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In this work, a comprehensive characterisation and source apportionment of size-segregated aerosol collected using a multistage cascade impactor was performed. The samples were collected during wintertime in Milan (Italy), which is located in the Po Valley, one of the main pollution hot-spot areas in Europe. For every sampling, size-segregated mass concentration, elemental and ionic composition, and levoglucosan concentration were determined. Size-segregated data were inverted using the program MICRON to identify and quantify modal contributions of all the measured components. The detailed chemical characterisation allowed the application of a three-way (3-D) receptor model (implemented using Multilinear Engine) for size-segregated source apportionment and chemical profiles identification. It is noteworthy that - as far as we know - this is the first time that three-way source apportionment is attempted using data of aerosol collected by traditional cascade impactors. Seven factors were identified: wood burning, industry, resuspended dust, regional aerosol, construction works, traffic 1, and traffic 2. Further insights into size-segregated factor profiles suggested that the traffic 1 factor can be associated to diesel vehicles and traffic 2 to gasoline vehicles. The regional aerosol factor resulted to be the main contributor (nearly 50%) to the droplet mode (accumulation sub-mode with modal diameter in the range 0.5–1 μm), whereas the overall contribution from the two factors related to traffic was the most important one in the other size modes (34–41%). The results showed that applying a 3-D receptor model to size-segregated samples allows identifying factors of local and regional origin while receptor modelling on integrated PM fractions usually singles out factors characterised by primary (e.g. industry, traffic, soil dust) and secondary (e.g. ammonium sulphate and nitrate) origin. Furthermore, the results suggested that the information on size-segregated chemical composition in different size classes was exploited by the model to relate primary emissions to rapidly-formed secondary compounds. [ABSTRACT FROM AUTHOR]

Lustre is characterized by a few hundreds of nanometers thick heterogeneous metal-glassy nano-composite film. Silver and copper nanoparticles are dispersed within the outermost layers of the glaze, conferring peculiar optical properties to the whole material. Even though numerous studies have been carried out, many questions regarding the chemical composition, the mechanism of metal reduction and the optical properties of lustre still remain. Synchrotron radiation techniques are suitable for detailed studies on metal-glassy nano-composites. For example, X-ray absorption fine structure spectroscopy (EXAFS) can provide useful information on oxidized phases or atomic clusters dispersed in an amorphous medium, otherwise not achievable with diffraction techniques. In this work, we try to get information on the chemical state and local environment of metal atoms in the lustre and in the blue pigment, in order to achieve a better understanding of the reduction mechanism of different metals present and the manufacturing techniques related to different productions (Hispano-Moorish and Italian Renaissance lustred majolicas). In particular, different samples characterized by lustre and blue decorations only, produced in Spain and in central Italy in XIV–XV cent., are compared. [ABSTRACT FROM AUTHOR]

The Angera stone is a sedimentary Triassic dolostone mainly composed of dolomite, which was widely employed in the Lombard architecture. In the present work, the study of the Angera stone of the 'Cortile del Richini', a masterpiece of the Lombard baroque, is discussed as an example of a particularly challenging conservation issue. The courtyard suffered from a particularly troubled conservative history and the highly polluted urban environment of Milan provided very favourable conditions for the decay of such a delicate stone type. The last extensive conservative intervention was performed during the nineties due to massive black crust formation and granular disintegration of the stone. Almost 20 years later, a thorough study of the stone has been aimed at the definition of a long-term maintenance project. The Angera stone has been investigated in order to define an updated version of its state of conservation, as well as to track any changes in the degradation mechanisms due to the environmental variations of the Milan city centre. In particular, the soluble salts' content of the stone substrate has been evaluated as an indicator of the damage level. The results highlighted that the stone is currently in critical condition: An extensive sulphation process is taking place, leading to the chemical transformation of the dolomitic substrate into gypsum. Moreover, the powder deposits affecting the stone surfaces have a similar composition to those generally found in the black crusts growing in urban environment. Therefore, they can be considered as precursor of this particularly dangerous decay mechanism. [ABSTRACT FROM AUTHOR]

