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X-ray Diffractometry is a very useful analytical technique to achieve detailed information about the crystal structure and mineralogical composition, qualitative and quantitative, of matter. It is a technique that exploits the interaction between solid matter and X-rays that, converged on a substance, are diffracted. The outgoing X-rays, on the basis of the wavelength of the incident beam and according to the path within the analyzed sample provide information on fundamental param- eters of the crystalline state as the distance of the lattice planes and the parameters of the elementary cell. The analytical result is called diffraction pattern containing a series of peaks that show the intensity and angular position of the diffracted X-rays. Typically, a diffraction pattern represents, for individual minerals, a kind of distinct fingerprint and can be used to easily identify the material or distinguish it from others, especially with the use of modern databases. X-Ray Diffractometry can be successfully used in a variety of fields: building materials, geological sam- ples, environmental pollutants and increasingly by forensic sciences as a scientific aid for the analysis of evidence from crime scenes.

In the last few years Sr isotope geochemistry has contributed substantially to environmental and food traceability research. This is achievable because soils, plants and waters all have a peculiar Sr isotopic signature (87Sr/86Sr) inherited from the local geological substratum and affected by geological processes as well as the age and initial rubidium concentration of the rocks. Strontium ions released from the bedrock by weathering processes deriving by the interaction of circulating fluids with rocks, enter the environment and accumulates in water and soils. This reservoir of bioavailable Sr may represent a reliable tracer useful to determine the geographical origin of wines as it is known that strontium is taken first by plant roots, then by grapes, and lastly by wine, with no isotope fractionation when compared to the original 87Sr/86Sr ratio in the soil and rocks. As a result, the study of the Sr isotope ratio in the final product (wine) links directly to its geological origin thus representing a specific geofingerprint for any selected wine. Based on these premises this work aims at confirming the strong link between the product (wine) and its territory, with the final purpose to make it recognizable and distinguishable from similar products and protecting it from possible fraud and adulteration. In this work the 87Sr/86Sr systematics has been used to analyze a total of 39 samples (37 soil samples and 2 wine samples) from Campania (Italy). For a better understanding, both total Sr fraction and bioavailable Sr fraction were analyzed in soil samples (rhizospheric soils, bulk soils and samples collected from different horizons) in order to better investigate the environmental processes involved during the wine production cycle.

This paper reports a detailed study on some relevant portions of the main façades of Caserta Royal Palace (Reggia di Caserta), one of the most important Italian monuments, comparable for its impressive architecture to the Royal Palace of Versailles in France and considered the largest royal palace in the world by volume. The research was focused on the weathering pathologies affecting the stone surfaces that, in the last decades, suffered several detachments of fragments from the coatings and from other architectural elements such as string courses, eaves, and capitals. A preliminary characterization of the materials of the façades and an evaluation of the relative weathering pathologies provided the information required for appropriate restoration and securing of these portions of the building. In particular, an innovative evaluation procedure which draws on techniques typical of the earth sciences allowed the proposal of a ‘risk attitude’ applied to discrete portions of the geomaterials used in the built heritage which is based on the influence of different factors leading to weakening of the stone and to the final detachment of rock fragments. Such a large and complete set of information should be carefully considered by the project planners to adopt the required steps for a suitable risk mitigation and for securing the site during restoration.

For this study, the rare Cu-bearing silicate fumarolic assemblages from the Somma–Vesuvius volcano, Italy, characterised by the rare mineral litidionite, CuKNaSi4O10, were investigated. We report new data about Cu- and Ti-bearing phases found in these mineralisations, in which Ti-bearing litidionite occurs together with kamenevite, perovskite and rutile. Ti-bearing litidionite appears on the latest stages of partial crystallisation of Ti-bearing silica glass. Incorporation of Ti4+ into the litidionite crystal structure was investigated in detail. The Raman spectra of Ti-bearing litidionite contains an intense band at 597 cm−1 related to anti-symmetric bending vibrations of Si‒O bonds or overlapping stretching vibrations of Ti‒O bonds. The bands in the range 350‒500 cm−1 correspond to symmetric bending vibrations of O‒Si‒O bonds and overlapping stretching vibrations of Ti‒O bonds. The crystal structure of Ti-litidionite has been refined in the P$\bar{1}$ space group, a = 6.9699(7), b = 7.9953(10), c = 9.8227(10) Å, α = 105.186(9), β = 99.458(8) and γ = 114.489(10) to R1 = 0.064 for 1726 unique observed reflections. The refinement of the site-occupation factors confirmed the presence of Ti at a five-coordinated M site. The mean bond distance of 2.125 Å for the M site agrees with its refined occupancy (Ti0.32Cu0.30Ca0.29Fe0.09)1.00. The incorporation of Ti into the litidionite structure is accompanied by the complex heteropolyhedral substitution according to the scheme VTi4+ + VII–VIII□ + IVAl3+ ↔ VCu2+ + VII-VIII(Na,K)+ + IVSi4+. Two possible configurations for the phase with maximal TiO2 content (12.06 wt.% or 0.56 Ti apfu) CuTiK□Na2Si7AlO20 (Z = 1) or CuTiK2Na□Si7AlO20 (Z = 1) have been proposed.

The Real Museo Mineralogico of the University of Naples Federico II was established in 1801 by Ferdinando IV of Bourbon and his queen, Maria Carolina. Their aim was to create a centre for minerals research and education. The museum at present preserves over 50,000 objects, mainly minerals, but also books, teaching models and instruments. The last of these form a little-known collection of considerable scientific and historical value. Historical studies of the instruments collection are based on extensive archival research conducted on documents and ancient catalogues of the museum and the Archivio di Stato in Naples. This study describes the main instruments, detailing their date of acquisition, typology and use. Its goal is to provide a testimony to the contribution of the Real Museo Mineralogico to the development of the science of mineralogy in Naples, and at the same time to extend, by means of new data (suppliers, acquisition methods, price), the catalogue of the instruments collection.

