Analytical study of the XIV century wall painting and lime mortars in the "St. George" church in Staro Nagoričane, Republic of Macedonia

Lidija Robeva Čukovska, Tena Šijakova Ivanova, Živko Kokolanski


This work presents the first comprehensive study of the wall painting in the “St. George” church accomplished mainly by means of Fourier Transform Infrared Spectroscopy using Diffuse Reflectance and Micro-Infrared method (FTIR/DRS/Micro-IR) and the other analytical techniques Optical microscopy (OM), X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD) and Inductively Coupled Plasma – Mass Spectrometry (ICP-MS). The main research objective was characterization of the artistic palette and painting technique, but also determination of the degradation products and observed alterations to the wall painting. Additionally, the lime mortars (plaster and renders) located immediately behind the studied wall painting were analyzed. The analysis demonstrated that mainly natural/mineral pigments were used in the artwork and the majority of painting was executed in combination of fresco and lime-painting technique. The major risk factor in the painting deterioration was found to be the salt efflorescence, which mostly occurred as oxalates and sulfates. 



Full Text:



B. Todić, Staro Nagoričine, RZZSK, Beograd, 1993, pp 25–27.

Project for Conservation and revitalization of the cultural touristic site "St. George" – Staro Nagoričane, un-published documentation, National Conservation Center – Skopje, Department for informative documentation, INDOC 08–25/27, 2015.

Conservation-restoration project for preservation of the "St. George" church in Staro Nagoričane, unpublished documentation, National Conservation Center – Skopje, Department for informative documentation, INDOC 08–1299, 1997.

B. H. Stuart, Analytical techniques in materials conser-vation, John Wiley and Sons, Ltd, 2007.

D. Pinna, M. Galeotti, R. Mazzeo, Scientific Examination for the Investigation of Paintings: A Handbook for Conservators-Restorers, Centro Di, Firenze, 2009.

L. Robeva-Čukovska, B. Minčeva-Šukarova, A. Llu-veras-Tenorio, A. Andreotti, M. Perla Colombini, I. Nastova, Micro-Raman and GC/MC analysis to charac-terize the wall painting technique of Dicho Zograph in churches from Republic of Macedonia, J. Raman Spectrosc. 43 (11), 1685–1693 (2012).

M. D. S. Gomez de Segura, Histochemical Staining Test for Protein and Oil Substances, ICCROM, Roma, 1994.

M. Horgnies, M. Bayle, E. Gueit, Darque-Ceretti, M. Aucoutturier, Microstructure and surface properties of frescoes based on lime and cement: The influence of the artist’s technique, Archaeometry 57 (2), 344–361 (2015).

R. Piovesan, C. Mazzoli, L. Maritan, P. Cornale, Fresco and Lime-paint: An experimental study and objective criteria for distinguishing between these painting tech-niques, Archeometry 54 (4), 723–736 (2012).

S. Mugnaini, A. Bagnoli, P. Bensi, F. Droghini, A. Scala, G. Guasparri, Thirteenth century wall paintings under the Siena Cathedral (Italy). Mineralogical and petrographic study of materials, painting techniques and state of conservation, J. Cult. Herit. 7, 171–185 (2006).

Sister Daniilla, A. Tsakalof, K. Bairachtari, Y. Chryssoulakis, The Byzantine wall paintings from the Protaton Church on Mount Athos, Greece: Tradition and Science, J. Archaeol. Sci. 34 (12), 1971–1984 (2007).

P. Mora, L. Mora, P. Philippot, Conservation of Wall Paintings, ICCROM, Rome, 1984.

M. P. Merrifield, The Art of Fresco Painting in the Mid-dle Ages and the Renaissance, Dover Publications, 2004.

L. Čukovska, O. Grupče, B. Minčeva-Šukarova, I. Kuzmanovski, Characterization of salt efflorescence using target factor analysis. Development of the Method, J. Braz. Chem. Soc., 20 (1), 57–63 (2009).

R. Nyquist, R. Kagel, Infrared Spectra of Inorganic Compounds, Academic Press, New York, 1971.

N. V. Chukanov, Infrared Spectra of Mineral Species: Extended Library, Springer Science & Business Media, 2013.

R. M. Derrick, D. Stulik, M. J. Landry, Infrared Spec-troscopy in Conservation Science, The Getty Conserva-tion Institute, Los Angeles, 1999.

R. L. Frost, D. L. Wain, W. N. Martens, B. J. Reddy, Vibrational spectroscopy of selected minerals of the rosasite group, Spectrochim. Acta, Part A 66 (4–5), 1068–1074 (2007).

F. Ospitali, D. Bersani, G. D. Lonardo, P. P. Lottici, ‘Green earths’: vibrational and elemental characterization of glauconites, celadonites and historical pigments J. Raman Spectrosc. 39, 1066–1073 (2008).

N. Eastaugh, V. Walsh, T. Chaplin, R. Siddall, Pigment Compendium: A Dictionary and Optical Microscopy of Historical Pigments, 1st Ed., Butterworth Heinemann, London, 2008.

S. Akyuz, T. Akyuz, G. Emre, A. Gulec, S. Basaran, Pigment analyses of a portrait and paint box of Turkish artist Feyhaman Duran (1886–1970): The EDXRF, FT-IR and micro Raman spectroscopic studies, Spectrochim. Acta A 89, 74–81 (2012).

