Elucidation of the Chemical Role of the Pyroclastic Materials on the State of Conservation of Mural Paintings from Pompeii.

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.

Raman imaging to quantify the thermal transformation degree of Pompeian yellow ochre caused by the 79 AD Mount Vesuvius eruption.

Most of the wall paintings from Pompeii are decorated with red and yellow colors but the thermal impact of 79 AD Mount Vesuvius eruption promoted the partial transformation of some yellow-painted areas into red. The aim of this research is to develop a quantitative Raman imaging methodology to relate the transformation percentage of yellow ochre (goethite, α-FeOOH) into red color (hematite, α-Fe2O3) depending on the temperature, in order to apply it and estimate the temperature at which the pyroclastic flow impacted the walls of Pompeii. To model the thermal impact that took place in the year 79 AD, nine wall painting fragments recovered in the archeological site of Pompeii and which include yellow ochre pigment were subjected to thermal ageing experiments (exposition to temperatures from 200 to 400 °C every 25 °C). Before the experiments, elemental information of the fragments was obtained by micro-energy dispersive X-ray fluorescence (µ-ED-XRF). The fragments were characterized before and after the exposition using Raman microscopy to monitor the transformation degree from yellow to red. The quantitative Raman imaging methodology was developed and validated using synthetic pellets of goethite and hematite standards. The results showed almost no transformation (0.5% ± 0.4) at 200 °C. However, at 225 °C, some color transformation (26.9% ± 2.8) was observed. The most remarkable color change was detected at temperatures between 250 °C (transformation of 46.7% ± 1.7) and 275 °C (transformation of 101.1% ± 1.2). At this last temperature, the transformation is totally completed since from 275 to 400 °C the transformation percentage remained constant.

Optimization of sample treatment for the identification of anthraquinone dyes by surface-enhanced Raman spectroscopy.

The study and characterization of old artifacts such as pigments requires the use of techniques that need a small amount of sample to perform the analysis because of the high value of these samples. In recent years, organic molecules such as anthraquinone dyes have been identified by surface-enhanced Raman spectroscopy (SERS). However, different sample treatments must be applied to isolate the organic dye from the mordant, which produces great fluorescence in the Raman measurements. In this work, optimization of sample treatment for the SERS analysis of anthraquinone dyes was performed. Sample mass, the organic solvent, and its volume were optimized and different slide materials and excitation lasers were compared to choose the best conditions for the identification of the dyes. The optimization of sample treatment resulted in 5 mg of sample as the optimum amount. Further, two consecutive extractions with 0.5 mL of ethyl acetate was the best option for the extraction of the dye. A quartz slide was used instead of a glass slide to reduce background signal, and an excitation laser of 532 nm offers better results than one of 785 nm. The optimized method was applied to the characterization of the dyes used in Pompeian pink and purple lake pigments. Alizarin and purpurin anthraquinone dyes, obtained from madder lake, were identified as the organic colorants. The SERS results were confirmed by those obtained by means of UV-visible spectroscopy. Graphical Abstract ᅟ.

In situ X-ray fluorescence-based method to differentiate among red ochre pigments and yellow ochre pigments thermally transformed to red pigments of wall paintings from Pompeii.

Most of the magnificent wall paintings from the ancient city of Pompeii are decorated with red and yellow colors coming from the ochre pigments used. The thermal impact of the pyroclastic flow from the eruption of Vesuvius, in AD 79, promoted the transformation of some yellow painted areas to red. In this work, original red ochre, original yellow ochre, and transformed yellow ochre (nowadays showing a red color) of wall paintings from Pompeian houses (House of Marcus Lucretius and House of Gilded Cupids) were analyzed by means of a handheld energy-dispersive X-ray fluorescence spectrometer to develop a fast method that allows chemical differentiation of the original red ochre and the transformed yellow ochre. Principal component analysis of the multivariate obtained data showed that arsenic is the tracer element to distinguish between both red colored ochres. Moreover, Pompeian raw red and yellow ochre pigments recovered from the burial were analyzed in the laboratory with use of a benchtop energy-dispersive X-ray fluorescence spectrometer to confirm the elemental composition and the conclusions drawn from the in situ analysis according to the yellow ochre pigment transformation in real Pompeian wall paintings.