This research is based on the characterization of ancient mortars from the Anfiteatro Flavio (Pozzuoli) dating back to the 1st and 2nd century CE through a multi-analytical approach involving macroscopic, mineralogical, petrographic, and chemical investigations. The goal that has been set is to deepen knowledge about mortar mix design, the provenance of used raw materials, and secondary minerogenetic processes that have occurred within ancient Roman mortars. Results show that: (i) raw materials for mortar preparation have a local provenance, i.e., Phlegraean Fields area; (ii) mortars can be considered as hydraulic; (iii) calcite presence could be due to a non-complete calcination process, an improper slaking or to exposition of materials to the subaerial environment; (iv) gypsum is due to calcite sulfation process; (v) halite presence is due to marine aerosol exposition. The achieved information testifies that, for at least two centuries, Roman builders considered the identified mortar mix as optimal for their buildings, but also contributes to the understanding of their technical skills and represents an important first step to planning future restoration operations.

The purpose of this study is to evaluate different lightweight concretes for the first time formulated with lightweight expanded aggregates produced only with industrial waste. The motive is that a lack of knowledge still exists in the literature about how to integrate these waste-based aggregates in lightweight concrete. To achieve the desired bloating and aggregates physical properties, PC-TV screen glass and ceramic tile polishing sludge were selected as suitable raw materials. Both were characterized by mineralogical and chemical analyses and the effect of different combinations was pointed out. Hot-stage microscopy was used to determine the bloating rates and firing behavior. Lightweight expanded aggregates were obtained using both static laboratory kiln and rotating pilot kiln, by firing at maximum temperatures between 1150 and 1200 ◦C, to simulate the industrial production process and favor scaling up. The so obtained aggregates were characterized from the physical-mechanical point of view, highlighting an important bloating attitude and bulk density lower than 700 kg/m3 for all the test conditions. Bulk density, water absorption and mechanical properties are fully comparable to commercial counterparts. The best material was used as coarse aggregate in lightweight structural concrete and cellular concrete prepared at pilot scale (for structural application and thermal/acoustic insulation, respectively). The technical properties are consistent with standard requirements of compressive strength (>25 MPa for lightweight structural concrete) and thermal conductivity (18–24 W/m*K for cellular concrete). These results demonstrate the technological feasibility of using waste-based aggregates into lightweight concrete design, according to a circular economy vision.

Ancient pozzolanic mortars show the high technological quality achieved by Roman construction workers, due to their ‘excellent state’ of preservation in every environment. These workers well knew that thanks to the combination of lime with specific volcanic products (pozzolana), mortar and concrete become hydraulic, allowing underwater hardening and increasing mechanical strength. The use of pozzolana in a mortar provides the underwater curing (hydraulic limes) of whatever construction with higher speed compared to carbonation processes of slaked lime. Whenever pozzolana is not available, it is substituted by ceramic fragments, which possess similar hydraulic properties. This research focuses, for the first time, on the detailed characterization of mortars coming from the Thermal Complex of Baia, which represents one of the most important archaeological sites in the Campania region. Thanks to several thermal springs, the ancient city of Baiae (Campi Flegrei) was the holiday resort of the Roman aristocracy. The former Soprintendenza Archeologia della Campania, allowed us to perform non-invasive, but representative, sampling of mortars that were characterised by multianalytical methodologies (POM, XRPD, SEM-EDS, TGA, and MIP) providing useful information on possible future activities of restoration. Results confirmed the expertise of Roman workers, who skilfully combined volcanic tuff aggregate, hydrated lime, and ceramic fragments. In particular, the typical zeolitic mineral association of phillipsite > chabazite > analcime found in the tuff aggregate pointed out their provenance from the Neapolitan Yellow Tuff related to the volcanic activity of Campi Flegrei of ca. 15 ka BP. The most relevant characteristic detected in all studied samples is the mortar hydraulicity testified by evidences such as reaction rims between pozzolana and binder, Hydraulicity Index (HI), and thermal analyses investigation. Also, composition of secondary mineralogical phases in the cementiceous matrix is particularly relevant. Distinctive is the contemporary presence of C-A-S-H gel, calcite and gypsum. C-A-S-H gel is derived from lime/ceramic fragments reaction; calcite is likely related to the partial reaction of underburned lime; and gypsum could be ascribable to the sulphation process of calcite. These secondary minerogenetic products fill pore space and enhance bonding in pumice fragments, thus contributing to long-term durability of mortars.

This paper describes a novel methodology where Machine Learning Algorithms (MLAs) have been integrated to assess the landslide risk for slow moving mass movements, processes whose intermittent activity makes challenging any risk analysis worldwide. MLAs has been trained on datasets including Interferometric Synthetic Aperture Radar (InSAR) and additional remote sensing datasets such as aerial stereo photographs and LiDAR and tested in the Termini-Nerano landslides system (southern Apennines, Italy). The availability of such a wealth of materials allows also an unprecedented spatio-temporal reconstruction of the volume and the kinematic of the landslides system through which we could generate and validate the hazard map. Our analysis identifies fifteen slow-moving phenomena, traceable since 1955, whose total area amounts to 4.1 × 105 m2 and volume to ~1.4 × 106 m3. InSAR results prove that seven out of the fifteen slow-moving landslides are currently active and characterized by seasonal velocity patterns. These new insights on the dynamic of the landslides system have been selected as the main independent variables to train three MLAs (Artificial Neural Network, Generalized Boosting Model and Maximum Entropy) and derive the landslide hazard for the area. Finally, official population and buildings census data have been used to assess the landslide risk whose highest values are located in the crown area, south of Termini village, and nearby Nerano. This new methodology provides a different landslide risk scenario compared to the existing official documents for the study area and overall new insights on how to develop landslide risk management strategies worldwide based on a better understanding of slope processes thanks to the latest satellite technologies available.

