Use of portable devices and confocal Raman spectrometers at different wavelength to obtain the spectral information of the main organic components in tomatoes (Solanum Lycopersicum) fruits

Tomato (Solanum lycopersicum) fruit samples, in two ripening stages, ripe (red) and unripe (green), collected from a cultivar in the North of Spain (Barrika, Basque Country), were analyzed directly, without any sample pretreatment, with two different Raman instruments (portable spectrometer coupled to a micro-videocamera and a confocal Raman microscope), using two different laser excitation wavelengths (514 and 785 nm, only for the confocal microscope). The combined use of these laser excitation wavelengths allows obtaining, in a short period of time, the maximum spectral information about the main organic compounds present in this fruit. The major identified components of unripe tomatoes were cutin and cuticular waxes. On the other hand, the main components on ripe tomatoes were carotenes, polyphenoles and polysaccharides. Among the carotenes, it was possible to distinguish the presence of lycopene from b-carotene with the help of both excitation wavelengths, but specially using the 514 nm one, which revealed specific overtones and combination tones of this type of carotene.This work has been financially supported by Research Project S-PE11-UN128 of the Basque Country government. Technical and support provided by SGIker (UPV/EHU, MICINN, GV/EJ, ESF) is gratefully acknowledged

A non-invasive study of the effect of three commercial cleaning products on shellac-coated mahogany

The Royal Palace of Norway has a large 19th century wooden furniture collection and most of it is coated with shellac-based varnishes. Since these objects are part of the royal collections, they are still in daily use at the different residences and, therefore, need to be frequently cleaned. In this work, the effect of three cleaning commercial products (Baolin, Centurio, Fulgentin) used at the royal collections on shellac-coated mahogany is investigated for the first time. A non-invasive methodology (portable ER-FTIR spectroscopy and colorimetry) was applied to assess whether the chemical composition and the color of fresh and artificially aged mahogany wood mock-ups coated with shellac were affected by the above-mentioned cleaning products. This study shows that one of them causes changes in the varnished wood, thus potentially affecting the long-term conservation of this furniture collection.This work has been supported by grant TED2021-129299A-I00, funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGenerationEU/PRTR

Nature and origin of white efflorescence on bricks, artificial stones, and joint mortars of modern houses evaluated by portable Raman spectroscopy and laboratory analyses

Bricks and mortar currently constitute one of the most important building materials used in the construction of most modern facades. The deterioration of these materials is caused primarily by the impact of numerous external stressors, while poor manufacturing quality, particularly of mortars, can also contribute to this process. In this work, the non-invasive Raman spectroscopy technique was used to identify the recently formed deterioration compounds (primarily sulfates and nitrates) in bricks, artificial stones, and joint mortars from detached houses in the Bilbao metropolitan area (Basque Country, North of Spain), as well as to investigate the deterioration processes taking place in these materials. Additionally, to confirm and in some cases complement the results obtained with Raman spectroscopy, SEM-EDS and XRD measurements were also carried out.This work was financially supported by DEMBUMIES (ref.BIA2011-28148) and funded by the Spanish Ministry of Economy and Competitiveness (MINECO). H. Morillas is grateful to the University of the Basque Country (UPV-EHU) and particularly to the UFI 11-26 Global Change and Heritage, who funded his pre-doctoral fellowship. Technical support provided by the Raman-LASPEA and General X-ray Service: Rocks and Minerals laboratories of SGIker (UPV/EHU, MICINN, GV/EJ, ERDF and ESF) is also gratefully acknowledged

A study of the artistic corpus of red cave paintings in El Buxu cave (Cangas de Onís, Asturias, Spain)

El Buxu cave, which is located in the village of Cardes (Cangas de Onís, Asturias), has been studied since the 1980s, with multiple excavations taking place inside the cave. This work has uncovered a complete artistic corpus, marking out several phases of occupation, with paintings dating to the first phases of the Upper Palaeolithic, Solutrean and Lower and Middle Magdalenian periods. This paper presents a new review of its rock art, documenting all of the red paintings inside the cave, most of which have never been published up until this point. The most notable inclusion is the new description of a zoomorphic figure painted in red, which has previously been interpreted as an aurochs, but whose features are in fact closer to those of a deer or reindeer. In addition, stratigraphic analysis of some of the paintings has revealed that they are overlapped by Solutrean and Magdalenian engravings and black paintings inside the cave. Elemental analysis was performed on series of red pigments and ochre samples, recovered from various strata using X-ray fluorescence spectroscopy. The resulting dataset was treated using Principal Component Analysis, providing a deeper understanding of the composition of the rock art in El Buxu cave, while uncovering potential correlations between the samples ac- cording to their elemental composition. After comparing additional evidences from other red cave paintings in the region with the red pictographs in the cave, along with the stratification of paint pigments and their relationship with the ochre samples in each stratum, it appears that the red paintings comprise the oldest group of pictures inside the cave and can be broadly dated to the pre-Magdalenian cultural period.Our special aknowledgment to the National University of Distance Education (UNED), for its funding for open-access publishin