Multispectroscopic and Isotopic Ratio Analysis To Characterize the Inorganic Binder Used on Pompeian Pink and Purple Lake Pigments.

Because of the fact that pigments are not ubiquitous in the archeological record, the application of noninvasive analytical methods is a necessity. In this work, pink and purple lake pigments recovered from the excavations of the ancient city of Pompeii (Campania, Italy) and preserved in their original bowls at the Naples National Archaeological Museum (Italy) were analyzed to characterize the composition of their inorganic binders (mordants). In situ preliminary analyses using a hand-held energy dispersive X-ray fluorescence spectrometer (HH-ED-XRF) allowed us to determine the use of an aluminosilicate enriched in Cu and Pb. Scanning electron microscopy coupled to energy dispersive X-ray spectrometry (SEM-EDS) and benchtop ED-XRF analyses confirmed these results, while inductively coupled plasma mass spectrometry (ICPMS) allowed one to determine the concentration of major, minor, and trace elements. The use of other techniques such as X-ray diffraction (XRD), and micro-Raman and infrared spectroscopies allowed one to characterize the pigments at the molecular level. The high concentration of Cu detected in the pigments (1228-12937 µg g(-1)) could be related to the addition of Cu salts to obtain the desired final hue. The concentrations of Pb (987-2083 µg g(-1)) was also remarkable. Lead isotopic ratio analysis ((206)Pb/(207)Pb) suggested a possible origin related to the leaching of the ancient lead pipes from Pompeii and the subsequent transfer to the buried pigments or to the inorganic binder. Molecular analysis also showed that the binder is composed of an allophane-like clay. Moreover, it was possible to determine that to obtain the final purple hue of a specific pigment, Pompeian blue pigment was also mixed into the dyed clay.

The cauliflower-like black crusts on sandstones: A natural passive sampler to evaluate the surrounding environmental pollution.

Black crust in buildings can be formed as a result of different kind of chemical and physical reactions between the stone surface and environmental factors (e.g. acid aerosols emitted to the atmosphere, airborne particulate matter, etc.). Moreover, biological colonizations can also be present on them. This kind of pathology is widely present in limestones, but fewer are the case study dealing with the characterization of black crusts on sandstones. In this work we present an innovative methodology based on the use of cauliflower-like black crusts formed on sandstone material as natural passive sampler to evaluate the environmental pollution related with the emission of natural (crustal particles and marine aerosol particles) and metallic elements in the airborne particulate matter from the surrounding atmosphere. To illustrate its usefulness, different cauliflower-like black crusts growing in areas protected from the rain growing in an historical construction, La Galea Fortress, made up of sandstone and placed in the Abra Bay (Getxo, Basque Country, Spain) were characterized. This area suffers the anthropogenic emissions coming from the surrounding industry, traffic, sea port, and the natural ones coming from the surrounding marine atmosphere. The applied analytical methodology began with a previous elemental in situ screening in order to evaluate and compare the presence of the metals trapped in black crusts from different orientations using a hand-held energy dispersive X-Ray Fluorescence spectrometer. After this preliminary study, samples of black crusts were taken in order to characterize them in the laboratory using molecular techniques (Raman spectroscopy and XRD) and elemental techniques (ICP-MS, SEM-EDS and micro energy dispersive X-Ray Fluorescence). With the last two elemental techniques, imaging analyses were performed at different lateral resolutions in order to observe the distribution of the metals and other kind of particles trapped in the black crust samples. Additionally, a biological colonization found beneath the black crusts was also characterized using Phase Contrast microscopy.

Metals, nonmetals and metalloids in cigarette smoke as hazardous compounds for human health.

