This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief... more This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief of the 15th century entitled “Madonna with Child, Saint Catherine of Siena, and a Carthusian Prior”, attributed to Giovanni Antonio Amadeo (Pavia, 1447–Milan, 1522) and owned by the Sforzesco Castle Museum of Milan. The artwork underwent a cleaning procedure whose aims were the removal of the dark coating that obscured its surface and restoration work that could bring back its original features. Before the cleaning, six microsamples were collected and analysed using optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDXS), and Fourier-transform infrared microspectroscopy in ATR mode (ATR-FTIR), providing the restorers with decisive information on the materials underlying the coating. After the cleaning, the terracotta appeared vibrantly coloured, mainly with bright red, blue, green, black, and white tones. Then, some in situ, non...
The Cultural Heritage deterioration is a spontaneous decay process due to water percolation and a... more The Cultural Heritage deterioration is a spontaneous decay process due to water percolation and air pollutant deposition. In this context, novel acrylic (Twinswet, TW) and siloxane-based (Alpha®SI30) resins were exploited starting from commercial products and then modified by adding either a commercial polysiloxane-based additive (TegoPhobe 1500N) or a precursor of SiO2 nanoparticles (Tetraethyl ortosilicate, TEOS) to improve the Vicenza stone surface hydrophobicity. Properties of the coated materials were studied using different techniques such as water contact angle (WCA), capillary absorption, colorimetric and water vapor permeability measurements. Accelerated UV aging and eight-month outdoor exposure tests (at Milan University campus) were also performed to determine the coatings durability. Notably, the addition of both additives slightly enhanced the surface hydrophobicity resulting in WCAs of about 140°, and decreased the water absorption especially for Alpha-based resins. Co...
The study of the chemical composition of wines is nowadays a topic of great interest because of t... more 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...
Deterioration phenomena of ancient and modern stone cultural heritage are natural and unrestraina... more Deterioration phenomena of ancient and modern stone cultural heritage are natural and unrestrainable decay processes mainly arising from water percolation into stone building materials [1]. Thus, the application of hydrophobic coatings to stone surfaces is mandatory to protect them from the deleterious effects of water exposition. Hence, the aim of the present work was to synthesize new polymeric coatings as stone protective with satisfactory water repellency and improved durability, thanks to the combined use of fluorinated and long alkyl chain monomers and without the use of any photo-stabilizers agents. Herein, new types of polymer protectives were prepared via free radical polymerization between either 1H,1H,2H,2H-Perfluoro-octyl-methacrylate (POMA) 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. 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 polymers was estimated by means of accelerated aging tests exploiting UV radiations. Their behavior over time was checked via Size Exclusion Chromatography (SEC) by evaluating Mn and D data of aged polymeric samples and by Fourier Transform Infrared (FT-IR) spectroscopy. By evaluating Mn and D data, 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 (Figure 1). 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. Hence, the use of these polymer resins can be a way to create tailor-made water repellent materials
J. Santiago Pozo-Antonio thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for ... more J. Santiago Pozo-Antonio thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for his “Juan de la Cierva-incorporacion” (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).
Environmental Science and Pollution Research, 2021
Black crusts (BCs) are one of the most critical alteration forms found on stones belonging to arc... more 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) dete...
Abstract Modification of IR spectral features were reported in the literature when surfaces with ... more Abstract Modification of IR spectral features were reported in the literature when surfaces with diverse morphologies were analysed. In this study, five surfaces at different average roughness (Sa) were created on a massive slice of malachite with the final aim to investigate possible variations of spectral features collected through non-contact infrared reflection spectroscopy. Modifications were investigated as a function of Sa, with five frequency intervals being considered. The spectral acquisition was carried out by two portable spectrometers equipped with specific non-invasive optical heads, operating in External Reflection (ER) and Diffuse Reflection (DR) modes, respectively. A comparison study of the collected spectral profiles is proposed in this work . The analysis of spectra produced by surfaces at different roughness allowed for evaluating the effectiveness of each device in the different spectral ranges. The ER spectra were generally more resolved and cleaner compared to the DR ones. The ER module was able to return spectra whose features - both specular and diffuse - consistently follow the variation of Sa in the investigated spectral ranges. A lack of sensitivity was instead registered when working in DR mode, especially in the frequency intervals where the contribution of the diffuse component dominates the spectra.
