Search

An analytical investigation performed on Southern Italy pottery highlighted the usefulness of Raman spectroscopy to give answers to archaeological questions. It can provide important information concerning the production technology and raw materials constituting the glassy coatings. Raman spectroscopy was supported by Scanning Electron Microscopy coupled with Energy Dispersive X‐ray Spectroscopy (SEM‐EDS) for observations and elemental analysis. The studied samples, ranging from the 13th century lead‐tin‐glazed protomajolica to the 15th –16th enamelled pottery, come from the Castles of Montella and Ariano Irpino (Campania), from the castles of Scicli and Modica and from surveys carried out in Buscemi and Caltagirone (Sicily). Glassy matrices, opacifying agents, colour‐related raw materials and body‐coating interface crystalline phases were investigated. Though the coatings resulted all typically lead‐rich glass types, lumps showing a different Raman profile suggested that at least in one case, the batch was adultered with recycled glass waste. Furthermore, samples coming from Montella, belonging to the three main classes of ceramics defined by archaeological hypothesis, could be grouped according to their cassiterite content. The crystallization of lead–potassium feldspars at the coating‐body interface in a group of samples was ascertained. With regard to the origin of colours, the spectra of blue coatings highlighted phases that can be traced back to the use of Co‐based and Co–As‐based raw materials, while turquoise decorations were found to contain malayaite. Highlights: Medieval and renaissance pottery from Southern Italy were analysed.Raman analyses provided unexpected results and answers to archaeological questions.SnO2 Raman bands confirmed the grouping of Montella samples in three classes.Neoformed phases due to reactions during the production processes were discovered.Different cobalt‐based phases were found in the blue enamels. [ABSTRACT FROM AUTHOR]

The results of a petrographic and geochemical study carried out on archeological grindstones allow to provide new constraints on protohistoric commercial exchanges over the Mediterranean area. Eleven grindstones, discovered in an archeological site located in Milazzo (Messina, Sicily) and dated from the Early Bronze Age, have been investigated by geochemical and petrographic techniques. The raw materials are mainly volcanic rocks characterized by calc-alkaline and K-alkaline affinities with volcanic arc geochemical signature. Only one sample, made of basalt belonging to the Na-alkaline series, shows an intraplate signature. The comparison with the available literature data for similar rocks allowed constraining the volcanic origin of the exploited lavas. While the intraplate-type raw material came from Mt. Etna Volcano (Sicily), the arc-type volcanic rocks are mostly trachyandesites, basaltic andesites, and one rhyolite. Although most of them come from the Aeolian Arc, a provenance of some samples from the Aegean Arc cannot be excluded. This last region could represent the most probable provenance area for the rhyolite sample. [ABSTRACT FROM AUTHOR]

Blackening and disaggregation of exposed surfaces of stone monuments are well-known effects of stone decay taking place in polluted urban environments all over the world. This paper aims to assess the contribution of natural and anthropogenic sources of total suspended particulate (TSP) causing permanent damage (black crusts) to the stone monuments of Catania (Sicily), one of the most popular 'cities of art' of southern Italy. Atmospheric pollution of Catania, a typical Mediterranean coastal town, is mainly contributed by vehicle exhaust emissions rather than industrial ones. Episodically, the city also suffers gaseous and ash emissions (plumes) from the nearby Mount Etna volcano. Thus, to discriminate between natural and anthropogenic contributions to stone decay on Catania monuments, black crusts and TSP were sampled within the urban area and subjected to specific analytical procedures (optical microscopy, X-ray powder diffraction, Fourier transformed infrared spectroscopy, scanning electron microscopy equipped with energy dispersive spectrometry, ionic chromatography and dual inlet mass spectrometry). Mineralogical, chemical and isotopic characterization of black crusts and TSP provided new insights concerning the partition of sulfate sources in this particular urban context. The influence of Mount Etna emissions on both TSP and black crusts compositions was shown. Nevertheless, the key role of anthropogenic sources in the total sulfate budget was confirmed, while sea spray and volcanic emissions were found to make subordinate contributions. Quantitative data useful for the identification of the threshold pollution levels for preventive conservation of Catania monuments were obtained. [ABSTRACT FROM AUTHOR]