Secco painting technique revealed in non-restored Pompeian murals by analytical and imaging techniques

The fresco technique appears to have been widely used on Roman mural paintings. The close observation of many of such murals suggests, however, the application of a secco technique over the fresco background. In this work, for the first time, fragments from Pompeian mural paintings that had never been restored have been investigated by optical microscopy, reflectance transformation imaging, micro-Energy-Dispersive X-Ray Fluorescence, micro-Fourier Transform Infrared Spectroscopy, and Direct Temperature-resolved Mass Spectrometry. A small number of fragments from restored paintings from the same Archaeological Park was also analyzed by the same techniques for the sake of comparison. The results of this multi-analytical approach that involves - for the first time on this type of samples - scientific photographic investigation, point out to the use of a protein- based medium, most probably egg, to execute the secco layers. On the other hand, wax was ubiquitous in samples taken from restored mural paintings. This last evidence further highlights the importance of selecting appropriate candidates for the study of original organic binders.Silvia Pérez-Diez: “la Caixa” Foundation-Fellowship code LCF/BQ/ES18/11670017 Francesco Caruso: Maria Zambrano fellowship from the University of the Basque Country (UPV/ EHU), funded by the Spanish Ministry of Universities and the European Union NextGenerationEU/PRTR. Project DEMESOS (PES21/85), UPV/EH

Unraveling the role of the thermal and laser impacts on the blackening of cinnabar in the mural paintings of Pompeii

The blackening of red cinnabar (α-HgS) pigment has traditionally been explained by its conversion into black metacinnabar (β-HgS). Scarce is however the scientific evidence that supports this hypothesis in polychrome artworks. As such transition occurs at around 345 °C, the thermal impact of the eruption of Mount Vesuvius in 79 AD could have induced this structural change of the pigment present in the mural paintings of Pompeii. This work aims to assess whether the mentioned volcanic eruption could be responsible of the cinnabar blackening through the formation of metacinnabar. The thermodiffractometry study of cinnabar-decorated fresco mock-ups stated that the formed β-HgS is not stable, observing its reversion into α-HgS. Moreover, sublimation of the cinnabar pictorial layer was registered, also when the cinnabar paint layer was protected by a coating of pyroclastic materials. In real blackened cinnabar Pompeian samples, it was not possible to identify metacinnabar by X-ray diffraction (XRD), but evidence of sublimation of mercury due to the thermal impact was observed. Hence, this blackening seems to be related mainly to the presence of calomel (Hg2Cl2) and a gypsum (CaSO4·2H2O) crust as degradation products of red cinnabar and the calcite mortar, respectively, and not to the formation of metacinnabar. Finally, laser-based techniques could also induce modifications in the HgS crystalline structure, resulting in an amorphous black product. Therefore, the elemental and molecular study of the species promoted by laser impact was carried out to avoid false positives in the metacinnabar detection or when the decorated surface has been subjected to laser cleaning.The research leading to these results has received funding from “la Caixa” Foundation (Silvia Pérez-Diez, ID 100010434, Fellowship code LCF/BQ/ES18/11670017). This work has been supported by the project IT1446-22 for Consolidated Research Groups, funded by the Basque Country Government. The authors acknowledge as well the funding provided by University of the Basque Country through the Institutionally Sponsored Open Access

Portable and Raman imaging usefulness to detect decaying on mortars from Punta Begoña Galleries (Getxo, North of Spain)

Punta Begoña Galleries were built in 1918 in Getxo (Basque Country, North of Spain) but were abandoned in 1960. Nowadays, their conservation state is very poor. In this work, portable Raman spectroscopy was applied to evaluate the original composition and possible deterioration products of the mortars used in the inner walls and those covering the concrete of the ceilings allowing us to select the most appropriate sampling points. In the laboratory, Raman microscopy and Raman imaging, assisted with scanning electron microscopy equipped with an energy dispersive spectrometer (SEM‐EDS), X‐ray diffraction and energy dispersive X‐ray fluorescence (ED‐XRF) imaging, allowed to identify the key compounds to understand the deterioration processes taking place in the mortars of the galleries. The main components of the mortars from the walls were calcite and gypsum. In some cases, alite (Ca3SiO5) and belite (Ca2SiO4) were identified; these components are characteristic of Portland cement clinker. The main components of the mortar covering the concrete were calcite, quartz, aragonite and gypsum. The aragonite identification confirmed the use of beach sand as the aggregate in the mortar. The concrete from the ceiling of the lower gallery is covered with three different mortar layers; the outermost layer is covered with a black crust. In the three mortars, the main components are similar to those used in the mortar covering the concrete from the upper gallery. Thanks to Raman, ED‐XRF and SEM‐EDS imaging, it was possible to map the distribution of the main components through the three mortar layers and also to identify the presence of dolomite {[CaMg(CO3)2]}, which was not possible to detect following single‐point micro‐Raman analyses.This work has been funded by the Ministry of Economy and Competitiveness and the European Regional Development Fund (ERDF) through the project DISILICA‐1930 (ref. BIA2014‐59124‐P) and by the cooperation agreement between the University of the Basque Country (UPV/EHU) and the City Council of Getxo (OTRI2014‐0639). C. García‐Florentino is grateful to the University of the Basque Country (UPV/EHU), which funded her predoctoral fellowship. Technical support provided by Raman‐LASPEA Laboratory and General X‐ray Service of the SGIKer (UPV/EHU, Ministry of Economy and Competitiveness of Spain, Basque Government, ERDF and European Social Fund) is also gratefully acknowledged

