Mapeo de fluorescencia inducida por láser de pigmentos en murales secco pintados

María Auxiliadora  Gómez-Morón; Rocío  Ortiz; Franceso  Colao; Roberta  Fantoni; Javier Becerra Luna; Pilar  Ortiz

doi:10.37558/gec.v17i1.759

María Auxiliadora Gómez-Morón Instituto Andaluz del Patrimonio Histórico (IAPH), Seville, Spain
Rocío Ortiz Department Physical, Chemical and Natural Systems, University Pablo de Olavide, Seville, Spain
Franceso Colao Fusion and Technology for Nuclear safety and Security. Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA). Frascati, Italy
Roberta Fantoni Fusion and Technology for Nuclear safety and Security. Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA). Frascati, Italy.
Javier Becerra Luna Universidad Pablo de Olavide
Pilar Ortiz Department Physical, Chemical and Natural Systems, University Pablo de Olavide, Seville, Spain

DOI: https://doi.org/10.37558/gec.v17i1.759

Keywords: UV-Laser Induced Fluorescence, a secco technique database, surface mapping of pigments, smalt and carmine, non-invasive technique, cultural heritage application

Abstract

Laser-induced fluorescence is a remote analysis tool, successfully applied to real-time diagnosis of historical artworks, allowing the observation of features invisible to naked eye, as traces of retouches or presence of modern consolidants.

Aim of the present paper is to introduce an historical database of pigments with respective binders and consolidants, realized to support the remote identification and mapping of these materials onto a mural in the least invasive way. To this aim, a monochromatic ultraviolet laser source emitting at 266nm with remote scanning has been used in combination with reflectance. Wall painted models have been built with a secco technique according to traditional recipes of XVII century.

Digital image analysis, principal component analysis and spectral angle mapping have been carried out on data to get the mapping of two selected pigments, blue smalt and red carmine, in a real mural painting (XVII century). This non-invasive technique allowed us to operate remotely, a distance up to 11 m from the artwork. Results are consistent with traditional microanalysis performed to identity major pigments.

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Author Biographies

María Auxiliadora Gómez-Morón, Instituto Andaluz del Patrimonio Histórico (IAPH), Seville, Spain

BSc Chemistry 1989-1994 and Master “Quimilaser.Laser application in Chemistry” 2012 (University of Sevilla). Member, since 2016, of the project “Art-Risk (Artificial Intelligence applied to preventive conservation of heritage buildings)” to investigate and develop a new computerized tool for preventive conservation of heritage in urban centres based on models of artificial intelligence. Art-Risk will be available to organizations and companies dedicated to the restoration and rehabilitation. Member, since 1995, of the research group “Remote Sensing and Geochemistry”, with long-term experience in the research line in Archaeometry. Socrates grant at the University la Sapienza, where she worked in the project “Testaccio” (1999). An 18 months training grant at the IAPH (Andalusian Institution for Historical Heritage), from 1.11.1999 to 30.4.2001. A grant for conservation and restoration of cultural heritage at the Institution for Spanish Historical Heritage (2001). Since 2001, she works at IAPH (Andalusian Institution for Historical Heritage), where she takes part in projects such as Giraldillo’s restoration and is responsible of the project for application of non-destructive analytical techniques for Historical Heritage. Part time professor at University Pablo de Olavide (Sevilla) since 2009, where she has taught three editions of the on-line course of non-destructive analytical techniques for Historical Heritage.

Rocío Ortiz, Department Physical, Chemical and Natural Systems, University Pablo de Olavide, Seville, Spain

Graduated in Architecture in 2001, she obtained a Master’s degree in Protection of Built Heritage with a project oriented to a case study in Marchena in 2012. In 2014 she earned a Ph.D with European mention in University Pablo de Olavide (Seville).

She is currently working as Professor at the UPO, where she develops research focus on the fields of: Preventive Conservation; Risks and Vulnerability of Patrimony

She is also director of the Mater in Diagnosis of the state of preservation of Cutural Heritage and is responsible of the area of crystallography and mineralogy of the same University.

Dr. Ortiz’s expertise is in diagnosis of Cultural Heritage, management, e-learning, and her scientific works appeared in 30 books, conference proceedings, and journals. Her research projects have been supported by the European Union, national and regional governments, and private organizations.

