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In the view of the recycling and upscaling processes of waste materials, three different precursors, namely metakaolin, fly ash and volcanic ash, were mixed with Na- or K-silicate to produce binders aimed for the synthesis of geopolymer mortars based on construction and demolition wastes (CDWs). These later, used as aggregates in amount of 50 wt.%, were sampled in two geologically different Italian areas. A comparative study was carried out through a multidisciplinary approach using mineralogical–chemical analyses and physical–mechanical tests for the characterization of six binders and twelve mortars. The aim was to verify the effects of CDW interactions on binders as well as the extent of their compositional influences on the final properties. The chemical and mineralogical results evidenced strong compositional differences among the CDWs, differently influencing the physical–mechanical performances (i.e., compressive strength, density, water absorption and porosity) of the mortar samples. Regardless of the types of precursors and CDWs used, a better influence of K-silicate than sodium on the synthetised samples was observed. Furthermore, the higher versatility of metakaolin mortars with any type of CDW used was noted. Contrary, fly ash and volcanic ash mortars showed better properties with CDWs based on their high silica content and volcanic minerals. The study highlighted the critical roles of the CDW composition and precursor selection in mortar production. It confirmed that CDWs can be recycled for geopolymeric synthesis through proper characterisation and binder selection. Optimising these parameters allows for the successful integration of CDWs into geopolymeric materials. This process supports the advancement of a circular economy in the construction industry. [ABSTRACT FROM AUTHOR]

The present work discusses the challenges and approaches involved in conserving cultural heritage (CH), specifically focusing on eco-friendly conservation methods and the management of biodeterioration. It highlights the need for innovative protocols that align with green conservation criteria, aiming to replace traditional, potentially harmful practices with sustainable alternatives. This study is based on the role of nanomaterials like halloysite in developing protective coatings for CH materials. Additionally, the issues of biological colonization on CH assets, the difficulties in controlling environmental factors affecting biodeterioration, and the use of direct methods in outdoor conservation were also evaluated. This work is specifically focused on a case study: the "Palazzo Centrale dell' Università" in Catania (Italy), where alternative, eco-friendly protectives and biocides have been tested on Hyblean limestones. After a preliminary study of the lithology and the forms of degradation which affect the whole monument, laboratory tests were carried out using the newly developed protective coatings on several types of Hyblean limestone in order to assess their efficacy and their impact on the stone. Furthermore, cleaning operations were also tested on-site by comparing an eco-friendly biocide with commercial counterparts in order to evaluate the effectiveness of the products and establish an efficient restoration protocol for future projects. [ABSTRACT FROM AUTHOR]

The recent upgrading of synchrotron radiation (SR) sources has favored, in the last few years, the construction and design of beamlines optimized for the study of cultural heritage materials, which may require ad hoc setups, specific spatial resolutions, and detection limits. In the field of cultural heritage, integrated approaches combining different techniques are often required, even at large facilities, where some beamlines offer the possibility of performing different types of measurements at the same point of analysis, complementing preliminary information usually obtained by conventional laboratory and/or portable in situ methods. An overview of the last ten years of synchrotron applications for the study of pigments is given, with discussion of upstream and downstream challenges to methods and techniques. The possibilities offered by the synchrotron techniques are illustrated by a case study of a particular class of painted ceramics, as an example of different research questions that are solved by a combination of SR-based methods. [ABSTRACT FROM AUTHOR]

This paper aimed to investigate the possibility of using alkaline-based binders made from the industrial waste produced by ceramic tiles in the field of conservation and the restoration of monuments and archaeological heritage. Geopolymer mortars, which are environmentally sustainable products obtained by chemical consolidation at room temperature, are studied for their versatility in applications as reintegration or bedding mortars and pre-cast elements, namely bricks, tiles or missing parts for archaeological pottery, as an alternative to traditional not sustainable products. Starting from a well-established formulation, the function of the product, meaning its technical characteristics and its workability, was optimized by changing the aggregates used, by adding a Ca-rich compound or by changing the liquid/solid ratio with the use of tap water. The possibility of tailoring the finishing of the obtained products was also evaluated. X-ray diffraction analysis showed the influence of adding the additive with the presence of newly formed phases, which positively affect the product's workability. On the contrary, no important variations were observed with the increase in the water content of the same formulation, opening up the possibility of managing it according to the required fluidity of the final product. Good results were observed, jumping above the laboratory scale and overcoming criticalities linked to the variabilities on site and the higher volume of materials used for industrial processes. The present research also demonstrates that ceramic-based geopolymers are suitable for application in a large variety of cultural heritage projects and with different purposes. Therefore, the paper encourages the use of alkali-activated mortars for green restoration, specifically given the wide range of ceramic materials. [ABSTRACT FROM AUTHOR]

