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1.
Sci Rep ; 14(1): 15945, 2024 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-38987581

RESUMO

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument onboard the Mars 2020 Perseverance rover detected so far some of the most intense fluorescence signals in association with sulfates analyzing abraded patches of rocks at Jezero crater, Mars. To assess the plausibility of an organic origin of these signals, it is key to understand if organics can survive exposure to ambient Martian UV after exposure by the Perseverance abrasion tool and prior to analysis by SHERLOC. In this work, we investigated the stability of organo-sulfate assemblages under Martian-like UV irradiation and we observed that the spectroscopic features of phthalic and mellitic acid embedded into hydrated magnesium sulfate do not change for UV exposures corresponding to at least 48 Martian sols and, thus, should still be detectable in fluorescence when the SHERLOC analysis takes place, thanks to the photoprotective properties of magnesium sulfate. In addition, different photoproduct bands diagnostic of the parent carboxylic acid molecules could be observed. The photoprotective behavior of hydrated magnesium sulfate corroborates the hypothesis that sulfates might have played a key role in the preservation of organics on Mars, and that the fluorescence signals detected by SHERLOC in association with sulfates could potentially arise from organic compounds.

2.
Gels ; 9(11)2023 Oct 25.
Artigo em Inglês | MEDLINE | ID: mdl-37998933

RESUMO

Marble is one of the materials most susceptible to copper leaching, resulting in easily identifiable turquoise stains on the marble. This problem is particularly relevant when we are talking about marble structures of heritage value. For this reason, conservators look for cleaning materials that are specific to the structure to be treated without damaging the original surface. Materials such as agar have been studied for a long time. Agar creates a controlled water release system that adapts to the needs of conservators who seek the greatest possible cleanliness without damaging the material to be treated. To improve the cleaning, chelating agents such as EDTA are added to the agar composition. However, the microbiological growth and the damage it produces to the original material are disadvantages to take into account. In order to solve these problems, other natural materials with cleaning potential such as kudzu and konjac gels were studied in combination with other chelating agents such as citrate, oxalate, and gluconic acid. For the characterization and evaluation of copper cleaning, various analytical techniques were used, including Raman spectroscopy, colorimetry, X-ray fluorescence (XRF), and inductively coupled plasma mass spectrometry (ICP-MS). In this study, both konjac and kudzu emerged as promising alternatives to agar, revealing distinctive features such as simplified preparation methods and inherent antimicrobial properties. The EDTA chelator was found to be the most harmful for marble surfaces, as it extracted a greater amount of calcium from the marble during application of the gels doped with it. Citrate and gluconic acid have been identified as a promising substitute to prepare doped gels for the removal of copper stains. These compounds exhibit comparable or potentially superior cleaning capabilities than EDTA, with no negative side effects.

3.
Sci Total Environ ; 905: 167186, 2023 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-37730051

RESUMO

This work presents the geochemical characterization of two Martian analogues located in the Basque-Cantabrian Basin: Enekuri and Fruiz. In contrast to previous works carried out on the coastline analogues Meñakoz and Armintza (Biscay, Spain), these new outcrops are not in contact with sea-water nowadays. Hence, the weathering processes observed in Enekuri and Fruiz (inland) are different from those observed in Armintza and Meñakoz (coastline). In this way, among all the mineral phases found the only ones in common between inland and coastline outcrops are albite and chlorites, minerals that were formed in aqueous conditions. Understanding the differences presented in both types of outcrops could help to interpret the future results from the missions Mars2020 and the ExoMars2022, since coastline outcrops are affected by sea-water weathering and inland outcrops are altered by the high biological activity.