Dr. Ortiz’s research interests have focused on risk and vulnerability of Cultural Heritage, GI applied to Cultural Heritage studies, Construction materials, Urban Planning and hazards and innovation in science teaching with the emphasis on cultural heritage diagnosis

Franceso Colao, Fusion and Technology for Nuclear safety and Security. Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA). Frascati, Italy

Senior Scientist, Technology Application for Security and Heath Division, Diagnostic and Metrology Laboratory (FSN-TECFIS-DIM).

Specialist in laser applications, signal processing and data acquisition, current interests concern the development of fluorescence lidar for the analysis of pigments, binders and consolidants.

Since 1987 he is researcher at ENEA, carrying out research in design and development of remote sensing laser-based systems for atmospheric studies. Known expert in the field of laser spectroscopy and diagnostics, including lidar for atmospheric studies, Raman spectroscopy, visible/UV emission spectroscopy, Laser Induced Fluorescence (LIF). He gained large experience of remote sensing systems for different applications: environmental control of pollutants, and remote diagnostic in the field of cultural heritage. Currently the main activities in the latter field are related to the development of fluorescence lidar, used to monitor the water quality (chemical and biochemical pollution) and the vegetation health (both on phytoplankton species and on green plants), cultural heritage (analysis of pigments, binders and consolidants), application of laser induced breakdown spectroscopy (LIBS) and lidar remote sensing of the statosphere.

He was involved in the study of LIBS and its application to the field of laser matter interaction and monitoring of soil and water. He has been responsible for several research projects, among these it is worth of mention the followings: application of LIBS to identification of asbestos’ fibres in environmental samples (ISPESL programme 2003-04), development of a LIBS system for extraterrestrial soil analysis (ASI programme 2001-02), study of polar stratospheric clouds by lidar remote sensing (2006, 2017-19), development of a LIBS system for use in hostile environment (MURST programme 2004-07) , development of an integrated system for drug discovery by laser spectroscopy (CUSTOM – EU FP7 2010-2012), development of LIF system for forensic investigation (FORLAB– EU FP7 2011-2013), development of standoff Raman system for prompt identification of explosive substances (NATO project RADEX 2014-16, EXTRAS 2018-20).

He has been tutoring of thesis and has given lectures to universities and research centers. The results of his researches have been presented at international conferences and published in peer review journals in more than fifty regulars.

Roberta Fantoni, Fusion and Technology for Nuclear safety and Security. Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA). Frascati, Italy.

Dr. Roberta Fantoni is the head of the division “Technology Applications for Security and Health” at Fusion and Technology for Nuclear Safety and Security (ENEA). Her role is to coordinate researches in the field of development of applications of ionizing and non-ionizing radiations, including processes and diagnostics based on lasers and particles (electrons, protons) beams for the Industry, Environment, Cultural Heritage and Bio-medicine, and Micro-Nanotechnology.

After a degree in chemistry she became a specialist in optoelectronics dealing with laser applications. She is a known expert in the field of laser spectroscopy and diagnostics. Major activities concern applications of the spectroscopic techniques as on-line diagnostics during different process. Recently she coordinated the regional project COBRA dedicated to innovation and technology transfer in Cultural Heritage conservation.

Author of 164 scientific papers of peer review papers and 25 book chapters in the field of spectroscopy and laser applications.

Javier Becerra Luna, Universidad Pablo de Olavide

PhD in History and Humanities: Europe, America, Arts and Language, degree in Conservation and Restoration and MSc Diagnosis of the State of Preservation of the Historical Heritage. Now, Javier is researcher at the Pablo de Olavide University in Seville, Spain. His research activity has focused on a) studies of new conservation-restoration treatments, especially based on nanomaterials b) vulnerability and risk studies in cultural heritage and c) diagnosis, analytical techniques and interventions in cultural heritage. This scientific production has resulted in a patent, 15 journal publications (10 in high impact indexed journals) and 12 book chapters. The results of the investigations carried out have been presented at 10 international conferences with a total of 18 communications.

He has collaborated in the diagnosis of samples from national and international monuments (Villa Adriana in Rome, Medina Azahara, archaeological museum of Écija, churches in Seville, contemporary buildings in La Havana, historical buildings in Oxford and Panama City, etc.) and has participated in analytical reports of national and international artworks requested from institutions such as the Andalusian Institute of Historical Heritage or the Pablo de Olavide University.

