Analytical Techniques Applied to the Study of Industrial Archaeology Heritage: The Case of Plaiko Zubixe Footbridge

[EN] In this work, micro-Raman spectroscopy and micro-energy-dispersive X-ray fluorescence spectroscopy (µ-EDXRF) were applied on microsamples taken from the Plaiko Zubixe footbridge (1927) located in Ondarroa (Basque Country, Spain) in order to investigate the original paint coating and make an evaluation of the conservation state before its restoration. Elemental and molecular images were acquired for the study of the compounds distribution. Some modern pigments such as phthalocyanine blue and green pigments, minium, calcium carbonate, Prussian blue, and hematite were identified. Barium sulfate and titanium dioxide were recognized as opacifier agents. Thanks to the study of the stratigraphies, it has been possible to determine the original paint layer, which includes lead white, ultramarine blue, carbon black, and barium sulfate. In addition, colorimetric analyses made it possible to know the CIELab values of the original layer in order to reproduce the original colour during the planned restoration work. The massive presence of chlorine detected by µ-EDXRF and the corrosion products of the rust layer, in particular akaganeite and hematite, highlighted the atmospheric impact in the conservation of the bridge because they were due to the effect of both marine aerosol and to the presence of acidic components in the environment coming from anthropogenic activity. This work demonstrated the usefulness of a scientific approach for the study of industrial archaeology heritage with the aim to contribute to its conservation and restorationThis research was funded by DEMORA project (Grant No. PID2020-113391GB-I00), funded by the Spanish Agency for Research (through the Spanish Ministry of Science and Innovation, MICINN, and the European Regional Development Fund, FEDER)

Geochemical study of the Northwest Africa 6148 Martian meteorite and its terrestrial weathering processes

The number of studies of Mars geology through the geochemical analysis of Martian meteorites has been increasing in the last years because of the amount of information that can be obtained about the planet. In this study, a Martian meteorite, the Northwest Africa 6148 nakhlite, has been analysed and characterised, as there were few studies about it. After analysing it by Raman spectroscopy and Scanning Electron Microscope–Energy Dispersive X-ray Spectroscopy coupled to the Structural and Chemical Analyser interface, augite and olivine were identified as the main mineral phases of the sample. Moreover, using the Raman bands position, both minerals’ metal proportions were estimated. This methodology used in meteorite studies provides good semi-quantitative results and can offer some advantages to other techniques. In addition, calcite was found, being associated with Earth weathering processes. Surprisingly, Co3O4 was detected in the matrix of the meteorite. This is the first time that this oxide is observed in ameteorite. Itwas not possible to determine if it is an original compound fromMars or a product of a weathering process on Earth. However, whichever the case may be, solely the presence of this cobalt oxide represents a relevant finding, as it could provide a deeper knowledge of theMartian geochemistry or the Earth weathering processes. Copyright © 2017 John Wiley & Sons, Ltd.Proyecto MINECO Retos de la Sociedad. Ref. ESP2014-56138-C3-2-

Spectroscopic analysis used to uncover the original paint colour of the Helsinki Government Palace tower clock faces

The paint stratigraphy of the two clock faces from the tower clock of the Government Palace in Helsinki (Finland) was analysed in order to determine their original colour before restoration works. Paint cross-section samples from both clock faces were analysed by confocal Raman microscopy and scanning electron microscopy coupled to an energy dispersive X-ray spectrometer (SEM-EDS). The results revealed the complex superimposition of paint layers applied over the original black colour. FTIR/ATR analyses proved that the original paint was prepared with linseed oil-resin media. Most likely not all of the different layer colours were visible. Some of the layers were likely to have been a primer or for rust protection.Peer reviewe

Detection of organic compounds in impact glasses formed by the collision of an extraterrestrial material with the Libyan Desert (Africa) and Tasmania (Australia)

Impact glasses are rich silica melted formed at high temperature and pressure by the impact of an extraterrestrial body on Earth. Here, Libyan Desert glasses (LDGs) and Darwin glasses (DGs) were studied. Two non-destructive analytical techniques were used to detect and characterize organic compounds present in their inclusions: Raman spectroscopy and scanning electron microscopy coupled to energy-dispersive X-ray spectroscopy (SEM-EDS). Phytoliths, humboldtine, palmitic acid, myristic acid, oleic acid, 4-methyl phthalic acid, and S-H stretching vibrations of amino acids were identified. The presence of these particular organic compounds in such materials has not been reported so far, providing information about (a) the ancient matter of the area where the impact glasses were formed, (b) organic matter belonging to the extraterrestrial body which impacted on the Earth, or (c) even to current plant or bacterial life, which could indicate an active interaction of the LDG and DG with the surrounding environment. Moreover, the identification of fullerene allowed us to know a pressure (15 GPa) and temperatures (670 K or 1800– 1900 K) at which samples could be subjected.Proyecto MINECO Retos de la Sociedad. Ref. ESP2014-56138-C3-2-