Cigarette smoke contains many chemicals that are harmful to both smokers and non-smokers. Breathing just a little cigarette smoke can be harmful. There are >7000 chemicals in cigarette smoke, at least 250 are known to be harmful and many of them can cause cancer. Currently, many studies reported the types of harmful organic compounds in cigarette smoke; instead, there are almost no works that describe the presence of inorganic compounds. In this work, a cost-effective self-made passive sampler (SMPS) was tested as a tool to collect different types of particulate matter (PM) from cigarette smoke containing metals as hazardous compounds (HCs). To determine the nature of the metals, nonmetals and metalloids as HCs, a direct qualitative analysis of the particulate matter (PM) was conducted without developing any special sample preparation procedure. For that, non-invasive elemental (Scanning Electron Microscope coupled to Energy Dispersive X-ray Spectrometry) and molecular (Raman microscopy) micro-spectroscopic techniques were used. Thanks to this methodology, it was possible to determine in deposited PM, the presence of metals such as Fe, Cr, Ni, Ti, Co, Sn, Zn, Ba, Al, Cu, Zr, Ce, Bi, etc. most of them as oxides but also embedded in different clusters with sulfates, aluminosilicates, even phosphates.

Non-Adherence in Adult Male Patients with Community-Acquired Pneumonia: Relative Forgiveness of Amoxicillin versus Respiratory Fluoroquinolones.

The consequences of non-adherence to treatment (NAT) on antimicrobial efficacy may depend on drug forgiveness-a property that should account for pharmacokinetics (PK) and pharmacodynamics (PD) as well as interindividual variability. In this simulation study, relative forgiveness (RF) in NAT, defined as the probability of a successful PK/PD target (PTA) attained under perfect adherence compared to imperfect adherence, was evaluated for amoxicillin (AMOX) (oral 1000 mg/8 h) and two respiratory fluoroquinolones-levofloxacin (LFX) (oral 750 mg/24 h) and moxifloxacin (MOX) (oral 400 mg/24 h)-in virtual outpatients with community-acquired pneumonia for S. pneumoniae. Several NAT scenarios (delay in dose intake and a missed dose) were considered. PK characteristics of virtual patients, including variability in creatinine clearance (70-131 mL/min) and S. pneumoniae susceptibility variability associated with geographical location, were simulated in NAT. In this regard, in regions of low MIC delays from 1 h to 7 h or omission of dose ingestion would not have negative consequences on the efficacy of AMOX because of its good RF associated with the AMOX PK and PD properties; RF of LFX 750 mg or MOX 400 mg/24 h regimen vs. AMOX 1000 mg/8 h is one. However, in regions of elevated MIC for S. pneumoniae AMOX loses its RF, LFX and MOX vs. AMOX, showing higher RF (>1) depending on the CLCR of patients. These results illustrate the importance of considering the RF of antimicrobial drugs in NAT and provide a framework for further studying its implications for clinical success rates.

Elemental imaging approach to assess the ability of subaerial biofilms growing on constructions located in tropical climates as potential biomonitors of atmospheric heavy metals pollution.

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.

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.

Chemometrics and elemental mapping by portable LIBS to identify the impact of volcanogenic and non-volcanogenic degradation sources on the mural paintings of Pompeii.

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.

The influence of marine environment on the conservation state of Built Heritage: An overview study.

Marine aerosol is a chemical complex system formed by inorganic salts and organic matter, together with airborne particulate matter from the surrounding environment. The primary particles transported in the marine aerosol can experiment different chemical reactions in the atmosphere, promoting the so-called Secondary Marine Aerosol particles. These kinds of particles (nitrates, sulfates, chlorides etc.), together with the natural crustal or mineral particles and the metallic airborne particulate matter emitted by anthropogenic sources (road traffic, industry, etc.) form clusters which then can be deposited on building materials from a specific construction following dry deposition processes. Apart from that, the acid aerosols (e.g. CO2, SO2, NOX, etc.) present in urban-industrial environments, coming also from anthropogenic sources, can be deposited in the buildings following dry or a wet deposition mechanisms. The interactions of these natural and anthropogenic stressors with building materials can promote different kind of pathologies. In this overview, the negative influence of different marine environments (direct or diffuse influence), with or without the influence of an urban-industrial area (direct or diffuse), on the conservation state of historical constructions including a wide variety of building materials (sandstones, limestones, artificial stones, bricks, plasters, cementitious materials, etc.) is presented.

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.

Decay processes in buildings close to the sea induced by marine aerosol: Salt depositions inside construction materials.

