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In the present work, the microclimatic conditions (temperature (T), relative humidity (RH), and illuminance (I)), together with the air quality (both aerosol particulate matter (PM) and gaseous pollutants), were monitored to evaluate the environmental conditions inside the Santuario della Beata Vergine dei Miracoli in Saronno (VA), a masterpiece of the Italian Renaissance. For this purpose, dataloggers were used to carry out the T, RH, and I measurements, whereas an optical particle counter (OPC) was employed to perform the particle count and determine the concentration of the aerosol PM. Finally, diffusive passive samplers were used to determine the concentration of nitrogen dioxide (NO2) and BTEX (benzene, toluene, ethylbenzene, and xylenes). To identify possible spatial variations, the studies were conducted at different sites and different heights in the Sanctuary. Particular focus was given to the Easter week during which liturgical services attracting large numbers of people were carried out. Additionally, a comparison with the outdoor values was performed to highlight the accumulation phenomena and other variations in the concentrations of the species. Despite the indoor concentrations of pollutants and variations in the thermohygrometric parameters being generally lower compared to the outdoors (e.g., 5.2-15.0 µg m-3 versus 17.7-45.3 µg m-3 for NO2), the microclimatic conditions were often not in line with the Italian legislation and technical standards.
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Poluentes Atmosféricos , Poluição do Ar em Ambientes Fechados , Poluição do Ar , Poluentes Ambientais , Humanos , Poluentes Atmosféricos/análise , Poluição do Ar em Ambientes Fechados/análise , Dióxido de Nitrogênio , Monitoramento Ambiental , Poluição do Ar/análise , Material Particulado/análiseRESUMO
COVID-19 has reduced tourism in both museums and historical sites with negative economic effect. The wellbeing and good preservation of monuments is a key factor to encourage again tourism. Historical monuments exposed to outdoor pollution are subjected to well known degradation phenomenon including the formation on their surface of black crusts (BCs) causing blackening and deterioration of the monuments and, as a consequence, a worst fruition by the visitors. The aim of this research is the development and validation of a novel method to characterize and quantify the various components present in the black crusts. SO2 together with the carbonaceous fraction (i.e. OC, organic carbon, and EC, elemental carbon) represent the main atmospheric pollutants involved in the process of BCs formation which consists in the partial transformation of the carbonate substrate into gypsum where black particles are embedded. A new methodology based on the use of TGA/DSC (Thermogravimetric Analysis/Differential scanning calorimetry) and CHN (Carbon, Hydrogen, Nitrogen) analysis was set up allowing to determine organic carbon and elemental carbon together with other components such as gypsum. Four standard mixtures simulating BCs composition were prepared and analysed by the set-up methodology. The new procedure was subsequently applied to study real BCs samples taken from monuments and historical buildings placed in cities heavily affected by atmospheric pollution and by PCA (principal component analysis) their main features, from the point of view of carbonaceous fraction, were highlighted.
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Poluentes Atmosféricos , COVID-19 , Aerossóis , Poluentes Atmosféricos/análise , Carbono/análise , Materiais de Construção , Monitoramento Ambiental , Poluição Ambiental , Humanos , Material Particulado , SARS-CoV-2RESUMO
The adverse effects of fine particulate matter (PM) and many volatile organic compounds (VOCs) on human health are well known. Fine particles are, in fact, those most capable of penetrating in depth into the respiratory system. People spend most of their time indoors where concentrations of some pollutants are sometimes higher than outdoors. Therefore, there is the need to ensure a healthy indoor environment and for this purpose the use of an air purifier can be a valuable aid especially now since it was demonstrated that indoor air quality has a high impact on spreading of viral infections such as that due to SARS-COVID19. In this study, we tested a commercial system that can be used as an air purifier. In particular it was verified its efficiency in reducing concentrations of PM10 (particles with aerodynamic diameter less than 10 µm), PM2.5 (particles with aerodynamic diameter less than 2.5 µm), PM1 (particles with aerodynamic diameter less than 1 µm), and particles number in the range 0.3 µm-10 µm. Furthermore, its capacity in reducing VOCs concentration was also checked. PM measurements were carried out by means of a portable optical particle counter (OPC) instrument simulating the working conditions typical of a household environment. In particular we showed that the tested air purifier significantly reduced both PM10 and PM2.5 by 16.8 and 7.25 times respectively that corresponds to a reduction of about 90% and 80%. A clear reduction of VOCs concentrations was also observed since a decrease of over 50% of these gaseous substances was achieved.