A collection of Hellenistic–Roman glyptics, kept at the Regional Archaeological Museum "Paolo Orsi" (Syracuse, Italy), was investigated in situ with portable Raman spectroscopy with the aim of assessing the viability of this approach, not only for the immediate identification of the gemstones but also for a more in‐depth successive data treatment. At the same time, a corroboration of the autoptic identification of the materials, both archeological and belonging to historical collections, was looked for in order to verify and potentially correct what reported in the museum catalogue. Actually, most of the identifications could be confirmed, the glyptics being mainly made of chalcedony. Other materials found were garnet, glass, and amber. The larger group of chalcedony Raman spectra was subjected to principal components analysis treatment that, after appropriate pretreatment, resulted successful in separating spectra with higher or lower contribution of the band due to the presence of moganite and SiOH bonds. The garnet spectra were instead subjected to quantitative study to identify the main end member. Both the quick identifications and the more detailed studies on chalcedonies and garnets were achieved thanks to the nondestructive and noninvasive investigation, directly in situ, with no sample preparation and minimal interference with the museum's activities. [ABSTRACT FROM AUTHOR]

The implementation of analytical techniques able to certify food quality and origin in a fast and non-destructive way is becoming a widespread need in the agri-food sector. Among the physical non-destructive techniques, X-ray fluorescence (XRF) spectrometry is often used to analyze the elemental composition of biological samples. In this study, X-ray fluorescence (XRF) elemental profiles were measured on tomato samples belonging to different geographical areas in Sicily (Italy). The purpose of this investigation was aiming to establish a protocol for in-situ measurement and analysis able to provide quality assessment and traceability of PGI agri-food products, specifically sustaining health safety and self qualifying bio-chemical signature. In detail, sampling was performed in one of the most tomato productive area of south-eastern Sicily (Pachino district), characterised by a relative higher amount of Organic Carbon and Cation Exchange Capacity, and compared with samples from other growing areas of Sicily, falling in Ragusa province and Mt. Etna region. Experimental data were analyzed in the framework of multivariate analysis by using principal component analysis and further validated by discriminant analysis. The results show the presence of specific elemental signatures associated to several characterizing elements. This methodology establishes the possibility to disentangle a clear fingerprint pattern associated to the geographical origin of an agri-food product. [ABSTRACT FROM AUTHOR]

Today, the need to dispose of a huge amount of ceramic industrial waste represents an important problem for production plants. Contextually, it is increasingly difficult to retrieve new mineral resources for the realization of building materials. Reusing ceramic industrial waste as precursors for building blocks/binders, exploiting their aluminosilicate composition for an alkaline activation process, could solve the problem. This chemical process facilitates the consolidation of new binders/blocks without thermal treatments and with less CO2 emissions if compared with traditional cements/ceramics. The alkali-activated materials (AAMs) are today thought as the materials of the future, eco-sustainable and technically advanced. In this study, six different kind of industrial ceramic waste are compared in their chemical and mineralogical composition, together with their thermal behaviour, reactivity in an alkaline environment and surface area characteristics, with the aim of converting them from waste into new resources. Preliminary tests of AAM synthesis by using 80%–100% of ceramic waste as a precursor show promising results. Workability, porosity and mechanical strengths in particular are measured, showing as, notwithstanding the presence of carbonate components, consolidated materials are obtained, with similar results. The main factors which affect the characteristics of the synthetized AAMs are the precursors' granulometry, curing temperature and the proportions of the activating solutions. [ABSTRACT FROM AUTHOR]

Due to the surprising lack of knowledge concerning raw materials and production technology employed to make mosaics after the twelfth century, an archaeometric investigation was carried out on the materials constituting the mosaic decoration of the South aisle wall of Monreale Cathedral (Italy), taking advantage of a conservation intervention. In this work, fallen coloured or gilded glass tesserae to be repositioned were studied by means of a combination of a molecular technique (Raman spectroscopy) and an elemental one (portable X-ray Fluorescence, pXRF); also, efflorescences affecting the general conservation state and samples of the respective bedding mortar were analysed with the former technique and with X-ray diffraction (XRD). The raw materials used and, consequently, the different compositions characterizing gilded vs. coloured glass tesserae were highlighted with the vibrational spectroscopy; chromophores and trace elements were detected by pXRF. This complementary approach allowed to disclose clues about glass-manufacturing technique and raw materials. The nature of the salts was also ascertained through Raman spectroscopy and XRD, for the benefit of the conservation procedure, and connected to the mortars' composition. [ABSTRACT FROM AUTHOR]