Non-Destructive Analytical Investigation of Decorative Wallpapers Samples of the Nineteenth Century before Their Restoration

In this work, decorative wallpapers (19th century) from an historical palace located in Oiartzun (Basque Country, Spain) were analyzed before their restoration. Micro-energy dispersive X-ray fluorescence spectroscopy, Raman spectroscopy, and attenuated total reflectance infrared spectroscopy were used to investigate the elemental and molecular composition of pigments, the presence of binders, and the state of conservation of the paper support. The aim of the investigation was trying to understand the possible degradation pathways and identify the raw materials in order to choose the best restoration protocol according to the original aspect of wallpapers. As stated from both the elemental distribution and the identification of mineral phases by Raman spectroscopy, the most used pigment was lead chromate. It was mixed with other pigments such as ultramarine blue, zinc chromate, hematite, and atacamite among others to obtain different shades and they were applied mixed with an animal glue. Brass, identified thanks to elemental micro-EDXRF maps, was employed as a shiny decorative element. In addition, a partial degradation of cellulose was detected due to its natural ageing, the acidic nature of lignin, and to a phenomenon of humidity of the walls. Probably the deposition of black particulate matter was the cause of the darkening of the painting surfaces.This work has been funded by the DEMORA project (Grant No. PID2020-113391GB-I00), funded by the Spanish Agency for Research (through the Spanish Ministry of Science and Innovation, MICINN, and the European Regional Development Fund, FEDER) I. Costantini thanks their post-doctoral contracts from the University of the Basque Country (UPV/EHU)

Misinterpretation in microplastic detection in biological tissues: When 2D imaging is not enough

The presence of microplastics in the food chain is a public concern worldwide, and its analysis is an analytical challenge. In our research, we apply Raman imaging to study the presence of 1mum polystyrene microplastics in cryosections of Mytilus galloprovincialis due to its wide geographic distribution, widespread occurrence in the food web, and general high presence in the environment. Ingested microplastics are accumulated in the digestive tract, but a large number can also be rapidly eliminated. Some authors state that the translocation of microplastics to the epithelial cells is possible, increasing the risk of microplastics transmission along the food chain. However, as seen in our study, a surface imaging approach (2D) is probably not enough to confirm the internalization of particles and avoid misinterpretation. In fact, while some microplastic particles were detected in the epithelium by 2D Raman imaging, further 3D Raman imaging analysis demonstrated that those particles were dragged from the lumens to the epithelium during sample preparation due to the blade drag effect of the cryotome, and subsequently located on the surface of the analyzed cryosection, discarding the translocation to the epithelial cells. This effect can also happen when the samples are fortuitously contaminated during sample preparation. Several research articles that use similar analytical techniques have shown the presence of microplastics in different types of tissue. It is not our intention to put such results in doubt, but the present work points out the necessity of appropriate three-dimensional analytical methods including data interpretation and the need to go a step further than just surface imaging analysis.This work was funded by Basque Government (KK 2021/00001 ELKARTEK 2021/2022, IT1743-22); MINECO (PID 2020-118685RB-I00, PLASTeMER); further financial support by grant CEX2020-001038-M funded by MCIN/AEI/ 10.13039/50110001103

Multianalytical Approach to explain the darkening process of hematite pigment in paintings from ancient Pompeii after accelerated weathering experiments

[EN] In this paper, recently excavated fresco painting fragments from the House of Marcus Lucretius (Pompeii) and not exposed to the atmosphere since the eruption of the Mount Vesuvius were subjected to a controlled SO2 atmosphere and high relative humidity. These experiments were conducted in order to simulate under accelerated conditions the possible deterioration of the hematite pigment and plaster. The mineralogical transformation of the polychromy and plaster was monitored using mainly Raman spectroscopy, a non-destructive technique, but also infrared spectroscopy (FT-IR) and scanning electron microscopy energy-dispersive X-ray spectroscopy (SEM-EDS). After different exposure cycles to SO2, it was confirmed that hematite red pigment (Fe2O3) can be reduced into magnetite (Fe3O4), which provides the darkened colour to the pigment. While Fe(III) from hematite is reduced into Fe(II) or mixed Fe(III) and Fe(II), the SO2 can be oxidized (SO3) and hydrated to experience a subsequent wet deposition (H2SO4 aerosol) causing also the transformation of calcite into gypsum. Finally, it was assessed that high concentrations of SO2 can also cause the sulphation of hematite pigment promoting its transformation into paracoquimbite/coquimbite (Fe2(SO4)3$9H2O). Moreover, in some areas of the deteriorated painting fragments, non-expected iron(II) sulphate and sulphite species were also identified

Combined in situ XRF–LIBS analyses as a novel method to determine the provenance of central Mediterranean obsidians

