Mobile spectroscopic instrumentation in archaeometry research

Mobile instrumentation is of growing importance to archaeometry research. Equipment is utilized in the field or at museums, thus avoiding transportation or risk of damage to valuable artifacts. Many spectroscopic techniques are nondestructive and micro-destructive in nature, which preserves the cultural heritage objects themselves. This review includes over 160 references pertaining to the use of mobile spectroscopy for archaeometry. Following a discussion of terminology related to mobile instrumental methods, results of a literature survey on their applications for cultural heritage objects is presented. Sections devoted to specific techniques are then provided: Raman spectroscopy, X-ray fluorescence spectrometry, Fourier transform infrared spectroscopy, laser-induced breakdown spectroscopy, and less frequently used techniques. The review closes with a discussion of combined instrumental approaches

Assessment of conservation state of gothic wall paintings: from scientifc diagnostic to a new monitoring approach

El capítulo 9 está sujeto a confidencialidad por la autora. 210 p.La presente tesis doctoral se centra en el diagnostico de pinturas murales góticas que pertenecen al territorio vasco e italiano mediante el uso de metodologías no invasivas. Los escenarios investigados han sido, las pinturas murales conservadas en la iglesia de Sant Esteban de Ribera de Valderejo (Álava, País Vasco) y , las de la capilla de San Esteban en Montani (Bolzano, Italia). Gracias al uso de técnicas espectroscopícas portatiles, la caracterización elemental y molecular de la mayoría de los materiales constituyentes ha podido ser determinada in situ. Los resultados obtenidos evidencian la necesidad de realizar un estudio de diagnóstico científico, que permita caracterizar los materiales presentes (originales, modernos y de degradación), y establecer la influencia y acción del entorno. Solo de esta manera se podrán seleccionar métodos de restauración adecuados que eviten tratamientos incorrectos para su preservación. Además, los casos bajo estudio demuestran que no solo el impacto antropogénico es importante sino que el impacto en medios naturales, no agresivos, puede derivar a largo plazo en los mismos efectos perjudiciales, sin un plan de conservación adecuado. A la par, el estudio de las eflorescencias salinas mediante la aplicación del software PALME ha proporcionado información semicuantitativa, demostrando ser una herramienta sencilla, rápida y de gran utilidad en el estudio in situ. Por último, en la linea de investigación de dispositivos no invasivos para la detección y monitorización de los contaminantes atmosféricos, se ha desarrollado un dispositivo portátil de tecnología microfluídica para la detección de amonio en materiales pétreos, permitiendo así la toma de medidas protectoras en antelación al daño

Assessment of conservation state of gothic wall paintings: from scientifc diagnostic to a new monitoring approach

El capítulo 9 está sujeto a confidencialidad por la autora. 210 p.La presente tesis doctoral se centra en el diagnostico de pinturas murales góticas que pertenecen al territorio vasco e italiano mediante el uso de metodologías no invasivas. Los escenarios investigados han sido, las pinturas murales conservadas en la iglesia de Sant Esteban de Ribera de Valderejo (Álava, País Vasco) y , las de la capilla de San Esteban en Montani (Bolzano, Italia). Gracias al uso de técnicas espectroscopícas portatiles, la caracterización elemental y molecular de la mayoría de los materiales constituyentes ha podido ser determinada in situ. Los resultados obtenidos evidencian la necesidad de realizar un estudio de diagnóstico científico, que permita caracterizar los materiales presentes (originales, modernos y de degradación), y establecer la influencia y acción del entorno. Solo de esta manera se podrán seleccionar métodos de restauración adecuados que eviten tratamientos incorrectos para su preservación. Además, los casos bajo estudio demuestran que no solo el impacto antropogénico es importante sino que el impacto en medios naturales, no agresivos, puede derivar a largo plazo en los mismos efectos perjudiciales, sin un plan de conservación adecuado. A la par, el estudio de las eflorescencias salinas mediante la aplicación del software PALME ha proporcionado información semicuantitativa, demostrando ser una herramienta sencilla, rápida y de gran utilidad en el estudio in situ. Por último, en la linea de investigación de dispositivos no invasivos para la detección y monitorización de los contaminantes atmosféricos, se ha desarrollado un dispositivo portátil de tecnología microfluídica para la detección de amonio en materiales pétreos, permitiendo así la toma de medidas protectoras en antelación al daño

Visualization and mapping of literature on the scientific analysis of wall paintings: a bibliometric analysis from 2011 to 2021