This paper presents the results obtained from the thermal analysis of a set of geomaterials (clays, pyroclastic materials, and industrial recycled materials) to be used as raw materials for the synthesis of geopolymers, specifically designed for the conservation of Cultural Heritage (CH) buildings, particularly in seismic hazard zones such as Sicily. X-ray diffraction and gas volumetric analysis (calcimetry) were applied to this set of raw materials in order to characterize the materials from the chemical and structural point of view. Thermogravimetric analysis (TG), TG coupled to Fourier transform infrared spectroscopy (TG-FTIR), and differential scanning calorimetry were used to characterize their thermal behavior. The statistical treatment of the thermogravimetric data by principal component analysis and hierarchical clustering analysis highlights the direct relation between the thermal data and the material composition that will be exploited for the selection of the best materials to obtain geopolymers specifically designed for the conservation of CH buildings. [ABSTRACT FROM AUTHOR]

In this contribution a non-destructive approach has been used aiming at investigating the chemical composition of 35 ceramic items belonging to the collections of the Regional Aeolian Museum "Luigi Bernabò Brea" in the Lipari Island (Sicily, Italy). Different vessel types have been selected for analysis, including aryballoi, kotylai, olpai, anforiskoi, oinochoai, and alabastra, belonging to the "Proto-Corinthian and Corinthian" ware classes. The items, dating back to the period comprised between the early eighth and the first half of the sixth century BC, come from two different archaeological sites in the province of Messina (Sicily), specifically the Istmo necropolis of Milazzo, in the northern Sicilian coast, and the acropolis and necropolis of Lipari, in the Aeolian islands. The chemical characterization of ceramics, carried out through portable X-ray fluorescence spectroscopy (pXRF), aimed at gaining information on the production area of examined items whose autoptic analysis pointed to Corinthian imports. The possibility of carrying out experimental investigations on the most ancient materials from the archaic necropolis of Milazzo and on fragments from Lipari, albeit limited to pXRF investigations, allowed to enrich the knowledge on the Corinthian production exported to western areas as well as to discriminate, no longer based solely on autoptic observations and stylistic evaluations, between Corinthian productions and "local" imitations. [ABSTRACT FROM AUTHOR]

Zeolites are present in numerous outcrops of volcanites of different ages in Sicily (Italy). Some of these outcrops are important because they constitute the ideal genesis conditions of some of these minerals, which represent geological indicators of chemical and geothermal gradients involved during their formation. For this purpose, a group of zeolites coming from areas of the Ionian coast and Palagonia village (Eastern Sicily) was investigated by means of Raman spectroscopy. In the geological record, these areas have been influenced by intense volcanic events that produced mineralization of hydrothermal origin. Sicilian zeolite samples were analysed in situ using different mobile Raman apparatus, directly on the outcrops of Aci Castello and the nearby Lachea Island, or in local collections where they are preserved. Some of these samples have been then analysed using laboratory micro‐Raman to compare the results and identify the zeolite types. The strength and weakness points of each instrument have been highlighted. Often, the Raman spectra of zeolites are affected by broad fluorescence, making them of difficult interpretation. However, satisfying results were obtained with portable devices, whose identifications were confirmed by micro‐Raman, discerning zeolites of different groups, such as analcime, chabazite, natrolite and phillipsite. The use of portable instruments has demonstrated the possibility to obtain identification of zeolites and related minerals both on site and in the laboratory, whose results match with the geological setting of the considered areas. [ABSTRACT FROM AUTHOR]

Tanzanite is the blue to violet‐blue variety of the sorosilicate zoisite; its colour is due to vanadium substitution of aluminium in the octahedral sites and is proved to appear after natural or artificial heating to approximately 500°C. Its colour makes it a highly appreciated gemstone, for this reason often imitated or thermally treated with the aim of enhancing its hue. Tanzanite loose gemstones are easily identified by classical gemmology methods that are not always applicable to mounted jewels. At the same time, zoisite Raman spectra are rarely reported in literature and never with a systematic approach. In this work, zoisite samples and cut tanzanite gemstones were considered, with the aim of filling this gap by addressing different methodological aspects. Namely, the orientational effects were investigated to explain the spectral variability, the photoluminescence bands were differentiated from the Raman signals using different excitation wavelengths, and the effectiveness of portable instrumentation in the correct identification of tanzanite was evaluated. The results are encouraging, showing that zoisite is revealed, notwithstanding orientational effects, by both portable and laboratory Raman instruments with comparable performances, opening the way to an effective identification of mounted tanzanite gemstones. Furthermore, the employ of different excitation wavelengths allowed to distinguish the photoluminescence bands with both categories of devices, thus identifying rare earth elements (REEs) likely associated with the mineral's genesis. [ABSTRACT FROM AUTHOR]