Finally, his research activity has been recognized with different awards at national and international level.

Pilar Ortiz, Department Physical, Chemical and Natural Systems, University Pablo de Olavide, Seville, Spain

The research and teaching experience developed has been focused on the diagnosis, preservation and conservation of cultural heritage. For this task, she has collaborated with museums and cultural institutions, such as the IVCR+i, IAPH, Cádiz Museum, Écija Museum, etc. Additionally, I have developed works related to cultural heritage issues in several countries, i.e., the United Kingdom, Belgium, Italy, Romania, Cuba, Peru, Colombia, Panama, etc. Her scientific production can be summarized in 38 publications on indexed journals; 50 books and book chapters, more than 25 attendances to international congresses, chairman and member of scientific committee in several international congresses, etc. She has worked at the University of Amberes (Belgium) as assistant lecturer, invited professor at the University of Oxford (UK), and invited researcher at ENEA (Italy).

She has participated in 24 national and international projects, contracts and agreements and has the head researcher in 16 of those projects, highlighting a Project of Excellence of the Junta de Andalucía, a RETOS project of the Government of Spain, an International Cooperation project of the Junta de Andalucía and International Erasmus+.

She has opened and leadership important research lines as the application of Lasers techniques for in situ diagnosis in cultural heritage materials, the development of non-destructive techniques for diagnosis of cultural heritage, or the application of risk maps, vulnerability index and artificial intelligence to the preventive conservation of cultural heritage.

Dr. Ortiz is member of the International Excellency Campus of the University of Jaén in cultural and natural heritage, of the “Cambio” work group in the International Excellency Campus of the Pablo de Olavide University (UPO), of the Andalusian Council of Cultural Heritage and Dean of the faculty of Experimental Sciences of the UPO.

References

ACQUAVIVA, S, D’ANNA, E, DE GIORGI, ML, DELLA PATRIA, A & PEZZATI, L. 2008. Optical characterization of pigments by reflectance spectroscopy in support of UV laser cleaning treatments. Applied Physics A. 92(1):223–227.

AENOR. 2014. UNE-EN 16085. Conservation of Cultural property. Methodology for sampling from materials of cultural property. General rules.

ANGLOS, D, SOLOMIDOU, M, ZERGIOTI, I, ZAFIROPULOS, V, PAPAZOGLOU, TG & FOTAKIS, C. 1996. Laser-Induced Fluorescence in Artwork Diagnostics: An Application in Pigment Analysis. Applied Spectroscopy. 50(10):1331–1334.

BORGIA, I, FANTONI, R, FLAMINI, C, DI PALMA, TM, GUIDONI, AG, MELE, A, GIARDINI GUIDONI, A & MELE, A. 1998. Luminescence from pigments and resins for oil paintings induced by laser excitation. Applied Surface Science. 127–129:95–100.

BRUNI, S, CARIATI, F, CONSOLANDI, L, GALLI, A, GUGLIELMI, V, LUDWIG, N & MILAZZO, M. 2002. Field and Laboratory Spectroscopic Methods for the Identification of Pigments in a Northern Italian Eleventh Century Fresco Cycle. Applied Spectroscopy. 56(7):827–833.

BURRAFATO, G, CALABRESE, M, COSENTINO, A, GUELI, AM, TROJA, SO & ZUCCARELLO, A. 2004. ColoRaman project: Raman and fluorescence spectroscopy of oil, tempera and fresco paint pigments. Journal of Raman Spectroscopy. 35(10):879–886.

CANEVE, L, COLAO, F, FIORANI, L & PALUCCI, A. 2010. Patent No. RM2010A000606.

CARCAGNÌ, P, DELLA PATRIA, A, FONTANA, R, GRECO, M, MASTROIANNI, M, MATERAZZI, M, PAMPALONI, E & PEZZATI, L. 2007. Multispectral imaging of paintings by optical scanning. Optics and Lasers in Engineering. 45(3):360–367.

CARDON, D. 2007. Natural Dyes - Sources, Tradition, Technology and Science. Lon-don, U.K.: Archetype Publications Ltd.

CECCHI, G, PANTANI, L, RAIMONDI, V, TOMASELLI, L, LAMENTI, G, TIANO, P & CHIARI, R. 2000. Fluorescence lidar technique for the remote sensing of stone monuments. Journal of Cultural Heritage. 1(1):29–36.