Buildings close to the sea experience different kinds of decay processes related with the influence of marine aerosol. This sea spray is a chemically complex system formed by inorganic salts (sulfates, nitrates and mainly chlorides) and organic matter, together even with airborne particulate matter from the surrounding environment. Buildings close to the sea, erected using different materials such as bricks, plasters, limestones and sandstones, can experience many kinds of chemical reactions promoted by the impact of this sea spray, which favour the formation of salt crystallizations. In this work, a study of salts crystallizing in different kinds of building materials of a construction close to the Bay of Biscay (Villa Belza, Biarritz, France) has been studied in order to evaluate the state of conservation of the materials under study. The construction materials affected by salts were analyzed by means of X-ray Diffraction (XRD) and µ-Raman spectroscopy (µ-RS) for molecular analyses, Energy dispersive X-ray Fluorescence spectrometry (µ-ED-XRF) for elemental analyses and soluble salts tests by means of ion chromatography. These analyses revealed different levels of chlorides, nitrates and sulfates. Moreover, using this methodology, some specific chemical reactions that take place in the Villa Belza were understood. This knowledge can help to lay the foundations for possible future restoration works.

Impact assessment of metals on soils from Machu Picchu archaeological site.

Machu Picchu is an archaeological Inca sanctuary from the 15th century, located 2430 m above the sea level in the Cusco Region, Peru. In 1983, it was declared World Heritage Site by UNESCO. The surroundings and soils from the entire archaeological site are carefully preserved together with its grass parks. Due to the importance of the archaeological city and its surroundings, the Decentralized Culture Directorate of Cusco-PAN Machu Picchu decided to carry out a careful monitoring study in order to determine the ecological status of the soils. In this work, elemental and molecular characterization of 17 soils collected along the entire park was performed by means of X-ray Diffraction (XRD) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) after acidic digestion assisted by microwave energy. Thanks to the combination of these analytical techniques, it was possible to obtain the mineral composition and metal concentrations of all soils from these 17 sampling points. Finally, different statistical treatments were carried out in order to confirm the ecological status of the different sampling points from Machu Picchu archaeological site concluding that soils are not impacted.

Characterization of restoration lime mortars and decay by-products in the Meditation area of Machu Picchu archaeological site.

Machu Picchu citadel is the main archaeological Inca sanctuary widely known around the world, and a World Heritage Site of high cultural and natural value. For its construction a whitish granitic rock, extracted from the "Vilcapampa or Vilcabamba" batholith formation was used. During time, some of the granitic rocks from the natural stonewalls of the Meditation area of the Archaeological Park were restored. For the restoration works done in the 50s' a specific lime mortar called Clarobesa was used. After the inclusion of this joining mortar, many efflorescences are nowadays visible in the mortar itself and on the surface of the edges of the annexed rocks. To evaluate the possible impact of these salts crystallizations in the conservation state of these natural stonewalls, a multi-analytical methodology was designed and applied. With a combination of non-invasive and destructive techniques such as X-ray Diffraction, Raman microscopy, Scanning Electron Microscope coupled to an Energy Dispersive X-ray Spectrometer and ion chromatography, the mineralogical composition and the nature/concentration of the soluble salts present in the Clarobesa mortar was determined. The experimental results suggest that Clarobesa mortar is a hydraulic lime mortar. The study of salts crystallizations by Raman microscopy allowed identifying the presence of calcium sulfates with different hydration waters and also nitrates. In some samples, the concentration of sulfates was high, reaching values up to 10% w/w. Although the concentration of nitrates is not extremely high, a clear contribution of ammonium nitrates coming from the decomposition of the nearby vegetation was assessed. Since the Clarobesa mortar can be considered an important input of ions that can migrate to the joined granitic rocks, in the future, it will be recommendable to monitor possible changes in the conservation state of the joined rocks.

Evaluation of the role of biocolonizations in the conservation state of Machu Picchu (Peru): The Sacred Rock.

