Integrated analytical methodologies for the study of corrosion processes in archaeological bronzes

Abstract The investigations on structure and micro-chemical composition of archaeological metal alloys are needed in archaeometry. The aim of this study is devoted both to acquire information about their provenance and production technology, and to improve our understanding about the corrosion processes. In this paper we present the study of the corrosion phenomena of bronze samples, laboratory-made according to binary, ternary and quaternary alloys typical of Roman archaeometallurgical production through an integrated methodology based on the use of non or micro invasive physical techniques. Among the analysed samples, two were artificially aged through burial in the archaeological site of…

How Many Secret Details Could a Systematic Multi-Analytical Study Reveal About the Mysterious Fresco Trionfo della Morte?

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"Historical pigments characterisation by quantitative X-ray fluorescence"

Abstract Most of the historical paints are mainly constituted by inorganic pigments, either pure or mixed, spread on the surfaces using different binding agents. The knowledge of the exact amount of different constituents of the paint, as well as of the mixing and pictorial techniques, is crucial for a careful program of conservation of polychrome works. Moreover, since the availability of these pigments has been changing through the centuries, their identification and chemical characterisation is useful to acquire or deepen information about the artist and his/her work. This information can also be useful for authentication purposes through relative dating because the identification of one…

Degradation study of XVIII century graffiti on the walls of Chiaramonte Palace (Palermo, Italy)

A systematic investigation of the original materials and the degradation phenomena induced by soluble salts on the wall matrix and on the graffiti of the Inquisition jails of Chiaramonte Palace in Palermo (Italy) was carried out. Built in the XIV century, Chiaramonte Palace was used as Inquisition court during the XV–XVI centuries. The ancient graffiti, recently discovered, represent a unique historical witness of the prisoners that lived during that terrible period. In order to study the nature, the amount and the distribution of the salts in the masonry, stone materials sampled at different depth from the wall matrix and saline efflorescences were analysed. Different physical techniques w…

X-ray CT imaging as a scientific tool to study the capillary water absorption in sedimentary rocks used in cultural heritages

This paper proposes the X-Ray CT imaging as appropriate tool for investigating the capillary water absorption in sedimentary rocks. This technique, in fact, provides information useful for deeping the knowledge about of the porosity and the kinetics of the water capillary absorption in porous materials. The possibility to improve in non invasive manner, the understanding of this phenomenon, constitutes a fundamental aspect to take actions in the restoration and conservation of lapideous artifact and monuments from cultural heritages. The investigated sedimentary rocks come from different Sicilian quarries and were used for the building of the Greek temples in the archaeological areas of Agr…

XRF ANALYSES ON MOSAIC TESSERAE OF THE PALATINE CHAPEL OF PALERMO

Surface and volume non-invasive methods for the structural monitoring of the bass-relief ‘Madonna con Bambino’ (Gorizia, Northern Italy)

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 d…

Integrated three-dimensional models for noninvasive monitoring and valorization of the Morgantina silver treasure (Sicily)

The Morgantina silver treasure belonging to the Archaeological Museum of Aidone (Sicily) was involved in a three-dimensional (3-D) survey and diagnostics campaign for monitoring the collection over time in anticipation of their temporary transfer to the Metropolitan Museum of Art in New York for a period of 4 years. Using a multidisciplinary approach, a scientific and methodological protocol based on noninvasive techniques to achieve a complete and integrated knowledge of the precious items and their conservation state, as well as to increase their valorization, has been developed. All acquired data, i.e., 3-D models, ultraviolet fluorescence, x-ray images, and chemical information, will be…

Archaeometric Study of Two Tanagra Type Statuettes of Unknown Provenance to Support Forensic Study

This paper is concerned with a morphological-stylistic and archaeometric study of two small pottery statues, confiscated by the Cosenza Carabinieri Unit for the Protection of Cultural Heritage and Anti-Counterfeiting (Calabria, Italy). The research aimed to establish the authenticity of the artworks and to verify a possible origin from the same workshop manufacturing, by providing indications about the textural features and raw materials used for their production. For these purposes, the analytical approach involved the use of minero-petrographic and physical analysis, as follows: petrographic analysis (OM), X-ray diffraction (XRD) and thermoluminescence tests (TL). The preliminary observat…

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” prese…

Characterization of foxing stains in early twentieth century photographic and paper materials

The subject of this present work is a group of nine historical pictures shot in Palermo by the Sicilian photographer E. Interguglielmi in 1912. They are nine matte-collodion prints mounted on the original cardboard supports and all of them show foxing stains affecting the paper surface. In order to characterise the chemical composition of the supports and investigate foxing spots, non-destructive and micro-destructive analysis were carried out. X-rays fluorescence (XRF) analysis was used to characterise the elemental composition of all the mounting boards, allowing a comparison between the foxing spots and non-affected areas. Laser-Induced Breakdown Spectroscopy was used to investigate the …

