The effects of air pollution on cultural Heritage : the case study of Santa Maria delle Grazie al Naviglio Grande (Milan)

Atmospheric pollution causes monuments surface degradation in urban environments. Among the degradation processes the formation of black crusts (BCs) is one of the most dangerous phenomenon. During this process, aerosol particulate matter (PM) can be embedded into gypsum, one of the main crusts constituents, providing the characteristic black colour. EC (elemental carbon) and OC (organic carbon) are the responsible for the yellowing and blackening processes occurring on the surfaces and their quantification in the crusts can provide information on the contribution of atmospheric pollution sources to the degradation products formation. This research study is focused on the characterization of BCs collected from the Church of Santa Maria delle Grazie al Naviglio Grande in Milan, from the point of view of the effects of atmospheric pollution on cultural heritage. The analysed samples consist of mortars and bricks partially degraded and covered with black crusts. Appling different analytical techniques, such as FTIR/ATR, CHN, TGA and IC, the crusts composition has been investigated focusing on the quantification of the carbonaceous fraction. This integrated approach has allowed to identify the sources of pollution responsible for the decay of the different building materials of the church

A multi-analytical approach to assess the impact of air pollution on cultural heritage : degradation of stones, mortars and bricks

Air pollution is one of the most important causes of surface decay in urban environment. Among the degradation processes due to airborne pollutants, the formation of black crusts is one of the most dangerous one. Currently, emissions from mobile combustion sources are the main agents responsible for pollution, although a significant decrease is expected in Europe within the next decade. The surfaces of architectural heritage in urban environment are exposed to degradation due to the interaction with atmospheric pollutants both in gaseous and in the particulate phase. Monuments located in the historic centres of large cities are subjected to typical anthropogenic emissions. The precise identification of the main substances responsible for the surface degradation phenomena, in particular leading to blackening, erosion of carbonatic matrices and disintegration, is essential for the definition of conservative intervention and maintenance strategies, as well as for the development of emission reduction policies on a larger scale. Black crusts and substrate (stones, mortars or bricks) specimens have been sampled in Milan and Monza from monuments of historical interests and analyzed by a multi-analytical approach including FT-TIR spectroscopy, ion chromatography (IC) and electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The characterization of the carbon fraction (organic carbon, OC, and elemental carbon, EC) was performed using a new approach based on a thermal protocol and on the use of CHN analysis and thermogravimetric analysis (TGA). This integrated approach has been already applied in some case studies [1-4]. Data acquired on the specimens have been compared with those collected by the regional environmental protection agency (ARPA Lombardia) in order to assess, also through the use of dose-response functions, the degradation phenomenon that occur

Efficiency of an Air Cleaner Device in Reducing Aerosol Particulate Matter (PM) in Indoor Environments

Abstract: 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 eciency in reducing the mass concentration and particle number of aerosol particulate matter (PM). The eciency has been tested measuring, while the instrument was working, PM10 (particles with aerodynamic diameter less than 10 m), PM2.5 (particles with aerodynamic diameter less than 2.5 m), PM1 (particles with aerodynamic diameter less than 1 m), and 7 size-fractions in the range between 0.3 and >10 m. 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\u20130.5 m, allowing an improvement of indoor air quality

Marble hydrophobicity tuned by Si-based coatings

Hydrophobic polymers applied on stone materials increase their durability against undesired weathering processes [1]. The achievement of a certain degree of surface hydrophobicity (reducing the water permeation) constitutes one of the main research focuses [2]. Herein, two commercial Si-based resins (e.g. Alpha\uaeSI30 and Bluesil\uaeBP9710), directly applied on Carrara marble substrates and a silanization process, by using trichloromethylsilane (TCMS), were adopted. Contact angle measurements were carried out to evaluate the hydrophobic features. Hence, since only in the case of TCMS a good hydrophobicity was achieved (\uf071 around 150\ub0), two commercial polysiloxane-based additives (e.g. TegoPhobe 1500N and TegoPhobe 1650) were added respectively to Alpha\uaeSI30 and Bluesil\uaeBP9710, according to their chemical compatibility. These auxiliary substances allowed to decrease the wettability features of marble. Furthermore, since all the investigated coatings could be used as stone materials protective agents, water capillary absorption and vapor permeability tests were performed. Also, in this case, TCMS revealed to be the most performing one among the adopted silane-based resins, thanks to the drastic reduction of absorbed water and the decrease of vapor permeability within the threshold value of 50%. Finally, the coatings stability was evaluated by accelerated ageing tests. References [1] Cappelletti G., Fermo P., Pino F., Pargoletti E., Pecchioni E., Fratini F., Ruffolo S.A., La Russa M.F., On the role of hydrophobic Si-based protective coatings in limiting mortar deterioration, Environ Sci Pollut Res, 22 (2015) 17733\u201317743. [2] Cappelletti G., Fermo P., Camiloni M., Smart hybrid coatings for natural stones conservation, Progress in Organic Coatings 78 (2015) 511\u2013516

The hydrophobicity modulation of glass and marble materials by different Si-based coatings