4.
Molecules ; 28(15)2023 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-37570822

RESUMO

In this work, some micro-samples belonging to the open-air rock art site of Cueva de la Vieja (Alpera, Albacete, Spain) were analysed. These samples were collected after and before a desalination treatment was carried out, with the aim of removing a whitish layer of concretion that affected the painted panel. The diagnostic study was performed to study the conservation state of the panel, and to then confirm the effectiveness of the treatment. Micro energy dispersive X-ray fluorescence spectrometry, Raman spectroscopy, and X-ray diffraction were employed for the characterization of the degradation product as well as that of the mineral substrate and pigments. The micro-samples analysis demonstrated that the painted layer was settled on a dolomitic limestone with silicon aggregates and aluminosilicates as well as iron oxides. The whitish crust was composed by sulfate compounds such as gypsum (CaSO4·2H2O) with a minor amount of epsomite (MgSO4·7H2O). An extensive phenomenon of biological activity has been demonstrated since then in almost all of the samples that have been analysed, and the presence of calcium oxalates monohydrate (CaC2O4·H2O) and dehydrate (CaC2O4·2H2O) were found. The presence of both calcium oxalates probably favoured the conservation of the pictographs. In addition, some carotenoids pigments, scytonemin (C36H20N2O4), and astaxanthin (C40H52O4) were characterized both by Raman spectroscopy and by X-ray diffraction. Hematite was found as a pigment voluntarily used for the painting of the panels used in a mixture with hydroxyapatite and amorphous carbon. The results of the analyses of the samples taken after the cleaning treatment confirmed a substantial decrease in sulphate formation on the panel surface.

5.
Environ Sci Pollut Res Int ; 30(37): 87561-87574, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-37428320

RESUMO

High-altitude Pyrenean lakes are ecosystems far from local pollution sources, and thus they are particularly sensitive to the atmospheric deposition of metals and metalloids. This study aims to quantify the effect of human activity in 18 lakes located in both side of the France-Spain frontier. Sediment cores were collected in summer 2013, sampled at a 1cm resolution and the concentration of 24 elements was measured by ICP-MS. Statistic and chemometric analysis of the results highlights the influence of the geographical position and lithogenic features of each lake basin on trapping pollutants. More than the 80% of the lakes showed values of enrichment factor (EF) above 2 for at least one of the elements investigated in at least one core interval, which corroborates the existence of historical anthropogenic inputs of elements in the studied area. The results demonstrate the natural origin of As and Ti in Pyrenees, together with the significant anthropogenic inputs of Cd, Pb, Sb and Sn from ancient times. The data set points mining activities as the main historical source of pollution and illustrate the large impact of the industrial revolution. The regional variability could reflect also differential long-range transport, followed by dry or wet deposition.


Assuntos
Monitoramento Ambiental , Lagos , Metais , Poluentes Químicos da Água , Humanos , Altitude , Ecossistema , Monitoramento Ambiental/métodos , Sedimentos Geológicos , Lagos/química , Metaloides/análise , Metais/análise , Metais Pesados/análise , Poluentes Químicos da Água/análise , Espanha , França
6.
Chemosphere ; 309(Pt 2): 136743, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-36209867

RESUMO

Over the last decades, the concern about air pollution has increased significantly, especially in urban areas. Active sampling of air pollutants requires specific instrumentation not always available in all the laboratories. Passive sampling has a lower cost than active alternatives but still requires efforts to cover extensive areas. The use of biological systems as passive samplers might be a solution that provides information about air pollution to assist decision-makers in environmental health and urban planning. This study aims to employ subaerial biofilms (SABs) growing naturally on façades of historical and recent constructions as natural passive biomonitors of atmospheric heavy metals pollution. Concretely, SABs spontaneously growing on constructions located in a tropical climate, like the one of the city of Barranquilla (Colombia), have been used to develop the methodological approach here presented as an alternative to SABS grown under laboratory conditions. After a proper identification of the biocolonizers in the SAB through taxonomic and morphological observations, the study of the particulate matter accumulated on the SABs of five constructions was conducted under a multi-analytical approach based mainly on elemental imaging studies by micro Energy Dispersive X-ray fluorescence spectrometry (µ-EDXRF) and Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectrometry (SEM-EDS) techniques, trying to reduce the time needed and associated costs. This methodology allowed to discriminate metals that are part of the original structure of the SABs, from those coming from the anthropogenic emissions. The whole methodology applied assisted the identification of the main metallic particles that could be associated with nearby anthropogenic sources of emission such as Zn, Fe, Mn, Ni and Ti by SEM-EDS and by µ-EDXRF Ba, Sb, Sn, Cl and Br apart others; revealing that it could be used as a good alternative for a rapid screening of the atmospheric heavy metals pollution.