CENNINI, C. 1859. Il libro dell’arte, o Trattato della pittura. G. Milanesi. & F. Le Monnier, Eds. Firenze.

COLAO, F, FANTONI, R, FIORANI, L & PALUCCI, A. 2007. Patent No. RM2007A000278.

COLAO, F, CANEVE, L, FANTONI, R, FIORANI, L, PALUCCI, A, FANTONI, R & FIORANI, L. 2008. Scanning hyperspectral lidar fluorosensor for fresco diagnostics in laboratory and field campaigns. In Lasers in the Conservation of Artworks - Proceedings of the International Conference LACONA 7. CRC Press. 149–155.

COMELLI, D, D’ANDREA, C, VALENTINI, G, CUBEDDU, R, COLOMBO, C & TONIOLO, L. 2004. Fluorescence lifetime imaging and spectroscopy as tools for nondestructive analysis of works of art. Applied Optics. 43(10):2175–2183.

COMELLI, D, NEVIN, A, VALENTINI, G, OSTICIOLI, I, CASTELLUCCI, EM, TONIOLO, L, GULOTTA, D & CUBEDDU, R. 2011. Insights into Masolino’s wall paintings in Castiglione Olona: Advanced reflectance and fluorescence imaging analysis. Journal of Cultural Heritage. 12(1):11–18.

DOMINGO, C, SILVA, D, GARCÍA-RAMOS, J V., CASTILLEJO, M, MARTÍN, M, OUJJA, M, TORRES, R & SÁNCHEZ-CORTÉS, S. 2001. Spectroscopic Analysis of Pigments and Binding Media of Polychromes by the Combination of Optical Laser-Based and Vibrational Techniques. Applied Spectroscopy, Vol. 55, Issue 8, pp. 992-998. 55(8):992–998.

EASTAUGH, N, WALSH, V, CHAPLIN, T & SIDDALL, R. 2004. Pigment Compendium: A Dictionary of Historical Pigments - Nicholas Eastaugh, Valentine Walsh, Tracey Chaplin, Ruth Siddall - Google Books. 3th ed. New York: Elsevier Butterworth-Heinemann.

FANTONI, R, PALUCCI, A, RIBEZZO, S, BORGIA, I, BACCHI, E, CAPONERO, MA, BORDONE, A, BUSINARO, L, FERRI DE COLLIBUS, M, FORNETTI, GG & POGGI, C. 2000. Laser diagnostics developed for conservation and restoration of cultural inheritance. In SPIE Proceed. Conf. ALT’99. V. 4070. V.I. Pustovoy & V.I. Konov, Eds. Bellingham: V.I.
Pustovoy and V.I. Konov Eds. 2–7.

FANTONI, R, CANEVE, L, COLAO, F, FIORANI, L, PALUCCI, A, DELL’ERBA, R & FASSINA. 2013. Laser-induced fluorescence study of medieval frescoes by Giusto de’ Menabuoi. Journal of Cultural Heritage. 14(3 SUPPL):S59–S65.

FIORANI, L, CANEVE, L, COLAO, F, FANTONI, R, ORTIZ, P, GÓMEZ & MA, VÁZQUEZ. 2010. Real-Time Diagnosis of Historical Artworks by Laser-Induced Fluorescence. Advanced Materials Research. 133–134:253–258.

FOTAKIS, C, ANGLOS, D & COURIS, S. 1997. Laser Diagnostics of Painted Artworks: Laser-Induced Breakdown Spectroscopy in Pigment Identification. Applied Spectroscopy, Vol. 51, Issue 7, pp. 1025-1030. 51(7):1025–1030.

GIARDINI-GUIDONI, A, VENDITTELLI, M, FLAMINI, C, FANTONI, R, SCIUTI, S & MELE, A. 2000. Experimental comparison of three nondestructive testing diagnostics on pigments and ligands. In Proceedings of the SPIE, Volume 4070, p. 8-17 (2000). V. 4070. V.I. Pustovoy & V.I. Konov, Eds. 8–17.

GIROUARD, G, BANNARI, A, HARTI, A EL & DESROCHERS, A. 2004. Validated spectral angle mapper algorithm for geological mapping: comparative study between QuickBird and Landsat-TM. In XXth ISPRS Congress. Istambull. 599–604.