The present paper assesses petrographic, mineralogical, chemical, and technological features of different zeolitic tuff samples from various western USA districts of the Basin and Range Province containing mainly erionite, mordenite, clinoptilolite/heulandite and phillipsite. The aim of this characterization is to evaluate the pozzolanic activity of these samples according to European normative UNI-EN 196/5 (Fratini test) to program a possible use as addition for blended cements. Petrographic and mineralogical results show that the two phillipsite-bearing tuffs have a higher theoretical Cation Exchange Capacity (CEC) than the other samples; technological characterization shows a pozzolanic behavior for all the samples but higher for the tuff samples containing phillipsite, which shows a higher reactivity with CaO. All the samples could be thus advantageously employed for the preparation of blended cements, potentially reducing CO2 emissions by 70–90%.

Zn-phyllosilicates are common minerals in nonsulfide Zn deposits and can give crucial information about the genesis of these oxidized mineralizations. They seldom represent the prevailing economic species but might have a significant impact on mineral processing. This study has been carried out on the Mina Grande and Cristal Zn-sulfide/nonsulfide deposits, which occur in the Bongará district (Amazonas region, northern Peru). The Cristal and Mina Grande orebodies are hosted by the sedimentary (prevailingly carbonate) successions of the Pucará Group (Condorsinga formation, Lower Jurassic), in an area affected by Neogene tectonics and characterized by Late Miocene and Pliocene-Early Pleistocene uplift phases (Andean and Quechua tectonic pulses). The Cristal deposit consists of both sulfide (sphalerite with minor pyrite and galena) and nonsulfide concentrations. The nonsulfides consists of smithsonite, hemimorphite, hydrozincite, chalcophanite, goethite, and greenockite, locally associated with Zn-bearing phyllosilicates. The Mina Grande deposit consists almost exclusively of Zn-oxidized minerals in limestone host rocks. The nonsulfides association consists of hydrozincite, hemimorphite, smithsonite, fraipontite, and Fe-(hydr)oxides, also containing a clayey fraction. The study deals with TEM-HRTEM and AEM investigations on clayey materials, to determine their crystal-chemical features and the origin of the complex Zn-clays-bearing parageneses. In both deposits, Zn-bearing illites (1Md and 2M polytypes) and I/S clay minerals (I3) are the main detected phases, with few compositions close to (Zn-bearing) muscovite. In the clayey fraction at Mina Grande, fraipontite, a Zn-bearing mica called K-deficient hendricksite, and (Zn-bearing) kaolinite also occur. Zn-illites and smectites (always containing Zn in variable amounts) characterize the mineral association at Cristal. The investigated compositional gap between di- and tri-octahedral Zn-phyllosilicates gives indications on the genetic relationships between them and advances on the knowledge of these species. The present work gives an insight into the Zn-bearing phyllosilicates systems by determining the amount/mode of metal incorporation in their lattices and understanding the relationships of natural occurring clay-rich complex associations, which can act as models for possible synthetic counterparts., This work was partly supported by Departmental funds 2017 (University of Napoli Federico II) granted to G. Balassone and by the research projects CGL201675679-P from the Spanish Government and the Research Group RNM-179 of the Junta de Andalucìa

The evolution of hydrothermal alteration in glassy and variably palagonitized tuff, erupted as tephra in 1963 – 1964 on Surtsey, an island built in the offshore extension of Iceland’s southeast rift zone, is documented through a comparative petrographic study of samples from drill cores recovered in 1979 and 2017. Time-lapse alteration within the low-temperature meteoric to seawater dominated hydrothermal system of the volcano is characterized in terms of secondary mineral contents, alteration rates and alteration style with depth. Between 1979 and 2017 palagonitization and cementation by secondary minerals has progressed into previously poorly altered parts of the system, leading to increased consolidation of the basaltic tephra. Alteration rates range between 1.05 – 42.5 μm∙yr-1 for palagonitization of glass and 0.4 – 8.33 μm∙yr-1 for pseudomorphic olivine replacement by clay minerals over a temperature interval of 47 – 140°C. Five distinct zones of alteration style, distinguished through alteration mineralogy, development of authigenic phases over time, as well as degree of alteration are described. Alteration of basaltic tephra at Surtsey volcano is defined by an early stage of phillipsite and clay mineral formation, followed by a later stage of analcime and tobermorite formation as well as replacement of phillipsite below the water table in zone 2 between 65.4 and 138.4 m. Only minor advancement of alteration is detected in zone 3 between 138.4 – 150.3 m depth, where the primary tephra remains largely unpalagonitized and unconsolidated. In contrast, from 1979 to 2017 alteration has increased between 150.3 – 177.8 m depth, in zone 4, leading to rapid and extensive glass and olivine alteration. The quantification of these time-lapse hydrothermal alteration processes at Surtsey provides an important reference for studies of the evolution of young oceanic islands hosting hydrothermal systems., International Continental Scientific Drilling Program (ICDP); Icelandic Research Fund, ICF-RANNÍS; Bergen Research Foundation and K.G. Jebsen Centre for Deep Sea Research at the University of Bergen, Norway; German Research Foundation; DiSTAR, Federico II, University of Naples, Federico II, Italy; University of Utah, USA; Reykjavík Energy; Landsvirkjun, Pre-print

Quantitative mineralogical analysis of clay-bearing rocks is often a non-trivial problem because clay minerals are characterized by complex structures and are often affected by structural disorder, layer-stacking disorder, and interstratification. In the present study, internal-standard Rietveld X-ray powder diffraction (XRPD) analyses were combined with X-ray fluorescence (XRF) chemical analyses for the mineralogical characterization and quantitative analysis of heterogeneous clay-rich sedimentary rocks that are involved in a slow-moving landslide in the Termini-Nerano area, Sorrento Peninsula (Italy), in order to investigate the relationship between the mineralogy of these rocks and landslides. Slow-moving landslides are usually considered to be associated with the more weathered and surficial parts of structurally complex slopes, and mineralogical analysis can help to clarify the degree of weathering of siliciclastic rocks. XRPD quantitative analyses were conducted by combining the Rietveld and internal standard methods in order to calculate the amounts of poorly ordered phyllosilicate clays (considered amorphous phases in Rietveld refinements) by difference from 100%. The vbAffina program was used to refine the amounts of mineral phases determined with XRPD using the element compositions determined by XRF analysis. XRPD analyses indicated that the samples mainly contain several different clay minerals, quartz, mica, and feldspars. Analysis of the clay fraction identified kaolinite, chlorite, and interstratified illite-smectite (I-S) and chlorite-smectite (C-S). The mineralogy of the materials involved in the landslide in comparison with the mineralogy of the "undisturbed" rocks showed that the landslide is located in the weathered realm that overlies an arkosic bedrock. The interstratified I-S and C-S occurred at landslide activity locations and confirmed that areas more susceptible to sliding contained the most weathered parts of the rocks and perhaps represent areas of past and currently active fluid flow.