study has been realised to elucidate the first step of lustre production in Italy. With this aim in mind, an investigation was carried out on an emblematic lustred object: Baglioni’s albarello. It is conserved at Louvre museum and it is considered as one of the very first examples of lustred object produced in Italy. The characteristics of the lustred film have been determined, identifying interesting aspects that may be used to scientifically confirm the origin of this object. This study was completed by the investigation of other objects: a not lustred albarello, still decorated with the coat of arms of Baglioni’s family and a lustred plate with the coat of arms of the Montefeltro family. The two Baglioni’s albarelli are stylistically and historically considered as produced in one of the numerous workshops of Deruta. The origin of the Montefeltro’s plate, although from central Italy, is not precisely attested. In order to acquire more information, clarifying the origin and place of production of these objects, a comparison of their physico-chemical characteristics with results obtained and already published on different well-attested productions, such as Islamic, Hispano-Moresque and Italian, was carried out. For what concerns the museum objects, the use of non-destructive investigation techniques was mandatory. For this reason, ion beam techniques as PIXE and RBS have been used at AGLAE facility, as well as a new X-ray micro-diffraction equipment, at C2RMF. Moreover, the results were compared with data obtained on shards of certain production origin, by means of chemometric techniques. Some hypothesis concerning the place of production of the examined objects have been formulated. [ABSTRACT FROM AUTHOR]

For the first time some excellent pieces belonging to the majolica production of the great master Giorgio Andreoli from Gubbio (Central Italy) have been characterized from a chemical and structural point of view with the aim to identify the composition of both pigments and lustres. A series of particle-induced X-ray emission (PIXE), Rutherford backscattering spectrometry (RBS) and Raman analyses have been performed on some plates coming from Museo del Palazzo dei Consoli (Gubbio) and several French museums (Louvre, Musée National de la Céramique, Musée National de la Renaissance) lustred by Giorgio Andreoli and decorated by famous majolica painters such as Francesco Xanto Avelli. The three techniques are complementary and useful in the investigation of art objects since they are non-destructive. Furthermore, the low detection limits allow the identification of all elements and compounds present, and RBS allows concentration profiling, too. It is worth noticing that the examined objects are characterized by the presence of both gold and ruby-red lustres, a peculiarity of Mastro Giorgio’s technique. The measurements by PIXE and RBS have been carried out on the AGLAE accelerator at C2RMF, Louvre Palace. [ABSTRACT FROM AUTHOR]

The aim of this work is to gain a further insight into the knowledge of the production process of lustre-decorated ancient majolicas. Lustre is a sophisticated technique employed in the decoration of majolicas as used in central Italy during the Renaissance period. It consists of a beautiful iridescent gold or ruby-red thin metallic film, containing silver, copper and other substances and obtained in a reducing atmosphere on a previously glazed ceramic. Nowadays, it is not possible to replicate the outstanding results obtained by the ancient ceramicists, since the original recipes were lost. It is quite interesting to study lustre-production technology by means of analytical techniques now employed for advanced research on materials (XRD, ETAAS, ICP-OES, TEM-EDX-SAED and UV-Vis). In this work, we have focussed our attention on ceramic fragments decorated with both gold and ruby-red lustres, which were difficult to obtain due to complex reduction conditions required and which were a prerogative of Gubbio production. The two lustre colours differ in their chemical composition as well in their nanostructure. The presence of bismuth was disclosed and it was ascertained to be a distinctive feature of the Italian production. [ABSTRACT FROM AUTHOR]

The knowledge of bismuth during the XV and XVI centuries represents an open question since, according to some authors, this element was confused with lead, tin and silver. On the contrary, G. Agricola (1494–1555), the pioneer of mineralogical science in Europe, in his two works (De Natura Fossilium, Lib X, 1546 and Bermannus Sive De Re Metallica Dialogus, 1528) asserts that bismuth was considered as an element distinct from the other metals at that time. This question gave rise to some interest, and von Lippmann in 1930 wrote a treatise dealing with the history of bismuth between 1400 and 1800. In this work we present the results obtained on Italian and Hispano–Moresque shards studied by means of X-ray diffraction, atomic absorption spectrometry with electrothermal atomisation, inductively coupled plasma optical emission spectrometry and scanning electron microscopy. It seems that our work could provide a new and important contribution to this debate, because we found bismuth in lustre composition of Renaissance shards produced in central Italy. Furthermore, we found that it could also be considered as a discriminating element between Italian and Hispano–Moresque productions, useful to assess their origin. [ABSTRACT FROM AUTHOR]