Abstract: This work focuses on the petro-archaeometric analysis of several transport amphorae dated back from 4th to 2nd century BC which were found in various archaeological excavations recently carried out in Messina and Milazzo (north eastern Sicily). These amphorae, generally known as Graeco-Italic, raise the problem of the identification of their production areas. Petrographic analyses proved the presence of two groups characterised by the presence of coarse metamorphic or volcanic inclusions and one group with finer metamorphic inclusions. Multivariate statistical analyses made it possible to detect the production area of the amphorae with metamorphic inclusion in north eastern Sicily, comparing them with locally produced bricks and clay sediments cropping out near the ancient cities. On the contrary, the studied amphorae rich in volcanic inclusions have petrographic and chemical features which can be attributed to production areas in the Campanian region. [Copyright &y& Elsevier]

Noto is an important Baroque urban center in south-eastern Sicily, which was completely reconstructed after the severe earthquake of 1693. Most of its monuments and historic buildings were built in Pietra di Noto stone, a pale cream calcarenite, quarried in outcrops located near the city. This stone, still currently used as building material, is undergoing many forms of alteration and degradation, which cause significant damage to monuments. In this study, three commercial protective products were tested on some Noto calcarenite samples from quarries, with the aim of assessing their protective effectiveness. In particular, petrographic analyses by optical microscopy were carried out for textural characterization of the stone materials. Capillary water absorption, porosimetric and colorimetric procedures, UV radiation and salt crystallization aging tests were performed to better evaluate interactions between protective products and substrate. [ABSTRACT FROM AUTHOR]

This paper presents new petro-chemical data on some typical mortars found in many buildings in the historic city centre of Catania (Eastern Sicily). Extensively used in the architecture of the city from the second half of the nineteenth century until the mid-twentieth century, these mortars are characterised by a particular aggregate locally known as “ agghiara” or “ ghiara”. This is the product of thermal transformation induced by the heating undergone by palaeo-soils, originally rich in organic matter, covered by lava flows, which change their colour to reddish nuances. The volcanic origin of ghiara is a peculiar feature of the Etnean area. Mixed with lime, it gives to mortars an intense reddish colour, as well as hydraulic properties, which are comparable with those of the historically used pozzolana. This work aimed at complete characterisation of these ghiara mortars, for providing information on several important technological aspects. In order to get information on used raw materials, sampling of some ancient underground quarries, located both in the historic city centre and at the periphery, was also performed. Results led to the complete characterisation of the selected ghiara mortars and yielded information on some technological features and the composition of both newly formed and secondary phases, these latter due to alteration processes. The hydraulic properties of mortars have been related to the occurrence of amorphous phases within the ghiara aggregate, which were identified by means of SEM morphological observations. These phases, formed during the “firing” process of palaeo-soils, react with lime producing hydraulic compounds (C–S–H and C–A–H), which are responsible for the mortars durability. [ABSTRACT FROM AUTHOR]

Copyright of Conservation Science in Cultural Heritage / Quaderni di Scienza della Conservazione is the property of Salvatore Lorusso and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Micro-FTIR and FTIR spectroscopy is useful for the study of degradation forms of cultural heritage. In particular it permits to identify the degradation phases and to establish the structural relationship between them and the substratum. In this paper, we report the results obtained on marble from a Roman sarcophagus, located in the medieval cloister of St. Cosimato Convent (Rome), and on oolitic limestone from the facade of St. Giuseppe Church in Syracuse (Sicily). The main components found in the samples of both monuments are: gypsum, calcium oxalate, and organic matter due to probably conservation treatments. In particular, the qualitative distributionmaps of degradation products, obtained by means of micro-FTIR operating in ATR mode, revealed that the degradation process is present deep inside the stones also if it is not visible macroscopically. This process represents the main cause of crumbling of the substrate. The results of this research highlight the benefits of the μ-FTIR analysis providing useful insights on the polishing and consolidation processes of stone materials. [ABSTRACT FROM AUTHOR]

