Hostname: page-component-8448b6f56d-cfpbc Total loading time: 0 Render date: 2024-04-18T22:32:51.064Z Has data issue: false hasContentIssue false
  • English
  • Français

On the Use of the Unusual Green Pigment Brochantite (Cu4(SO4)(OH)6) in the 16th-Century Portuguese-Flemish Paintings Attributed to The Master Frei Carlos Workshop

Published online by Cambridge University Press:  23 February 2015

Sara Valadas ,
Rita V. Freire ,
Ana Cardoso ,
José Mirão ,
Cristina B. Dias ,
Peter Vandenabeele  and
António Candeias
Sara Valadas
Affiliation:
Évora University, HERCULES Laboratory, School of Sciences and Technology, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal
Rita V. Freire
Affiliation:
Évora University, HERCULES Laboratory, School of Sciences and Technology, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal Évora University, CHAIA- Centro de História de Arte e Investigação Artística, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal
Ana Cardoso
Affiliation:
Évora University, HERCULES Laboratory, School of Sciences and Technology, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal
José Mirão
Affiliation:
Évora University, HERCULES Laboratory, School of Sciences and Technology, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal
Cristina B. Dias
Affiliation:
Évora University, HERCULES Laboratory, School of Sciences and Technology, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal
Peter Vandenabeele
Affiliation:
Department of Archaeology, Ghent University, Sint-Pietersnieuwstraat 35, B-9000 Ghent, Belgium
António Candeias*
Affiliation:
Évora University, HERCULES Laboratory, School of Sciences and Technology, Largo Marquês de Marialva 8, 7000-809 Évora, Portugal Jose de Figueiredo Lab., General Directorate of Cultural Heritage, Rua das Janelas Verdes 37, 1300-001 Lisbon, Portugal
*
*Corresponding author.candeias@uevora.pt
Get access

Abstract

This paper reports an unusual green pigment, brochantite (Cu4(SO4)(OH)6), on 16th-century Portuguese-Flemish paintings, attributed to the Master Frei Carlos workshop. This green mineral is usually identified as an impurity or alteration product in the green pigments verdigris (Cu(CH3COO)2nCu(OH)2) or malachite (CuCO3 Cu(OH)2). However, after thorough investigation with a broad range of analytical techniques, it became clear that, in this case, brochantite was applied as a pigment. The abundance, pigment granulometry, and pigment morphology suggest intentional use by this Portuguese-Flemish Master as a natural pigment rather than its accidental use as an alteration product. This seems to be a distinguishable feature to other painters (Flemish and Portuguese) working in Portugal at the beginning of the 16th century.

The multi-analytical study of these easel paintings was first performed by physical imaging techniques and material characterization was carried out by optical microscopy, micro-Fourier-transform infrared-spectroscopy, micro-Raman spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, and micro-X-ray diffraction analysis (XRD).