Alkali‐activated materials (AAMs) and "geopolymers" are inorganic polymeric materials obtained by mixing of solid aluminosilicate precursors with an alkaline solution (generally, KOH or NaOH and Na2SiO3 mixed in various ratios). This class of aluminosilicate materials has emerged as a greener alternative to traditional concrete, for large‐scale as well as for niche applications such as conservation and restoration of built heritage. In this work we apply Raman spectroscopy both to aluminosilicate precursors (metakaolin, pumice, volcanic ash, volcanic soils, clayey sediments, ceramic waste) and to the respective AAMs. In the field of vibrational spectroscopy, Raman is much less employed in the literature with respect to Fourier transform infrared (FTIR) to have insights into the alkali activation process from a molecular point of view. The aim of this paper is to investigate the potentiality of a Raman approach to the comparison of the employed raw materials with the respective AAMs. Raman analyses during the first hours of geopolymerization were also carried out on the clayey sediments and ceramic waste‐based products. The results, differentiated according to the employed precursors, exhibit spectra relative to crystalline and amorphous phases that can give an indication about the newly formed aluminosilicate gel. [ABSTRACT FROM AUTHOR]

Archaic Roman painted antefixes, architectural slabs and louteria from the Palatine Hill in Rome, Italy, were studied by non‐destructive and micro‐destructive methods: Portable X‐ray fluorescence (XRF), micro‐Raman spectroscopy, optical microscopy, scanning electron microscopy with energy‐dispersive spectroscopy (SEM‐EDS) and X‐ray diffraction (XRD). The investigation enabled the characterization of raw materials and ceramic technology, providing insights on provenance. In fact, similarities were recognized with terracottas from the neighbouring Etruscan Veii. The analysis of pictorial layers revealed the use of Fe‐ and Mn‐based pigments, as well as the identification of more precious pigments on worthy pieces. The research intended to support the archaeological discussion about the frame of the nascent city of Rome, also in relation to the coeval Etruscan culture. [ABSTRACT FROM AUTHOR]

Synchrotron X-ray µ- and nano-probes are increasingly affirming their relevance in cultural heritage applications, especially in material characterization of tiny and complex micro-samples which are typical from archaeological and artistic artifacts. For such purposes, synchrotron radiation facilities are tailoring and optimizing beamlines and set-ups for CH, taking also advantages from the challenges offered by the third-generation radiation sources. In ancient ceramics studies, relevant information for the identification of production centers and manufacture technology can be obtained in a non-invasive and non-destructive way at the micro-sample level by combining different SR based methods. However, the selection of appropriate beamlines, techniques and set-ups are critical for the success of the experiments. Fine and varnished wares (e.g., Attic and western-Greek colonial products) are an excellent case study for exploring challenges offered by synchrotron X-ray microprobes optimized to collect microchemical and phase-distribution maps. The determination of provenance and/or technological tracers is relevant in correctly classifying productions, often based only on ceramic paste, gloss macroscopic features or style. In addition, when these vessels are preserved in Museums as masterpieces or intact pieces the application of non-invasive approach at the micro sample is strictly required. Well-designed synchrotron µXRF and µXANES mapping experiments are able providing relevant clues for discriminating workshops and exploring technological aspects, which are fundamental in answering the current archaeological questions on varnished Greek or western-Greek colonial products. [ABSTRACT FROM AUTHOR]

Volcanic rocks have been used for building activity by the inhabitants of important cities located on the slopes of Mt. Etna, Italy. In this paper, the potential use of volcanic residues (code 20 03 03—"Municipal waste" residues from road cleaning in the European Waste Catalogue (EWC)) for the production of alkali activated material, especially devoted to the restoration of buildings belonging to the Baroque Sicilian architecture, was investigated. In particular, large volcanic pyroclastic deposits of recent eruptions considered waste materials were studied and a volcanic paleo-soil, locally named ghiara, widely used for mortars and plaster production in XVII–XVIII century with good pozzolanic features, was also considered. Both volcanic materials were activated using different mixtures of NaOH and Na2SiO3. Furthermore, formulations with different amount of metakaolin addition (10–25 wt%) were prepared due to low reactivity of volcanic materials and to allow the activation at room temperature. X ray diffraction revealed the formation of small quantities of zeolites as a result of the alkali activation process. The mechanical-physical results evidenced that the mechanical strength is strongly dependent on the metakaolin amount (10–38 MPa); accessible porosity average 25% and an average pore diameter of 0.06 µm; water absorption range 9–15%, eluates conductivity in the range 20–350 µS/m. These results confirm the occurring of alkali activation and the good potential for these pyroclastic wastes for valorization in the restoration field. [ABSTRACT FROM AUTHOR]