The Cathedral of St. Giorgio in Ragusa Ibla (Sicily) is one of the most important Baroque monuments of eastern Sicily. The restoration of the monument underway has put forward notable questions regarding the stone materials used and their state of degradation. The façade appears to be made mainly of a creamy white calcarenite, and of mortars and plasters. However, detailed analysis has highlighted a more complex use of the raw material. The mortar and plaster have a different composition in regards to their architectural use while the natural stone material is distinguished not only by a creamy-white calcarenite but also by a dark coloured bituminous calcarenite (pitch rock), which now appears whiter because of superficial chromatic alterations. This process was reproduced in the laboratory using an accelerated aging technique on samples of bituminous calcarenite, which allowed the cause of the alternation to be identified as photo-oxidation of the asphaltenes. Following this process of photo-oxidation, other forms of chromatic alterations affected the façade (brown–orange-coloured patinas). FTIR, Scanning Electron Microscope and thin section microscopic observation allowed the characterization of also the products of this process to be carried out, highlighting the complex mechanism which the processes underwent. [ABSTRACT FROM AUTHOR]

The Cathedral of St. Giorgio in Ragusa Ibla like the majority of historic buildings in the Ragusa area is constructed mainly from locally outcropping calcarenite belonging to the Ragusa Formation. Through the years, the cathedral has undergone diverse restoration procedures using different protective products , the nature of which was determined by means of Fourier transform infrared spectroscopy (FT-IR) and gas chromatography coupled with mass spectrometry (GC–MS). Regardless of these interventions, the materials used today are still subject to diverse forms of alterations and degradation (alveolitation, differential degradation, decohesions, chromatic alterations and the formation of biological patinas correlated to lichen activity), which cause considerable damage to the façade. In this paper, three protective products were tested on the calcarenite of the Ragusa Formation taken from a quarry: a fluorurated elastomer , a fluorurated anionic polyurethane and linseed oil. The protective efficiency was determined, after undergoing UV radiation aging by means of capillary water absorption, porosimetric and colorimetric procedures. The results highlighted a good and persistent protective capability of both the elastomer and the fluorurated polyurethane, whereas, the linseed oil not only provoked strong chromatic variations but also quickly lost its hydro-repellant capacity with aging. [ABSTRACT FROM AUTHOR]

On the axial zone of the Southern Apennines the major tectonic boundary between the inner platform (Western platform unit) and the pelagic (Lagonegro units) domains is represented by a thick level of highly deformed rock-assemblage. Structural analysis reveals that this tectonic unit represents an intracontinental melange complex characterized by a block-in-matrix fabric that contains blocks from both hangingwall platform and footwall basin units. This unit comprises different sets of structures that, caused by shearing processes, developed at depths ranging from about 8–9 km to the surface. These tectonites represent the product of a crustal shear zone developed at the major boundary between platform-basin domains of Adria during the thick-skinned tectonic processes controlling the Southern Apennines mountain building. [ABSTRACT FROM AUTHOR]

An archaeometric study of the stone materials employed in the Late Baroque historical monuments of the ancient city centre of Catania was carried out. Lithological maps of a selection of monuments, transferred to a digital format, revealed that the stone materials are both magmatic and sedimentary rocks, the colours of which are matched in a peculiar type of bichromy. Particular attention focused on sedimentary rocks, which consist of various types of limestone quarried near the city of Syracuse (Hyblean Plateau, south-eastern Sicily). Carbonate rocks were characterised in terms of mineralogy, petrography and geochemistry, by studying rock samples from both monuments and historical extraction sites. Results showed that, although only one name was historically attributed to the above lithotypes (i.e. “Pietra di Siracusa‘’), they were quarried from many locations and, as they belong to various geological formations, they therefore exhibit great variety. In order to examine the durability of Hyblean limestones employed in works of cultural heritage interest, salt crystallisation tests were carried out according to standard procedure norms (UNI EN 12370 () Determination of resistance to crystallisation of salts, 6p). Results are consistent with the forms of deterioration observed in the monuments, and highlight the close relationship between textural characteristics and damage. Our purpose is to provide a basic tool, which may be useful both for conserving monuments of cultural heritage and for their restoration. [ABSTRACT FROM AUTHOR]