GÓMEZ MORÓN, MA. 2008. Analytical report of the paintings of the San Telmo vaults “Informe analítico de las pinturas de las bóvedas de San Telmo”. (Internal report). Sevilla (Spain).

ICOMOS. 2003. Principles for the preservation and conservation-restoration of wall paintings. Victoria Falls (Zimbabwe): 14a Asamblea General del ICOMOS.

DE LA RIE, ER 1982. Fluorescence of Paint and Varnish Layers (Part III). Studies in Conservation. 27(3):102.

LOGNOLI, D, LAMENTI, G, PANTANI, L, TIRELLI, D, TIANO, P & TOMASELLI, L. 2002. Detection and characterization of biodeteriogens on stone cultural heritage by fluorescence lidar. Applied optics. 41(9):1780–7.

LOGNOLI, D, CECCHI, G, MOCHI, I, PANTANI, L, RAIMONDI, V, CHIARI, R, JOHANSSON, T, WEIBRING, P, HEDNER, H & SVANBERG, S. 2003. Fluorescence lidar imaging of the cathedral and baptistery of Parma. Applied Physics B: Lasers and Optics. 76(4):457–465.

MIYOSHI, T. 1985. Fluorescence from Oil Colours, Linseed Oil and Poppy Oil under N2 Laser Excitation. Japanese Journal of Applied Physics. 24(Part 1, No. 3):371–372.

MOUNIER, A, LE BOURDON, G, AUPETIT, C, BELIN, C, SERVANT, L, LAZARE, S, LEFRAIS, Y & DANIEL, F. 2014. Hyperspectral imaging, spectrofluorimetry, FORS and XRF for the non-invasive study of medieval miniatures materials. Heritage Science. 2(1):24.

NABAIS, P, MELO, MJ, LOPES, JA, VITORINO, T, NEVES, A & CASTRO, R. 2018. Microspectrofluorimetry and chemometrics for the identification of medieval lake pigments. Heritage Science. 6(1):1–11. https://doi.org/10.1186/s40494-018-0178-1.

NEVIN, A & ANGLOS, D. 2006. Assisted Interpretation of Laser-Induced Fluorescence Spectra of Egg-Based Binding Media Using Total Emission Fluorescence Spectroscopy. Laser Chemistry. 2006:1–5.

NEVIN, A, CATHER, S, ANGLOS, D & FOTAKIS, C. 2006. Analysis of protein-based binding media found in paintings using laser induced fluorescence spectroscopy. Analytica Chimica Acta. 573–574:341–346.

OUJJA, M, VÁZQUEZ-CALVO, C, SANZ, M, DE BUERGO, MÁ, FORT, R & CASTILLEJO, M. 2012. Laser-induced fluorescence and FT-Raman spectroscopy for characterizing patinas on stone substrates. Analytical and Bioanalytical Chemistry. 402(4):1433–1441.

PACHECO, F. 1871. The Art of painting “El arte de la pintura”. Revised ed ed. Madrid: Librería de D. León Pablo Villaverde.

RAIMONDI, V, ANDREOTTI, A, COLOMBINI, MP, CUCCI, C, CUZMAN, O, GALEOTTI, M, LOGNOLI, D, PALOMBI, L, PICOLLO, M & TIANO, P. 2015. Test measurements on a secco white-lead containing model samples to assess the effects of exposure to low-fluence UV laser radiation. Applied Surface Science. 337:45–57.

RASHMI, S, ADDAMANI, S, VENKAT & RAVIKIRAN, S. 2014. Spectal Angle Mapper Algorithm for remote Sensing Image Classification. International Journal of Innovative Science, Engineering & Technology. 1(4):201–205.

RENCHER, AC. 2002. Methods of Multivariate Analysis. 2nd ed. New York: Wiley Interscience.

SIMONOT, L, THOURY, M & DELANEY, J. 2011. Extension of the Kubelka–Munk theory for fluorescent turbid media to a nonopaque layer on a background. Journal of the Optical Society of America A. 28(7):1349.

VERRI, G, CLEMENTI, C, COMELLI, D, CATHER, S & PIQUÉ, F. 2008. Correction of Ultraviolet-Induced Fluorescence Spectra for the Examination of Polychromy. Applied Spectroscopy. 62(12):1295–1302.