About one hundred Etruscan ceramic shards dating from the VIII to the IV century BC and coming from the archaeological excavation at Pian di Civita in Tarquinia (central Italy) have been analyzed by inductively coupled plasma optical emission spectrometry and flame atomic emission spectrometry in order to settle their provenance and to acquire knowledge about the ceramic production technology. The examined shards belong to the class of the depurata pottery, a fine ware produced in Tarquinia over a long period, and are representative of different sub-classes. The samples have been analyzed for fifteen elements (Ca, Al, Mg, Fe, Ti, Cr, Cu, Ni, Zn, Mn, Zr, Sr, Na, K and Rb). The data acquired have been treated by multivariate analysis techniques such as principal component analysis and Kohonen artificial neural networks. Most of the analyzed shards have been locally produced as belonging to a unique large group. A continuity in usage of both choice of materials and technology has been recognized. [ABSTRACT FROM AUTHOR]

In order to recover the ancient tradition concerning the materials used for the decoration, majolica shards produced during the Renaissance period in Casteldurante, a famous centre for ceramic production in Italy (Marche), have been examined. In the present study, pigments used for the decorations have been investigated by means of inductively coupled plasma optical emission spectrometry (ICP-OES), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDX) and diffuse-reflectance UV-Vis spectroscopy. Ochre, lead antimonate yellow, copper-based pigment and smalt have been used as colourants to obtain respectively yellow-orange, yellow, green and blue decorations in accordance with what is reported by the ancient recipes. [ABSTRACT FROM AUTHOR]

Luminescence measurements have been performed on several Italian Renaissance ceramic shards produced in central Italy, as well as on some others from Hispano–Moresque and Fatimid periods. The aim of this study was the characterisation of the raw materials used to manufacture lustre decorated majolica. At first, the thermoluminescence (TL) dating of all ceramic bodies was performed, because the shards lacked sure chronological attribution, having been provided by private collectors, or found during emergency restoration works or archaeological surveys. To characterise the defects and the recombination centers of the different components of the ceramics (ceramic body, glaze, glaze, and lustre), radioluminescence (RL) measurements have been performed on samples representative of each historical period. The dating results are reported, as well as the preliminary RL results. [ABSTRACT FROM AUTHOR]

Lustre was one of the most sophisticated techniques for the decoration of majolicas during the Renaissance period. Lustre consists of a thin metallic film containing silver, copper and other substances like iron oxide and cinnabar applied in a reducing atmosphere on a previously glazed ceramic. In this way, beautiful iridescent reflections of different colours (in particular gold and ruby-red) are obtained. The characterisation and the study of lustre-decorated majolicas is of great interest for archaeologists, but also offers possibilities for producing pottery with outstanding decoration today, following ancient examples, since nowadays Italian artisans are interested in the reproduction of the ancient recipes and procedures. Moreover, it can even suggest new procedures for obtaining uniform thin metallic films for technological applications. A study has been carried out on ancient lustre layers using numerous different analytical techniques such as XRD, SEM–EDX, TEM–EDX–SAED, ETAAS, ICP–OES, UV–vis reflectance spectroscopy and SAXS. Lustre films were shown to be formed by copper and silver clusters of nanometric dimension. The colour and the properties of the lustre films depend on the elemental composition of the impasto applied to the ceramic surface as well as on other factors like the metallic nanocluster dimension, the firing conditions, the underlying glaze composition and the procedure used. [ABSTRACT FROM AUTHOR]

Abstract: Particle-bound benzo(a)pyrene (B(a)P) constitutes an air pollution problem in many areas of Europe and has been linked to biomass burning (BB). The present study, conducted in 2007 and 2009 at ten stations in the North Italian Po Plain and Valtelline Valley, examines four methods for the quantification of BB contributions to particle-bound B(a)P using data for 61 predictor compounds in more than 700 ambient PM10 and PM2.5 samples. The study was carried out during the heating season – a period of the year with minimal volatilization and atmospheric degradation of B(a)P, which favour source apportionment by receptor modelling. The lowest estimates of the source contribution (SCE) from BB were obtained with the levoglucosan tracer method and multi-linear regression analysis of daily variations in B(a)P concentrations using levoglucosan as the main predictor in combination with a few other predictors including gaseous pollutants and meteorological data. The standard uncertainty of these methods was driven by the uncertainty in the BB emission factor for levoglucosan and mounted to 90% (1 σ). Positive matrix factorization (PMF), using only PAH congeners as predictors, did not produce factors interpretable as emission sources. However, PMF utilizing a broad range of predictor compounds afforded five factors with compositions similar to emission sources. The yielded B(a)P SCEs for BB agreed well with results of chemical mass balance modelling (CMB). Both receptor models gave good predictions (p) of the observed (o) B(a)P concentrations (PMF: p/o = 89 ± 9%, CMB: p/o = 114 ± 17%) with lower uncertainties than the tracer methods (CMB 60%; PMF 54%; 1 σ). The average BB SCEs (mean ± 95% confidence interval) from these models were: 1.0 ± 0.4 ng m−3 at a kerbside in Milan, 1.0 ± 0.2 ng m−3 at six urban background stations in the Po Plain, 0.7 ± 0.3 ng m−3 at two rural background stations in the Po Plain, and 2.1 ± 1.1 ng m−3 at an urban background station in the Valtelline Valley representing 74 ± 32%, 79 ± 18%, 85 ± 33%, and 84 ± 46% of all modelled B(a)P sources, respectively. [Copyright &y& Elsevier]

