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In the last decades there have been several studies on cultural heritage regarding the performance of protective and consolidating coatings for the prevention of decay. A coating must have several characteristics such as: efficiency, breathability, and must be durable and reversible. In this research work we tried to verify the performance of a commercial protective product such as Fosbuild FBLE 200, which is composed of a TiO2 nanopowder dispersed in an aqueous solution of an acrylic polymer. This product, which exhibits depolluting, antimicrobial, water-repellent and self-cleaning characteristics, has been applied on different lithotypes such as: Carrara marble, Noto and Comiso stone and exhibited in two different outdoor environments such as Catania and Palermo. These two cities are mostly affected by pollution produced by vehicular traffic; moreover, Catania is also affected by pollution produced by the activity of Mount Etna.

The present study concerns the identification of the colouring matter in ancient tapestries of different historical periods. The investigation was performed using HPLC-DAD-ESI-MS and the results were compared with a previously created reference database. Furthermore, the characteristic fragmentation pathway provided additional information for the identification of the dyes employed.

La qualità dell'aria negli edifici storici e negli ambienti museali è oggetto di crescente preoccupazione da parte sia della comunità scientifica che degli addetti al restauro e alla manutenzione delle opere stesse. Molte fonti di inquinanti, sia in fase gas che in fase particellare, sono responsabili del decadimento accelerato delle opere d'arte. Conoscere i livelli di inquinamento indoor è quindi di fondamentale importanza per applicare le strategie di conservazione del patrimonio culturale. In questo studio è stata monitorata la qualità dell'aria all'interno della Pinacoteca Ambrosiana di Milano (nei due periodi ottobre-novembre 2017 e marzo 2018) nella sala in cui si trova il cartone preparatorio della Scuola di Atene (1509-1511), uno dei più importanti capolavori di Raffaello. Il cartone durante la campagna di misura era in fase di restauro per poi essere esposto in una nuova teca da realizzare in base alle specifiche condizioni ambientali e microclimatiche riscontrate nella stanza. Il particolato atmosferico (PM) è stato monitorato fino alla frazione nano ovvero quella più pericolosa per le superfici delle opere d'arte. Le campagne di monitoraggio sono state condotte in parallelo nella sala del cartone, che all'epoca del restauro non era accessibile ai visitatori, e in una sala limitrofa aperta al pubblico. La strumentazione utilizzata ha incluso un campionatore TSP (particelle sospese totali), un analizzatore ottico Dust Monit (Contec) che ha permesso di misurare la concentrazione di PM10, 2.5 e PM1 fornendo anche 7 classi granulometriche (fino a 300 nm), uno strumento NanoScan (SMPS Nanoparticle Sizer 3910, TSI) che ha permesso di misurare la concentrazione di particelle fino a 10 nm e due strumenti per la determinazione del black carbon in continuo ovvero un micro etalometro e uno strumento SILIIS (spettroscopia di incandescenza indotta da laser) che consente di rilevare nanoparticelle di black carbon fino a qualche nanometro con un detection limit di 200 ng/m3. I filtri in fibra di quarzo raccolti mediante il campionatore TSP sono stati caratterizzati mediante IC (cromatografia ionica), TOT (trasmittanza termo ottica) e SEM-EDX (microscopia elettronica con analisi a dispersione di energia). Col presente studio si è dimostrato che in entrambe le stagioni la penetrazione di PM dall'esterno risulta essere la principale sorgente di particelle. Inoltre durante l'autunno i limiti massimi di concentrazione suggeriti per il PM10 sono spesso superati. Il fatto che le particelle più fini (0,3-0,5 micron) siano di gran lunga le più abbondanti deve destare preoccupazione poiché sono quelle maggiormente capaci di interagire con la porosità delle superfici delle opere d'arte inclusa la carta avente una porosità molto elevata. In particolare, il black carbon, responsabile dell'annerimento delle superfici stesse, è risultato essere maggiormente concentrato nella frazione più fine.