In this study, simultaneous monitoring of indoor and outdoor Volatile Organic Compounds (VOCs) wa... more In this study, simultaneous monitoring of indoor and outdoor Volatile Organic Compounds (VOCs) was carried out in a school, by both Radiello® cartridges and real-time monitors (Corvus, IonScience Ltd., Fowlmere UK). Moreover, an outdoor air quality assessment was performed with data from an air quality monitoring station (ARPA Puglia) located close to the school. In particular, VOCs, Benzene, Toluene, Ethylbenzene, and Xilenes concentrations, obtained by using Radiello® diffusive samplers, were monitored in two classrooms, two bathrooms, and outside of the school building for three weeks during winter 2019. Simultaneously, the Total VOC (TVOC) concentrations were measured by means of real-time monitors inside and outside the classroom in order to individuate the activation of sources during the sampling campaign days. The results evidence that indoor TVOC concentrations were bigger than those outdoors; this suggests the presence of indoor pollutant sources, both in the classrooms an...
COVID-19 has reduced tourism in both museums and historical sites with negative economic effect. ... more 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 to the set-up the 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.
This work concerns the characterisation of a set of wall painting and stucco fragments collected ... more This work concerns the characterisation of a set of wall painting and stucco fragments collected during a rescue excavation carried out in 2013 by the Soprintendenza Archeologica in the Monte d’Oro area (Rome). Due to the contextless archaeological situation, analyses were performed to obtain more information about the collected materials. A multi-analytical approach has been applied including spectroscopic (FTIR, Raman and visible reflectance analyses) and elemental analysis (SEM-EDS) techniques. The chromatic palette has been in this way disclosed evidencing the use of pigments such as cinnabar, Egyptian blue, red and yellow ochre and green earth, but also the simultaneous use of them. The presence of a decoration achieved by using a gold leaf has been highlighted also, indicating the preciousness of the decorations. The convenience and advantages linked to the use of portable instrumentation have been also evidenced.
International Journal of Architectural Heritage, 2017
ABSTRACT During the last restoration of the Fontana di Trevi -Rome (2014–2015), it has been perfo... more ABSTRACT During the last restoration of the Fontana di Trevi -Rome (2014–2015), it has been performed a diagnostic investigation to characterize the materials used to build and obtain the colors of the surfaces of some architectural elements of this fountain. According to the restoration teamwork needs, we focussed our efforts on the dome over the central statue of Oceanus, on the bas-relieves on the sides of the dome, and on the cliff where the water flows. Several samples were collected from these elements and therefore, they were subjected to an analytical approach including infrared spectroscopy, optical and scanning electron microscopy. The achieved results indicated the use of red earth pigments on the dome. The same pigment has been revealed on the bas-relieves, although their colors have an additional contribution due to degraded layers. Samples taken from the cliff showed a complex stratigraphy, although a white scialbo has been identified as original layer, testifying the intentions of the authors in term of color rendering. This information was essential for the restores in order to choose the proper intervention procedure for each investigated surface. The research testified the importance of an integrated diagnostic analysis to preserve the original colours of monuments and building.
On November 2, 2001, the UNESCO Convention on the Protection of the Underwater Cultural Heritage ... more On November 2, 2001, the UNESCO Convention on the Protection of the Underwater Cultural Heritage provided a detailed state cooperation system and set out the basic principles for the protection of underwater cultural heritage. To date, the Convention has been ratified by 51 countries. One of the four main principles states that the In situ preservation of underwater cultural heritage should be considered as the first option before allowing or engaging in any further activities. In accordance with these principles and recommendations, in the last years many projects intended for developing and testing new techniques and tools to support In situ conservation of underwater archaeological remains have been funded and are now underway.This paper describes the contribution of the CoMAS project (In situ conservation planning of Underwater Archaeological Artifacts—http://www.comasproject.eu), funded by the Italian Ministry of Education, Universities and Research (MIUR) and run by a partners...