The Neotethyan oceanic Diamante-Terranova unit (DIATU; southern Apennines-Calabria-Peloritani Terrane system) includes basic rocks that during the Cenozoic were subducted and metamorphosed to lawsonite-blueschist facies conditions. Petrological and structural observations (both at the meso- and micro-scale) show that lawsonite growth was continuous during three distinctive ductile deformation stages (D1-D3). These likely occurred close to the metamorphic peak, estimated at 350-390 °C and 0.9-1.1 GPa, producing an equilibrium assemblage made of blue Na-amphibole, lawsonite, chlorite and pumpellyite. Locally, pods dominated by quartz and epidote (plus chlorite, calcite and green Ca-amphibole), developed at similar conditions (350-370 °C, 0.8-0.9 GPa). Post-peak evolution during the final exhumation of the DIATU along the subduction channel, also consisted of three deformation stages, defined by folding (D4) and normal faulting (D5) and finally by strike-slip faulting (D6), affecting both the blueschist unit and the unconformably overlying Tortonian conglomerates. Vorticity analysis on syn-tectonic lawsonite crystals indicates that severe flattening occurred during the D2 stage, with a significant secondary non-coaxial strain component along the W-E plane. This is associated with an eastward tectonic vergence, consistent with the subsequent D3 and D4 folding stages characterized by a dominant ENE tectonic transport. It is suggested that exhumation started from the D2 stage and continued during D3 at similar HP/LT metamorphic conditions. The widespread occurrence of unreacted lawsonite crystals suggests that exhumation was very fast and supports the idea that concurrent ductile deformation might play a role in its preservation.

The present research accounted for an accurate selection of representative samples from zeolitized deposits of different world geographical areas commonly mined and marketed by American and European mining companies. These geomaterials displayed high contents of clinoptilolite, phillipsite, and chabazite and were deeply characterized from mineralogical, chemical, and technological points of view. A preliminary quality control of the selected materials allowed us to determine the presence of undesired minerals and/or elements. A thermodynamic investigation of the surface exchange reactions between the selected zeolite-rich rocks and the surfactant agents (HDTMA-Br/Cl, hexadecyltrimethylammonium bromide/chloride, BC-Cl, benzalkonium-chloride, CP-Cl, cetylpiridinum-chloride) enabled us to verify the extent and the compactness of the formed micelle and to foresee their future behavior through interaction with molecules of anti-inflammatory drugs (drug delivery). The encouraging results pave the way towards good perspectives on the possible use of zeolite-rich rocks in the pharmaceutical sector through a preliminary basic protocol for the characterization and monitoring of the batches to be employed.

The Neapolitan Yellow Tuff (hereafter NYT) is definitely the building material most used in the historical architecture of Naples (Southern Italy) since Greek times. The high heterogeneity of NYT, resulting from the concomitant occurrence of lithic fragments, pumices, crystals and glass cemented by crystalline or amorphous phases, the latter highly sensitive to acid environments, define a strong attitude to weathering. This research confirmed the inhomogeneous features of this volcanic formation, within the same deposit and sometimes within the same outcrop. Based on these premises, the investigation was carried out on four most representative lithofacies, according to their different textural and petrophysical features. Actually, mechanical features are governed by two concurring factors: a) the mineralogical composition; b) the texture of the rock. In the first case, the predominance of anhydrous phases (analcime + feldspar) over zeolites improves its mechanical strength. By contrast, if the mineralogical composition is constant (similar total wt.% zeolite content), the petrophysical parameters are strictly related to the texture of the rock.

The present research deals with the evaluation of a clinoptilolite-rich rock, occurring in the Nižný Hrabovec deposit (Slovakia), for high-value technological applications based on sorption and in vitro release of nonsteroidal anti-inflammatory drugs (i.e., ibuprofen sodium salt). This georesource was surface modified (SMNZ) using four cationic surfactants. Results demonstrate that ibuprofen sorption is very fast and SMZNs can sorb up to ˜26 mg/g of drug as a function of the type of counterion and morphology of surfactant, as well as the hydrophobicity and molecular structure of the drug. Maximum sorption capacities observed for all SMNZs are fully comparable to other adsorbent carriers usually used for removal of contaminants in wastewaters. Sorption of ibuprofen is controlled by a dual mechanism: external anionic exchange and partition into the hydrophobic portion of the patchy bilayer. A prompt drug release in simulated intestinal fluid (SIF) was also observed, making this natural material also suitable to provide rapid soothing effects in potential pharmacological applications. Comparing the results of this study with other recent investigations, a good technological performance of clinoptilolite-rich rock can be inferred despite the relatively low zeolite content (˜56 wt.%).