Air pollution is the major responsible for the formation of damage layers on stone monuments and historic buildings in urban areas (Bonazza and Sabbioni, 2016). Among widely used building materials, marble and limestone were selected in previous studies on pollution impact, thanks to their chemical homogeneity (mainly composed by calcium carbonate) and low porosity. The effects of pollution have been heretofore assessed by analyzing samples collected from historic buildings or performing tests in simulation chamber and/or in field but gaps still remain in measuring deposition fluxes on materials and developing proper tools for long-term management of cultural heritage. Moreover, the possible effects on built heritage of the current atmosphere poorer than in the past of SO2 but richer of NOx and organic compounds (mainly released by vehicular traffic) should be considered. Field exposure tests with model samples are currently under execution in Italian cities characterized by different environmental conditions as a non invasive methodological approach for studying the impact of urban pollution on carbonate stones. The methodological approach selected for this investigation as well as first available results are here discussed. Marble (Carrara Marble) and limestone (Red Verona Marble) were selected as model samples as they were widely used as construction and ornamental elements in historic Italian architecture. They will be exposed at least for 2 years in Bologna, Ferrara, and Florence. Preference for samples exposure were given to sites located outdoor, partially sheltered from the rain wash-out, in areas strongly affected by pollution due to vehicular traffic. Galvanized metallic racks was prepared to host samples with different exposure orientations: horizontal, oblique (tilted with 45° slope) and vertical, in order to identify how positioning may reflect on deposition and removal of pollutants. The exposed samples will undergo mineralogical, petrographic and geochemical analyses (Optical Microscopy, Scanning Electron Microscopy coupled with Energy Dispersive X-ray Analysis, Inductively Coupled Plasma Mass Spectrometry, Ion Chromatography analysis and Thermal-chemical methodology using a CHNSO combustion analyzer (Ghedini et al., 2006)) at predefined time intervals to characterise the products derived from pollutants-stone interaction in terms of typology, origin and impact on stone. Moreover, the integration with colorimetric analysis will allow to identify a connection between the deposited soluble and carbon fractions and changes of colorimetric parameters, for setting up damage functions. Simultaneously passive sampling of aerosol has been designed by the exposure of filters while seasonal environmental monitoring campaigns of particulate matter will allow to compare the quantity of soluble ions and carbon fractions present into atmosphere with that actually accumulated on samples surface. Additionally, monitoring campaigns of bioaerosol has been planned in Bologna in order to quantify the microbial load (fungi and bacteria) in air. Data of environmental monitoring campaigns as well as results of analyses carried out after the first year of exposure will be also reported. References Bonazza A. and Sabbioni C., 2016. Composition and Chemistry of Crusts on Stone, in Brimblecombe P. (Ed.), Urban Pollution and Changes to Materials and Building Surfaces, Imperial College Press, Singapore, 103-126. Ghedini N., Sabbioni C., Bonazza A. and Gobbi G., Chemical-Thermal quantitative methodology for carbon speciation in damage layers on building surfaces, Environmental Science and Technology, 40 (2006), 939-944.