This work presents a new calibration method for determining the provenance of obsidian artefacts based on the combined use of XRF and laser-induced breakdown spectroscopy (LIBS). At first, obsidian samples collected from the main Mediterranean sources were characterized using portable XRF and LIBS systems. After data treatment, elemental information was used to carry out principal component analysis (PCA) for each technique. Rb, Sr, Zr, Y and Fe elements, detected by using XRF, were found to be the key parameters enabling obsidians discrimination. Likewise, LIBS data helped differentiating the analysed patterns by the intensity of their main elemental components (Ca, Al, Mg and K). After selecting the key parameters detected by each technique, a new data matrix combining XRF and LIBS data was finally built. According to PCA results, the discrimination of Mediterranean sources based on combined XRF–LIBS data ensured a higher reliability over mono-analytical models, by increasing the Euclidean distance between sources projections over three-dimensional principal components plots. Knowing that the representativeness of elemental data could be compromised by the presence of superficial degradation products or deposition patinas, a shot-to-shot comparison of in-depth LIBS analyses is finally proposed as a method to disclose whether the spot under analysis was superficially contaminated or altered. Thus, the proposed strategy based on the combined use of portable XRF and LIBS spectrometers could be particularly useful for the in situ analysis of obsidian artefacts that underwent superficial alteration or could be covered by patina products.This work has been financially supported by the DEMORA project (Grant No. PID2020-113391GB-I00), funded by the Spanish Agency for Research (through the Spanish Ministry of Science and Innovation (Grant No. BIA2017-870´63-P), MICINN, and the European Regional Development Fund (Grant No. BIA2017-870´63-P), FEDER). I. Costantini gratefully acknowledges to the UPV/EHU for her postdoctoral contract. Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature

Non-destructive characterisation of the Elephant Moraine 83227 meteorite using confocal Raman, micro-energy-dispersive X-ray fluorescence and Raman-scanning electron microscope-energy-dispersive X-ray microscopies

The application of a non-destructive analytical procedure to characterise the mineral phases in meteorites is a key issue in order to preserve this type of scarce materials. In the present work, the Elephant Moraine 83227 meteorite, found in Antarctica in 1983 and originated from 4 Vesta asteroid, was analysed by micro-Raman spectroscopy, micro-energy-dispersive X-ray fluorescence and the structural and chemical analyser (Raman spectroscopy coupled with scanning electron microscopy-energy-dispersive spectroscopy) working in both point-by-point and image modes. The combination of all these techniques allows the extraction of, at the same time, elemental, molecular and structural data of the studied microscopic area of the meteorite. The most relevant results of the Elephant Moraine 83227 were the finding of tridymite for the first time in a 4 Vesta meteorite, along with quartz, which means that the meteorite suffered high temperatures at a certain point. Moreover, both feldspar and pyroxenewere found as the main mineral phases in the sample. Ilmenite, apatite, chromite and elemental sulphur were also detected as secondary minerals. Finally, calcite was found as a weathering product, which was probably formed in terrestrial weathering processes of the pyroxene present in the sample. Besides, Raman spectroscopy provided information about the conditions that the meteorite experienced; the displacements in some feldspar Raman bands were used to estimate the temperature and pressure conditions to which the Elephant Moraine 83227 was subjected, because we obtained both low and high formation temperature feldspar.Proyecto MINECO Retos de la Sociedad. Ref. ESP2014-56138-C3-2-

Development of a Novel Method for the In-Situ Dechlorination of Immovable Iron Elements: Optimization of Cl- Extraction Yield Through Experimental Design

The conservation of iron objects exposed to marine aerosol is threatened by the formation of akaganeite, a highly unstable Cl-bearing corrosion phase. As akaganeite formation is responsible of the exfoliation of the rust layer, chlorides trigger a cyclic alteration phenomenon that often ends with the total consumption of the iron core. To prevent this degradation process, movable iron elements (e.g. archaeometallurgical artefacts) are generally immersed in alkaline dechlorination baths. Aiming to transfer this successful method to the treatment of immovable iron objects, we propose the in-situ application of alkaline solutions through the use of highly absorbent wraps. As first step of this novel research line, the present work defines the best desalination solution to be used and optimizes its extraction yield. After literature review, a screening experimental design was performed to understand the single and synergic effects of common additives used for NaOH baths. Once the most effective variables were selected, an optimization design was carried out to determine the optimal conditions to be set during treatment. According to the experimental work here presented, the use of 0.7 M NaOH solutions applied at high temperatures (above 50 °C) is recommended. Indeed, these conditions enhance chloride extraction and iron leaching inhibition, while promoting corrosion stabilization.This work has been funded by the DEMORA project (Grant No. PID2020-113391GB-I00), funded by the Spanish Agency for Research (through the Spanish Ministry of Science and Innovation, MICINN, and the European Regional Development Fund, FEDER)