The topic of this study is the archaeometric characterization of mortars from Villa del Pezzolo, a Roman Villa located in Seiano (Napoli-Campania, Italy), dated between the 1st century B.C. and the 3rd century A.D. Mortars were analyzed by means of a multi-analytical approach (polarized optical microscopy, X-ray powder diffraction, scanning electron microscopy and energy-dispersed spectrometry, thermal analyses and mercury intrusion porosimetry) according to existing recommendations. Analytical results evidenced the use of local geomaterials composed of sedimentary and volcanic aggregates in the mix design and confirmed the three distinct building phases identified by archaeologists. Volcanic tuff fragments, identified in the 1st building phase can be ascribed to Campanian Ignimbrite formation, widely cropping out in the Sorrento Peninsula, as confirmed by the presence of glassy shards, partially devitrified and replaced by authigenic feldspar, a typical feature of welded grey ignimbrite lithofacies (WGI). Volcanic aggregates in samples of the 2nd and 3rd building phases show, instead, the presence of leucite-bearing volcanic scoriae and garnet crystal fragments related to Somma-Vesuvius products. Study of these mortars allowed us to: (1) understand the production technologies, (2) highlight use of materials with hydraulic behavior, such as volcanic and fictile fragments, (3) confirm the three building phases from compositional features of mortars and (4) highlight the change over time of the volcanic aggregate for mortars mix-design.

This work is the result of a geoarchaeological investigation on the Anfiteatro Flavio, one of the most important archaeological sites in the Campania region (southern Italy), situated in an area of great geological and archaeological interest, the Campi Flegrei volcanic field. The aim of this research was to characterise building stones employed for structural use, focusing on the type of materials and their provenance. The mineralogical-petrographic characterization of 27 samples from corbels and pillars involved X-ray powder diffraction analyses (XRPD), thin section optical microscopy observations (OM) and energy dispersive spectrometry microanalyses (EDS). The results revealed that the source materials are represented by two distinctive trachytic/phonolitic lava deposits. Pillar light grey block samples are made of a feldspar-phyric (F-p) lava type that shares many petrographic and mineral chemical features with the Campi Flegrei Accademia lava dome, cropping out in the immediate proximities of the Anfiteatro Flavio. On the other hand, pillar grey block and corbel samples are made of an alkali feldspar and sodalite-phyric (KS-p) lava that has been correlated to an Ischian lava deposit based mainly of the peculiar composition of the observed amphibole crystals. Previous data attesting for the use of the Piperno welded tuff for the pillar grey blocks were likely driven by the “eutaxitic-like” fluidal oriented texture and by the alveolitization alteration displayed by the samples. This however does not exclude that the Piperno had been employed as a building stone for other structural elements of the amphitheatre. The use of the Ischia lavas as an exported building material had been never reported before, possibly suggesting that current knowledges about the use and trade of building materials in the Campania area during the Roman period need to be reconsidered.

This research provides a characterization of ancient Roman mortars from “Villa del Capo di Sorrento” (commonly known as “Villa di Pollio Felice” or “Bagni della Regina Giovanna”). A deepened analysis of cementitious binding matrix and aggregates was conducted with the aims of determining possible sources of raw materials and the mix recipe, and to evaluate the minerogenetic secondary processes. Twenty samples taken from the Villa were investigated by means of a multi-analytical approach, including polarized optical microscopy on thin sections, X-ray powder diffraction, scanning electron microscopy analysis, energy dispersed spectrometry, simultaneous thermal analyses, and mercury intrusion porosimetry. Bedding mortars were made with slaked lime mixed with volcanic materials, whereas coating mortars were made adding to previous recipe as ceramic fragments. All samples were classified as hydraulic mortars. Cementitious binding matrix was characterized by gel-like C-A-S-H, calcite, hydrocalumite, and gypsum, deriving from lime/pozzolanic material. Geomaterials used for mortar production had a local origin. Pozzolanic materials, such as volcanic fragments, scoriae, pumice, and crystal fragments derived from both pyroclastic rocks of the Campi Flegrei district and from rocks of the Somma-Vesuvio complex, porosity test suggest that the products related to minerogenetic secondary processes, make mortars more resistant.

Main purpose of the research was to define an operative protocol, applicable at industrial scale, optimizing the functionalization of natural zeolites with surfactants, especially in pharmaceutical and environmental sphere. Three zeolite-rich samples from Italy (PHI_SAV), Slovakia (CLI_SK) and California (CLI_CA) were used for preparation of SMNZ. Two different protocols allowed to carry out surfactant adsorption equilibrium runs and surfactant sorption kinetics by varying different parameters: mixing speed (4000, 6000, and 8000 rpm); contact time (15 ÷ 90 min) and initial surfactant concentration (from 25% to 200% of the external cation exchange capacity - ECEC) at a constant solid/liquid ratio (1 g/50 mL). Zeolite-rich materials were treated with solutions of cetylpiridinium chloride (CP-Cl). The functionalization of SMNZ was obtained by using a high-speed disperser. The amount of absorbed surfactant onto two carriers (CLI_SK and PHI_SAV) was evaluated through kinetic experiments under the following conditions: the initial CP-Cl concentration of 150% of the ECEC and a disperser speed of 8000 rpm. Results showed that after 15 min, equilibrium was attained with the adsorbed amount of about 0.14 meq/g of CP-Cl (equivalent to the ECEC of the investigated zeolitic support), confirming formation of monolayer (emi-micelle). The functionalization (micelle formation) of two samples occurred after 70 min of solid/liquid interaction with a total yield equal to 150% of the ECEC, thus indicating formation of a patchy bilayer. By contrast, CLI_CA behaves completely differently since the formation of emi-micelle was achieved only at much higher speed (18000 rpm) and not earlier than 90 min of mixing.

Incorporation of diclofenac sodium into phillipsite modified with cetylpyridinium chloride (CP-Cl) or hexadecyltrimethyl ammonium bromide (HDTMA-Br) was followed by batch equilibrium adsorption studies in buffer solution at pH = 7.4. Characteristics of the drug/surfactant/zeolite complexes were investigated by UV/VIS, FTIR spectroscopy, thermal (DTA/TG) analysis and ζ-potential measurements. The obtained data confirmed that organic cations at phillipsite surface were responsible for incorporation of diclofenac sodium. Diclofenac sodium incorporated amounts increased with increasing the amount of each surfactant as well as with increasing the initial drug concentration. Langmuir model was the best model for fitting the experimental data of diclofenac adsorption on surfactant/phillipsite composites, suggesting complex adsorption mechanism. The physico-chemical properties of surfactant/phillipsite composites and enhanced incorporation of diclofenac sodium suggests that it might be possible to use these materials as drug carriers.

