Development of in situ non destructive analytical methodologies for the conservation diagnosis of urban built heritage

226 p.Se desarrollan metodologías analíticas no destructivas para el diagnostico in situ del Patrimonio Construido afectado por factores ambientales. A lo largo del trabajo, la caracterización y severidad de daño sufrido por los materiales es evaluada en casos reales, prestando especial atención a establecer el origen y el proceso químico involucrado en las patologías, contribuyendo a la preservación. Además, para comprobar la efectividad de un innovativo método de conservación, se realiza su monitoreo a través de un enfoque multianalítico, evaluando su capacidad para reducir el deterioro así como, para determinar los requerimientos para su implementación.Las metas propuestas han sido logradas gracias al desarrollo de diferentes metodologías, destacando la utilidad de la espectroscopia Raman. Los hándicaps resultantes del análisis de campo han sido reducidos gracias a la implementación de DRIFT. Paralelamente, técnicas como SEM y XRF han sido propuestas para detectar la capacidad de penetración de los agentes de deterioro así como, IC para cuantificar la severidad del daño salino, de acuerdo a la legislación existente. A sí mismo, los datos cuantitativos son sometidos a estudios quimiométricos y termodinámicos con objeto de corroborar el análisis espectroscopico. Finalmente, dadas las diferencias observadas en los análisis por cambios estacionales, se llevo a cabo un estudio para describir el comportamiento del contenido salino bajo condiciones climáticas variables con objeto de seleccionar las acciones preventivas, evitando la necesidad de tomar decisiones solamente basadas en la experiencia del conservador

Development of in situ non destructive analytical methodologies for the conservation diagnosis of urban built heritage

226 p.Se desarrollan metodologías analíticas no destructivas para el diagnostico in situ del Patrimonio Construido afectado por factores ambientales. A lo largo del trabajo, la caracterización y severidad de daño sufrido por los materiales es evaluada en casos reales, prestando especial atención a establecer el origen y el proceso químico involucrado en las patologías, contribuyendo a la preservación. Además, para comprobar la efectividad de un innovativo método de conservación, se realiza su monitoreo a través de un enfoque multianalítico, evaluando su capacidad para reducir el deterioro así como, para determinar los requerimientos para su implementación.Las metas propuestas han sido logradas gracias al desarrollo de diferentes metodologías, destacando la utilidad de la espectroscopia Raman. Los hándicaps resultantes del análisis de campo han sido reducidos gracias a la implementación de DRIFT. Paralelamente, técnicas como SEM y XRF han sido propuestas para detectar la capacidad de penetración de los agentes de deterioro así como, IC para cuantificar la severidad del daño salino, de acuerdo a la legislación existente. A sí mismo, los datos cuantitativos son sometidos a estudios quimiométricos y termodinámicos con objeto de corroborar el análisis espectroscopico. Finalmente, dadas las diferencias observadas en los análisis por cambios estacionales, se llevo a cabo un estudio para describir el comportamiento del contenido salino bajo condiciones climáticas variables con objeto de seleccionar las acciones preventivas, evitando la necesidad de tomar decisiones solamente basadas en la experiencia del conservador

TECHNART 2017. Non-destructive and microanalytical techniques in art and cultural heritage. Book of abstracts

440 p.TECHNART2017 is the international biannual congress on the application of Analytical Techniques in Art and Cultural Heritage. The aim of this European conference is to provide a scientific forum to present and promote the use of analytical spectroscopic techniques in cultural heritage on a worldwide scale to stimulate contacts and exchange experiences, making a bridge between science and art. This conference builds on the momentum of the previous TECHNART editions of Lisbon, Athens, Berlin, Amsterdam and Catania, offering an outstanding and unique opportunity for exchanging knowledge on leading edge developments. Cultural heritage studies are interpreted in a broad sense, including pigments, stones, metal, glass, ceramics, chemometrics on artwork studies, resins, fibers, forensic applications in art, history, archaeology and conservation science. The meeting is focused in different aspects: - X-ray analysis (XRF, PIXE, XRD, SEM-EDX). - Confocal X-ray microscopy (3D Micro-XRF, 3D Micro-PIXE). - Synchrotron, ion beam and neutron based techniques/instrumentation. - FT-IR and Raman spectroscopy. - UV-Vis and NIR absorption/reflectance and fluorescence. - Laser-based analytical techniques (LIBS, etc.). - Magnetic resonance techniques. - Chromatography (GC, HPLC) and mass spectrometry. - Optical imaging and coherence techniques. - Mobile spectrometry and remote sensing

Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2+

The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2−, CdHL−, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3−, whose formation constant values at infinite dilution were log β = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCd ≥ CGLDA and concentrations of >0.1 mmol dm−3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration.The authors C.B., P.C., A.I., G.L. and C.D.S. thank the University of Messina for the Research and Mobility 2017 Project (cod. 009041). Authors thank COST action CA18202—Network for Equilibria and Chemical Thermodynamics Advanced Research for the support to this study. O.G.-L. is grateful to the project IT-742-13 for Consolidated Research Groups, funded by the Basque Country Government, for her post-doctoral contract

Sugar-derived bio-based resins as platforms for the development of multifunctional hybrids with potential application for stone conservation

This research is focused on the design of a bio-based epoxy-silica hybrid, enriched with SiO2 nanoparticles, to be used in stone conservation. For this purpose, isosorbide, a sugar derivative coming from renewable sources, was selected for the development of epoxy thermosets that were functionalized adding fixed amounts of silicaforming mixtures, to gain hybrid organic-inorganic networks. Fourier Transform Infrared (FTIR), Attenuated Total Reflection Infrared (ATR-FTIR) and Raman spectroscopies were exploited to follow the synthetic procedures, whereas the homogeneity of the networks was ascertained by scanning electron microscopy/energydispersive X-ray spectroscopy (SEM-EDS). The materials were investigated by thermogravimetric (TG-DTA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and contact angle measurements. Once the proper epoxy-silica product was identified, specifically synthesized nanoparticles were incorporated. The obtained nanocomposite showed excellent thermo-mechanical (Tonset, Tg and Tα of 327, 55.9 and 70.1 ◦C, respectively) and hydrophobic (105◦) properties making it a potential candidate for stone conservation.This work has been financially supported by the project PHETRUM (CTQ2017-82761-P) from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO) and by the European Regional Development Fund (FEDER). The authors gratefully acknowledge Open Access funding provided by University of Basque Country. P. Irizar gratefully acknowledges his predoctoral grant from the MINECO (PRE2018-085888). O. Gomez-Laserna is grateful to the projects IT-742-13 for Consolidated Research Groups, funded by the Basque Country Government, and PHETRUM (CTQ2017-82761-P) from the MINECO for her post-doctoral contract. P. Cardiano thanks the Italian Ministry of University and Research (MIUR), PON R&I project AGM for CuHe (ARS01_00697), for Contact Angle measurements. The authors are grateful to the technical support provided by the Raman-LASPEA laboratory, the Nuclear Magnetic Resonance laboratory and to the Macrobehaviour, Mesostructure, Nanotechnology: Unit of Materials and Surfaces of The Advanced Research Facilities of the SGIker (UPV/EHU, MICINN, GV/EJ, ERDF and ESF)

Non-Invasive Approach to Investigate the Mineralogy and Production Technology of the Mosaic Tesserae from the Roman Domus of Villa San Pancrazio (Taormina, Italy)

The archaeological excavations at Villa San Pancrazio (Taormina, Italy) are bringing to light a vast Roman-Imperial residential quarter featuring luxurious dwellings decorated with wall paintings and mosaic floors, pointing it out as one of the most significant archaeological sites of the city. The polychrome and black and white mosaics recovered date back to the middle Imperial period, during the 2nd century AD. This work deals with the first archaeometric investigations of the materials employed for the tesserae production with the aim of elucidating the mineralogical composition and obtaining analytical evidence that can contribute to extracting information related to their production technology. For that purpose, a non-invasive methodology, based on micro energy dispersive X-ray fluorescence (μ-EDXRF) spectrometry and Raman spectroscopy, was used to characterize a wide selection of stone, ceramic and glass tesserae. Chemometric tools were exploited to manage the large set of elemental data collected on black and white lithic samples, providing essential clues for the subsequent investigations. The results evidenced the employment of natural lithotypes (calcareous sedimentary, dolomitic and volcanic) local and imported, and also artificial materials, such as ceramic made firing magnesium-rich clays, soda-lime-silica glasses made with different opacifying and coloring agents (such as calcium antimoniate, cobalt and copper)This work was supported by project IT-742-13 for Consolidated Research Groups, funded by the Basque Country Government. P. Irizar gratefully acknowledges his predoctoral grant (PRE2018-085888) from the MINECO Spanish Ministry. O. Gómez-Laserna is grateful to the University of the Basque Country (UPV/EHU) for her postdoctoral contract. P. Cardiano also thanks University of Messina (FFABR UNIME 2020) for funding