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Filtros de Ar , Poluentes Atmosféricos , Poluição do Ar em Ambientes Fechados , COVID-19 , Compostos Orgânicos Voláteis , Aerossóis , Poluentes Atmosféricos/análise , Poluição do Ar em Ambientes Fechados/análise , Monitoramento Ambiental , Humanos , Tamanho da Partícula , Material Particulado/análise , SARS-CoV-2 , Compostos Orgânicos Voláteis/análiseRESUMO
This study is focused on the identification of pollutant sources on black crust (BC) samples from the Monumental Cemetery of Milan (Italy), through a multi-analytical approach based on the determination of stable isotope ratios of carbon, sulphur, and oxygen. Six black crust samples, mainly developed on marble sculptures over a time span of 100-150â¯years, were analysed. For the first time, δ13C was measured for BC samples: δ13C values of the pulverized samples (from -1.2 to +1.3â¯) are very close to the values obtained from the carbonate matrix, whereas after the removal of the matrix through acidification, δ13C values of BC samples from Milan range from -27.2 to -22.1â¯, with no significant variation between samples with different ratios of organic carbon to elemental carbon. In sum, the δ13C values obtained for all BC samples fall within the range of anthropogenic emissions such as vehicle traffic, coal combustion and industrial emissions. δ34S and δ18O values of sulphate from BC samples range from -6.3 to +7.0⯠and from +7.6 to +10.5â¯, respectively. Coupling the analysis of the oxygen isotope ratio with that of sulphur enables a more precise identification of the origin of sulphates: the observed isotopic composition falls in the range typical for anthropogenic emission of sulphur dioxide. Overall, in this study, C, S and O isotopes were combined for the first time to assess pollutant sources on black crust samples: this multi-stable isotope approach allowed to show that the BC formation on monuments from the Monumental Cemetery of Milan mostly results from anthropogenic emissions from fossil fuels combustion by road vehicles and factories, as well as domestic heating.
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Currently, the specifications for the assessment of saffron quality are contained in the ISO 3632 technical standard. This norm evaluates saffron quality through a UV-Vis spectrophotometric method and grades the spice into three commercial categories. However, numerous studies have highlighted several weaknesses and limitations of the ISO method. For this reason, a new multi-analytical approach for the determination of saffron quality is proposed in this work. Different techniques were employed to assess saffron quality: UV-visible spectroscopy (UV-Vis), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The results show that the commercial grading based on the ISO 3632 methodology is not always in line with the observations made with the other techniques. Moreover, the use of two new techniques in the field of saffron quality determination, i.e., SEM-EDX and ICP-OES, proved to be effective for the determination of elemental composition and metal content, which are two important parameters to take into consideration when assessing the quality of the spice.
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Black crusts (BCs) are one of the most critical alteration forms found on stones belonging to architectural heritage. Since they could be considered as passive samplers of atmospheric pollution, it would be plausible to establish relations between the air contamination and the BCs. With this aim, we have characterized BCs collected on historic buildings from two Spanish cities (Granada and Vigo) with different polluted atmospheres, as well as formed on stone substrates of varied mineralogy and texture. Likewise, in order to assess the impact of the atmospheric pollutants on the growth of BCs, quartz fiber filters were used as surrogate substrates and placed nearby the studied buildings to collect and analyze the aerosol particulate matter (PM). To this end, an array of complementary analytical techniques was used to evaluate the mineralogy, chemical composition, and texture of the BCs and to establish the correlation with the ions, OC (organic carbon), and EC (elemental carbon) detected in the PM on the quartz fiber filters. As result, BCs developed on carbonate substrates from Granada show more complex structure than those from Vigo, which are thinner because of frequent rain episodes. In both cities, NaCl, Pb-Cl, and Ca-Cl-rich particles, Ca-phosphate particles and clusters of Ba-sulfate-rich particles were detected. However, metal-rich rounded particles were more abundant in Granada's BCs, including soot particles. BCs from Granada were richer in carbonaceous components (OC and EC) than the Vigo's BCs. Although in the filters PM did not show EC-mainly due to traffic-, in the BCs from both locations OC and EC were detected. Therefore, this different composition was related to the mineralogy of the stones and the higher pollution of Granada in contrast to the industrial and sea-exposed city of Vigo.