Identification of metals and metalloids as hazardous elements in PM2.5 and PM10 collected in a coastal environment affected by diffuse contamination

The nature of the PM2.5 and PM10 varies enormously depending on the anthropogenic activities developed in the surrounding environment. These particles can include Hazardous Elements (HEs), such as heavy metals, which can be considered dangerous for the human health. For this reason, determining the nature of those HEs that are present in the surrounding atmosphere can help to comprehend possible emission sources and to establish new strategies to reduce air pollution. In this work, a cost-effective self-made passive sampler (SMPS) was tested as a tool to collect different size of PM containing metals as HEs. The SMPS was installed in a 20th century historic building (Punta Begona Galleries, Getxo, ~ Basque Country, Spain), located just in front of the sea and thus, immersed in a coastal environment. This location is affected by the activities developed in a marina and in a port, and by the diffuse influence of several industries and a power station. The annual average for PM10 and PM2.5 were approximately 22 mg/ m3 and 10 mg/m3 , respectively. For develop this study, non-invasive elemental (Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectrometry) and molecular (Raman microscopy) microspectroscopic techniques were used. Thanks to this methodology it was possible to determine in PM10 and PM2.5, the presence of heavy metals such as Fe, Cr, Ti, Pb, Zn, Ce, etc., most of them as oxides but also embedded in different aggregations with aluminosilicates, phosphates, halides, sulfates, etc

PM10 spatial distribution and metals speciation study in the Bilbao metropolitan area during the 2017–2018 period

Speciation of respirable particles is becoming increasingly important from an epidemiological and analytical point of view to determine the potential effects of air pollution on human health. For this reason, current laws and analytical sampling methods focus on particle size, as it turns out to be the main factor for the greater or lesser penetration into the airways. In this sense, particles of less than 10 μm in diameter (<10 μm), referred to as PM10, are the particles that have a higher capacity for access to the respiratory tract and, therefore, more significant effect on them. In this sense, one of the most important factors that have a key role in the PM10 atmospheric pollution effect is the dispersion effect with the direct influence of natural effects such as wind, rain, topography apart from others. In this work, PM10 data extracted from the Basque Government environmental stations (19 sampling points) in the Biscay province (Basque Country, north of Spain) were combined with the results obtained from the use of self-made passive samplers (SMPS) in the same sampling points areas and subsequently, the sample analysis with a non-invasive elemental technique (Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectrometry) was carried out. Thanks to this methodology, it was possible to determine a wide variety of metals in PM10 such as Al, Fe, Cr, Ni, Pb, Zn, Ti, etc. Most of them present as oxides and others as part of natural aggregations such as quartz, aluminosilicates, phosphates etc

Naturally growing grimmiaceae family mosses as passive biomonitors of heavy metals pollution in urban-industrial atmospheres from the Bilbao Metropolitan area

In analytical chemistry, biomonitoring is known as the methodology, which consider the use of living organisms to monitor and assess the impact of different contaminants in a known area. This type of monitoring is a relatively inexpensive method and easy to implement, being a viable alternative to be developed in sites where there is no infrastructure/instruments for a convenctional air quality monitoring. These organisms, having the capability to monitor the pollution, are also known as passive biomonitors (PBs), since they are able to identify possible contamination sources without the need of any additional tool. In this work, a multianalytical methodology was applied to verify the usefulness of naturally growing Grimmia genus mosses as PBs of atmospheric heavy metals pollution. Once mosses were identified according to their morphology and taxonomy, thei ability to accumulate particulate matter (PM) was determined by SEM. EDS coupled to SEM also allowed to identify the main metallic particles deposited and finally, an acid digestion of the mosses and a subsequent ICP-MS study define more precisely the levels of metals accumulated on each collected moss. The study was focused on six sampling locations from the Bilbao Metropolitan area (Biscay, Basque Country, north of Spain). The experimental evidences obtained allowed to propose naturally growing Grimmia genus as PB of atmospheric heavy metals pollution and to identify the anthropogenic sources that contribute to the emission of the airborne particulate matter rich in metals, evaluating in this sense the atmospheric heavy metals pollution of the selected locations