This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief... more This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief of the 15th century entitled “Madonna with Child, Saint Catherine of Siena, and a Carthusian Prior”, attributed to Giovanni Antonio Amadeo (Pavia, 1447–Milan, 1522) and owned by the Sforzesco Castle Museum of Milan. The artwork underwent a cleaning procedure whose aims were the removal of the dark coating that obscured its surface and restoration work that could bring back its original features. Before the cleaning, six microsamples were collected and analysed using optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDXS), and Fourier-transform infrared microspectroscopy in ATR mode (ATR-FTIR), providing the restorers with decisive information on the materials underlying the coating. After the cleaning, the terracotta appeared vibrantly coloured, mainly with bright red, blue, green, black, and white tones. Then, some in situ, non...
The Cultural Heritage deterioration is a spontaneous decay process due to water percolation and a... more The Cultural Heritage deterioration is a spontaneous decay process due to water percolation and air pollutant deposition. In this context, novel acrylic (Twinswet, TW) and siloxane-based (Alpha®SI30) resins were exploited starting from commercial products and then modified by adding either a commercial polysiloxane-based additive (TegoPhobe 1500N) or a precursor of SiO2 nanoparticles (Tetraethyl ortosilicate, TEOS) to improve the Vicenza stone surface hydrophobicity. Properties of the coated materials were studied using different techniques such as water contact angle (WCA), capillary absorption, colorimetric and water vapor permeability measurements. Accelerated UV aging and eight-month outdoor exposure tests (at Milan University campus) were also performed to determine the coatings durability. Notably, the addition of both additives slightly enhanced the surface hydrophobicity resulting in WCAs of about 140°, and decreased the water absorption especially for Alpha-based resins. Co...
The study of the chemical composition of wines is nowadays a topic of great interest because of t... more 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...
Deterioration phenomena of ancient and modern stone cultural heritage are natural and unrestraina... more Deterioration phenomena of ancient and modern stone cultural heritage are natural and unrestrainable decay processes mainly arising from water percolation into stone building materials [1]. Thus, the application of hydrophobic coatings to stone surfaces is mandatory to protect them from the deleterious effects of water exposition. Hence, the aim of the present work was to synthesize new polymeric coatings as stone protective with satisfactory water repellency and improved durability, thanks to the combined use of fluorinated and long alkyl chain monomers and without the use of any photo-stabilizers agents. Herein, new types of polymer protectives were prepared via free radical polymerization between either 1H,1H,2H,2H-Perfluoro-octyl-methacrylate (POMA) 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. 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 polymers was estimated by means of accelerated aging tests exploiting UV radiations. Their behavior over time was checked via Size Exclusion Chromatography (SEC) by evaluating Mn and D data of aged polymeric samples and by Fourier Transform Infrared (FT-IR) spectroscopy. By evaluating Mn and D data, 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 (Figure 1). 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. Hence, the use of these polymer resins can be a way to create tailor-made water repellent materials
J. Santiago Pozo-Antonio thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for ... more J. Santiago Pozo-Antonio thanks the Spanish Ministry of Economy and Competitiveness (MINECO) for his “Juan de la Cierva-incorporacion” (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).
Environmental Science and Pollution Research, 2021
Black crusts (BCs) are one of the most critical alteration forms found on stones belonging to arc... more 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) dete...
Abstract Modification of IR spectral features were reported in the literature when surfaces with ... more Abstract Modification of IR spectral features were reported in the literature when surfaces with diverse morphologies were analysed. In this study, five surfaces at different average roughness (Sa) were created on a massive slice of malachite with the final aim to investigate possible variations of spectral features collected through non-contact infrared reflection spectroscopy. Modifications were investigated as a function of Sa, with five frequency intervals being considered. The spectral acquisition was carried out by two portable spectrometers equipped with specific non-invasive optical heads, operating in External Reflection (ER) and Diffuse Reflection (DR) modes, respectively. A comparison study of the collected spectral profiles is proposed in this work . The analysis of spectra produced by surfaces at different roughness allowed for evaluating the effectiveness of each device in the different spectral ranges. The ER spectra were generally more resolved and cleaner compared to the DR ones. The ER module was able to return spectra whose features - both specular and diffuse - consistently follow the variation of Sa in the investigated spectral ranges. A lack of sensitivity was instead registered when working in DR mode, especially in the frequency intervals where the contribution of the diffuse component dominates the spectra.