The investigation on the reticulation degree of volcanic alkali-activated materials, AAMs, were experimentally determined in terms of chemico-physical properties: weight loss after leaching test in water, ionic conductivity and pH of the leachate and compressive strength. Artificial neural network (ANN) was successfully applied to predict the chemical stability of volcanic alkali-activated materials. Nine input data per each chemico-physical parameter were used to train each ANN. The training series of specific volcanic precursors were tested also for the other one. Excellent correlations between experimental and calculated data of the same precursor type were found reaching values around one. The evidence of strong effect on chemical stability of the alkaline activator SiO2/Na2O molar ratio as well as the Si/Al ratio of precursor mixtures on the reticulation degree of ghiara-based formulation with respect to volcanic ash-based materials is presented. It must be noted that such effect was much less pronounced on the compressive strength values, appearing more insensitive the molar ratio of the alkaline activator. The comparison of the ANN results with more conventional multiple linear regression (MLR) testifies the higher prediction performance of the first method. MLRs results, less significant, are useful to confirm the powerful capacity of ANNs to identify the more suitable formulation using a set of experimental AAMs. This study, as few others, on the correlation between chemical stability and compressive strength of AAMs provide a great contribution in the direction of durability and in-life mechanical performance of these class of materials. [ABSTRACT FROM AUTHOR]

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 surface texture of a stone represents a sensitive parameter in evaluating its conservation state. In monuments and sculptures, in fact, external agents continuously alter the appearance of stones, determining peculiar weathering patterns and modifying properties such as retention of water and particles, interaction with light, color, and finishing. The application of protective coatings also determines changes in surface appearance of a stone, usually evaluated and monitored by color change tests. Surface metrology methods offer the possibility to quantify these changes, evaluating the impact of external agents (natural, i.e. weathering, and artificially, i.e. protective coatings) on natural stones. In this research, we demonstrate the potential of surface areal measurements in describing the evolution of weathering processes and the effects of protective treatments on porous stone materials. The obtained results suggest that the extent of the modifications is related to the scale of observation (small- vs. large-scale undulations, i.e. roughness and waviness, respectively), with an overall increase of surface roughness as the weathering proceeds. Unexpectedly, coatings based on nanoparticle dispersions increase the topographic height parameters, due to the absence of a homogeneous film. [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]

The Peloritani Mountains, in the southern part of the Calabrian Terranes, southern Italy, have been classically interpreted as the product of the Paleogene brittle deformation of the European continental back-stop of the Neotethyan subduction complex. This reconstruction conflicts with the occurrence of an Alpine metamorphic overprint that affected portions of both the Variscan metamorphic units and part of the Mesozoic sedimentary covers of the mountain belt. New field data, integrated with petrographic, micro- and meso-structural analyses and stratigraphic investigation of the syn-tectonic terrigenous covers, well constrain a Paleogene collision event along the Africa–Nubia convergent margin that caused the exhumation of the Alpine metamorphic units of the Peloritani Mountains. The syn-collisional exhumation was associated with shearing along two major Africa-verging crustal thrusts arising from the positive tectonic inversion of the former European palaeomargin. Early tectonic motions occurred within the mountain belts and produced the exhumation of the external portions of the edifice. Later tectonic motions occurred along the sole-thrust of the entire edifice and caused the definitive exhumation of the entire mountain belt. The whole crustal thrusting lasted for a period of c. 10 Ma, during the entire Oligocene. The definitive southwestward emplacement of the Peloritani Mountain Belt onto the Neotethyan accretionary wedge was followed by two Late Oligocene – Early Miocene NW–SE-oriented right lateral shear zones, replacing the previous crustal thrust. These two strike-slip belts are interpreted as the surface expression of the deep-seated suture zone between the colliding Africa and Europe continental crusts. [ABSTRACT FROM AUTHOR]

Introduction: Environmentally-related health and disease are the result of the exposome, the totality of a person's environmental exposures, from all sources and routes, across their lifespan. Epigenetic phenomena, including DNA methylation, can be potentially modified by environmental and lifestyle factors, and result in environmental reprogramming of the genome for exposed individuals and for future generations of offspring. Objective: The objective of the project is to evaluate the risk of DNA hypomethylation due to air pollution, Mediterranean diet adherence, folate intake, and demographic and socioeconomic factors, in healthy women living in the metropolitan area of Catania, Italy. Methods and analysis: Non-pregnant healthy women will be enrolled in a cross-sectional study. Sociodemographic, lifestyle and dietary intake information will be collected. LINE-1 methylation will be measured by pyrosequencing. The participants' home addresses will be geocoded and each woman will be assigned to the closest monitoring station for particulate matter (PM) exposure assessment. Mineralogical-chemical characterisation of PM and cellular model assays will be performed. An integrated approach will be designed to estimate the combined possible effect of air pollution, Mediterranean diet adherence, folate intake and other lifestyle characteristics on LINE-1 methylation levelss. Ethics and dissemination: The project has been approved by the ethics committees of the involved institution and funded by the University of Catania (Finanziamento della Ricerca, FIR 2014). All participants will be fully informed of the purpose and procedures of the study, and signed written consents will be obtained. All the data collected will be treated confidentially and analysed in an aggregate and anonymous way. The results will be published in peerreviewed journals and communicated to local public health agencies, in order to provide essential information for timely and effective public health action. [ABSTRACT FROM AUTHOR]

