A Multianalytical Investigation to Preserve Wall Paintings: A Case Study in a Hypogeum Environment.

In the present study, a diagnostic approach was used to analyze the wall painting in the apse of the Sotterra church at Paola, in the province of Cosenza, Italy. The Sotterra church is nowadays located 6 m under the ground level. The presbytery area houses valuable pictorial evidence attributable to different phases. The oldest painting, visible in the apse area, dates back to the 11th-12th centuries, and it represents the subject of the present study, while the later decorations are placed in a chronological range from the 14th to the 15th centuries. Due to the peculiar environmental conditions, the conservation of subterranean sites represents a debated issue and must be properly investigated. For this reason, in this research, noninvasive analysis and laboratory-based methods were planned to obtain information about both the composition of original materials and the mechanisms and causes of alterations affecting the wall painting in the apse. Simultaneously, an environmental monitoring campaign of the indoor climate for the duration of nine months was conducted. The results highlighted the use of natural mineral pigments such as ochres and earths. The analysis of the painting stratigraphy revealed that the mural painting consists of two plaster layers characterized by lime-based binder. Moreover, the presence of a high amount of calcium sulfate has been discovered; this latter result, combined with the monitoring of the microclimate, allowed for the establishment of the crystallization and the condensation risks which occur on the investigated surfaces.

In-Situ Comparative Study of Eucalyptus, Basil, Cloves, Thyme, Pine Tree, and Tea Tree Essential Oil Biocide Efficacy.

Bio-colonization is a dynamic and multiphasic process headed by microorganisms. Conventional treatments to process affected stone materials include chemical biocides, whose formulations are mainly composed of quaternary ammonium salts(QAs), reported to be toxic for human health, dangerous for the environment, and not biodegradable. Accordingly, novel green and eco-friendly products are a promising alternative to treat stone materials deteriorated by microorganism colonization. In this study, the efficacy of pure essential oils (EOs) and a mix of EOs was assessed in situ and compared to a conventional biocide based on QAs, and two commercially green products based on EOs, which were taken as references, through application on a mosaic located at the Archaeological Park of Ostia Antica (Rome). The EO biocide efficacy was analyzed by ultraviolet induced luminescence, spectro-colorimetry and bio-luminometry analyses while the possibility of their permanence on simulated substrate was studied by FTIR spectroscopy. It was observed by FTIR analysis, that EOs considered volatile can leave a residue after the application; typical fingerprint bands at about 2926, 1510, and 1455 cm-1 were recorded in the EO spectra. Every tested oil was confirmed to have a biocide action although minimal in relation to the most conventional products based on QAs. The synergy of the essential oils revealed positive results, showing a stronger biocide efficacy. Further investigation should be carried out to develop the method of application and study of essential oils on cultural heritage.

Deep Eutectic Solvents (DESs): Preliminary Results for Their Use Such as Biocides in the Building Cultural Heritage.

Biodeterioration is an increasingly widespread process of degradation in the context of the conservation of cultural heritage, which involves a combination of physical and chemical damages together with an aesthetic alteration of materials. For biological damage on monuments caused by pathogens, macro- and microorganisms, chemical treatments are generally used, most of the time dangerous for the environment and for the operator. In this context, new eco-friendly products represent necessary tools for the treatment of biologically deteriorated stone surfaces and represent a new challenge in the field of restoration and conservation of materials of cultural interest. A relatively new class of unconventional green solvents are deep eutectic solvents (DESs), which have peculiar chemical-physical characteristics such as being non-toxic, ecological, biodegradable, non-flammable, and stable in the presence of water. Furthermore, many DESs known in the literature have also been shown to have a biocidal action. All these characteristics make DESs very advantageous and safe, and they could be used as biocidal agents for the treatment of biodegraded surfaces of cultural heritage, being non-toxic for the environment and for the operator. So far, they are used in various fields, but they still represent a novel frontier in the cultural heritage sector. The present research aims at testing five different DESs for the first time in cultural heritage. In particular, DESs are applied to a mosaic located in the Ostia Antica Archaeological Park (Rome), and their efficiency is compared with a biocide product currently used in the restoration field, namely, Preventol RI50, through luminescence, bio-luminometry, and spectrocolorimetry analysis. The preliminary results achieved show the different behaviors of each DESs, highlighting the possibility of employing them in the field of cultural heritage. Further studies have been planned, some of which are already underway, to investigate the properties of DESs and indicate any improvements to make them more effective, both as solvents and as biocides, and easy to apply to various types of materials. The results obtained from this first study are very promising for the use of DES as a new green strategy for cleaning and conservation treatments of materials in the field of cultural heritage.

Antifouling Mortars for Underwater Restoration.

This research has focused on the assessment of the compositional features and mechanical and antifouling performances of two different mortars formulated for an underwater setting, and which contain Mg(OH)2 as an antifouling agent. Regarding the mechanical characterization, the uniaxial compressive strength and flexural strength were measured. The composition of the materials was explored by differential thermal/thermogravimetric analysis (DTA-TG), X-ray diffraction analysis (XRPD), and scanning electronic microscopy (SEM) coupled with EDS microanalysis. The assessment of the biological colonization was evaluated with colorimetric analysis and image analysis. The results suggest that both mortars have good mechanical resistance once set underwater. Moreover, the adding of Mg(OH)2 improves the resistance toward biofouling; this was observed both in laboratory and sea-exposed specimens.

