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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 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., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

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., (© 2021. The Author(s).)

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., (© 2021. The Author(s).)

Atmospheric pollutants, such as NO x , SO 2 , 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., (© 2021. The Author(s).)

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., (© 2021. The Author(s).)

The aim of this study is to setup a first chemical database that could represent the starting point for a reliable classification method to discriminate between Archaic Phoenician and Punic pottery on the base of their chemical data. This database up to now can discriminate between several different areas of production and provenance and can be applied also to unknown ceramic samples of comparable age and production areas. More than 100 ceramic fragments were involved in this research, coming from various archaeological sites having a crucial importance in the context of the Phoenician and Punic settlement in central and western Mediterranean: Carthage (Tunisia), Toscanos (South Andalusia, Spain), Sulci, Monte Sirai, Othoca, Tharros (Sardinia, Italy) and Pithecusa (Campania, Italy). Since long-time archaeologists hypothesised that Mediterranean Archaic Phoenician and Punic pottery had mainly a local or just a regional diffusion, with the exception of some particular class like transport amphorae. To verify the pottery provenance, statistical analyses were carried out to define the existence of different ceramic compositional groups characterised by a local origin or imported from other sites. The existing literature data are now supplemented by new archaeometric investigations both on Archaic Phoenician ceramics and clayey raw materials from Sardinia. Therefore, diffractometric analyses, optical microscopy observations and X-ray fluorescence analyses were performed to identify the mineralogical and chemical composition of Othoca ceramics and clayey raw material. The obtained results were then compared with own literature data concerning Phoenician and Punic pottery in order to find features related to the different ceramic productions and their provenance. Principal component analysis (PCA) and hierarchical cluster analysis (HCA) were also performed on the chemical compositional data in order to discriminate ceramic groups. A very complex situation was found: imported ceramics coming from Carthage, with a large-scale distribution, were found together with a predominant local production pottery. The archaeometric results demonstrate that historical and typological approach has to be supported by scientific analyses to better understand local or Mediterranean exchanges.

In the present work, two kinds of hybrid polymeric-inorganic coatings containing TiO 2 or SiO 2 particles and prepared starting from two commercial resins (Alpha®SI30 and Bluesil®BP9710) were developed and applied to two kinds of mortars (an air-hardening calcic lime mortar [ALM] and a natural hydraulic lime mortar [HLM]) to achieve better performances in terms of water repellence and consequently damage resistance. The two pure commercial resins were also applied for comparison purposes. Properties of the coated materials and their performance were studied using different techniques such as contact angle measurements, capillary absorption test, mercury intrusion porosimetry, surface free energy, colorimetric measurements and water vapour permeability tests. Tests were also performed to determine the weathering effects on both the commercial and the hybrid coatings in order to study their durability. Thus, exposures to UV radiation, to UV radiation/condensed water cycles and to a real polluted atmospheric environment have been performed. The effectiveness of the hybrid SiO 2 based coating was demonstrated, especially in the case of the HLM mortar.

A total of 85 PM 2.5 samples were collected at a site located in a large industrial zone (Porto Marghera, Venice, Italy) during a 1-year-long sampling campaign. Samples were analyzed to determine water-soluble inorganic ions, elemental and organic carbon, and levoglucosan, and results were processed to investigate the seasonal patterns, the relationship between the analyzed species, and the most probable sources by using a set of tools, including (i) conditional probability function (CPF), (ii) conditional bivariate probability function (CBPF), (iii) concentration weighted trajectory (CWT), and (iv) potential source contribution function (PSCF) analyses. Furthermore, the importance of biomass combustions to PM 2.5 was also estimated. Average PM 2.5 concentrations ranged between 54 and 16 μg m -3 in the cold and warm period, respectively. The mean value of total ions was 11 μg m -3 (range 1-46 μg m -3 ): The most abundant ion was nitrate with a share of 44 % followed by sulfate (29 %), ammonium (14 %), potassium (4 %), and chloride (4 %). Levoglucosan accounted for 1.2 % of the PM 2.5 mass, and its concentration ranged from few ng m -3 in warm periods to 2.66 μg m -3 during winter. Average concentrations of levoglucosan during the cold period were higher than those found in other European urban sites. This result may indicate a great influence of biomass combustions on particulate matter pollution. Elemental and organic carbon (EC, OC) showed similar behavior, with the highest contributions during cold periods and lower during summer. The ratios between biomass burning indicators (K + , Cl - , NO 3 - , SO 4 2- , levoglucosan, EC, and OC) were used as proxy for the biomass burning estimation, and the contribution to the OC and PM 2.5 was also calculated by using the levoglucosan (LG)/OC and LG/PM 2.5 ratios and was estimated to be 29 and 18 %, respectively.

In order to avoid both natural and artificial stone decay, mainly due to the interaction with atmospheric pollutants (both gases such as NOx and SO2 and particulate matter), polymeric materials have been widely studied as protective coatings enable to limit the penetration of fluids into the bulk material. In the current work, an air hardening calcic lime mortar (ALM) and a natural hydraulic lime mortar (HLM) were used as substrates, and commercially available Si-based resins (Alpha®SI30 and Silres®BS16) were adopted as protective agents to give hydrophobicity features to the artificial stones. Surface properties of coatings and their performance as hydrophobic agents were studied using different techniques such as contact angle measurements, capillary absorption test, mercury intrusion porosimetry, surface free energy, colorimetric measurements and water vapour permeability tests. Finally, some exposure tests to UV radiation and to real polluted atmospheric environments (a city centre and an urban background site) were carried out during a wintertime period (when the concentrations of the main atmospheric pollutants are higher) in order to study the durability of the coating systems applied. The effectiveness of the two commercial resins in reducing salt formation (sulphate and nitrate), induced by the interaction of the mortars with the atmospheric pollutants, was demonstrated in the case of the HLM mortar. Graphical Abstract ᅟ.

The issue of conservation of the monumental heritage worldwide is mainly related to atmospheric pollution that causes the degradation of stone surfaces. The powder deposits present on the stone monuments reflect the composition of the aerosol particulate matter (PM) to which the surfaces are exposed, so the chemical characterization of the outermost damaged layers is necessary in order to adopt mitigation measurements to reduce PM emissions. In the present paper, a new analytical approach is proposed to investigate the chemical composition of powder deposits present on Angera stone, a dolomitic rock used in the Richini courtyard, a masterpiece of Lombard Baroque and placed in Milan. Inorganic and organic components present in these deposits have been analyzed by IC (ion chromatography) and a new approach mainly bases on thermal analyses, respectively. Gypsum is the main inorganic constituent indicating a composition similar to that of black crusts, hard black patina covering the degraded building surfaces. Ammonium nitrate present in the powder is able to react with the stone substrate to form magnesium nitrate which can migrate into the porous stone. The carbonaceous fraction powder deposits (i.e. OC = Organic Carbon and EC = Elemental Carbon) have been quantified by a new simple thermal approach based on carbon hydrogen nitrogen (CHN) analysis. The presence of high concentration of EC confirms that the powder deposits are evolving to black crust. Low values of water-soluble organic carbon (WSOC, determined by total organic carbon-TOC), with respect to what is normally found in PM, may indicate a migration process of organic substances into the stone with a worsening of the conservation conditions. The presence of heavy metals of anthropogenic origin and acting as catalysts in the black crust formation process has been highlighted by SEM-EDS (electron microscopy coupled with an energy dispersive spectrometer) as well.