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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

  • Sara Valadas (a1), Rita V. Freire (a1) (a2), Ana Cardoso (a1), José Mirão (a1), Cristina B. Dias (a1), Peter Vandenabeele (a3) and António Candeias (a1) (a4)...


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)2 nCu(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).


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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), 261269.
Batoreo, M. (2004). Pintura Portuguesa do Renascimento. O Mestre da Lourinhã. casal de cambra: caleidoscópio.
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), 24092417.
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), 97102.
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), 22472266.
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), 14911521.
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.
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. 185188. [Lisbon]: CNCDP.
Caetano, J.O. (1998). O melhor oficial de pintura que naquele tempo havia. In O Tempo De Vasco Da Gama, Difel (Ed.), pp. 333345. Lisboa: CNCDP.
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. 276293. Lisboa: IMC/MNAA.
Campbell, L. (forthcoming). Catalogue of sixteen century Netherlandish and French schools. New catalogue—National Gallery Publications.
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. 75104. Évora: C.M.
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, 155169. Lisboa: CNCDP.
Carvalho, J.A.S. (2006). Frei carlos pintor no convento. In Convento do Espinheiro, Memória e Património, SPPTH (Ed.), pp. 186231. Évora: Convento do Espinheiro Heritage Hotel & SPA.
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. 156173. Lisboa: IMC/ MNAA.
Carvalho, J.A.S. (2013). O São Vicente de Frei Carlos. In O Frei Carlos da América: Investigação e crítica, MNAA, 4155. Lisboa: Museu Nacional de Arte Antiga.
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), 41034110.
Cennini, C.d.A. (Ed.) (1933). The Craftsman’s Handbook. The Italian ‘Il Libro dell’ Arte. New York: Dover Publications.
Coremans, P. (1954). ‘La technique des “primitifs flamands”, part III. Stud Conserv 1(4), 145161.
Coremans, P., Gettens, R.J. & Thissen, J. (1952). La techniques des «primitifs flamands». Stud Conserv 1(1), 129.
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), 14821492.
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, 319. Évora: C.M.
Couto, J. (1955). A Oficina de Frei Carlos. Nova Colecção de Arte Portuguesa, Lisboa: Artis.
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.
Eastaugh, N. (2004). The Pigment Compendium: Optical Microscopy of Historical Pigments. Oxford/Boston: Elsevier/Butterworth-Heinemann.
Feller, R.L. & Roy, A. (1993). Artists’ Pigments: A Handbook Of Their History and Chara cteristics . Washington, DC: National Gallery of Art.
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.
Ferreira, M.J.P. (1963). A Sé do Funchal. Funchal: Junta Geral do Distrito Autónomo do Funchal. pp. 239–243.
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), 24802509.
Frost, R.L. (2003). Raman spectroscopy of selected copper minerals of significance in corrosion. Spectrochim Acta A Mol Biomol Spectrosc 59(6), 11951204.
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), 11301137.
Gettens, G.L. & Stout, R.J. (1947). Painting Materials, A Short Encyclopedia. New York: D. Van Nostrand Co.
Gilbert, B., Denoel, S., Weber, G. & Allart, D. (2003). Analysis of green copper pigments in illuminated manuscripts by micro-Raman spectroscopy. Analyst 128(10), 12131217.
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), 229239.
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), 145151.
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.
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.
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), 121128.
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), 14811492.
Santos, A.V. (1971). Pintura Luso-Flamenga. In Dicionário de Pintura Universal—Pintura Portuguesa, volume III, Lisboa: Estúdios Cor.
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), 2732.
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), 201206.
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. 1823. Paris: CNRS Editions.
Van Der Marel, H.W. & Beutelspacher, H. (Eds.) (1976). Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures. Amsterdam: Elsevier.
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, 117130. New York: Oxford University Press, Inc.
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), 269271.
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), 3950.



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