This study provides experimental insights into the optimization of alkali-activated materials (AAMs) carried out in situ at the restoration site of Monreale Cathedral, Italy. Volcanic ash from Mt. Etna volcano (Italy) was used as a precursor to obtain AAMs. Standard and modified pastes with a small amount of slaked lime paste were compared in terms of setting time, rheology, mineralogy, chemical morphology, and mechanical performance. The modified pastes exhibited a faster setting time, superior mechanical strength and rheological properties. Mineralogically, no difference was observed between the two pastes for the small amount of slaked lime paste added very close to the detectable limit (<2 wt%). Moreover, its addition causes slight differences in the morphology of the gel without changing the chemical composition of the Na 2 O–CaO–Al 2 O 3 –SiO 2 –H 2 O ((N,C)-A-S-H)) type. The results obtained may be useful for the development and optimization of building materials (especially for restoration purposes) where appropriate physico-mechanical performance is required. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: This work is focused on the petro-archeometric characterization of the fine pottery production of the archaeological site of Gela (Sicily). Thirty-five samples coming from three Archaic and Hellenistic kilns and five coming from an Hellenistic house, were investigated by means of optical microscopy, XRD and XRF analysis. With the exception of some ceramics which are undoubtedly imported, all the samples have similar petrographic features, but on the basis of chemical composition, we can distinguish two different groups. The presence of two local productions is confirmed by the comparison with locally outcropping sediments and with archaic and modern bricks of sure Geloan production. This result is particularly significant for the definition of reference groups of this wealthy polis that played an important trading role in the Mediterranean area. [Copyright &y& Elsevier]

Abstract: Mineralogical (X-ray diffraction) and geochemical (X-ray fluorescence) compositional data of Alpine Tethyde mudrocks from Sicily were used to unravel the interplay of provenance and diagenesis by means of multivariate statistical methods (PCA, discriminant function analysis) designed for non-negative constant-sum data. The Sicilian Alpine Tethydes comprise Cretaceous–Eocene scaly shales (Mt. Soro and Upper Scagliose Shales Units), Eocene–Oligocene variegated shales (Troina and Nicosia Units), and Miocene Numidian shales (Nicosia Unit). The use of biplots of clr-transformed variables allows discrimination of two different groups of shales. High CIA values reveal a strongly weathered source area especially for the Numidian shales. The analyses of mixed-layered clay minerals indicate that the behaviour of K2O and geochemical affine elements is controlled by the diagenetic grade, which increases from south-west to north-east in response to tectonic loading. Ratios of selected elements (Zr, Y, La, Nb, Ti, Co, Cr, Ni), considered essentially unchanged with respect to the source rocks, are similar in the scaly and variegated shales, and resemble the Variscan Peloritani metamorphic basement. In contrast, the distinct geochemical signature of the Numidian shales reveals a source similar to the average cratonic sandstone, suggesting derivation from external sources located in the foreland. Multivariate discriminant analysis performed on selected trace elements confirms the previous suggestions. [Copyright &y& Elsevier]

[Display omitted] • Evaluation of activating solution influence on high temperature resistance in AAMs. • Higher availability of silicon and aluminum and better feasibility of the pastes. • Monitoring formation of Si-O-Si and Si-O-Ca networks. • Positive influence of the new crystallizations on mechanical resistance after 1000 °C. • Densification behavior of K sample contrary to the melting of that Na. Thermal performances at 1000 °C of volcanic ash-based alkali-activated materials by both sodium or potassium solutions have been tested. Once defined the feasibility for the potassium set, a multidisciplinary characterization including spectroscopic, thermal, mechanical, diffractometric before and after treatment and dilatometric analyses was applied. The formation kinetics of different networks was evaluated. A correlation between the high mechanical properties and the least amount of water was observed in non-treated samples. Treated samples at 1000 °C showed higher compressive strengths due to the crystallization of wollastonite, leucite and nepheline. Thermal stability was observed increased with the solid content in the potassium-based formulations. [ABSTRACT FROM AUTHOR]

Abstract: This paper is focused on a spectroscopic study of some pottery shards from an archaeological site in Syracuse (Sicily, Southern Italy), dating back to the Hellenistic–Roman period. Structural characterization was performed at different scales of observation, i.e. from macroscopic to mesoscopic. The main goal was to point out the potentiality of the small angle neutron scattering (SANS) technique as a non-invasive analytical tool in archaeometry, also in conjunction with other, more usual, methodologies. Correlation of experimental data, i.e. macroscopic typology and texture, obtained from petrographic analysis, and radius of gyration and fractal dimension of the interfaces of the mesoscopic aggregates obtained using SANS, together with mineralogical X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, allowed hypotheses to be made on the production technology of the investigated samples. [Copyright &y& Elsevier]