Preliminary Study of the Mural Paintings of Sotterra Church in Paola (Cosenza, Italy).

A multi-analytical approach was employed to study wall paintings located in the Sotterra church at Paola, in the province of Cosenza, Italy. The site is an underground church (hence the name of Sotterra, which means "under the earth") rediscovered in the second half of the 19th century, during the building works of the Madonna del Carmine church on the same area. This underground church preserves valuable mural paintings having different styles. The construction's dating and overlapped modifications made until the site was abandoned is also debated. A wall painting, depicting "The Virgin" as part of the "Annunciation and the Archangel Gabriel" present on the opposite side of the apse, was selected and investigated using both in situ and laboratory-based analysis. Preliminarily, the non-destructive investigations involved several analytical techniques (IR imaging, UV-Induced Visible Fluorescence, and X-ray Fluorescence analyses) that provided mapping and characterization of pictorial layers and first data about deterioration phenomena. On the basis of this information, a more in-depth study was conducted on micro-fragments aimed at characterizing the stratigraphy and to identify the artist's technique. Cross-sections were analysed using polarized optical microscopy and electron scanning microscopy coupled with energy-dispersive X-ray spectroscopy to obtain morphological and chemical information on the selected pictorial micro-fragments of the wall painting. The results allowed to characterize the pigments and provide better readability of the whole figure, revealing details that are not visible to the naked eye, important for future historical-artistic and conservative studies. The results represent the first step of a systematic archaeometric research aimed at supporting the ongoing historical-stylistic studies to distinguish the different building phases hypothesized for this religious site which remained buried for three centuries.

Multitechnique diagnostic analysis and 3D surveying prior to the restoration of St. Michael defeating Evil painting by Mattia Preti.

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 impact of atmospheric pollution on outdoor cultural heritage: an analytic methodology for the characterization of the carbonaceous fraction in black crusts present on stone surfaces.

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 by the set-up 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.

Biodeterioration of marble in an underwater environment.

This study examines the deterioration of geomaterials used throughout history that today may be found lying on the ocean floor. Submerged archaeological sites including cargoes from shipwrecks or ancient city ruins have been a topic of interest from a perspective of in situ musealization, as a way of making underwater cultural heritage accessible to the public. In an experimental study conducted at an underwater archaeological site in the Bay of Cádiz (SW Spain), we subjected two types of marble (Carrara and Macael) to three conditions to which submerged archaeological objects are often exposed: full exposure to the water column, natural processes of burial and unearthing, or permanent burial. After an 18-month study period, the factor found to mostly affect these materials was their biological colonization. This factor was assessed by estimating total surface biocover and the rate of surface biocolonization, and also through the identification of skeletons and associated alteration forms by light microscopy, and scanning electron microscopy (SEM). Biofouling and bioerosion were the main causes of biodeterioration and dependent on the position of the marble specimens in the seawater. The response of both materials was similar, though dolomite crystals in the Carrara marble acted as a protective barrier against actively penetrating microorganisms. These investigations have allowed the study of tracers left by epilithic encrusting organisms and endolithic bioeroders on marbles intentionally exposed to seawater, providing new insights to the understanding of the biodeterioration processes occurring in cultural heritage stones, with significant implications when they are part of underwater archaeological remains.

The Oceanus statue of the Fontana di Trevi (Rome): The analysis of black crust as a tool to investigate the urban air pollution and its impact on the stone degradation.

This paper deals with the analysis of black crust coming from the statue of Oceanus belonging to the Fontana di Trevi (Rome). This monument is undoubtedly one of the main touristic attractions of Rome. During the restoration held between 2014 and 2015, some diagnostic analyses had been carried out. It has been highlighted that the sheltered surfaces suffer the formation of black crust, especially on the marble statues. The possibility to sample those degradation products, together with the unaltered substrate, represented an excellent opportunity to characterize the marble itself, to assess the impact of the urban air pollution on the stone material, and to detect the pollutant on a precise timescale. In fact, it is known that the previous restoration of the fountain had been carried out between 1989 and 1991 then, information about the air pollution over the last 25years can be highlighted, because it has been proved that black crusts act as passive samplers of pollution. In order to fully characterize those samples, several techniques were used, including optical and scanning electron microscopy, X-ray diffraction, laser ablation inductively coupled plasma mass spectrometry, infrared spectroscopy and ion chromatography. Furthermore, a new methodology based on CHN (Carbon, Hydrogen, Nitrogen) analysis has been developed for the quantification of the two main constituents of the carbonaceous fraction present in the black crusts, i.e. OC (organic carbon) and EC (elemental carbon). This integrated approach proposed in the present study allowed us to gain information about the mineralogical phases and the elements within the crusts and at the crust-substrate interface, giving the possibility to identify the pollution sources causing the stone decay within the monument.