In this study, simultaneous monitoring of indoor and outdoor Volatile Organic Compounds (VOCs) wa... more In this study, simultaneous monitoring of indoor and outdoor Volatile Organic Compounds (VOCs) was carried out in a school, by both Radiello® cartridges and real-time monitors (Corvus, IonScience Ltd., Fowlmere UK). Moreover, an outdoor air quality assessment was performed with data from an air quality monitoring station (ARPA Puglia) located close to the school. In particular, VOCs, Benzene, Toluene, Ethylbenzene, and Xilenes concentrations, obtained by using Radiello® diffusive samplers, were monitored in two classrooms, two bathrooms, and outside of the school building for three weeks during winter 2019. Simultaneously, the Total VOC (TVOC) concentrations were measured by means of real-time monitors inside and outside the classroom in order to individuate the activation of sources during the sampling campaign days. The results evidence that indoor TVOC concentrations were bigger than those outdoors; this suggests the presence of indoor pollutant sources, both in the classrooms an...
COVID-19 has reduced tourism in both museums and historical sites with negative economic effect. ... more 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 to the set-up the 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.
This work concerns the characterisation of a set of wall painting and stucco fragments collected ... more This work concerns the characterisation of a set of wall painting and stucco fragments collected during a rescue excavation carried out in 2013 by the Soprintendenza Archeologica in the Monte d’Oro area (Rome). Due to the contextless archaeological situation, analyses were performed to obtain more information about the collected materials. A multi-analytical approach has been applied including spectroscopic (FTIR, Raman and visible reflectance analyses) and elemental analysis (SEM-EDS) techniques. The chromatic palette has been in this way disclosed evidencing the use of pigments such as cinnabar, Egyptian blue, red and yellow ochre and green earth, but also the simultaneous use of them. The presence of a decoration achieved by using a gold leaf has been highlighted also, indicating the preciousness of the decorations. The convenience and advantages linked to the use of portable instrumentation have been also evidenced.
International Journal of Architectural Heritage, 2017
ABSTRACT During the last restoration of the Fontana di Trevi -Rome (2014–2015), it has been perfo... more ABSTRACT During the last restoration of the Fontana di Trevi -Rome (2014–2015), it has been performed a diagnostic investigation to characterize the materials used to build and obtain the colors of the surfaces of some architectural elements of this fountain. According to the restoration teamwork needs, we focussed our efforts on the dome over the central statue of Oceanus, on the bas-relieves on the sides of the dome, and on the cliff where the water flows. Several samples were collected from these elements and therefore, they were subjected to an analytical approach including infrared spectroscopy, optical and scanning electron microscopy. The achieved results indicated the use of red earth pigments on the dome. The same pigment has been revealed on the bas-relieves, although their colors have an additional contribution due to degraded layers. Samples taken from the cliff showed a complex stratigraphy, although a white scialbo has been identified as original layer, testifying the intentions of the authors in term of color rendering. This information was essential for the restores in order to choose the proper intervention procedure for each investigated surface. The research testified the importance of an integrated diagnostic analysis to preserve the original colours of monuments and building.
On November 2, 2001, the UNESCO Convention on the Protection of the Underwater Cultural Heritage ... more On November 2, 2001, the UNESCO Convention on the Protection of the Underwater Cultural Heritage provided a detailed state cooperation system and set out the basic principles for the protection of underwater cultural heritage. To date, the Convention has been ratified by 51 countries. One of the four main principles states that the In situ preservation of underwater cultural heritage should be considered as the first option before allowing or engaging in any further activities. In accordance with these principles and recommendations, in the last years many projects intended for developing and testing new techniques and tools to support In situ conservation of underwater archaeological remains have been funded and are now underway.This paper describes the contribution of the CoMAS project (In situ conservation planning of Underwater Archaeological Artifacts—http://www.comasproject.eu), funded by the Italian Ministry of Education, Universities and Research (MIUR) and run by a partners...
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