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Poluentes Atmosféricos , Poluição do Ar , Aerossóis/análise , Poluentes Atmosféricos/análise , Carbono/análise , Cidades , Monitoramento Ambiental , Tamanho da Partícula , Material Particulado/análise , QuartzoRESUMO
The aim of this work has been the identification of the painter's materials employed in the wall decoration of some destroyed buildings dating approximately between the first century B.C. and the first century A.D. This research originates from a previously started joined archaeological and analytical investigation concerning a varied group of findings that resulted from a rescue excavation performed by Soprintendenza Archeologica in the area of Monte d'Oro in Rome. The focus of this study progression has been directed to a numerous selection of monochrome red, pink and yellow-pigmented fragments. The analyses were performed by means of scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDX) combined with Raman and Fourier transform infrared (FTIR) spectroscopies; visible reflectance measurements have also been carried out and the relevance of this technique in such a kind of archaeological studies has been highlighted. Most attention has been given to the assessment of the performances of non-destructive techniques achieved by portable Raman, and visible reflectance instrumentation to test their diagnostic capabilities. In addition to the expected and well-known pigments such as cinnabar, red ochre, hematite for the reds and yellow ochre for the yellows, the study highlighted a diffuse use of mixed colours and in some cases the possible presence of overlapped painted layers and confirmed the presence of gildings. Among the mixtures of pigments, the most singular outcome concerns the pink fragments revealing the possible application of bone white, which seems to be rather uncommon as a pigment in Roman wall decorations.
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Análise Espectral Raman , Análise de Fourier , Cidade de Roma , Espectrometria por Raios X , Espectroscopia de Infravermelho com Transformada de Fourier , Análise Espectral Raman/métodosRESUMO
The surface coating present on a marble Piety dating to the Renaissance period and stored at the Castello Sforzesco-Museum of Ancient Art (Milan, Italy) was studied and chemically characterised. For this purpose, both portable non-invasive (XRF and colorimetric measurements) and micro-invasive techniques (FTIR-ATR and SEM-EDS), have been applied. The statue has been recently submitted to a restoration, since its surface appeared dark and yellowed, before an exhibition at the Louvre Museum and the original appearance of the marble surface recovered thanks to the surface coating removal. Through the analytical characterisation carried out before and after the marble cleaning, the presence of a degradation layer composed by gypsum was evidenced on the stone. The origin of this layer is ascribable to the exposure of the statue to outdoor environment and interaction with atmospheric pollution. The chemical nature of the coating applied at the end of nineteenth century also responsible for the surface alteration was hypothesized.
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Arte , Museus , Carbonato de Cálcio , Sulfato de Cálcio , ColorimetriaRESUMO
Atmospheric pollutants, such as NOx, SO2, and particulate matter, together with water percolation inside the stone pores, represent the main causes of cultural heritage decay. In order to avoid these undesired phenomena, the application of protective coatings represents a reliable solution. In this context, the present study focused on the synthesis of low-fluorine content methacrylic-based (MMA) polymeric resins characterized by seven F atoms (namely F7 monomer) in the lateral chains. Four different percentages (1.0, 2.5, 5.0, and 10.0%) of the present monomer were adopted to obtain a final polymeric structure showing the desired hydrophobicity, processability, and structural and thermal stability (even after accelerated UV aging tests). MMA_F7(1.0) seemed to be the optimal one; therefore, it was further applied onto Candoglia marble. Specifically, the treated substrates showed good surface hydrophobicity, water repellency, and water vapor transpirability. No color variation was observed even after a 1.5-year exposure in a real polluted environment (Monza Cathedral). Interestingly, the application of this coating hindered the atmospheric nitrates penetration inside the stones and, at the same time, it limited the sulfates (gypsum) formation, thus revealing a very promising marbles protection resin.