As non-renewable cultural heritage, wall paintings play an important role in society. To reveal the trends in the scientific analysis of mural paintings, 845 relevant research articles published from 2011 to 2021 were collected from the Web of Science database and analyzed. The VOSviewer software was adopted to map the network data of scientific publications, so that relationships among authors, countries, institutions can be displayed, and the co-occurrence of keywords and co-citation can be analyzed. The results revealed close and strong interconnections between the top authors, suggesting a considerable strong research link in this field. The cooperation between research institutions was relatively close. The most productive country of relevant publications was Italy. The leading journals for the scientific analysis of wall paintings were Journal of Raman Spectroscopy and Journal of Cultural Heritage. At present, the hotspots of scientific analysis and research on wall painting are revealing the composition, distribution, origin, and deterioration mechanism of pigments, alongside with evaluating the effects and mechanism of conservation materials and techniques. On the one hand, a possible development direction in this field is introducing more cutting-edge analysis and data processing methods. On the other hand, scientific analysis is increasingly adopted to guide the research and development of mural conservation materials.Introduction Methodology Results and discussion - Analysis of publications - Article network analysis -- Analysis of author cooperation relationship -- Analysis of country cooperation -- Institutional analysis -- Journal analysis -- Keyword co‑occurrence and keyword cluster analysis - Analysis of frequently cited literatur

New methodologies for the characterisation and biodegradation assessment of mural paintings

Mural paintings are an ancient art form, with historic and cultural value, whose preservation is imperative. These artworks have suffered degradation, promoted by several agents, however, the contribution of the microorganisms on the paintings alteration has been undervalued. This work aimed the development of innovative strategies that allow to identify and characterise the role of the microorganisms in the degradation/deterioration of mural paintings. Complementary methodologies, including culture-dependent methods and molecular approaches were used, combining with microanalytical techniques to material characterisation. This enabled the development of novel analytical protocols for microbial population assessment. Following the characterisation of the microbial diversity, the metabolically active population were assessed by enzymatic markers and viability assays, in order to signalise the main biodeteriogenic agents involved in the biodeterioration of these heritage assets. Through simulation assays, using high cells density from the microbial isolates, complemented with in situ tests, it was possible to detect the presence of several alteration products namely oxalates, plattnerite and carotenoids, attributed to specific biodeteriogenic agents. Mitigation strategies, directed to the identified biodeteriogenic agents, were also developed; Novas metodologias para Caracterização e Avaliação da Biodegradação de pinturas murais Resumo: A pintura mural é uma ancestral forma de arte, com enorme valor histórico e cultural, cuja preservação é imperativa. Estas obras de arte têm sido alvo de degradação, provocada por diversos agentes, no entanto, a contribuição dos microrganismos para o processo de alteração das pinturas tem sido pouco valorizada. Este trabalho teve como objetivo o desenvolvimento de estratégias inovadoras que permitam identificar e caracterizar o papel dos microrganismos no processo de degradação/deterioração de pinturas murais. Metodologias complementares, incluindo métodos de cultura e abordagens moleculares, foram usadas em combinação com técnicas micro-analíticas de caracterização material, permitindo o desenvolvimento de protocolos analíticos inovadores para avaliação da população microbiológica. Após a caracterização da diversidade microbiológica avaliou-se a população metabolicamente ativa recorrendo a marcadores enzimáticos e testes de viabilidade celular para sinalizar os principais agentes biodeteriogénicos envolvidos na biodeterioração destes bens patrimoniais. Através de ensaios de simulação laboratorial, utilizando elevadas densidades celulares de isolados microbianos, complementadas com ensaios in situ, foi possível detetar a presença de diversos produtos de alteração nomeadamente oxalatos, platenerite e carotenoides, atribuídos a agentes biodeteriogénicos específicos. Foram ainda desenvolvidas estratégias de mitigação direcionadas para os agentes biodeteriogénicos identificados

Mural paintings characterisation using X-ray fluorescence and Raman spectroscopy-a case study: Nossa Senhora das Neves chapel, Vilar de Perdizes, Galicia-North Portugal Euroregion

Sixteenth-century mural paintings of Nossa Senhora das Neves in Vilar de Perdizes (Galicia—North Portugal Euroregion) were analysed. An iconographic study has allowed us to understand the meaning of the seven scenes that constitute the mural painting. X-ray fluorescence (XRF) and Raman spectroscopies determined the compounds used in this mural painting, both in the original and in later repaintings. The black paint was bone black. Hydroxyapatite characteristic bands and those of the associated phosphates have been identified. White lime was used as white paint. Lepidocrocite and goethite were used to make yellows, and hematite was used to make red shades. Cinnabar has been used for a later red repaint. Carbon-based compounds and rutile were used to create different tonalities by darkening or lightening colours. It is of great significance to obtain accurate and reliable mural painting information through scientific means, since preservation, restoration, and repainting without detailed information can be harmful to mural paintings.Fundação para a Ciência e Tecnologia | Ref. UIDB/00073/2020Fundação para a Ciência e Tecnologia | Ref. UIDP/00073/202

The fresco wall painting techniques in the Mediterranean area from Antiquity to the present: A review