L. Berzina-Cimdina, N. Borodajenko, Research of calci-um phosphates using Fourier Transform Infrared Spec-troscopy, Infrared Spectroscopy – Materials Science, Engineering and Technology, Prof. Theophanides Theophile (Ed.), (2012). InTech, books/infrared-spectroscopy-materials-science-engine¬ering-and-technology/research-of-calcium-phosphates-using-fourier-transformation-infrared-spectroscopy.

Shipman, P., Foster, G., Schoeninger, M., ‘Burnt bones and teeth: an experimental study of color, morphology, crystal structure and shrinkage’, J. Archaeol. Sci. 11, 307–325 (1984).

E. Tomasini, G. Siracusano, M. S. Maier, Spectroscopic, morphological and chemical characterization of historic pigments based on carbon. Paths for the identification of an artistic pigment, Microchem. J. 102, 28–37 (2012).

A. Veiga, J. Mirao, A. J. Candeias, P. S. Rodrigues, D. M. Teixeira, V. S. F. Muralha, J. G. Teixeira, Pigment analysis of Portuguese portrait miniatures of 17th and 18th centuries by Raman microscopy and SEM-EDS, J. Raman Spectrosc. 45 (10), 947–957 (2014).

G. A. Mazzocchin, F. Agnoli, S. Mazzocchin, I. Colpo, Analysis of pigments from Roman wall paintings found in Vicenza, Talanta 65, 565–572 (2003).

J. Van der Weerd, A. Van Loon, J. J. Boon, FTIR studies of the effects of pigments on the aging of Oil, Stud. Conserv. 50, 3–22 (2005).

R. Mazzeo, S. Prati, M. Quaranta, E. Joseph, E. Kendix, M. Galeotti, Attenuated total reflection micro FTIR characterization of pigment–binder interaction in recon-structed paint films, Anal. Bioanal. Chem. 392, 65–76 (2008).

F. Rosi, A. Daveri, C. Miliani, G. Verri, P. Benedetti, F. Pique, B. G. Brunetti, A. Sgamellotti, Non-invasive identification of organic materials in wall painting by fiber optic reflectance infrared spectroscopy: A statistical multivariate approach, Anal. Bioanal. Chem. 395 (7), 2097–2106 (2009).

V. Otero, D. Sanches, C. Montagner, M. Vilarigues, L. Carlyle, J. A. Lopes, M. J. Melo, Characterization of met-al carboxylates by Raman and infrared spectroscopy in works of art, J. Raman Spectrosc. 45, 1197–1206 (2014).

N. A. Nikonenko, D. K. Buslov, N. I. Sushko, R. G. Zhbankov, Investigation of stretching vibrations of glycosidic linkages in disaccharides and polysaccharides with use of IR spectra deconvolution. Biopolymers 57 (4), 257–62 (2000).

J. Lojewska, P. Miskowiec, T. Lojewski, L. M. Proniewicz, Cellulose oxidative and hydrolytic degrada-tion: In situ FTIR approach, Polym. Degrad. Stab. 88, 512–520 (2005).

A. Srivastava, V. Mishra, P. Singh, A. Srivastava, R. Kumar, Comparative study of thermal degradation be-havior of graft copolymers of polysaccharides and vinyl monomers, J. Therm. Anal. Calorim. 107, 211–223 (2012).

P. Ropret, R. Zoubek, A. S. Škapin. P. Bukovec, Effects of ageing on different binders for retouching and on some binder–pigment combinations used for restoration of wall paintings, Mater. Charact. 58 (11–12), 1148–1159 (2007).

C. Liu, Q. Liu, J. Sun, B. Jiang, J. Yan, Extraction of water-soluble polysaccharide and the antioxidant activity from Semen cassia, J. Food Drug Anal. 22 (4), 492–499 (2014). DOI:

H. Jedrzejewska, Old mortars in Poland: A New method of investigation, Stud. Conserv. 5 (4), 132–138 (1960).

J. I. Alvarez, A. Martin, P. J. G. Casado, I. Navarro, A. Zornoza, Methodology and validation of a hot hydro-chloric acid attack for the characterization of ancient mortars. Cem. Concr. Res. 29 (7), 1061–1065 (1999).

J. I. Alvarez, I. Navarro, P. J.G. Casado, Thermal, min-eralogical and chemical studies of the mortars used in the cathedral of Pamplona (Spain), Thermochim. Acta 365 (1), 177–187 (2000).

F. Casadio, G. Chiari, S. Simon, Evaluation of bind-er/aggregate ratios in archaeological lime mortars with carbonate aggregate: A comparative assessment of chemical, mechanical and microscopic approaches, Archaeometry 47 (4), 671–689 (2005).

P. Maravelaki-Kalaitzaki, A. Bakolas, A. Moropoulou, Physico-chemical study of Cretan ancient mortars, Cem. Concr. Res. 33, 651–661 (2003).

МКС EN 1015-1:2009/A1:2009: Methods of test for mortar for masonry – Part 1: Determination of particle size distribution by sieve analysis.

ISO 14688-1:2002 – Geotechnical investigation and testing – Identification and classification of soil – Part 1: Identification and description.



  • There are currently no refbacks.

Copyright (c) 2017 Lidija Robeva Čukovska, Tena Šijakova Ivanova, Živko Kokolanski

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.