Building stones are frequently subjected to very intense degradation due to salt crystallization, often responsible for strong modifications of their pore network. These effects have a great influence on the mechanical properties and durability of the materials, and on the penetration of water. Therefore, the quantification and visualization of water absorption into the pore network of degraded stones could provide useful information to better understand the weathering process. In this study, neutron radiography has been used (1) to monitor and visualize in two dimensions the capillary water uptake in a Sicilian calcarenite widely used as building and replace stone (namely Sabucina stone) and (2) to quantify the water content distribution, as a function of time and weathering degree. Additionally, traditional experiments based on gravimetric methods have been performed, following the standard recommendations. Results demonstrated a change in the physical properties of Sabucina stones with the intensification of the degradation process, with severe effects on the capillary imbibition dynamics. The water penetration depth at the end of the experiment was substantially higher in the fresh than in the weathered stones. The water absorption kinetics was faster in the weathered samples, and the amount of water absorbed increased with the number of weathering cycles. Good agreement between classical and neutron imaging data has also been evidenced. However, neutron radiography has allowed retrieving additional spatial information on the water absorption process, and to better understand how salt weathering affects the petrophysical properties of the studied stone and how it influences then the stone response against water. [ABSTRACT FROM AUTHOR]

In this work, the results of a Raman campaign for studying seventeenth-century Sicilian frescoes, by using two portable Raman systems, equipped with different excitation sources (785 and 1064 nm), are proposed. The measurements were performed with the aim to provide an in situ diagnostic analysis of the wall paintings (in terms of colorants and preparation layer) and to support the conservators in the framework of the ongoing restoration. The combined use of the two Raman spectrometers has given a complete overview on the artist palette and on the state of preservation of frescoes, also informing us about the technique employed by the painter. Natural pigments as hematite, vermillion, goethite, lead red, lead white and carbon-based black pigments have been identified. Additionally, the application of a transitional Romanesque-Renaissance frescoes method has been noticed by the systematic combined presence of calcite and gypsum in the substrate. Finally, the analyses have highlighted the presence of degradation products, mainly related to alteration of lead-based pigments. [ABSTRACT FROM AUTHOR]

The excavations at Mount San Paolillo (Catania, Italy) led to the discovery of a Prehistoric site that still represents the most important evidence of Middle and Late Bronze Age settlement in this area. During the excavations, archeologists located a hut, a store for ceramic storage vessels, and a pottery workshop, all of which provided a large quantity of heterogeneous ceramics with apparent typological parallels in other areas of Sicily, such as Syracuse, Augusta, and Messina. A large number of specimens were selected in order to cover all the macroscopic types and the main classes. The results identified four petrographic fabrics. Most of the ceramics are characterized by abundant tempers consisting of volcanic rock fragments and occasionally of grog. Only a few samples contained common fine-grained quartz. The groundmass ranges from non-micaceous to very micaceous. In some cases, there is evidence of mixed clays. Analysis of the chemical composition of the ceramics revealed the existence of two groups with low and high CaO contents. The high FeO content (more than 8.7 wt%) is probably due to the use of temper from altered pyroclastic rocks which are of local provenance as SEM-EDX data suggest, even if petrographic and chemical results suggest that different raw materials may have been used. The data provided by these archeometric analyses have made a significant contribution to the study of Middle and Late Bronze Age pottery from the Catania area, by offering insights into the methods, production processes, and high technical level of the prehistoric craftsmen. [ABSTRACT FROM AUTHOR]

Self-cleaning photocatalytic coatings based on TiO nanoparticles obtained by sol-gel techniques at two different pH values (1.3-10.6) have been investigated on carbonatic stone. The selected material is the yellowish lithofacies of Palazzolo Formation calcarenite, commonly named Pietra di Noto, widely used in the Baroque monuments of the Noto Valley (Sicily, Italy). SEM-EDS, XRD and Raman investigations were carried out to characterize the TiO nanoparticles (mainly nanocrystalline anatase) obtained by the acid and basic nanosols and the corresponding coatings on pietra di Noto. To evaluate the effects of the treatments at two different pH values, changes in the stone color appearance, water absorption by capillarity and the behavior for salt crystallization were measured. The photocatalytic activity of the coatings was evaluated under UV irradiation, by monitoring methyl orange and methylene blue dye degradation as a function of time. The results highlight the compatibility of both treatments with respect to the properties of the calcarenite stone, showing no chromatic changes, no alteration of physical properties, an improvement in the resistance to salts crystallization and the good photocatalytic activity on both dyes. The experimental data suggest that the basic coating has to be preferred for carbonatic stones for its harmlessness and better performances in terms of self-cleaning action and protection against water and salts. Graphical Abstract: Self-cleaning photocatalytic coatings based on TiO, obtained by sol-gel at two different pH values, are applied on Pietra di Noto carbonatic stone. TiO nanoparticles and coatings are characterized by SEM, XRD and Raman. The photocatalytic activity of the coatings is evaluated under UV irradiation, by monitoring methyl orange and methylene blue dye degradation as a function of time. The basic coating is suitable for carbonatic stones for its harmlessness and better performances in terms of self-cleaning action and protection against water and salts.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