Stone conservation of historic built heritage of urban centres is continuously threatened by high pollution induced by heavy traffic and industrial activities. The deposition, accumulation and interaction with the substrate of complex mixture of pollutant particles and gases can lead to the formation of damage layers, responsible for chemical modification, physic-mechanical damages as well as aesthetic change of stone. The emissions of sulphur dioxide, considered as the most harmful pollutant for carbonate materials, underwent a decrease in the last decades due to environmental regulation but the current increase in vehicular traffic is causing higher concentration of ozone, nitrogen oxides and organic compounds. In this context, heritage materials undergo chromatic variations due to damage layers formation and enhancement of biodegradation. The impact of pollution on built heritage has been heretofore studied by analyzing samples collected from historic buildings or performing tests in simulation chamber and/or in field but gaps still remain in measuring deposition fluxes on materials and developing proper tools for long-term management of cultural heritage. Field exposure tests with model samples are currently under execution in Italian cities characterized by different environmental conditions as a non invasive methodological approach for assessing the effect of urban pollution on carbonate stones. The methodological approach selected for investigating the impact of pollution as well as first available results are here presented. Marble (Carrara Marble) and limestone (Nembro Limestone) widely used as construction and ornamental elements in historic Italian architecture were selected as model samples. They will be exposed at least for 2 years in Bologna, Ferrara, and Florence. Preference for samples exposure were given to sites located outdoor, partially sheltered from the rain wash-out, in areas strongly affected by pollution due to vehicular traffic. Galvanized metallic racks was purposely built to host samples with three different exposure orientations: horizontal, oblique (tilted with 45° slope) and vertical, in order to identify how positioning may reflect on deposition and removal of pollutants. The exposed samples will undergo mineralogical, petrographic and geochemical analyses (Optical Microscopy, Scanning Electron Microscopy coupled with Energy Dispersive X-ray Analysis, Inductively Coupled Plasma Mass Spectrometry, Ion Chromatography analysis and Thermal-chemical methodology using a CHNSO combustion analyzer [1]) at predefined time intervals to characterize the products derived from pollutants-stone interaction in terms of typology, origin and impact on stone. Moreover, the integration with colorimetric analysis will allow to identify a connection between the deposited soluble and carbon fractions and changes of colorimetric parameters, for setting up damage functions. Simultaneously passive sampling of aerosol has been designed by the exposure of filters while seasonal environmental monitoring campaigns of particulate matter will allow to compare the quantity of soluble ions and carbon fractions present into atmosphere with that actually accumulated on samples surface. Additionally, monitoring campaigns of bioaerosol has been planned in Bologna in order to quantify the microbial load (fungi and bacteria) in air. First data of winter and summer environmental monitoring campaigns as well as results of analyses performed after the first year of exposure will be also presented. [1] Ghedini N., Sabbioni C., Bonazza A., Gobbi G., 2006. Chemical-Thermal quantitative methodology for carbon speciation in damage layers on building surfaces. Environmental Science & Technology 40(3): 939-944.

This work was aimed to evaluate the features of mortar samples taken from the underwater archaeological area of Baia (Naples, Italy), an important site, where the remains of the ancient Roman city of Baiae and Portus Iulius are submerged after bradyseism events, started from 4th century AD. Several architectural structures are still preserved into the submerged environment, such as: luxurious maritime villas, imperial buildings, private houses, thermae, tabernae and warehouses. In particular, some samples were collected from the masonry walls belonging to a building of the underwater area called Villa a Protiro. A first archaeometric approach has been applied to analyse twelve archaeological mortars samples in order to define: textural features, chemical composition and raw materials used for their production. For this purpose different analytical methods were used, such as, polarizing optical microscope (POM) and scanning electron microscopy (SEM-EDS)., This work was financially supported by national national research project “COMAS” (Planned COnservation, “in situ”, of underwater archaeological artifacts), funded by the Italian Ministry of Education, Universities and Research (MIUR).

Air pollution usually derives in the development of black crusts on the surface of cultural heritage materials. A methodological approach for the morphological, mineralogical and chemical characterization of black crusts developed on limestone on historic buildings of Cairo, Milano, Budapest and Madrid, besides suspended and settling particulate matter, has been carried out. By means of traditional techniques, such as POM, XRD, SEM-EDS and FT-IR, combined with innovative application of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), a complete characterization in terms of trace elements distribution (including heavy metals) from the black crusts and host limestone has been achieved. Some studied areas display high levels of pollutants and important concentration of heavy metals (Cd, Cu, Pb, Ni, Zn) in the suspended dust (El-Bady, 2014). Within laminar and dendritic black crusts high concentration of gypsum was recorded with increased amount of different elements and metals (Si, Al, Ti, Fe) especially derived from atmospheric inputs and, in particular, by anthropogenic pollution; in dust samples siliceous fly-ash particles are more common than carbonaceous ones and mineral fragments representing windblown particles were also detected (Perez-Monserrat et al., 2011; Török et al., 2011). Heavy metals content (Pb, Zn) are higher in black crust than in substrate, suggesting that polluted atmosphere has a great influence on their formation. Moreover, some specific heavy metals tend to migrate from the crust to the unaltered stone, becoming catalysts for new crust (Barca et al., 2014; La Russa et al., 2014). Black crusts composition entails markers to evaluate the major combustion sources responsible for stone decay and the changes on the used fuels over time. As trace element concentration is directly related with environmental conditions, the study of black crusts can be a marker for human health.