Assuntos
Poluentes Atmosféricos , Metais Pesados , Monitoramento Ambiental/métodos , Clima Tropical , Metais Pesados/análise , Poluentes Atmosféricos/análise , Material Particulado/análise , Biofilmes
7.
Sci Adv ; 8(34): eabo3399, 2022 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-36007007

RESUMO

Before Perseverance, Jezero crater's floor was variably hypothesized to have a lacustrine, lava, volcanic airfall, or aeolian origin. SuperCam observations in the first 286 Mars days on Mars revealed a volcanic and intrusive terrain with compositional and density stratification. The dominant lithology along the traverse is basaltic, with plagioclase enrichment in stratigraphically higher locations. Stratigraphically lower, layered rocks are richer in normative pyroxene. The lowest observed unit has the highest inferred density and is olivine-rich with coarse (1.5 millimeters) euhedral, relatively unweathered grains, suggesting a cumulate origin. This is the first martian cumulate and shows similarities to martian meteorites, which also express olivine disequilibrium. Alteration materials including carbonates, sulfates, perchlorates, hydrated silicates, and iron oxides are pervasive but low in abundance, suggesting relatively brief lacustrine conditions. Orbital observations link the Jezero floor lithology to the broader Nili-Syrtis region, suggesting that density-driven compositional stratification is a regional characteristic.

8.
Molecules ; 27(11)2022 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-35684544

RESUMO

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 restoration.

9.
Anal Chim Acta ; 1197: 339499, 2022 Mar 08.
Artigo em Inglês | MEDLINE | ID: mdl-35168731

RESUMO

The study of space has always been a field of great interest and thus space missions are becoming more and more ambitious with time. Therefore, with the 50th anniversary of the first spacecraft to land on Mars, a review about how traditional analytical techniques have been adapted to the era of in situ space exploration is presented. From the Viking Project to the future MMX mission, the techniques used for the in situ study of the geochemistry of the Martian surface is described. These techniques have been differentiated according to the type of analysis: elemental and molecular. On the one hand, among the elemental analytical techniques the XRF, APXS, ISE and LIBS stand out. On the other hand, GCMS, TEGA, MBS, XRD, Raman and IR spectroscopy have been the molecular techniques used in the missions to Mars. Miniaturization, real-time measurements, automation, low power consumption and reliability of operation under extreme conditions are some of the major challenges that analytical chemistry has faced as a result of the technological and scientific requirements of space missions. In this way, this review gathers all the in situ analytical techniques that have reached the surface of Mars onboard landers or rovers with the aim of studying its geochemistry.


Assuntos
Marte , Voo Espacial , Exobiologia , Meio Ambiente Extraterreno , Reprodutibilidade dos Testes
10.
Anal Chem ; 93(48): 15870-15877, 2021 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-34817160

RESUMO

It is widely known that the vivid hue of red cinnabar can darken or turn black. Many authors have studied this transformation, but only a few in the context of the archeological site of Pompeii. In this work, the co-occurrence of different degradation patterns associated with Pompeian cinnabar-containing fresco paintings (alone or in combination with red/yellow ocher pigments) exposed to different types of environments (pre- and post-79 AD atmosphere) is reported. Results obtained from the in situ and laboratory multianalytical methodology revealed the existence of diverse transformation products in the Pompeian cinnabar, consistent with the impact of the environment. The effect of hydrogen sulfide and sulfur dioxide emitted during the 79 AD eruption on the cinnabar transformation was also evaluated by comparing the experimental evidence found on paintings exposed and not exposed to the post-79 AD atmosphere. Our results highlight that not all the darkened areas on the Pompeian cinnabar paintings are related to the transformation of the pigment itself, as clear evidence of darkening associated with the presence of manganese and iron oxide formation (rock varnish) on fragments buried before the 79 AD eruption has also been found.


Assuntos
Compostos de Mercúrio , Pinturas , Sepultamento , Erupções Vulcânicas
11.
Sensors (Basel) ; 21(13)2021 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-34203186

RESUMO

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.


Assuntos
Pintura , Pinturas , Animais , Corantes , Espanha , Análise Espectral Raman
12.
Molecules ; 26(10)2021 May 12.
Artigo em Inglês | MEDLINE | ID: mdl-34066114

RESUMO

The environmental weathering and the formation of efflorescences on the brick walls are studied at the "Casa di Diana" Mithraeum at Ostia Antica archaeological site. Previous studies on subsoil, bedrock, hydrological systems and environmental conditions, and new ion chromatography analysis combined with ECOS-RUNSALT and Medusa-Hydra thermodynamic modelling software, had allowed us to identify the subsoil contamination related to soluble salts. The atmospheric acidic gases, CO2 and SO2, are determined as the main salt weathering species. A dry deposition after a subsequent hydration action from the shallow freshwater aquifer that reaches up to 1 m on the walls is identified as the mechanism of salt formation. An evaluation of potential sources such as the nearby Fiumicino airport, CO2-rich gases inputs from fumaroles and CO2 inputs was also debated. The risk level of contamination the surfaces of the materials should be considered mildly/very polluted with a medium/high risk of hygroscopic moisture due to the high concentration of sulphates.