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Carbonato de Cálcio , Flúor , Carbonato de Cálcio/química , Fluoretos , Interações Hidrofóbicas e Hidrofílicas , Material Particulado , PolímerosRESUMO
In this study, a multimethodological analysis involving optical and physical/chemical diagnostic techniques and 3D photogrammetric survey was successfully applied, for the first time, on the large oil on canvas St. Michael defeating Evil painting by Mattia Preti, located inside the Church of the Immaculate Conception of Sarria (Floriana) in Malta. Pigmenting agents, binder media, and raw materials were first characterized, both at elemental and molecular scales, through X-ray fluorescence spectroscopy (XRF), optical stereo microscopy (SM), scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX), Fourier transform infrared spectroscopy (FT-IR), and gas chromatography coupled with mass spectrometry (GC-MS). The main goal was to properly identify the execution technique of this famous painter, the artist's palette, and possible nondocumented interventions. The 3D photogrammetric survey, on the other side, allowed us to noninvasively evaluate the extension of the areas that experienced restorations, and to properly map the domains of the different canvasses observed. The joints between canvasses suggested that the painting was folded and rolled up. In addition, the employment of a thermal camera gave evidence of the different consolidating material injection points used during the restoration to strengthen the painting. The obtained results offer useful information for the development of optimized restoration and conservation strategies to be applied and provide, at the same time, answers to open questions related to provenance and dating of the investigated artwork.
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Pinturas , Microscopia Eletrônica de Varredura , Pinturas/história , Espectrometria por Raios X/instrumentação , Espectrometria por Raios X/métodos , Espectroscopia de Infravermelho com Transformada de Fourier/instrumentação , Espectroscopia de Infravermelho com Transformada de Fourier/métodosRESUMO
The study of the chemical composition of wines is nowadays a topic of great interest because of the importance of this market, especially in Italy, and also considering the numerous cases of falsification of famous and very expensive wines. The present paper focused on the analysis of metals and polyphenols in Italian wines belonging to different provenance and types. At this purpose 20 elements were quantified by inductively coupled plasma optical emission spectrometry (ICP-OES) and ICP mass spectrometry (ICP-MS). Regarding polyphenols, a total of 32 were quantified, among 6 were anthocyanins. Furthermore, in 4 samples (1 rosè and 3 red wines) 42 anthocyanins and related compounds were identified by ultra-high performance liquid chromatography (UHPLC)-Orbitrap MS technique (among these, 6 were also quantified). Non-anthocyanins were determined using UHPLC coupled with a diode array detector and triple-quadrupole mass spectrometer (UHPLC-DAD-QqQ-MS). Total phenolic content (TPC) and radical scavenging activity (RSA) were measured using spectrophotometric methods. The results obtained by elemental techniques were submitted to principal components analysis (PCA) allowing to get information on both geographical and botanical origin of the examined wine samples. Some polyphenols have been detected in higher concentrations only in a certain type of wine, as for example in the case of Grechetto wine. Most of the identified anthocyanin derivatives (pyranoanthocyanins) are formed during the aging of wine by reaction with the other wine components.
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In the last decades, many researchers investigated the relation between environmental pollution and the degradation phenomena on the built heritage, because of their rapid increase and growing harmfulness. Consequently, the identification of the main pollution sources has become essential to define mitigation actions against degradation and alteration phenomena of the stone materials. In this way, the present paper is focused on the study of the effect of air pollution on archaeological buildings in Historic Cairo. A multi-methodological approach was used to obtain information about the chemical composition of examined black crusts and to clarify their correlation with the air pollution, specifically the heavy metals and the carbonaceous fraction, their main sources, and their impact on the state of conservation of the studied sites. All specimens were characterized by polarized optical microscopy (POM), X-Ray Diffraction (XRD), Electron Probe Micro Analyser coupled with energy dispersive X-ray spectrometry (EPMA-EDS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and Thermo-gravimetric analysis (TGA). The study conducted on heavy metals and carbonaceous fraction showed that the greatest contribution of the accumulation of pollutants is attributable to vehicular traffic and industrial activities, the main polluting sources in Cairo city. Furthermore, the comparison with other studies conducted on the carbonaceous fraction in the black crusts coming from both European and non-European cities, has allowed to discriminate the contribution of the primary and secondary polluting sources. Finally, the correlation of the data obtained on the heavy metals and the carbonaceous fraction allowed to formulate important hypothesis about the processes of sulphation.