Bio-based hybrid nanocomposites as multifunctional sustainable materials for stone conservation

This study was aimed at developing a sustainable versatile bio-based epoxy-silica material to be potentially employed as hydrophobic and biocidal consolidating product in the field of stone conservation. For this purpose, two hybrid formulations containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol diglycidylether (CBDO-DGE), a cycloaliphatic epoxy precursor derived from the arnica root, together with (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and octyltriethoxysilane (OcTES) as silica-forming additives, were chosen as the basis of the multifunctional material to be finely adjusted and gain biocidal properties. With this goal in mind, different synthetic strategies based on ionic liquids (ILs), essential oils (EOs) and nanoparticles (NPs) doping have been employed. Specifically, dimethyloctadecyl[3(trimethoxysilyl)propyl]ammonium chloride (QAS), tetradecyl phosphonium chloride (QPS) and thymol, as well as cerium-TiO2 NPs and thymol-loaded SiO2 NPs were incorporated into the starting hybrid formulations, during the sol-gel process, to investigate their influence on the network formation. First, distribution studies by scanning electron microscopy/energy-dispersive X-ray (SEM-EDS) analysis were performed, whereas the suitability of each formulation to match the main requirements for a stone conservation material was evaluated in terms of thermostability, hydrophobicity and inhibition of the microbiological growth by a combination of TG-DTA, DSC, dynamic mechanical analysis (DMA), with contact angle and disk-diffusion measurements, respectively. Based on the data analysis, it was observed that the direct incorporation of ILs and EOs had an adverse effect on the ability of GPTMS to act as a coupling agent. This resulted in decreased thermal stability and a 50 % reduction in glass transition temperatures, along with the retention of hydrophilic behavior. In contrast, the inclusion of NPs did not significantly interfere with the hybrid network formation, and effectively maintained the thermo-mechanical and hydrophobic properties of the hybrids within satisfactory parameters. Consequently, both nanocomposite materials were further tested on stone samples by artificial ageing experiments under acidic atmosphere. In view of the results, the hybrid enriched with thymol-loaded SiO2 NPs demonstrate the most suitable thermo-mechanical and hydrophobic properties (Tonset, Tα and CA values of 276 °C, 54 °C and 100°, respectively), as well as a proper biocidal capability against bacteria. Furthermore, the developed material provided effective stone protection, resulting in a 92 % reduction in material loss, while preserving the substrate chromatic characteristics (ΔE 2.23). These findings suggest that the proposed treatment meets the first main requirements for stone conservation.This work has been financially supported by the projects PHETRUM (CTQ2017-82761-P) and DEMORA (PID2020-113391GB-I00) from the Spanish Ministry of Economy, Industry and Competitiveness (MINECO) and the Spanish Ministry of Science and Innovation (MICINN), respectively, as well as by the European Regional Development Fund (FEDER). The authors gratefully acknowledge Open Access funding provided by University of Basque Country. P. Irizar gratefully acknowledges his predoctoral grant from the MINECO (PRE2018-085888). The authors are grateful to the technical support provided by the Raman-LASPEA laboratory, the Nuclear Magnetic Resonance laboratory and to the Macrobehaviour, Mesostructure, Nanotechnology: Unit of Materials and Surfaces of The Advanced Research Facilities of the SGIker (UPV/EHU, MICINN, GV/EJ, ERDF and ESF)

The potential of in situ Raman spectroscopy in the study of the health of cement-based materials of modern buildings during restoration works

Although Raman spectroscopy is a common technique for the analysis of cement-based materials in the research studies or in the field of Cultural Heritage to carried out multianalytical studies, it is not generally used as unique technique of a research or to carry out analysis during ordinary restoration works of modern urban buildings affected by environmental stressors. The disadvantages associated with Raman spectroscopy as fluorescence limits its implementation beyond research studies, more in the case of in situ equipment. However, the technological development allows high-quality results with in situ equipment, so its use could be useful during restoration works. Thus, this work demonstrates how the implementation of the correct methodology could lead to useful and fast results during restoration works. The proposed methodology is based on the use of in situ analysis (screening) on the scaffolding, followed by the sampling of layers based on the previous screening and a posterior exhaustive laboratory analysis. The research has been conducted during the restoration works of a reinforced concrete building in which the attack of atmospheric acid gases (CO2, SO2, and NOx) was identified as the main affection suffered, and the fixed sulfates were the most important intermediary compounds of decaying processes. Many of the pollutants and decaying compounds were even identified during the in situ analysis, improving the anticipation and responsiveness. Therefore, this methodology allows the understanding of the chemistry of the materials to evaluate its health state in a fast and reliable way.Spanish Agency for Research AEI (MICINN/FEDER-UE), Grant/Award Number: PID2020-113391GB-I0