Abstract: The concentration of carbonates in atmospheric Particulate Matter (PM) is usually quite low. The surroundings of marble quarries are peculiar sites where the impact of carbonates in PM levels can be significant. We present here the results of a PM10 sampling campaign performed in Carrara (Italy). The town lies between the famous marble quarries and the harbour: about 1000 trucks per day transport marble blocks and debris from the quarries to the harbour passing through the town centre. PM10 was collected on daily basis on PTFE filters analyzed by Energy-Dispersive X-Ray Fluorescence (ED-XRF) and Ion-Chromatography (IC). Carbonate concentration was measured by a non-destructive Infrared Spectroscopy analysis (FT-IR). Time series of elemental (Na–Pb by ED-XRF), ionic (SO4 2−, NH4 + by ion-chromatography) and carbonate (by FT-IR) concentration values were merged in a unique data set and a PMF analysis singled out the major PM10 sources in the area. Marble transportation turned out to be the major pollution source in the town accounting to PM10 for about 36%; this corresponded to a CaCO3 average level of about 8 μg m−3 during working days. The FT-IR analysis was a crucial part of the work and an ad-hoc analytical procedure was specifically set up, calibrated, and tested as described in the text. [Copyright &y& Elsevier]

Sub-micron sized particles are of increasing concern owing to their effects on human health and on the environment. Up to now there are still very few studies on PM1 (i.e. particulate matter with aerodynamic diameter smaller than 1μm) chemical characterisation; the sub-micron sized fraction is not under regulations although it is of interest because it is almost exclusively associated to anthropogenic sources. To perform the first large-scale assessment of sub-micron sized aerosol concentrations, composition and sources, two monitoring campaigns at three urban sites in Italy were carried out during the wintertime and summertime of 2004. Chemical characterisation (elements, soluble ionic fraction, elemental and organic carbon) was carried out on PM1 samples: major contributions were due to organic matter (about 30% in summer and 50% in winter) and ammonium sulphate (about 10% in winter and 40% in summer). During the cold season, nitrates also contributed up to 30% in Milan (lower contributions were registered at the other two urban sites). Chemical mass closure was achieved with an unaccounted mass in the range 14–22%. Positive Matrix Factorisation (PMF) was applied to identify the major sub-micron sized particles’ sources. [Copyright &y& Elsevier]

In the field of conservation of cultural heritage, one must always consider the environmental conditions in which the works of art are located and the level of atmospheric pollution to which they are exposed, especially in the case of monuments stored outdoors. The present study is focused on the detection and the quantification of polycyclic aromatic hydrocarbons (PAHs) in black crust samples from the Monumental Cemetery of Milan (Italy), and the assessment of their sources through the analysis of the distributions of the different compounds in the samples, together with the use of diagnostic ratios. Six black crust samples taken from funerary monuments were analyzed. Fourteen polycyclic aromatic hydrocarbons were identified (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene) by high-performance liquid chromatography with a diode-array detector (HPLC-DAD), with a total concentration from 0.72 to 3.81 μg/g (mean of 1.87 μg/g). The known carcinogenic benzo[a]pyrene accounted for 5-10% of the total polycyclic aromatic hydrocarbons in the samples analyzed, with concentrations up to 0.20 μg/g. Moreover, the study of the distribution and diagnostic ratios allowed us to confirm that anthropogenic sources such as traffic and the proximity of the train station are the major causes of the degradation of the monuments contained in this Cemetery., (© 2024. The Author(s).)