A Cs-bearing polyphase aggregate with composition (in wt%): 76(1)CsAlSi5O12 + 7(1)CsAlSi2O6 + 17(1)amorphous, was obtained from a clinoptilolite-rich epiclastic rock after a beneficiation process of the starting material (aimed to increase the fraction of zeolite to 90 wt%), cation exchange and then thermal treatment. CsAlSi5O12 is an open-framework compound with CAS topology; CsAlSi2O6 is a pollucite-like material with ANA topology. The thermal stability of this polyphase material was investigated by in situ high-T X-ray powder diffraction, the combined P–T effects by a series of runs with a single-stage piston cylinder apparatus, and its chemical stability following the “availability test” (“AVA test”) protocol. A series of additional investigations were performed by WDS–electron microprobe analysis in order to describe the P–T-induced modification of the material texture, and to chemically characterize the starting material and the run products. The “AVA tests” of the polyphase aggregate show an extremely modest release of Cs+: 0.05 mg/g. In response to applied temperature and at room P, CsAlSi5O12 experiences an unquenchable and displacive Ama2-to-Amam phase transition at about 770 K, and the Amam polymorph is stable in its crystalline form up to 1600 K; a crystalline-to-amorphous phase transition occurs between 1600 and 1650 K. In response to the applied P = 0.5 GPa, the crystalline-to-amorphous transition of CsAlSi5O12 occurs between 1670 and 1770 K. This leads to a positive Clapeyron slope (i.e., dP/dT > 0) of the crystalline-to-amorphous transition. When the polyphase aggregate is subjected at P = 0.5 GPa and T > 1770 K, CsAlSi5O12 melts and only CsAlSi2O6 (pollucite-like; dominant) and Cs-rich glass (subordinate) are observed in the quenched sample. Based on its thermo-elastic behavior, P–T phase stability fields, and Cs+ retention capacity, CsAlSi5O12 is a possible candidate for use in the immobilization of radioactive isotopes of Cs, or as potential solid hosts for 137Cs γ-radiation source in sterilization applications. More in general, even the CsAlSi5O12-rich aggregate obtained by a clinoptilolite-rich epiclastic rock appears to be suitable for this type of utilizations.

Two zeolite-rich rock samples extracted from Campanian Ignimbrite tuff quarries, southern Italy, usually used as binding and anticaking agents in animal feeding, were characterized and tested in terms of their resistance in stomach, small and large intestine of pig, using a three step in vitro digestibility trial. The mineralogical composition and major and trace-elements analysis were performed after each digestion step using XRPD and ICP-OES techniques. The main zeolite phases identified are phillipsite and chabazite. Results showed that in vitro physical-chemical conditions (pH 2–3 and T 39 °C) the release of Pb and other elements from the zeolite structure is extremely low and due to the limited breakdown of the zeolite framework and glass/amorphous matter hydrolysis, by the gastric liquids. This aspect also suggests that zeolites, after the total permanence in the animal body digestive tract, can further perform their important function of cation exchanger, with also relevant relapses on the growth and health of the animal species, as well as on the environment. Moreover, the contact of zeolite material with liquids of small and large intestine leads to negligible release of undesirable elements, which are far less than those envisaged by the European Regulations.

An integrate approach, aimed at allowing the access to a large dataset, concerning Cultural Heritage, is proposed. The research, developed within Databenc-SNECS (High-Tech District for Cultural Heritage – Social Network of Historic Center Entities) project, aimed to represent and promote the knowledge of Campania historical centres through paradigms of technological intelligence. An innovative ICT (Information and Communication Technologies) architecture was designed to contain data concerning geomaterials (and relative decay) used in the historical site of Saints Marcellino and Festo (Naples, Italy), along with other ones from selected monuments of the Ancient Centre of Naples. Data, collected into a no-relational database, were processed to realize a 3D model whose prototype will be useful for preserving Cultural Heritage. A further interface, a geo-touristic application for mobile devices, NAppSTONES (Naples – Application – STONES), was developed. This latter, promoting the cultural heritage of the Ancient Centre of Naples, highlighted the close relationship between its geological and urban setting.

The cation exchange capacity of a natural phillipsite-rich sample from the Neapolitan Yellow Tuff, Southern Italy (treated in order to obtain a 95 wt% zeolite-rich sample composed mainly of phillipsite and minor chabazite) for Cu was evaluated using the batch exchange method. The sample had previously been exchanged into its monocationic form (Na), and then used for the equilibrium studies of the exchange reaction 2Na+ ⇆ Cu2+. Reversibility ion exchange tests were performed. The isotherm displays an evident hysteresis loop. Interestingly, the final Cu-exchanged polycrystalline material was green-bluish. Natural, Na- and Cu-exchanged forms were analyzed by X-ray powder diffraction, and the Cu-phillipsite was also investigated by transmission electron microscopy (TEM). Structure refinement of Cu-phillipsite was performed by the Rietveld method using synchrotron data, and it indicates a small, but significant, fraction of Cu sharing with Na two–three independent extra-framework sites. The TEM experiment shows sub-spherical nano-clusters of crystalline species (with average size of 5 nm) lying on the surfaces of zeolite crystals or dispersed in the amorphous fraction, with electron diffraction patterns corresponding to those of CuO (tenorite-like structure) and Cu(OH)2 (spertiniite-like structure). X-ray and TEM investigations show that Cu is mainly concentrated in different species (crystalline or amorphous) within the sample, not only in phillipsite. The experimental findings based on X-ray and TEM investigations, along with the hysteresis loop of the ion exchange tests, are discussed and some general considerations about the mechanisms of exchange reactions involving divalent cations with high hydration energy are provided.