In the last decade, Raman spectroscopy has been used for routine investigation for gemmological purposes, being non-destructive and non-invasive. In addition, this technique grants short measurement times without any sample preparation. In this context, this work is focused on the spectroscopic characterization of different kinds of blue gems, including sapphires, by comparing the performance of a handheld Raman instrumentation along with a micro-Raman spectrometer, with the aim to provide gemmological certification and to get information on the provenance of the gems. The main goal of the present study is to identify imitation gems and to distinguish between natural and synthetic sapphire; in this latter case, micro-Raman measurements were fundamental for the characterization of the inclusions. Moreover, the chemical composition of blue gems has been obtained by portable XRF technique. The obtained data show that a portable Raman spectrometer can be recommended as a fast and easy instrument to discriminate sapphire from imitations. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

In recent years, the use of Raman spectroscopy as a gemological tool has largely increased, in particular in the conservation science field where a non-destructive and contactless identification is required. In this work, we show the large amount of information which is possible to obtain with Raman analysis on one of the most important gems, emerald, the green variety of beryl. In particular, 14 not certified faceted emeralds have been studied by means of a standard micro-Raman spectrometer, allowing also the identification of some fakes (garnet, glass, and quartz). All the emerald gems have been fully characterized from the vibrational point of view. In particular, the high frequency spectrum, in the OH region, has been exploited to estimate the amount of alkali ions present in the channels of the crystalline structure. In addition, solid and fluid inclusions have been identified and were useful to hypothesize the provenance of the mineral. The shape and position of the characteristic laser-induced luminescence of chromium ions have helped to better define the origin of the gems. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

In this paper, a multi-technique approach, at different scale of observation, is used to characterize a group of decorative stones and to permit to distinguish rocks with similar aspect but coming from different areas. In particular, the samples under study are sedimentary and metamorphic rocks, widely used as building blocks of modern and historical constructions and sculptures. The petrographic and mineralogical features of such rocks were performed by optical microscopy and Raman and Fourier transform infrared absorbance spectroscopies. These techniques permitted to obtain a complete structural, textural, and mineralogical characterization. At elemental level, the investigation was carried out by X-ray fluorescence (XRF). In particular, XRF and Raman measurements were collected using portable instrumentations, whose advantages for the in situ analysis have been pointed out. The obtained results evidenced the high discriminant capability of the portable XRF for the decorative stones especially when this method is coupled with mineralogical and petrographic information. In this context, we propose to create a database for precious ornamental stones, which could be a starting point for a non-destructive characterization, even useful for provenance study and/or certification of origin. Copyright © 2013 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Micro-destructive and non-destructive X-Ray fluorescence techniques and scanning electron microscopy coupled with energy-dispersive spectrometry have been applied for the analysis of ten samples of Hellenistic black-varnished pottery, coming from archaeological excavations in Syracuse and Adrano (South Italy, Sicily). Micro-morphological and compositional investigations, together with statistical data processing, have shown several differences among the varnishes of the specimen found in the two sites. In particular, Syracuse varnishes are characterised by a more homogeneous composition and well-defined raw materials, whereas Adrano samples show a higher variability, probably linked to the use of different raw materials and the poorer quality of the varnish as well. The obtained results attest that, as Syracuse black pottery is concerned, the production technique is at an advanced level, whereas Adrano manufacture seems to be less specialised. Copyright © 2012 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

The preciousness of historical artifacts leads to the performance of nondestructive and/or microdestructive analyses, especially when the archeological finds are stored in museums. The PXRF spectrometry represents a powerful technique for the chemometric study of the materials, in alternative to the more usual destructive X-ray-based methods. A large set of limestones belonging to several formations cropping out in the Hyblean area (south-eastern Sicily, Italy) was analyzed by means of a PXRF instrument. The main goal was to test the PXRF potentiality for the discrimination of rocks with similar features and to create a chemical database of carbonate rocks, which were commonly used in the past in the manufacturing of sculptures and stone artifacts. Fluorescence data were processed by means of multivariate statistical analysis. In particular, principal components analysis and linear discriminant analysis were applied. The results allowed us to classify the samples belonging to different formations and to distinguish different rock typologies within each formation. Finally, the investigation showed that the analytical PXRF data can be suitable for a substantial characterization of stone materials and this could be extended to museum materials belonging to cultural heritage. Copyright © 2012 John Wiley & Sons, Ltd. [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]

