of water and sulphur dioxide on glass surfaces. J Soc Glass Technol 33:289–335

    Google Scholar 

  • Drewello R, Weißmann R (1997) Microbially influenced corrosion of glass. Appl Microbiol Biotechnol 47:337–346

    Article  CAS  Google Scholar 

  • Drewello U, Weißmann R, Rölleke S, Müller E, Wuertz S, Fekrsanati F, Troll C, Drewello R (2000) Biogenic surface layers on historical window glass and the effect of excimer laser cleaning. J Cult Heritage 1:S161–S171

    Article  Google Scholar 

  • Etchepare J, Merian M, Smetankine L (1974) Vibrational normal modes of SiO2 I α and β-quartz. J Chem Phys 60:1873–1876

    Article  CAS  Google Scholar 

  • Farmer VC (ed) (1974) The Infrared spectra of minerals. Mineralogical Society monograph, London, p 539

  • Garcia-Valles M, Vendrell M (2002) The glasses of the transept’s rosette of the cathedral of Tarragona: characterization, classification and decay. Bol Soc Esp Cerám V 41(2):217–224

    CAS  Google Scholar 

  • García-Heras M, Villegas MA, Cano E, Cortés Pizano F, Bastidas JA (2004) A conservation assessment on metallic elements from Spanish Medieval stained glass windows. J Cult Herit 5:311–317

    Article  Google Scholar 

  • Garcia-Valles M, Blázquez F, Vendrell M (1996a) Studies of patinas and decay mechanisms leading to the restoration of Santa Maria de Montblanc. Stud Conserv 41:1–8

    Article  Google Scholar 

  • Garcia-Valles M, Krumbein WE, Urzì C, Vendrell-Saz M (1996b) Biological pathways leading to the formation and transformation of oxalate-rich layers on monument surfaces exposed to Mediterranean climate. The oxalate films in the conservation of works of art. Ed. Realini, Toriolo EDITEAM, Milan, pp 317–334

  • Garcia-Valles M, Vendrell M, Krumbein W, Urzì C (1997) Coloured mineral coatings on monument surfaces as result of biomineralization: the case of the Tarragona cathedral (Catalonia). Appl Geochem 12:255–266

    Article  CAS  Google Scholar 

  • Garcia-Valles M, Urzì C, De Leo F, Salamone P, Vendrell M (2000) Biological weathering and mineral deposits of the Belevi marble quarry (Ephesus, Turkey). Int J Biodeter Biodegrad 46(3):221–227

    Article  Google Scholar 

  • Garcia-Valles M, Urzì C, Vendrell M (2002) Weathering processes on the rock surface in natural outcrops: the case of an ancient marble quarry (Belevi, Turkey). Environ Geol 41:889–897

    Article  Google Scholar 

  • Garcia-Valles M, Gimeno D, Martínez-Manent S, Fernández-Turiel JL (2003) Medieval stained glass in a Mediterranean climate: typology, weathering and glass decay, and associated biomineralization processes and products. Am Mineralog 88:1996–2006

    CAS  Google Scholar 

  • Gimeno D, Pugès M (2002) Caracterización química de la vidriera de Sant Pere i Sant Jaume (segundo cuarto del s. XIV, Monestir de Pedralbes, Barcelona). Bol Soc Esp Cerám V 41:225–231

    CAS  Google Scholar 

  • Howari FM (2004) Chemical and environmental implications of visible and near-infrared spectral features of salt crust formed from different brines. Annali di Chimica 94(4):315–323

    Article  CAS  Google Scholar 

  • IRUG Spectral Database Edition (2000)

  • Krumbein WE, Urzì C, Gehrmann C (1991) Biocorrosion of antique and medieval glass. Geomicrobiol J 9:139–160

    Article  CAS  Google Scholar 

  • Libowitzky E, Rossman G (1997) An IR absorption calibration for water in minerals. Am Mineralog 82(11–12):1111–1115

    CAS  Google Scholar 

  • Meng L-Z, Gong S-L, Yin Y-H, Chen Y-Y, Wang Y-W (2003) Network crown ether resin with pendent sulfur ether group: preparation thermodegradation, and adsorption behaviour. J Appl Polym Sci 87:1445–1451

    Article  CAS  Google Scholar 

  • Martín-Gil J, Martín-Gil FJ, Ramos-Sánchez MC, Martín-Ramos PM (2005) The orange-brown patina of Salisbury Cathedral (West Porch) surfaces: evidence of its Man-Made origin. Environ Sci Pollut Res 12(5):285–289