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In this study, determinations of the aluminum content in meat and fish performed after having cooked these foods using commercially available aluminum foil have been performed. The release of this chemical element was evaluated by cooking beef, chicken, and fish wrapped with commercial aluminum foil using seasoning or without seasoning in order to evaluate the effect on Al leaching into the food. The characterization of the food samples was carried out using two different analytical methods: inductively coupled plasma optical emission spectrometry (ICP-OES), for the quantification of aluminum, and scanning electron microscopy coupled with energy dispersion spectroscopy (SEM-EDS) to evaluate any structural changes occurring inside the aluminum foil after the cooking procedure. It has been demonstrated that the leaching that occurs when the foods are cooked by wrapping them in Al foil is not negligible and that the consumption of these foods, together with the consumption of other foodstuffs, such as, for example, some vegetables that may naturally contain aluminum, can lead to consuming a weekly dose not far from the TWI (tolerable weekly intake).
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Alumínio , Culinária , Peixes , Carne , Alumínio/análise , Animais , Carne/análise , Espectrometria por Raios XRESUMO
In the present paper total suspended particulate matter (TSP) was collected at the S. Marco Museum in Florence during seasonal monitoring campaigns carried out in 2013 and 2014. The analyses focused on the determination of TSP chemical composition: main ions, organic carbon (OC), elemental carbon (EC), water soluble organic compounds (WSOC) and levoglucosa which is considered the specific marker for wood burning. The analysis of TSP composition in Florence historical centre is of interest to assess what the damage caused to the surfaces of the urban monumental heritage could be. TSP higher value has been registered during December 2013 (58,6 µg/m3 ± 7,3 µg/m3) while the lower value has been registered in July 2013 (28,5 µg/m3 ± 2,2 µg/m3). OC and EC were also higher in winter with respect to summer. Sulphate is characterized by quite constant values during all the examined periods while ammonium and nitrate were higher in winter. The seasonal contribution of different sources such as combustion processes (from traffic and wood burning) and soil dust resuspension has been evidenced. In particular during winter a high concentration of levoglucosan, the specific marker for wood combustion, has been determined. Finally, all the data obtained were correlated with those previously determined in another study carried out in 2003 at the Baptistery of San Giovanni in Florence in order to evaluate any possible change in the atmospheric pollution composition.
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Indoor air quality (IAQ) in household environments is mandatory since people spend most of their time in indoor environments. In order to guarantee a healthy environment, air purification devices are often employed. In the present work, a commercial household vacuum cleaner has been tested in order to verify its efficiency in reducing the mass concentration and particle number of aerosol particulate matter (PM). The efficiency has been tested measuring, while the instrument was working, PM10 (particles with aerodynamic diameter less than 10 µm), PM2.5 (particles with aerodynamic diameter less than 2.5 µm), PM1 (particles with aerodynamic diameter less than 1 µm), and 7 size-fractions in the range between 0.3 and >10 µm. Measurements have been carried out by means of a portable optical particle counter instrument and simulating the working conditions typical of a household environment. It has been found that the tested commercial device significantly reduces both PM concentrations and particle number, especially in the finest fraction, i.e., particles in the range 0.3-0.5 µm, allowing an improvement of indoor air quality.