Comparison of LIBS and micro-XRF measurements on bronze alloys for monitoring plasma effects

The laser-induced breakdown spectroscopy (LIBS) technique is often used as atomic spectroscopic technique for elemental analysis of materials. However, it presents some drawbacks that make an accurate quantitative analysis difficult. Since the plasma properties, such as spatial inhomogeneity and plume stoichiometry strongly depend on the experimental conditions, the measurements are less reproducible. In order to evaluate the measurement fluctuations, we propose to use the more established micro X-Ray fluorescence (μ-XRF) technique for validating LIBS data. In particular, the quantitative data, obtained by varying the laser fluence, the shot numbers and the temporal acquisition parameters, …

Mosaic floors of roman Villa del Casale: Principal component analysis on spectrophotometric and colorimetric data

Abstract Spectrophotometric and colorimetric data obtained during a measurement campaign aimed at supporting the Roman "Villa del Casale" (Piazza Armerina, Sicily, Italy) conservation activities, are presented. Special attention was paid to the possible variation of the chromatic coordinates, possibly due to the interventions of cleaning, consolidation, and protection. Data have been analyzed by the Principal Component Analysis (PCA) statistical technique, with the attempt to investigate its role in data variability reduction and verify its effectiveness in interpreting the phenomena occurring on the mosaic surface of the Villa, through grouping the observations into homogenous clusters. Ef…

Gilding and pigments of Renaissance marble of Abatellis Palace: non-invasive investigation by XRF spectrometry

Most of the artworks constituting the collection of Renaissance statuary of Abatellis Palace in Palermo (Sicily) show evidence of colour layers and fragments of gold foil that probably once covered the whole marble surface. The restoration of some of these statues has allowed to carry out archaeometric studies about the painting technique and to highlight the original materials and inclusion present on the precious marbles by two famous Italian sculptors of the Renaissance, Francesco Laurana and Antonello Gagini. The measurements have been performed in situ through the integrated use of two non-invasive techniques: visible fluorescence stimulated by ultraviolet light and X-ray fluorescence.…

Double Laser LIBS and micro-XRF spectroscopy applied to characterize materials coming from the Greek-Roman theater of Taormina

The laser-induced breakdown spectroscopy (LIBS) is an applied physical technique that has shown, in recent years, its great potential for rapid qualitative analysis of materials. The possibility to implement a portable instrument that perform LIBS analysis makes this technique particularly useful for in situ analysis in the field of cultural heritages. The aim of this work is to compare the results, obtained by LIBS measurements with X-Ray Fluorescence (XRF) ones, on calcareous and refractory materials coming from the Greek-Roman theater of Taormina. Calibration curves for LIBS and XRF were obtained by measuring certified reference materials and using them as standards. LIBS measurements we…

Decay assessment of stone-built cultural heritage: The case study of the cosenza cathedral façade (south calabria, italy)

This study aims to assess the different decay phenomena affecting the Cosenza Cathedral façade (Calabria, South Italy) through the evaluation of the relative damage indices. For this goal, a multidisciplinary approach was applied exploiting both nondestructive and microdestructive techniques. Such a combination enabled proposing an intervention priority scale that can be helpful to institutions when planning a prompt restoration intervention. The results suggest the efficiency of this approach to obtain a multidisciplinary diagnostic and conservation system for the management and valorization of the Cultural Heritage also in terms of monitoring, maintenance, and selection of the most suitab…

XRF analysis to identify historical photographic processes: The case of some Interguglielmi Jr.’s images from the Palermo Municipal Archive

Abstract In the early period, even though professional photographers worked with similar techniques and products, their artistic and commercial aims determined different choices and led them to follow different, often personal, recipes. For this reason, identification of the techniques through date and name of the photographer or through some visual features like colour, tonality and surface of the image layer, often needs further investigation to be proved. Chemical characterization, carried out in a non or micro destructive way, can be crucial to provide useful information about the original composition, degradation process, realization technique, in obtaining an indirect dating of the ph…

Comparison between mercury intrusion porosimetry and nuclear magnetic resonance relaxometry to study the pore size distribution of limestones treated with a new consolidation product

Abstract Pore-space properties, such as pore-size distribution and connected porosity, are relevant factors in the evaluation of the performance of a consolidation treatment. In this study, two different techniques – Mercury Intrusion Porosimetry (MIP) and Nuclear Magnetic Resonance Relaxometry (NMRR) – were adopted to study the compatibility and the efficacy of a new consolidation product for limestones. This work aims at comparing and combining data obtained by MIP and NMRR; to confirm the relationship between the quantitative results of MIP and the qualitative ones of NMRR, a calibration which leads to correlate T2 distribution and pore size distribution has been applied. Experimental re…