Fourteen samples of tourmaline from the Real Museo Mineralogico of Federico II University (Naples) have been characterized through multi-methodological investigations (EMPA-WDS, SEM-EDS, LA-ICP-MS, and FT-IR spectroscopy). The samples show different size, morphology and color, and are often associated with other minerals. Data on major and minor elements allowed to identify and classify tourmalines as follows: elbaites, tsilaisite, schorl, dravites, uvites and rossmanite. Non-invasive, non-destructive FT-IR and in-situ analyses were carried out on the same samples to validate this chemically-based identification and classification. The results of this research show that a complete characterization of this mineral species, usually time-consuming and expensive, can be successfully achieved through non-destructive FT-IR technique, thus representing a reliable tool for a fast classification extremely useful to plan further analytical strategies, as well as to support gemological appraisals.

Bricks are the most common building materials of Madagascar due to the large availability of clayey raw material, the simple technology of production and the ease of use. The brick production is mainly organised in local workshops close to supplying site of clayey deposit where sediments are extracted, moulded in bricks, dried and then fired in open-air furnaces. Fuel varies from peat soils to wood depending on the local availability. Correspondingly, firing time varies from few days in wood furnaces to some weeks in peat fired furnaces. Samples of bricks and raw materials as well as peat fuel, from four workshops located in central and southwestern Madagascar were collected and analysed to infer the technological skills of the Malagasy traditional brick manufacture. Central Highlands Madagascar workshops use clayey lateritic soils formed from in situ weathering of basement rocks. The main plastic component of these deposits is kaolinite. Also the clayey sediments from southwestern Madagascar have kaolinite along with low-ordered clay minerals and carbonates such as calcite and minor Sr-rich dolomite. As far as fired bricks are concerned, experimental data evidenced quite low firing temperatures (below 600 °C) in the two different furnaces, regardless the type of fuel. As far as peat fuel is concerned, its low calorific value along with a large amount of furnace energy dispersion does not allow to achieve the temperatures required to produce good quality bricks, notwithstanding long firing time (some weeks). On the other hand, firewood powdered furnaces, although providing much higher energy and a consequent much shorter firing process (few days), also suffer of diffuse heat dispersions which concur to the bad quality of the final product. The specific energy input calculated for type 1 furnace (peat fuel) ranges between 0.09 MJ/kg and 0.18 MJ/kg of clayey material thus confirming a rather inadequate firing process for the production of good quality bricks, and a rough estimate indicates that volume ratios between peat and clayey material as low as 1:1 should be used in order to reach “modern” specific energy inputs.

Author(s): Jackson, MD; Mulcahy, SR; Chen, H; Li, Y; Li, Q; Cappelletti, P; Wenk, HR | Abstract: Pozzolanic reaction of volcanic ash with hydrated lime is thought to dominate the cementing fabric and durability of 2000-year-old Roman harbor concrete. Pliny the Elder, however, in first century CE emphasized rock-like cementitious processes involving volcanic ash (pulvis) "that as soon as it comes into contact with the waves of the sea and is submerged becomes a single stone mass (fierem unum lapidem), impregnable to the waves and every day stronger" (Naturalis Historia 35.166). Pozzolanic crystallization of Al-tobermorite, a rare, hydrothermal, calcium-silicate-hydrate mineral with cation exchange capabilities, has been previously recognized in relict lime clasts of the concrete. Synchrotron-based X-ray microdiffraction maps of cementitious microstructures in Baianus Sinus and Portus Neronis submarine breakwaters and a Portus Cosanus subaerial pier now reveal that Al-tobermorite also occurs in the leached perimeters of feldspar fragments, zeolitized pumice vesicles, and in situ phillipsite fabrics in relict pores. Production of alkaline pore fluids through dissolution-precipitation, cation-exchange and/or carbonation reactions with Campi Flegrei ash components, similar to processes in altered trachytic and basaltic tuffs, created multiple pathways to post-pozzolanic phillipsite and Al-tobermorite crystallization at ambient seawater and surface temperatures. Long-term chemical resilience of the concrete evidently relied on water-rock interactions, as Pliny the Elder inferred. Raman spectroscopic analyses of Baianus Sinus Al-tobermorite in diverse microstructural environments indicate a cross-linked structure with Al3+ substitution for Si4+ in Q3 tetrahedral sites, and suggest coupled [Al3++Na+] substitution and potential for cation exchange. The mineral fabrics provide a geoarchaeological prototype for developing cementitious processes through low-temperature rock-fluid interactions, subsequent to an initial phase of reaction with lime that defines the activity of natural pozzolans. These processes have relevance to carbonation reactions in storage reservoirs for CO2 in pyroclastic rocks, production of alkali-activated mineral cements in maritime concretes, and regenerative cementitious resilience in waste encapsulations using natural volcanic pozzolans.

The Sabatini Volcanic District belongs to the Roman magmatic province of Central Italy, and the Tufo Giallo della Via Tiberina was one of the most voluminous pyroclastic flow-forming eruptions in this district. Post-depositional processes strongly affected this pyroclastic flow deposit leading to the crystallization of different authigenic phases (chabazite, phillipsite, feldspar). A field volcanological survey, along with a careful mineralogical characterization of a large amount of samples of the lithified facies, allowed us to reconstruct a type section primarily based on the amounts of the main authigenic phases. Chabazite always prevailed over phillipsite throughout the entire section, although in the innermost portions of the deposit, where temperatures remained high, chabazite mostly converted into a more stable phase such as an adularia-like phase. In addition to the zeolitization process, the fairly strong mechanical properties of this tuff can be also ascribed to the diffuse occurrence of microcrystalline calcite, which re-precipitated as a secondary phase after the dissolution of carbonaceous clasts.