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Aerossóis/isolamento & purificação , Poluição do Ar em Ambientes Fechados/análise , Material Particulado/análise , Ar Condicionado , Monitoramento Ambiental , Humanos , Tamanho da PartículaRESUMO
Structural analysis of marble statues, carried out by non-invasive and in situ methods, is crucial to define the state of conservation of the artworks and to identify the deterioration phenomena that can affect them. In this work, we combined in situ non-destructive techniques, ultrasonic tomography (US), ultraviolet-induced visible fluorescence (UV-IF) and X-ray fluorescence (XRF) to study the bass-relief 'Madonna con Bambino' (Gorizia, Italy). The US revealed the presence of some metallic pivots, associated with areas of high sound velocity; moreover, a more degraded area has been identified in the lower part of the bass-relief. The acquired UV-IF image confirmed the presence of surface degradation, allowing a preliminary evaluation of the extension of a fracture, from surface to bulk. In addition, the different materials (both original and/or integrations) that compose the studied surface have been identified. The XRF has contributed to define the nature of the inorganic materials applied during undocumented previous restoration works on the surface as filler for lacunae.
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Arte , Carbonato de Cálcio , Escultura , Fluorescência , Itália , Métodos , Propriedades de SuperfícieRESUMO
In this work, new co- and ter-polymers of methyl methacrylate (MMA), ethyl methacrylate (EMA), and N-butyl methacrylate (nBuMA), containing just 1% mol × mol-1 of a fluorinated co-monomer, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl methacrylate (POMA), were synthesized. After an UV accelerated aging test, the photo-chemical stability of the polymers prepared was determined by 1H NMR and FT-IR spectroscopy, size exclusion chromatography, differential scanning calorimetry and wettability measurements. The polymers were applied to Botticino tiles to achieve better performances in terms of water repellency and consequently deterioration resistance. One-year prolonged exposure to a real environment was conducted and the properties of the coated materials and their performances were studied using different surface techniques such as water contact angle (WCA) and colorimetric measurements (CIELaB), capillary absorption, permeability (RVP) tests and soluble salts determination. The effectiveness of the fluorinated methacrylic coatings was clearly demonstrated; among all the resins, the co-polymer MMA_POMA seems to be the most performing one. Furthermore, both the UV photo-chemical resistance and the easiness of removal was successfully studied.
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This paper deals with the analysis of black crust coming from the statue of Oceanus belonging to the Fontana di Trevi (Rome). This monument is undoubtedly one of the main touristic attractions of Rome. During the restoration held between 2014 and 2015, some diagnostic analyses had been carried out. It has been highlighted that the sheltered surfaces suffer the formation of black crust, especially on the marble statues. The possibility to sample those degradation products, together with the unaltered substrate, represented an excellent opportunity to characterize the marble itself, to assess the impact of the urban air pollution on the stone material, and to detect the pollutant on a precise timescale. In fact, it is known that the previous restoration of the fountain had been carried out between 1989 and 1991 then, information about the air pollution over the last 25years can be highlighted, because it has been proved that black crusts act as passive samplers of pollution. In order to fully characterize those samples, several techniques were used, including optical and scanning electron microscopy, X-ray diffraction, laser ablation inductively coupled plasma mass spectrometry, infrared spectroscopy and ion chromatography. Furthermore, a new methodology based on CHN (Carbon, Hydrogen, Nitrogen) analysis has been developed for the quantification of the two main constituents of the carbonaceous fraction present in the black crusts, i.e. OC (organic carbon) and EC (elemental carbon). This integrated approach proposed in the present study allowed us to gain information about the mineralogical phases and the elements within the crusts and at the crust-substrate interface, giving the possibility to identify the pollution sources causing the stone decay within the monument.
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During a sampling campaign, carried out during June 2012, inside some traditional households located in four villages (Phakding, Namche, Pangboche and Tukla) of Mt. Everest region in southern part of the central Himalaya (Nepal), particulate matter (PM) depositions and ashes have been collected. Moreover, outdoor PM depositions have also been analyzed. Chemical characterization of PM depositions and ashes for major ions, organic carbon, elemental carbon (EC), metal content and PAHs (Polycyclic Aromatic Hydrocarbons) allowed identifying, as major contributes to indoor PM, the following sources: biomass burning, cooking and chimney ashes. These sources significantly affect outdoor PM depositions: in-house biomass burning is the major source for outdoor EC and K+ as well as biomass burning and cooking activities are the major sources for Polycyclic Aromatic Hydrocarbons.