Fresco wall paintings are one of the oldest artforms in our cultural heritage, dating back to the second millennium BC. In this work, we carry out a thorough review on the evolution of the fresco wall painting technique from Antiquity to the present day. Focused on the Mediterranean area, the aim is to gather in-depth information on different technological aspects of this decorative artform such as execution pro- cedure, materials used and pictorial palette. Considering that the recognition of the pictorial technique ( a fresco, a secco, or a mezzo fresco ) is often difficult since the identification of organic binders can be a challenging issue, the assignment of well-known non-alkaline-resistant pigments to the fresco technique might not always be precise. With this in mind, this review aims to highlight the contradictions found between the bibliographical sources on the fresco technique and recent scientific studies in relation to the preparation of materials, the execution on the wall and the incompatibility of certain pigments with the alkaline environment created by this pictorial technique.Research Projects PID2020-119838RA- I00 and ED431F 2022/07Xunta de Galicia project Limpeza sostible do patrimonio pictorico: optimizacion dos procesos de ablacion laser ( ED431F 2022/07 )Spanish Science and Innovation Ministry project RYC2020-028902-ISpanish Science and Innovation Ministry project RYC2020-028902-IState Research Agency (SRA)Ministry of Science and Innovation under the Research Project PID2020-119838RA-I00Junta de Andalucía Research Group RNM179Funding for open access charge: Universidade de Vigo/CISU

The fresco wall painting techniques in the Mediterranean area from Antiquity to the present: A review

Fresco wall paintings are one of the oldest artforms in our cultural heritage, dating back to the second millennium BC. In this work, we carry out a thorough review on the evolution of the fresco wall painting technique from Antiquity to the present day. Focused on the Mediterranean area, the aim is to gather in-depth information on different technological aspects of this decorative artform such as execution procedure, materials used and pictorial palette. Considering that the recognition of the pictorial technique (a fresco, a secco, or a mezzo fresco) is often difficult since the identification of organic binders can be a challenging issue, the assignment of well-known non-alkaline-resistant pigments to the fresco technique might not always be precise. With this in mind, this review aims to highlight the contradictions found between the bibliographical sources on the fresco technique and recent scientific studies in relation to the preparation of materials, the execution on the wall and the incompatibility of certain pigments with the alkaline environment created by this pictorial technique.Agencia Estatal de Investigación | Ref. PID2020-119838RA-I00Xunta de Galicia | Ref. ED431F 2022/07Agencia Estatal de Investigación | Ref. RYC2020-028902-IUniversidade de Vigo/CISU

Development of novel procedures for the preservation of archaeological irons and mural paintings

281 p.El objetivo principal de la tesis es desarrollar metodologías innovadoras para caracterizar y conservar el patrimonio cultural. Siguiendo un enfoque interdisciplinar, el desarrollo de dichas tecnologías responde a la necesidad de minimizar/controlar algunos de los procesos de degradación detectados durante el estudio analítico de dos diferentes tipologías de patrimonio; restos arqueológicos de naturaleza metálica y pinturas murales. En ambos casos, el protocolo analítico empleado consta de 3 fases distintas. En primera estancia, se ha realizado una evaluación química in situ mediante el uso complementario de técnicas analíticas no destructivas (XRF, LIBS, FTIR y Raman). Posteriormente, se aplicaron instrumentación de laboratorio (Raman, FTIR, XRD y SEM) y técnicas de cuantificación de sales solubles (cromatografía iónica, ICP-MS) para el estudio de micro-muestras con el fin de esclarecer los principales procesos de degradación. Basándose en el conocimiento adquirido en las dos primeras fases fue finalmente llevado a cabo el desarrollo de nuevos métodos y protocolos de conservación.En el caso de las piezas metálicas se ha desarrollado un nuevo método para semi-cuantificar las fases de hierro que más comunmente afectan a los hierros arqueológicos. Además, se ha optimizado la capacidad extractiva del método de desalinización (baño de NaOH) más empleado para la conservación de hierros afectados por infiltración de cloruros. En el caso de las pinturas murales, ha sido evaluado el posible uso de aceites esenciales como productos ecológico para inhibir el crecimiento de patinas biológicas.Este trabajo subraya el rol de la química analítica como herramienta indispensable para el desarrollo de metodologías innovadoras que faciliten la comprensión y el tratamiento de las patologías del patrimonio cultural

Characterization of Zahari Zograph's nave wall paintings in the church "The nativity of the virgin" of Rila Monastery (Bulgaria) by vibrational spectroscopy and SEM-EDX analysis

An analytical study on the nave mural paintings of the church “The Nativity of the Virgin” of Rila monastery, Bulgaria, painted by Zahari Zograph was carried out. Vibrational spectroscopy was applied to identify the pigments and organic materials used in the mural paintings. To complement the spectral information, elemental composition of the samples was determined by SEM-EDX. The data showed that smalt with carbohydrate binder was applied for the blue background, green colour was executed by green earths and red-orange colour – by red lead. Azurite is the pigment used to paint the blue colour of the saints’ hoods. The mordant for gilding was prepared of drying oil, resin and siccative metal oxides as evidenced by SEM-EDX, ATR-FTIR and pyrolysis GC-MS analysis. The use of azurite is related to Zahari Zograph’s works as it was not found in any of the previously studied murals in the church painted by other artists