Keywords

microanalysiseasel paintingsgreen pigmentbrochantite
Type
Materials Applications
Information
Microscopy and Microanalysis , Volume 21 , Issue 2 , April 2015 , pp. 518 - 525
Copyright
© Microscopy Society of America 2015 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Arafat, A., Náes, M., Kantarelou, V., Haddad, N., Giakoumaki, A., Argyropoulos, V., Anglos, D. & Karydas, A.-G. (2013). Combined in situ micro-XRF, LIBS and SEM-EDS analysis of base metal and corrosion products for Islamic copper alloyed artefacts from Umm Qais museum, Jordan. J Cultur Herit 14(3), 261–269.Google Scholar
Batoreo, M. (2004). Pintura Portuguesa do Renascimento. O Mestre da Lourinhã. casal de cambra: caleidoscópio.Google Scholar
Bersani, D., Antonioli, G., Lottici, P.P. & Casoli, A. (2003). Raman microspectrometric investigation of wall paintings in s. Giovanni Evangelista Abbey in Parma: A comparison between two artists of the 16th century. Spectrochim Acta A: Mol Biomol Spectrosc 59(10), 2409–2417.Google Scholar
Bersani, D., Lottici, P.P., Casoli, A. & Cauzzi, D. (2008). Pigments and binders in “Madonna col Bambino e S. Giovannino” by Botticelli investigated by micro-Raman and GC/MS. J Cultur Herit 9(1), 97–102.Google Scholar
Bouchard, M. & Smith, D.C. (2003). Catalogue of 45 reference Raman spectra of minerals concerning research in art history or archaeology, especially on corroded metals and coloured glass. Spectrochim Acta A Mol Biomol Spectrosc 59(10), 2247–2266.Google Scholar
Burgio, L. & Clark, R.J.H. (2001). Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation. Spectrochim Acta A Mol Biomol Spectrosc 57(7), 1491–1521.Google Scholar
Carvalho, J.A.S. (2009–2010). Casa perfeitíssima: Celebrating 500 years of the foundation of the Convent of Madre de Deus—1509–2009. Lisboa: Museu nacional do Azulejo, Ministério da Cultura, Instituto dos Museus e da Conservação. pp. 273–276.Google Scholar
Caetano, J.O. (1997). Quatro painéis do retábulo da Sé de Viseu. In Francisco Henriques, Um Pintor Em Evora No Tempo De D. Manuel I, pp. 185–188. [Lisbon]: CNCDP.Google Scholar
Caetano, J.O. (1998). O melhor oficial de pintura que naquele tempo havia. In O Tempo De Vasco Da Gama, Difel (Ed.), pp. 333–345. Lisboa: CNCDP.Google Scholar
Caetano, J.O. (2011). Mestres Luso-Flamengos em Evora—A pintura e o desenho. In Primitivos Portugueses 1450–1550—O Seculo de Nuno Goncalves, IMC/MNAA Athena/Babel (Eds.), pp. 276–293. Lisboa: IMC/MNAA.Google Scholar
Campbell, L. (forthcoming). Catalogue of sixteen century Netherlandish and French schools. New catalogue—National Gallery Publications.Google Scholar
Carvalho, J.A.S. (1988–1993). Pintura luso-flamenga em Évora no início do século XVI. O Mestre da Lamentação da Oficina do Espinheiro. In A Cidade de Évora, Câmara Municipal de Évora, pp. 75–104. Évora: C.M.Google Scholar
Carvalho, J.A.S. (1998). Frei Carlos e o outro. Proposições sobre a pintura da Oficina do Espinheiro. In C. D. Exposição Do Mundo Antigo Aos Novos Mundos. Humanismo, Classicismo E Notícias Dos Descobrimentos Em Évora 1516–1624, Mafalda Soares da Cunha, 155–169. Lisboa: CNCDP.Google Scholar
Carvalho, J.A.S. (2006). Frei carlos pintor no convento. In Convento do Espinheiro, Memória e Património, SPPTH (Ed.), pp. 186–231. Évora: Convento do Espinheiro Heritage Hotel & SPA.Google Scholar
Carvalho, J.A.S. (2011). Dois mestres luso-flamengos: mestre da lourinha e frei carlos. In Primitivos Portugueses 1450–1550—O Seculo de Nuno Goncalves, mnaa & Athena/Babel (Eds.), pp. 156–173. Lisboa: IMC/ MNAA.Google Scholar
Carvalho, J.A.S. (2013). O São Vicente de Frei Carlos. In O Frei Carlos da América: Investigação e crítica, MNAA, 41–55. Lisboa: Museu Nacional de Arte Antiga.Google Scholar
Castro, K., Sarmiento, A., Martínez-Arkarazo, I., Madariaga, J.M. & Fernández, L.A. (2008). Green copper pigments biodegradation in cultural heritage: From malachite to moolooite, thermodynamic modeling, X-ray fluorescence, and Raman evidence. Anal Chem 80(11), 4103–4110.Google Scholar
Cennini, C.d.A. (Ed.) (1933). The Craftsman’s Handbook. The Italian ‘Il Libro dell’ Arte. New York: Dover Publications.Google Scholar
Coremans, P. (1954). ‘La technique des “primitifs flamands”, part III. Stud Conserv 1(4), 145–161.Google Scholar
Coremans, P., Gettens, R.J. & Thissen, J. (1952). La techniques des «primitifs flamands». Stud Conserv 1(1), 1–29.Google Scholar
Correia, Andreia M. et al. (2008). Characterization of Pousão Pigments and extenders by micro-X-ray diffractometry and infrared and Raman microspectroscopy. Analytical chemistry 80(5), 1482–1492.CrossRefGoogle ScholarPubMed
Couto, J. (1943). A pintura flamenga em Évora no século XVI. Variedade de estilos e de técnicas na obra atribuída a Frei Carlos. In Cidade de Évora, Câmara Municipal de Évora, 3–19. Évora: C.M.Google Scholar
Couto, J. (1955). A Oficina de Frei Carlos. Nova Colecção de Arte Portuguesa, Lisboa: Artis.Google Scholar