The present work reports a detailed investigation on the speciation of iron in the pigments of decorated pottery fragments of cultural heritage relevance. The fragments come from the Gioiosa Guardia archaeological site in the area of the `Strait of Messina' (Sicily, Southern Italy), and date back to VI-V century BC. The purpose of this study is to characterize the main pigmenting agents responsible for the dark-red coloration of the specimens using non-destructive analytical techniques such as synchrotron radiation X-ray absorption spectroscopy (SR-XAS), a well established technique for cultural heritage and environmental subjects. Absorption spectra were collected at the Fe K-edge on the Italian beamline for absorption and diffraction (BM8-GILDA) at the European Synchrotron Radiation Facility in Grenoble (France). In order to determine the speciation of Fe in the samples, principal component analysis and least-squares fitting procedures were applied to the near-edge part of the absorption spectra (XANES). Details on the local structure around the Fe sites were obtained by analyzing the extended part of the spectra (EXAFS). Furthermore, an accurate determination of the average Fe oxidation state was carried out through analysis of the pre-edge peaks of the absorption spectra. Samples resulted composed of an admixture of Fe2O3 (hematite or maghemite) and magnetite (Fe3O4), occurring in different relative abundance in the dark- and light-colored areas of the specimens. The results obtained are complementary to information previously obtained by means of instrumental neutron activation analysis, Fourier transform infrared absorbance and time-of-flight neutron diffraction. [ABSTRACT FROM AUTHOR]

We report on a non-destructive study of Sicilian ceramic fragments of cultural heritage interest, classified as 'proto-majolica' pottery and dating back to the twelfth to thirteen centuries AD. The analytical approach used is based on the employment of two totally non-invasive spectroscopic techniques: X-ray fluorescence (XRF), using a portable energy-dispersive XRF analyser, and X-ray absorption spectroscopy, using synchrotron radiation as a probe (SR-XAS). XRF measurements allowed us to collect elemental and spatially resolved information on major and minor constituents of the decorated coating of archaeological pottery fragments, so providing preliminary results on the main components characterizing the surface. In particular, we assigned to Fe and Mn the role of key elements of the colouring agent. With the aim of obtaining more detailed information, we performed SR-XAS measurements at the Fe and Mn K-edges at the Italian BM08 beamline at the European Synchrotron Radiation Facility (Grenoble, France). The experimental data were analysed by applying principal component analysis and least-squares fitting to the near-edge part of the spectra (X-ray absorption near-edge structure) to determine the samples' speciation. From the overall results, umber, a class of brownish pigments characterized by a mixture of hydrated iron and manganese oxides, has been ascribed as a pigmenting agent. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

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.)

The article discusses the use of maglietta interattiva computerizzata (MagIC) textile-based cardiorespiratory monitoring system. The issues regarding garment design and signal processing are discussed for the conversion of MagIC for nonclinical usage. It notes that several factors in the application of MagIC system should be considered such as movement artifacts, and adds that ergonomics using MagIC garment will have the ability to achieve online estimates of physiological parameters.

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]

The cardinal motor symptoms of Parkinson's disease (PD) have been widely investigated with particular reference to abnormalities of steady-state walking. The great majority of studies, however are related to severe forms of PD patients (phases > = 3 of Hoehn and Yahr scale), where locomotor abnormalities are clearly manifested. Goal of the present study was to quantitatively describe locomotor symptoms in subjects with mild PD. Accordingly, a multitask protocol involving instrumental analysis of steady-state linear walking, initiation of gait, and turning while walking was applied to a group of patients with idiopathic PD in their early clinical stage (phases 1 and 2 of Hoehn and Yahr scale), as well as in age-matched elderly controls. Kinematic, kinetic, and myoelectric measures were obtained by optoelectronic motion analysis, force platform, and telemetric electromyography. Results in PD patients showed a tendency to bradykinetic gait, with reduction of walking speed and cadence. Impairments of gait initiation consisted in reduction of the backward shift of the center of pressure (CoP) and prolongation of the stepping phase. Alterations of the turning task were more consistent and included delayed reorientation of the head toward the new direction, altered head- upper trunk rotational strategy, and adoption of a greater number of steps to complete the turning. It is concluded that patients in the early stage of PD reveal mild alterations of steady-state linear walking and more significant anomalies in the transitional conditions, especially during changes in the travel direction. Quantitative analysis of nonstationary locomotor tasks might be a potentially useful starting point for further studies on the pathophysiology of PD. [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]