We describe here the case of 41 yrs old male patient, who was admitted to the emergency department complaining for abdominal pain lasting for two days. The patient self-reported a history of idiopathic deep vein thrombosis five yrs before the visit. A subcutaneous cordlike induration, tender and painful, was clearly palpable in the left lower abdominal quadrant. Routine blood tests did not reveal any substantial abnormality, except increased D-dimer concentration. Ultrasound evaluation of the abdominal wall revealed diffuse thrombosis of the left superficial inferior epigastric vein, involving several small tributaries branches, extended until 1.5 cm from the confluence with the common femoral vein, which was finally classified as an atypical case of Abdominal Mondor's disease. Complete thrombophilia screening was negative. The patient was discharged with warfarin therapy 48 hours from admission. At 30 days follow-up, the patient self-reported a nearly complete recovery.

This research deals with the characterization of black crusts collected from the Dome of Monza (Milan, Italy). Air pollution is responsible for the degradation of historical buildings surfaces. In urban and industrial areas, the degradation process is accelerated, due to carbonaceous particles and heavy metals emitted by combustion processes which contribute to the formation of black crust (BCs). In this study the characterization of BC was performed using different analytical techniques such as: HRSEM-EDX, IC, LA-ICP/MS and digital image analysis. In particular, the research focused on the study of "heavy metals" which contribute to the identify the main sources of pollution responsible for the surface’s deterioration over time. BCs variability in composition also depends on the exposure of the analyzed surfaces., J. Santiago Pozo-Antonio thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for his “Juan de la Cierva-incorporación” (IJCI-2017-3277) contract. C. Cardell thanks the financial support provided by Spanish Research Projects AERIMPACT (CGL2012-30729) and EXPOAIR (P12-FQM-1889), the European Regional Development Fund (ERDF), and the Andalusian Research Group RNM-179. SEM-EDX analyses were performed in the Scientific Instrumentation Centre (CIC) of the University of Granada (Spain).

This research deals with the characterization of black crusts collected from Dome of Monza. Black crusts (BC) can be formed as a result of different chemical and physical reactions between the stone surface and environmental factors (such as gaseous pollutants, aerosol particulate matter and its specific chemical constituents-the carbonaceous fraction and the metals); therefore, they are considered as a passive sampler of pollutants. The specific focus of the current work is the study of the metals and their distribution within the samples. To characterize BC, several techniques were used such as: HRSEM-EDX, IC and LA-ICP/MS. This integrated approach allowed us to gain information about the mineralogical phases and the elements within the crusts giving the possibility to identify the pollution sources causing the stone decay, as well as the variability in composition depending on the exposure of the analysed surfaces.

Different Light-Absorbing Snow Impurities (LASI) can deposit on snow- and ice-covered surfaces. These particles are able to decrease snow and ice albedo and trigger positive albedo feedback. The aim of this work was to develop a new method to quantify the carbonaceous fractions that are present in snow and ice samples that contribute significantly to their darkening. Currently, in the literature, there is an absence of a unified and accepted method to perform these studies. To set up the method proposed here, snow samples were collected at two Italian locations, Claviere and Val di Pejo (Northern Italy). The samples were analyzed using two main techniques, Total Organic Carbon analysis (TOC analysis) and Thermal Optical analysis in Transmittance mode (TOT), which enabled the speciation of the carbonaceous fraction into organic (OC), inorganic (IC), and elemental carbon (EC), and further into the soluble and insoluble parts. The results highlighted a correlation between the nature of the sample (i.e., location, age, and exposure of the snow) and the experimental results, giving validity to the method. For example, the abundant presence of terrigenous constituents was reflected in high amounts of insoluble IC. Moreover, due to the trend between insoluble IC and Elemental Carbon (EC), the role of IC in TOT analysis was investigated. Indeed, IC turned out to be an interfering agent, suggesting that the two techniques (TOC analysis and TOT) are complementary and therefore need to be used in parallel when performing these studies. Finally, the results obtained indicate that the newly proposed method is suitable for studying the carbonaceous fractions in snow samples.