    Article  CAS  Google Scholar 

  • Monje PV, Baran EJ (2004) Characterization of calcium oxalates generated as biominerals in cacti. Plant Physiol 128:707

    Article  CAS  Google Scholar 

  • Monje PV, Baran EJ (2005) Evidence of formation of glushinskite as a biomineral in a Cactaceae species. Phytochem 66:611–614

    Article  CAS  Google Scholar 

  • Munier I, Lefèvre R, Losno R (2002) Atmospheric factors influencing the formation of neocrystallisations on low durability glass exposed to urban atmosphere. Glass Technol 43C:114–124

    Google Scholar 

  • Newton RG, Davison S (1997) Conservation of glass. Butterworth-Heinemann, London

    Google Scholar 

  • Petrov I, Soptrajanov B (1975) Infrared spectrum of whewellite. Spectrochim Acta 31A:309–316

    CAS  Google Scholar 

  • Quingping F, Xiaojun Z, Xiaojun Ma (1999) Effects of microbes on color changes of red lead in murals. J Gen Appl Microbiol 45:85–88

    Article  Google Scholar 

  • Rampazzi L, Andreotti A, Bonaduce I, Colombini MP, Colombo C, Toniolo L (2004) Analytical investigation of calcium oxalate films on marble monuments. Talanta 63:967–977

    Article  CAS  Google Scholar 

  • Schreiner M (1988) Deterioration of stained medieval glass by atmospheric attack. Glastech Ver 61(7):197–230

    CAS  Google Scholar 

  • Sterpenich J, Liboure G (2001) Using stained glass windows to understand the durability of toxic waste matrices. Chem Geol 174:181–193

    Article  CAS  Google Scholar 

  • Tennent NH (1981) Fungal growth on medieval glass. J Br Soc Master Glass Painters 17:64–68

    Google Scholar 

  • Urzì C, Realini M (1998) Colour changes of Noto’s Calcareous Sandstone as related with its colonisation by microorganisms. Int Biodeterm Biodegrad J 42:45–54

    Article  Google Scholar 

  • Urzì C, Garcia-Valles M, Vendrell M, Pernice A (1999) Biomineralisation processes on rock surfaces observed in field and in laboratory conditions. Geomicrobiol J 16:39–54

    Article  Google Scholar 

  • Watkinson D, Weber I, Anheuser K (2005) Staining of archaeological glass from manganese-rich environments. Archaeometry 47:69–82

    Article  CAS  Google Scholar 

  • Williams Q (1995) Infrared, raman and optical spectroscopy of Earth materials. Mineral Physics and Crystallography. A Handbook of Physical Constants. AGU Reference Shelf 2, pp 291–302

Download references

Acknowledgments

This work has been carried out in the framework of the Research Consolidated Groups SGR-2005-00795 PEGEFA (Applied and Basic Petrology and Geochemistry) and SGR-2005-00589 (Mineral Resources) funded by AGAUR-DURSI, Generalitat de Catalunya. The authors want to thank the staff from the Serveis Científico-Tècnics of the Universitat de Barcelona, the staff from the Pedralbes Monastery Museum, and the staff from the Servei d’Arqueologia del Museu d’Història de Barcelona. The English of the final version of the manuscript was improved by Frances Luttikhuizen.

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Authors and Affiliations

  1. Dep. Geoquímica, Petrologia i Prospecció Geològica, Universitat de Barcelona, c/ Martí i Franquès, s/n, 08028, Barcelona, Spain

    Meritxell Aulinas & Domingo Gimeno

  2. Dep. Cristal lografia, Mineralogia i Dipòsits Minerals, Universitat de Barcelona, c/ Martí i Franquès, s/n, 08028, Barcelona, Spain

    Maite Garcia-Valles

  3. Institute of Earth Sciences Jaume Almera, CSIC, Solé i Sabarís, 08028, Barcelona, Spain

    Jose Luis Fernandez-Turiel & Flavia Ruggieri

  4. Servei d’Arqueologia, Museu d’Història de la Ciutat, Ajuntament de Barcelona. Zona Franca, Sector C. C/F, 22, E-08038, Barcelona, Spain

    Montserrat Pugès

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  1. Meritxell Aulinas
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  2. Maite Garcia-Valles
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  3. Domingo Gimeno
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  4. Jose Luis Fernandez-Turiel
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Correspondence to Meritxell Aulinas.

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Aulinas, M., Garcia-Valles, M., Gimeno, D. et al. Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain). Environ Sci Pollut Res 16, 443–452 (2009). https://doi.org/10.1007/s11356-008-0078-0

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