In this work PM 2.5 was collected during winter and summer in a Sardinian village (Gonnostramatza, Italy) highly affected by biomass burning emissions. A multi-technique approach was adopted for the complete PM chemical characterization. The bulk characterization was performed by IC (Ion Chromatography), HPAEC (High-Performance Anion-Exchange Chromatography), TOT (Thermal Optical Transmittance) and ED-XRF (Energy-Dispersive X-Ray Fluorescence) while XPS (X-ray Photoelectron Spectroscopy) was used for the surface characterization. Using levoglucosan as specific tracer of biomass burning emissions, the assessment of the impact of this source was carried out and it represent the major PM source at the investigate site during winter. In winter the average levoglucosan concentration is 2096 ± 324 ng/m 3 while during summer its concentration is negligible (18 ± 7 ng/m 3 ). Levoglucosan content in PM 2.5 during winter is on average 13.7%; it is estimated that 65% of PM 2.5 is due to wood burning. XPS has been exploited in this work aiming at highlighting possible differences between surface and bulk composition of PM 2.5 . The surface of the particulate matter resulted enriched in carbon compared to the bulk. Among the components of XPS C1s signals recorded on the samples collected during winter, it was found that the signal at 286.5 eV, which is due to the presence of COH, reflects the bulk composition of levoglucosan., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This work is part of the TOBICUP (TOxicity of BIomass Combustion generated Ultrafine Particles) project which aimed at providing the composition of ultrafine particles (UFPs, i.e. particles with aerodynamic diameter, d ae , lower than 100nm) emitted by wood combustion and elucidating the related toxicity. Results here reported are from two ambient monitoring campaigns carried out at an alpine town in Northern Italy, where wood burning is largely diffused for domestic heating in winter. Wintertime and summertime UFP samples were analyzed to assess their chemical composition (i.e. elements, ions, total carbon, anhydrosugars, and polycyclic aromatic hydrocarbons) and biological activity. The induction of the pro-inflammatory cytokine interleukin-8 (IL-8) by UFPs was investigated in two human cells lines (A549 and THP-1) and in human peripheral blood leukocytes. In addition, UFP-induced oxidative stress and genotoxicity were investigated in A549 cells. Ambient UFP-related effects were compared to those induced by traffic-emitted particles (DEP) taken from the NIES reference material "vehicle exhaust particulates". Ambient air UFPs induced a dose-related IL-8 release in both A549 and THP-1 cells; the effect was more relevant on summer samples and in general THP-1 cells were more sensitive than A549 cells. On a weight basis our data did not support a higher biological activity of ambient UFPs compared to DEP. The production of IL-8 in the whole blood assay indicated that UFPs reached systemic circulation and activated blood leukocytes. Comet assay and γ-H2AX evaluation showed a significant DNA damage especially in winter UFPs samples compared to control samples. Our study showed that ambient UFPs can evoke a pulmonary inflammatory response by inducing a dose-related IL-8 production and DNA damage, with different responses to UFP samples collected in the summer and winter periods., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The carbonaceous component in the Milan urban particulate matter, i.e. the two components black carbon (BC) and organic carbon (OC), has been measured by means of a thermogravimetric analyzer combined with an infrared spectrophotometer (TGA/FT-IR). While black carbon may be considered a primary pollutant, organic carbon includes both primary emissions and secondary organic aerosols. Since carbonaceous aerosol (including a small quantity of inorganic carbon, too) makes up roughly from 25% to 50% of the average annual PM 2.5 mass concentration, a deeper understanding of this component is required. The TGA/FT-IR technique, employed for the first time to our knowledge for the quantification of the particulate matter carbonaceous component, allows, thought the results here presented are preliminary, to assess the two components BC and OC in a simple way especially if compared with the methods reported in the literature. The total carbon (TC) determinations performed by TGA/FT-IR on Milan urban particulate matter are in good agreement with the results obtained by a total organic carbon (TOC) analyzer operating directly on the solid sample.

The synergy of the micro FT-IR (Fourier Transform-Infrared) and SEM-EDX (Scanning Electron Microscopy-Energy Dispersive X-ray) techniques has been shown to be particularly helpful and effective for the characterization of inorganic compounds in fly ashes. The experimental data obtained by these techniques have been interpreted in comparison with those of other techniques. The presence of calcium carbonate, some sulfates, ammonium nitrate, calcium hydrogen phosphate, some chlorides, some oxides and aluminium silicates have been verified.