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.

The use of stone materials in cultural heritage and architecture represents a practice that has its roots in ancient times. Stone buildings, depending on the construction materials and their location in the urban context, are particularly vulnerable to weathering phenomena. These can be often accelerated by changes in environmental conditions linked mostly to the anthropic activities. In this way, the present work is addressed on the minero-petrographic and geochemical characterisation of samples taken from the built historical heritage in Cairo (Egypt), related to seven monumental areas. These sites have been chosen based on their historical importance, type of material, state of preservation and position in the Cairo context. The construction materials used and their degradation products were studied comparing the results obtained by means of different analytical techniques such as polarised light optical microscopy (POM), ion chromatography (IC), Fourier transform infrared spectroscopy (FT-IR) and the carbonaceous fraction, detected by using the thermogravimetry (TG). The results achieved demonstrated that black crusts and salt crystallisation represent the most common and damaging degradation products affecting all the monumental sites. Moreover, the environmental pollution produced by industrial activities and vehicular traffic has been identified as the main cause of these processes, followed by a marginal contribution of natural sources such as the sea spray. The data collected provide useful information to plan efficient conservation strategies in the future.

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.

This study focuses on the characterization of black crusts collected from the Monza cathedral located in the homonymous city (N Italy), a hot spot from the point of view of the atmospheric pollution. Black crusts and substrate marble specimens were analyzed by a multi-analytical approach including X-ray Diffraction (XRD), Fourier Transform-Infrared spectroscopy (FT-IR), Stereomicroscopy (SM), Polarized Light Microscopy (PLM), High Resolution Scanning Electron Microscopy coupled with Energy Dispersive X-ray spectroscopy (HRSEM-EDX) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP/MS). The characterization of the carbon fraction (organic carbon, OC, and elemental carbon, EC) was performed using a new approach based on the use of Carbon Hydrogen Nitrogen (CHN) analysis and Thermogravimetric Analysis (TGA). The integrated approach allowed the identification of the pollution sources responsible for black crusts forming process. The precise identification of the main substances responsible for the surface degradation phenomena, in particular those leading to the blackening and disintegration of the carbonate substrates, is essential for the definition of conservative intervention and maintenance strategies, as well as for the development of emission reduction policies on a local scale.

During the last decades, many studies have been carried out on environmental monitoring in specific sites aiming at their protection and conservation; however, researches focused on the direct implications, in terms of quantitative evaluation of stone deterioration, of these monitoring actions are still scarce. This experimental work aims at monitoring the degradation processes affecting historical buildings constituted by carbonate stones. Specifically, specimens of Carrara marble and two limestones largely used in the Sicilian Baroque architecture, namely Noto and Comiso stones, were exposed outdoor in two Italian sites (Catania and Palermo), which are characterized by different environmental conditions. The field exposure test lasted two years. Both the substrates and the deposited particulate collected at the end of the exposure underwent several analytical investigations including: i) optical microscopy, mercury intrusion porosimetry, colorimetric analysis and roughness analysis, for the characterization of stone substrates before exposure; ii) ion chromatography (IC), infrared spectroscopy analysis (FT-IR) and inductively coupled plasma mass spectrometry (ICP-MS), for the characterization of the particulate deposited on stone surfaces. The obtained results highlighted blackening and yellowing processes of the carbonate substrates, chiefly on those specimens exposed in Palermo where such processes were more noticeable. Furthermore, the high concentration of sulphates and heavy metals detected (mainly in Palermo site) pointed out that both cities are mainly interested by mobile emission sources such as vehicular traffic. Additionally, analyses demonstrated the key-role of intrinsic features of the lithotypes in the degradation processes. In this regard, the higher porosity and surface roughness of Noto stone explains the major deposition of particulate with respect to the other two examined carbonate rocks., Roughness analyses were carried out thanks to the financial support of the Community of Madrid “Geomateriales 2 programme (S2013/MIT-2914)”.

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.