This work is part of a project focused on the Somma&ndash, Vesuvius volcano and aimed at identifying Cu minerals related to mineralizing processes associated with magmatic activity in an active magmatic-hydrothermal system. A mineralogical survey was carried out on a set of samples represented by sublimates and fumarolic products from the collection of the Mineralogical Museum of the University of Naples Federico II (Italy). These samples are mainly related to most recent eruptive episodes of Vesuvius activity, from 1631 onward. Copper-bearing minerals were characterized, as well as associated minerals, by X-ray diffraction (XRD) scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS). An investigation on the structural complexity of Cu-mineral assemblages with different temperature formations was also carried out using the TOPOS software package. The main copper phases are sulfates, followed by vanadates, hydroxyhalides, oxides, carbonates, silicates and finally, phosphates. New mineral occurrences for Vesuvius, both Cu-bearing and Cu-free, are described. Nevertheless, the fumarolic/alteration minerals at Vesuvius cannot be considered of economic relevance as a copper reservoir, this type of mineralizations are significant for copper crystal chemistry and for the knowledge of the mineralogical variants. The obtained datasets can be of interest for the knowledge of volcanic byproducts of copper ore deposits (i.e., porphyry copper systems) and of (base) metal segregation processes.

Campi Flegrei is a large volcanic area situated northwest of Naples, Italy. Two archeological sites, the Sybil's Cave and the Piscina Mirabilis, are artificial caves dug in the yellow tuff and used during antiquity for various purposes. This paper describes for the first time the algal biodiversity of these caves and determines whether environmental factors such as light intensity and humidity are influential in species distribution. A total of twenty-two algal species were identified by molecular methods (18S rDNA); the largest group was Cyanobacteria (eleven species), followed by algae Chlorophyta (six), Rhodophyta (two) and Bacillariophyta (two). Cluster analysis of algal distribution in the caves in relation to light and humidity showed no relevant differences in algal distribution between the two caves. Three different algal groups were identified. The first one includes strains strictly dependent on low humidity, a second cluster was mainly associated with sites where humidity is not a severe constraint, and a third group, mainly represented by filamentous cyanobacteria, is probably dependent on high humidity, since it was detected only at Piscina Mirabilis.

The environmental status of the Falerno-Domitio littoral, a sector of the Italian south coast (Campania region) locally affected by an extensive anthropic pressure and pollution, was assessed by a multi-disciplinary approach, consisting of geological vs. biological studies. Geochemical abundance of potentially hazardous trace metals in beach sands is mainly constrained by the nature of the source rocks. Geochemical data of marine sediment quality with regards to possible heavy metal pollution and the enrichment factors of selected potentially toxic metals show that Cr and V values are higher in marine samples than in natural sources, suggesting that they are, at least in part, of anthropic derivation. A relationship between meiobenthos and heavy metals (Cr, Co, and V) has been also observed, providing a valuable biological marker to human-deriving chemical pollution. Ecotoxicological analyses confirm a relationship between enrichment in selected metals and moderate toxicity of some sea-bottom sediments closer to the coastline.

There is a growing concern on lightweight aggregates (LWA) for recycling of waste materials: this manufacturing technology is considered a flexible tool to make it possible the conversion of large amounts of residues into building products. The main challenge for this purpose is the control on the technological behavior during firing of waste-bearing batches. The target is engineering the sintering and expansion of LWA in order to tailor bulk density, mechanical strength and water absorption on various possible applications (e.g., structural and non-structural lightweight concretes, lightweight mortars, filtration substrates, floriculture). The prediction of the aggregate expansion - and hence the batch design - is usually carried out utilizing the Riley's and/or Cougny's schemes, which are based on the bulk chemical composition of clay bodies. However, collecting the literature data on waste-based LWA and plotting them in the Riley's and Cougny's diagrams, no reliable discrimination turns out between expanding and non-expanding batches. In the same way, the attempt to modify the Riley's and Cougny's parameters, including elements present in wastes but not in natural raw materials, was unsuccessful. From this standpoint, a new approach to assess the batch expandability was developed through a deeper comprehension of mechanisms acting on sintering and expansion of LWA. A specific characterization protocol was set up, entailing hot-stage microscopy and determination of phase composition and microstructure. This implies a paradigm shift from batch (chemical composition) to vitreous phase (amount, chemical composition, and viscosity at high temperature). The vitreous phase plays a key-role for bloating, microstructure and physical properties of LWA. A working example is presented about new LWA based on waste glasses, ceramic tile polishing sludge and clay raw materials. (C) 2016 Elsevier Ltd. All rights reserved.

Industrial minerals, particularly bentonites, have long been used in treatments to improve the stability and shelf life of white wines. We evaluated a new combination of rocks and minerals, including steam-treated bentonites and natural zeolites (chabazite and phillipsite), to greatly reduce the risk of protein and tartaric instability of wines. Detailed mineralogical, chemical and electrokinetic studies of these materials were conducted using powder X-ray diffraction (PXRD), X-ray fluorescence (XRF), microporosimetry, BET surface-area analysis and zeta-potential measurements. Several model wine solutions containing Bovine Serum Albumin (BSA) were prepared to evaluate the oenological performance of the rock/mineral combinations. UV-VIS spectrophotometry and ion chromatography were used to evaluate the degree of wine stabilization from the protein and tartaric point of view.The experimental results showed that steam treatment modifies both the microporosity and external surface area of the bentonite. These changes in surface area, along with creation of hydrophobic surfaces, significantly modified the behaviour of the steam-treated bentonites, requiring an increase in the amount of material necessary to bring the protein content to required levels. An important benefit derived from the use of steam-treated bentonites is that the pre-mixing with water before addition to wine is not necessary, as the material is readily dispersed. Finally, the addition of natural zeolites effectively decreased the potassium content, thereby improving the tartaric stability of white wines. In addition, this procedure results in minimal waste, as the bentonite-zeolite mixture can be reused as soil amendments in agriculture.

Companies from different industrial sectors regularly use biological aerated filters to reduce pollutants resulting from industrial productions. These filters use a bed of inert material for the growth of a microbial colony which has the key role to break down pollutants. The inert bed is usually formed by organic or inorganic material and always more often from natural products such as the commercial Biodagene which is the product of fired shales from France. This research aims to use clayey Italian rock formations for the production of lightweight expanded aggregates and to test physical -mechanical features of fired products, to verify the possibility of manufacturing a viable alternative media to inert products currently traded.