TECHNART 2017. Non-destructive and microanalytical techniques in art and cultural heritage. Book of abstracts

440 p.TECHNART2017 is the international biannual congress on the application of Analytical Techniques in Art and Cultural Heritage. The aim of this European conference is to provide a scientific forum to present and promote the use of analytical spectroscopic techniques in cultural heritage on a worldwide scale to stimulate contacts and exchange experiences, making a bridge between science and art. This conference builds on the momentum of the previous TECHNART editions of Lisbon, Athens, Berlin, Amsterdam and Catania, offering an outstanding and unique opportunity for exchanging knowledge on leading edge developments. Cultural heritage studies are interpreted in a broad sense, including pigments, stones, metal, glass, ceramics, chemometrics on artwork studies, resins, fibers, forensic applications in art, history, archaeology and conservation science. The meeting is focused in different aspects: - X-ray analysis (XRF, PIXE, XRD, SEM-EDX). - Confocal X-ray microscopy (3D Micro-XRF, 3D Micro-PIXE). - Synchrotron, ion beam and neutron based techniques/instrumentation. - FT-IR and Raman spectroscopy. - UV-Vis and NIR absorption/reflectance and fluorescence. - Laser-based analytical techniques (LIBS, etc.). - Magnetic resonance techniques. - Chromatography (GC, HPLC) and mass spectrometry. - Optical imaging and coherence techniques. - Mobile spectrometry and remote sensing

Raman imaging spectroscopic solutions for microplastics advanced analysis: Insights from Choqueyapu river basin (La Paz, Bolivia)

Microplastics (MPs) are causing global concern due to their role as vectors of environmental contaminants. Evaluating their impact on environmental compartments, particularly in sediment and freshwaters, remains challenging due to difficulties in gathering chemical and morphological data. In fact, the analytical process can vary depending on the matrix considered, the non-homogeneous characteristics of MPs, and the targeted size range. Sample treatment is crucial for sediments and waters, requiring a balance between matrix removal and preservation of the MPs. Consequently, MPs often remain embedded in significant amounts of the original matrices, compromising their characterisation. In this regard, Raman spectroscopy shows promise for their comprehensive molecular analysis. However, overcoming the drawbacks associated with fluorescence from organic matter, feldspar, or clays requires considerable effort. Effective signal acquisition necessitates fine-tuning parameters, including background reduction and signal-to-noise ratio amplification. Moreover, data handling involved in chemical scanning large surfaces at high resolution is a challenging task. To overcome these drawbacks, chemometrics have demonstrated high efficacy in processing and extracting targeted information. The application of chemometrics could be relevant in environmental studies due to the large number of samples, the complexity of signal acquisition, and the dataset volumes managed. As such, this study proposes spectroscopic analytical solutions, augmented by chemical imaging and algorithmic processing, for advanced MPs analysis. A spectroscopic working approach was devised and tested through a real case study conducted in the Choqueyapu River basin (La Paz, Bolivia). This methodology allowed the morphological, molecular and quantitative identification of over 44 particles/L and 91 MPs particles/kg, in water and sediment, respectively, consisting of PE, PET, PP, PS and PMMA. MP abundance varied significantly across studied areas, spanning 2 to 4 orders of magnitude. PET fibres predominated in freshwaters, while Lipari Sector sediments were hotspots for PE and PS fragments.This work has been financially supported by the Spanish Ministry of Science and Innovation (MCIN) project PLASTEMER (PID2020-118685RB-I00), by the Basque Government project “Consolidated Research Group 2022-2025 (IT1446-22) and by the European Regional Development Fund (FEDER). T. Maupas gratefully acknowledges his predoctoral grant contract from the University of the Basque Country (UPV/EHU). U. Uribe-Martinez also thanks the Consolidate Group (IT1446-22) project from the Basque Government for her predoctoral contract. D. Salazar thanks the Erasmus mundus program for the European MSc in Environmental Science: Chemicals in the Environment (ECT+) Program (SGA 2019-1485)