13.
Sci Rep ; 11(1): 10789, 2021 05 24.
Artigo em Inglês | MEDLINE | ID: mdl-34031454

RESUMO

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.

14.
Anal Chim Acta ; 1168: 338565, 2021 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-34051995

RESUMO

Crystallization of soluble salts is a common degradation phenomenon that threatens the mural paintings of Pompeii. There are many elements that contribute to the crystallization of salts on the walls of this archaeological site. Notably, the leachates of the pyroclastic materials ejected in 79 AD by Mount Vesuvius and local groundwater, rich in ions from the erosion of volcanic rocks. Both sources could contribute to increase the concentration of halides (fluorides and chlorides) and other salts in these walls. The distribution of volcanogenic salts and their impact on the conservation of Pompeian mural paintings have however not yet been fully disclosed. In this work, an analytical methodology useful to determine the impact of the main sources of degradation affecting the mural paintings of Pompeii is presented. This methodology combines the creation of qualitative distribution maps of the halogens (CaF and CaCl) and related alkali metals (Na and K) by portable Laser Induced Breakdown Spectroscopy (LIBS) and a subsequent Principal Component Analysis of these data. Such maps, together with the in-situ identification of sulfate salts by portable Raman spectroscopy, provided information about the migration and distribution of volcanogenic halides and the influence of ions coming from additional sources (marine aerosol and modern consolidation mortars). Additionally, the thermodynamic modeling developed using the experimentally determined ionic content of Pompeian rain- and groundwater allowed to determine their specific role in the formation of soluble salts in the mural paintings of Pompeii.

15.
Astrobiology ; 21(3): 332-344, 2021 03.
Artigo em Inglês | MEDLINE | ID: mdl-33481644

RESUMO

Calcium sulfates are known to be potential reservoirs of organic compounds and have been detected on Mars. However, not all data that indicate the presence of sulfates collected by the Mars Exploration Rovers (Spirit and Opportunity) and Curiosity rover can be explained by the different calcium sulfate polymorphs, and therefore, mixtures of calcium sulfates with other single sulfates must be considered. In addition, the presence of mixed calcium sulfates supports the data and indicates that the molar ratio of sulfate/calcium is >1. To obtain adequate spectroscopic information of mixed-cation sulfates to be used in the interpretation of data from Mars in the next few years, the thermodynamically stable syngenite (K2Ca(SO4)2·H2O) and görgeyite (K2Ca5(SO4)6·H2O) mixed-cation sulfates have been studied along with the interrelationships in the gypsum-syngenite-görgeyite system to understand their possible formation on Mars. Raman spectroscopy and Visible-Near Infrared-Shortwave Infrared (VisNIR) spectroscopy have been used for their characterization to increase the databases for the two future Mars exploration missions, Mars2020 and ExoMars2022, where both techniques will be implemented. These VisNIR data can also help with the interpretation of spectral data of salt deposits on Mars acquired by the OMEGA and CRISM spectrometers onboard the Mars Express and Mars Reconnaissance orbiters. This work demonstrates that syngenite (K2Ca(SO4)2·H2O) easily precipitates without the need for hydrothermal conditions, which, depending on the ion concentrations, may precipitate in different proportions with gypsum. Furthermore, in this study, we also demonstrate that, under hydrothermal conditions, görgeyite (K2Ca5(SO4)6·H2O) would also be highly likely to form and may also be identified on Mars together with syngenite and gypsum.


Assuntos
Sulfato de Cálcio , Marte , Meio Ambiente Extraterreno , Compostos Orgânicos , Análise Espectral Raman , Sulfatos
16.
ACS Earth Space Chem ; 5(6): 1333-1342, 2021 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-35673558

RESUMO

A lunar feldspathic breccia meteorite, the Northwest Africa (NWA) 11273, was analyzed to compensate the lack of scientific data available about its mineralogy and geochemistry. In order to obtain a deeper characterization of the sample, a strategy based on the combination of nondestructive spectroscopic techniques such as X-ray fluorescence and Raman spectroscopy is used. Both techniques are being used in spatial missions by the Perseverance Rover, so their combination in the laboratory is here proposed as an optimal strategy to study the complete mineralogy of the sample. In addition to finding the minerals indicated by the Meteoritical Society (anorthite, olivine, pyroxene, kamacite, and troilite), other minor minerals were identified, such as zircon and ilmenite, which are minerals related to the Moon geology, as well as calcite and sulfate which can be considered products of terrestrial weathering. Finally, secondary minerals related to alteration processes were also found, such as hematite, quartz, and anatase. In this work, the alteration processes that gave rise to the detected secondary minerals have been proposed.