Machu Picchu Inca sanctuary (Cusco Region, Peru) was constructed on a granitic plateau, better known as Vilcabamba batholith. One of the most important carved granitic rocks from this archaeological site is the Sacred Rock, used by Inca citizens for religious rituals. Due to the location and climatic conditions, different rocks from this archaeological site are affected by biocolonizations. Concretely, the Sacred Rock shows flaking and delamination problems. In this work, a non-destructive multi analytical methodology has been applied to determine the possible role of the biodeteriogens, forming the biological patina on the Sacred Rock, in the previously mentioned conservation problems. Before characterizing the biological patina, a mineralogical characterization of the granitic substrate was conducted using X-ray Diffraction, Raman microscopy (RM) and micro energy dispersive X-ray fluorescence spectrometry. For the identification of the main biodeteriogens in the biofilm, Phase Contrast Microscopy was used. RM also allowed to determine the distribution (imaging) and the penetration (depth profiling) of the biogenic pigments present in the biopatina. Thanks to this study, it was possible to asses that some colonizers are growing on inner areas of the rock, reinforcing their possible assistance in the delamination. Moreover, the in-depth distribution of a wide variety of carotenoids in the patinas allowed to approach the penetration ability of the main biodeteriogens and the diffusion of these biogenic pigments to the inner areas of the rocky substrate.

Trentepohlia algae biofilms as bioindicator of atmospheric metal pollution.

In this work, a reddish biocolonization composed mainly by Trentepohlia algae affecting a synthetic building material from a modern building from the 90s located in the Bizkaia Science and Technology Park (Zamudio, North of Spain) was characterized and its ability to accumulate metals coming from the surrounding atmosphere was evaluated. To asses if these biofilms can act as bioindicators of the surrounding metal pollution, a fast non-invasive in situ methodology based on the use of hand-held energy dispersive X-ray fluorescence (HH-ED-XRF) was used. In order to corroborate the in situ obtained conclusions, some fragments from the affected material were taken to analyze the metal distribution by means of micro-energy dispersive X-ray fluorescence spectroscopy (µ-ED-XRF) and to confirm the presence of metal particles deposited on it using Scanning Electron Microscopy coupled to an Energy Dispersive Spectrometer (SEM-EDS). In order to confirm if Trentepohlia algae biofilms growing on the surface of building materials could be a fast way to in situ provide information about the surrounding metal pollution, a second Trentepohlia algae biofilm growing on a different kind of material (sandstone) was analyzed from an older historical building, La Galea Fortress (Getxo, North of Spain).

Micro-Raman and SEM-EDS analyses to evaluate the nature of salt clusters present in secondary marine aerosol.

Marine aerosol is a complex inorganic and organic chemistry system which contains several salts, mainly forming different type of salt clusters. Different meteorological parameters have a key role in the formation of these aggregates. The relative humidity (%RH), temperature, CO, SO2 and NOx levels and even the O3 levels can promote different chemical reactions giving rise to salt clusters with different morphology and sizes. Sulfates, nitrates and chlorides and even mixed chlorosulfates or nitrosulfates are the final compounds which can be found in environments with a direct influence of marine aerosol. In order to collect and analyze these types of compounds, the use of adequate samplers is crucial. In this work, salt clusters were collected thanks to the use of a self-made passive sampler (SMPS) installed in a 20th century historic building (Punta Begoña Galleries, Getxo, Basque Country, Spain) which is surrounded by a beach and a sportive port. These salt clusters were finally analyzed directly by micro-Raman spectroscopy and Scanning Electron microscopy coupled to Energy Dispersive X-ray spectrometry (SEM-EDS).

Study of the soluble salts formation in a recently restored house of Pompeii by in-situ Raman spectroscopy.

The walls and mural paintings of Pompeii exposed directly to the rainfalls are the most impacted in view of the observed decay. However, there are also wall paintings in protected rooms showing evidences of decaying. The aim of this research was to study the salts formed in such protected wall paintings only by non-invasive and in-situ Raman spectroscopy to understand their decaying processes. The perystile of the House of the Gilded Cupids (Regio VI, Insula 16), one of the most important houses of Pompeii was studied. Although an exhaustive restoration was carried out in 2004, a new conservation treatment was needed in 2013 and only two years later, extensive crystallizations of soluble salts were again threatening several of the restored surfaces, thus, the presence of an unsolved degradation pathway was deduced. Thank to the proposed methodology, it was pointed out that the key is the acidified rainfall impact in the non-protected backside of the walls containing the wall paintings. Thus, a new concept in the preservation of the houses of Pompeii is provided, in which the need of the protection of those walls from both sides is suggested to avoid the movement of water through the pores of the walls.