Hydrophobic polymers applied on hydroxylated surfaces increase their durability against undesired weathering processes. The achievement of a certain degree of surface hydrophobicity (reducing the water permeation) constitutes one of the main research focuses. Herein, two commercial Si-based resins (e.g. Alpha\uaeSI30 and Bluesil\uaeBP9710), directly applied on both glass and Carrara marble substrates, and a silanization process by using trichloromethylsilane (TCMS) were adopted. Contact angle measurements together with hysteresis determination and Surface Free Energy (SFE) were carried out to evaluate the hydrophobic features. Hence, since only in the case of TCMS a good hydrophobicity was achieved (\uf071 around 150\ub0), two commercial polysiloxane-based additives (e.g. TegoPhobe 1500N and TegoPhobe 1650) were added respectively to Alpha\uaeSI30 and Bluesil\uaeBP9710, according to their chemical compatibility. These auxiliary substances allowed to decrease the wettability features of either glass or marble. Furthermore, since all the investigated coatings could be used as stone materials protective agents, water capillary absorption and vapor permeability tests were performed. Also in this case, TCMS revealed to be the most performing one among the adopted silane-based resins, thanks to the drastic reduction of absorbed water and the decrease of vapor permeability within the threshold value of 50%. Finally, the coatings stability was evaluated by accelerated ageing tests

The potential mechanism of black crust development on the historic buildings in Cairo and Venice

The development of black crusts on natural stones of historic buildings is mainly related to the surrounded polluted atmosphere. The blackening of surfaces is caused, in fact, by the accumulation of air pollutants produced by human activity, especially carbon particles originating from the incomplete combustion of fossil fuel. Investigations of the chemical composition of such layers in the monuments can be the basis for planning suitable strategies for the protection and conservation of the built cultural heritage. Cairo (Egypt) and Venice (Italy) are two cities with a large amount of cultural heritage buildings; moreover, they suffer high level of air pollution. Black crust with the hosted stones from different sites in Historic Cairo, as well as samples of different archaeological sites in Venice city, were collected and analyzed by using several techniques: polarizing optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDS), infrared spectroscopic techniques (FT-IR) and laser ablation inductively coupled mass spectrometry (LA-ICP-MS). The characterization of such samples provided information on the chemical composition of black crusts, the state of conservation of the substrates and the crust-stone interactions. The chemical study highlighted a different pattern of elements within the two cities. Regarding the black crusts of Cairo, results suggest that the air pollution in Cairo is mainly related to vehicular traffic. Indeed, in the city there is high vehicular traffic almost 24 h a day and the direct impact of vehicle emissions is particularly severe. Samples from the Venice show different composition in terms of heavy metals with respect to Cairo that can be explained with the emission from several industries sited in the near industrial center of Porto Marghera and Island of Murano. Moreover, the fuels used for marine transportation, which is abundant into the area, have a slight different fingerprinting in terms of metals with respect to the vehicles

Durable Modified Polyacrylic Coatings for Cultural Heritage Protection

INTRODUCTION Deterioration phenomena of ancient and modern stone cultural heritage are natural and unrestrainable decay processes mainly arising from water adsorption and percolation into stone building materials1. Once water attacks and penetrates stone surfaces, several chemical, physical and biological degradation processes can occur altering significantly, and in some cases even irreversibly, the properties of stone materials. The application of hydrophobic coatings to stone surfaces is mandatory to protect stone artefacts from the deleterious effects occurring in the case of water exposition. The protective agent must possess several features, i.e. high compatibility with the substrate, high durability, transparency, easiness of application and removal, water-repellency, capability to avoid the attack of organic and inorganic contaminants; moreover, it should be permeable to water vapor. The aim of the present work was to synthesize new polymer coatings as stone protective with satisfactory water repellent properties and improved durability, thanks to the combined use of fluorinated and long alkyl chain monomers and without the use of any photo stabilizers agents. EXPERIMENTAL/THEORETICAL STUDY New types of polymer protectives were prepared via free radical polymerization between either 1H,1H,2H,2H-Perfluoro-octyl-methacrylate (POMA) or commercial stearyl methacrylate (STEA, Sigma Aldrich) and methacrylic monomers (methyl, MMA, and n-butyl, nBuMA, methacrylates)2,3. Specifically, POMA was synthesized via esterification reaction using methacryloyl chloride and 1H,1H,2H,2H-Perfluoro-1-octanol. RESULTS AND DISCUSSION The properties of the home-made hydrophobizing polymers in terms of macromolecular structure, molecular weights, thermal features and water repellency were determined. Furthermore, the long-term behavior of these polymeric protective agents was estimated by means of accelerated aging tests exploiting UV radiations (in according to UNI 10925:2001 standard method for 100h, 315-400 nm for UVA rays and 280-315 nm for UVB ones). Their behavior over time was checked via Size Exclusion Chromatography (SEC) by evaluating Mn and D data of aged polymeric samples (Table 1) and by Fourier Transform Infrared (FT-IR) spectroscopy. By evaluating Mn and D data reported in Table 1, all the synthesized polymers seem to be unaffected by UV aging. Thus, the present stable resins were applied on both natural (Botticino marble) and artificial (mortar) stone substrates and their wetting properties together with their absorption by capillarity and water vapour permeability were successfully assessed and compared. All the covered substrates show an increase of water contact angle of around 50\ub0 and a decrease in water absorption and permeation of about 50% and 20%, respectively. Lastly, in order to evaluate the stability of the applied coatings towards degradation induced by solar radiation and interaction with the atmospheric pollution, exposure to a typical polluted urban environment for some months have been carried out. For this purpose, the following analyses have been performed: contact angle measurements, SEM-EDS (Scanning Electron Microscopy with X-ray microanalysis), IC (Ion Chromatography), and colorimetric tests by CIELab elaboration. CONCLUSION The use of polymeric protectives is very advantageous in fields when the hydrophobic properties and high chemical stability are required. Within this context, the use of polymer resins bearing methacrylic and fluorinated monomers along the polymeric chain can be a way to create tailor-made water repellent materials with enhanced durability, without the addition of any stabilizing agent