Abstract: The Palazzolo Formation calcarenite, commonly known as “Pietra di Noto”, has been widely used in the late Baroque monuments of the Val di Noto area. In this work, two different lithofacies have been identified through a minero-petrographic and physical–mechanical characterisation of the Noto stone samples. These latter have been taken out from three quarries, two of which are located near to Noto Antica (Porcari and Leone), and one next to Palazzolo Acreide (Camelio). Samples from Camelio have a white-cream colour and a higher sparry cement abundance than those from the Porcari and Leone quarries, which display a yellowish colour, a minor resistance and a more heterogeneous texture due to the presence of bioturbation (trace of fossils). The greater compactness of samples from Camelio compared to the other two is related to their higher ultrasonic velocities, better mechanical properties and reduced capability to absorb water by capillarity and total immersion which are related to the textural features. The existence of two lithofacies better explains the heterogeneity of degradation forms (chiefly consisting of differential degradation, alveolization, detachment and chromatic alteration) that can be observed on the monuments built in these stone materials. The main causes of deterioration have been related to bioturbation, as well as to the occurrence of expandable clay minerals (smectite) and to salt crystallization. The presence of bioturbation also affects the mechanical characteristics of these stones. [Copyright &y& Elsevier]

Abstract: In the present work, we report on a detailed characterization of Late Roman and Byzantine (from 2nd to 8th century A.D.) glass specimen found in Catania (Sicily, Southern Italy) by the employment of two complementary techniques, namely scanning electron microscopy coupled with energy-dispersive spectrometry (SEM–EDS) and Fourier transform infrared (FT-IR) absorbance spectroscopy. The glass fragments come from archaeological excavations in the courtyard of St. Agata la Vetere''s church in Catania. In particular, compositional data were obtained by scanning SEM–EDS measurements and the investigation of the degradation on the surface of the glass specimen was made combining the SEM–EDS observations with those performed through FT-IR absorbance. The whole set of results contributed to define the provenance of the specimens. Furthermore, the data furnished new evidences of the technical development of glass production in Late Roman and Byzantine period in Catania. [Copyright &y& Elsevier]

Abstract: In the present work, an analytical characterization of painted plaster samples coming from ancient buildings dated back to 2nd cent. B.C., located in Licata (Sicily, Southern Italy), has been carried out. The investigation has been performed through different spectroscopic techniques: X-ray fluorescence (XRF) using an handheld energy-dispersive XRF analyzer, scanning electron microscopy equipped with an Energy Dispersive Spectrometry microanalysis detector (SEM-EDS) and Fourier transform infrared absorbance spectroscopy (FT-IR). The main goal is to identify the plaster and pigments material. In particular, the XRF investigation of surfaces is the first step for a preliminary elemental characterization. Then, through SEM-EDS measurements, a quantitative analysis of the chemical composition of the plaster and the pigmenting agents along with eventual components related to deterioration processes has been obtained. Finally, FT-IR absorbance spectra have proven to be a useful tool to investigate the molecular nature of the used materials. [Copyright &y& Elsevier]

This work is a part of a research project conducted in order to characterize the volcanic ash from Mount Etna, focusing in particular on the surface reactivity of ashes and possible consequence for human health. In this framework, a sampling campaign began on 16 March 2013, taking advantage of the intense volcanic activity on Etna. The interaction between volcanic ash and human organism was simulated treating two classes of representative Etnean particles with ultrapure water (grainsize of 850 um) and Gamble's solution mimic lug fluids (grainsize <38 μm) with the aim to evaluate the risk due to gastric and respiratory exposure to volcanic particles. The leachates were analysed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Ionic Chromatography (CI) in order to highlight possible dangerous elements released in water solutions according to USGS protocol. Analyses of Gamble's solution highlighted a release of elements smaller than in watery solutions and always below the thresholds established by the Italian law. On the contrary, analyses of watery solutions evidenced, for some elements (B, Cd, Ni and As), levels higher than permitted by Italian law. Considering the effects of these elements on human health, further investigations are necessary and currently carried out in order to better constrain the release process and the specific effects on human organism., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)