17.
Spectrochim Acta A Mol Biomol Spectrosc ; 249: 119294, 2021 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-33360059

RESUMO

This work summarizes the spectroscopic-assisted archaeometric study of the most important terracotta statue of Poseidonia-Paestum (Italy), the so-called Zeus Enthroned (VI sec. BC). The selected analytical strategy combines the mineralogical and molecular information provided by X-Ray diffraction (XRD) and Raman analysis with the elemental data obtained from X-Ray fluorescence (XRF) and Scanning Electron Microscopy coupled to Energy Dispersive Spectrometry (SEM/EDS). To shed light on the raw materials used to create and decorate this unique artwork, the analytical results gathered in this study helped disclosing the applied production technology. As suggested by the detected mineral assemblages, the body was prepared in two steps, using calcareous clay (CC) rich in Mg- and Fe- minerals as raw materials. The inner core and the outer depurated layers were both fired in oxidizing conditions but reaching different temperatures (≥900 °C and 850-900 °C respectively). The statue was decorated by firing manganese- (jacobsite MnFe2O4) and iron- (hematite Fe2O3) oxides in oxidizing conditions. Knowing that the decoration techniques based on the use of Mn-oxides were mastered by Etruscans rather than by Ancient Greeks, the obtained results suggest a transfer of production technology across borders, thus providing an additional clue about the flourishing commercial and cultural exchanges occurred between Greek colonies and Italic pre-Roman societies.

18.
Angew Chem Int Ed Engl ; 60(6): 3028-3036, 2021 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-33064357

RESUMO

Pyroclastic strata have always been thought to protect the archaeological remains of the Vesuvian area (Italy), hence allowing their conservation throughout the centuries. In this work, we demonstrate that they constitute a potential threat for the conservation state of the mural paintings of Pompeii. The ions that could be leached from them and the ion-rich groundwater coming from the volcanic soil/rocks may contribute to salt crystallisation. Thermodynamic modelling not only allowed to predict which salts can precipitate from such leaching events but also assisted the identification of additional sources of sulfates and alkali metals to explain the formation of the sulfates identified in efflorescences from the mural paintings of Pompeii. For the future, fluorine, mainly related to a volcanic origin, can be proposed as a marker to monitor the extent of the impact in the mural paintings of Pompeii in situ.

19.
Chemosphere ; 263: 128190, 2021 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-33297155

RESUMO

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.


Assuntos
Poluentes Atmosféricos , Poluição do Ar , Briófitas , Metais Pesados , Poluentes Atmosféricos/análise , Atmosfera , Monitoramento Ambiental , Metais Pesados/análise , Espanha
20.
Anal Bioanal Chem ; 412(29): 8155-8166, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32979075

RESUMO

In this work, an innovative non-destructive monitoring methodology based on the analysis over time of open-air rock art sites is presented. This approach is based on the combination of in situ spectroscopic and chemometric studies to diagnose and monitor the state of conservation of rock art sites. Data acquired over a period of time by non-invasive analytical techniques such as portable Raman spectrometry (RS) and handheld energy-dispersive X-ray fluorescence (HH-EDXRF) spectrometry are compared to detect physicochemical changes that could affect the rock painting integrity. To demonstrate the applicability of the proposed procedure, three analysis campaigns (between 2013 and 2016) were carried out, analyzing Levantine rock pictographs preserved in the rock shelter of Solana de las Covachas VI (Albacete, Spain; see Electronic Supplementary Material (ESM) Fig. S1). The analyzed areas showed different types of active weathering processes such as gypsum and calcium oxalate formation, giving rise to conservation issues such as painting fading, surface loss, microbial colonizations, and formation of crusts. Results evidence that the proposed methodology can be very useful to monitor chemical changes in the surface of the walls where the rock art is located, thus obtaining crucial information for its preservation and management.

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