Doerner, M. (1934). The Materials of The Artist: And Their Use in Painting With Notes on The Techniques of The Old Masters. New York: Harcourt, Brace and Company.Google Scholar
Eastaugh, N. (2004). The Pigment Compendium: Optical Microscopy of Historical Pigments. Oxford/Boston: Elsevier/Butterworth-Heinemann.Google Scholar
Feller, R.L. & Roy, A. (1993). Artists’ Pigments: A Handbook Of Their History and Chara cteristics . Washington, DC: National Gallery of Art.Google Scholar
Fernandes, G. & Gaspar, M. (2012). Supergene copper alteration at miguel vacas mine, Ossa-Morena zone, Portugal, 2–6 september 2012. European Mineralogical Conference (Frankfurt am Main, Germany) Vol. 1, EMC2012-661-1, 2012.Google Scholar
Ferreira, M.J.P. (1963). A Sé do Funchal. Funchal: Junta Geral do Distrito Autónomo do Funchal. pp. 239–243.Google Scholar
FitzGerald, K.P., Nairn, J., Skennerton, G. & Atrens, A. (2006). Atmospheric corrosion of copper and the colour, structure and composition of natural patinas on copper. Corrosion Sci 48(9), 2480–2509.Google Scholar
Frost, R.L. (2003). Raman spectroscopy of selected copper minerals of significance in corrosion. Spectrochim Acta A Mol Biomol Spectrosc 59(6), 1195–1204.Google Scholar
Frost, R.L., Williams, P.A., Martens, W., Leverett, P. & Kloprogge, J.T. (2004). Raman spectroscopy of basic copper(II) and some complex copper(II) sulfate minerals: Implications for hydrogen bonding. Am Mineralogist 89(7), 1130–1137.Google Scholar
Gettens, G.L. & Stout, R.J. (1947). Painting Materials, A Short Encyclopedia. New York: D. Van Nostrand Co.Google Scholar
Gilbert, B., Denoel, S., Weber, G. & Allart, D. (2003). Analysis of green copper pigments in illuminated manuscripts by micro-Raman spectroscopy. Analyst 128(10), 1213–1217.CrossRefGoogle ScholarPubMed
Makreski, P., Jovanovski, G. & Dimitrovska, S. (2005). Minerals from macedonia: xiv. Identification of some sulfate minerals by vibrational (infrared and Raman) spectroscopy. Vibrational Spectrosc 39(2), 229–239.Google Scholar
Martens, W., Frost, R.L., Kloprogge, J.T. & Williams, P.A. (2003). Raman spectroscopic study of the basic copper sulphates—implications for copper corrosion and ‘bronze disease’. J Raman Spectrosc 34(2), 145–151.CrossRefGoogle Scholar
Martin, E., Duval, A. & Eveno, M. (1995). Une famille de pigments verts mal connue. TECHNE, no2, Réunion des musées nationaux. Paris: Laboratoire de recherche des musées de France.Google Scholar
Martin, E. & Eveno, M. (1992). Contribution to the study of old green copper pigments in easel paintings. In 3rd International Conference on Non-destructive Testing, Microanalytical Methods and Environment Evaluation for Study and Conservation of Works of Art, M. G. Gimma (Ed.), pp. 481–491. Viterbo.Google Scholar
Pérez-Alonso, M., Castro, K. & Madariaga, J.M. (2006). Investigation of degradation mechanisms by portable Raman spectroscopy and thermodynamic speciation: The wall painting of Santa María de Lemoniz (Basque Country, North of Spain). Analytica Chimica Acta 571(1), 121–128.Google Scholar
Pitarch, A., Ramón, A., Álvarez-Pérez, A. & Queralt, I. (2011). Characterization of “oil on copper” paintings by energy dispersive X-ray fluorescence spectrometry. Anal Bioanal Chem 402(4), 1481–1492.Google Scholar
Santos, A.V. (1971). Pintura Luso-Flamenga. In Dicionário de Pintura Universal—Pintura Portuguesa, volume III, Lisboa: Estúdios Cor.Google Scholar
Schmidt, M. & Lutz, H.D. (1993). Hydrogen bonding in basic copper salts: A spectroscopic study of malachite, Cu2(OH)2CO3, and brochantite, Cu4(OH)6SO4 . Phys Chem Miner 20(1), 27–32.Google Scholar
Stoch, A., Stoch, J., Gurbiel, J., Cichocinska, M., Mikolajczyk, M. & Timler, M. (2001). FTIR study of copper patinas in the urban atmosphere. J MolStruct 596(1–3), 201–206.Google Scholar
van den Berg, K.J., van Eikema Hommes, M.H., Groen, K.M., Boon, J.J. & Berrie, B.H. (2000). On copper green glazes in paintings. In Art et Chimie, la Couleur: Actes du congrès, Goupy J. & Paris J.-P. M. (Eds.), pp. 18–23. Paris: CNRS Editions.Google Scholar
Van Der Marel, H.W. & Beutelspacher, H. (Eds.) (1976). Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures. Amsterdam: Elsevier.Google Scholar
Westermann, E. (1999). Copper production, trade and use in Europe from the end of the fifteenth century to the end of the eighteenth century. In Copper As Canvas: Two Centuries of Masterpiece Paintings on Copper 1575–1775, Phoenix Art Museum, 117–130. New York: Oxford University Press, Inc.Google Scholar
Zamana, L.V. & Usmanov, M.T. (2007). Thermodynamic and hydrogeochemical formation conditions of brochantite as a crystalline hydrate: A case of the Udokan copper deposit. Doklady Earth Sci 413(1), 269–271.CrossRefGoogle Scholar
Zittlau, A.H., Shi, Q., Boerio-Goates, J., Woodfield, B.F. & Majzlan, J. (2013). Thermodynamics of the basic copper sulfates antlerite, posnjakite, and brochantite. Chemie der Erde—Geochemistry 73(1), 39–50.Google Scholar