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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.

In this work, four zeolite-bearing materials (three naturally occurring and one of synthetic origin) were considered for thermal energy capture and storage. Such materials can store thermal energy as heat of desorption of the water present therein, heat that is given back when water vapor is allowed to be re-adsorbed by zeolites. This study was carried out by determining the loss of water after different activation thermal treatments, the water adsorption kinetics and isotherm after an activation step of the zeolites, the intergranular and intragranular porosity, and the thermal conductivity of the zeolite-bearing materials. Moreover, the thermal stability of the framework of the zeolites of the four materials tested was investigated over a large number of thermal cycles. The results indicate that zeolite 13X was the most suitable material for thermal energy storage and suggest its use in the capture and storage of thermal energy that derives from thermal energy waste.

Six zeolite-bearing rocks, often used as building materials, were analyzed by thermodilatometry, together with a rock not bearing zeolites and a plaster covering a containing wall made of zeolite-bearing dimension stones, up to 250 °C. The main results obtained were the following: (i) the zeolite-bearing rocks exhibited very small, if any, positive variation of ΔL/Lo (%) up to about 100 °C, whereas they more or less shrank in the temperature range 100–250 °C (final values ranging from −0.21 to −0.92%), (ii) the rock not bearing zeolites regularly expanded through the whole temperature range, attaining a final value of 0.19%, (iii) the plaster showed a thermodilatometric behavior strongly affected by its water content. Obtained results were interpreted based on plain thermal expansion, shrinkage by dehydration, cation migration and thermal collapse of the zeolitic structure. The decay of the zeolite-bearing building materials was essentially related to: (i) the large differences recorded in the thermodilatometric behavior of the various rocks and the plaster, (ii) the different minerogenetic processes that resulted in the deposition of the various zeolite-bearing rocks.

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.

This paper aims at testing the use of mixtures constituted by natural zeolitized products and SiC-bearing industrial wastes (sludge deriving from polishing of porcelain stoneware tiles, hereafter DPM) for the production of lightweight expanded aggregates as constituents of structural and/or thermo-insulating lightweight concretes. Two commercial products have been used as zeolite natural source: Cab70 (Yellow facies of Campanian Ignimbrite) and IZclino (Turkish clinoptilolite-rich epiclastite). Different amounts of a calcareous material (Pozzano limestones — hereafter CP) from the Sorrento peninsula (Naples — Italy) were also added to a Cab70–DPM mixture. All raw materials were characterized by means of mineralogical (XRPD) and chemical (XRF) analyses. All the products and mixtures were tested from a technological point of view by means of fusibility and firing tests in order to evaluate the expanding properties. It was evidenced that the expansion of the mixture was deeply depending on the occurrence of SiC in the industrial waste. The addition of CP (10 wt.%) to the mixtures accounts for an even increased expansion, though this is accompanied by a worsening of the mechanical features of the material. These results along with literature data allowed to select 3 mixtures (70% Cab70–30% DPM, 70% IZclino–30% DPM, 60% Cab70–30% DPM–10% CP) and each of them was used for the preparation of 5 l of lightweight aggregates afterward employed for the manufacture of lightweight concretes. It was remarked that natural zeolitized materials mixed with DPM (30 wt.%) can provide lightweight aggregates with densities ranging between 0.8 and 1.0 g/cm 3 suitable for the preparation of structural lightweight concretes. The addition to the mixture of CP (10 wt.%) produces less dense aggregates (0.6–0.7 g/cm 3 ) potentially useful for the manufacture of thermo insulating lightweight concretes.

Aim of this research is an evaluation of the zeolitized facies of Campanian Ignimbrite as raw material for the production of lightweight expanded aggregates (LEA). A commercial product (Cab70) was used as reference for this rock. Tests were carried out on “pure” samples or mixed with an industrial waste mud (DPM — Dried Polishing Mud) deriving from a porcelain stoneware tile polishing process. This mud contains SiC, a phase known to act as bloating enhancer. Raw materials were subjected to mineralogical (XRPD–RIR method) and chemical (XRF) analyses. Bloating upon heating was measured (Leitz heating microscope) on Cab70, DPM and on three mixtures having the following Cab70/DPM ratios: 85/15 (Mix1); 70/30 (Mix2); 50/50 (Mix3). LEA production was assessed both in static (muffle kiln) and in dynamic (rotating kiln) conditions by firing pellets, 3–8 mm in size, between 1220–1380 °C. The unit weight of the single particle was determined on fired and unfired products. All materials evidenced a decreasing density with temperature whereas the same parameter decreases with DPM increasing content. Cab70 LEAs never dropped below 0.90 g/cm3, even at the highest temperature, whereas DPM LEAs range between 0.86 g/cm3 (at 1260 °C) and 0.46 g/cm3 (at 1380 °C). A direct but not linear relationship between DPM content and density was evidenced. Among the three mixtures, Mix2 showed the lowest DPM content able to produce the strongest density reduction. To get LEAs with the same density the rotating kiln required temperatures generally 60–80 °C higher than those of the muffle kiln. This difference should be related to the different thermal insulation of the two systems during firing. Two sets of LEAs were massively produced in dynamic conditions from Cab70 (at 1380 °C) and Mix2 (at 1300 °C). These latter showed better technical performances in terms of unit weight of the single particle (0.81 vs. 0.98 g/cm3), bulk unit weight (460 vs. 565 kg/m3), water absorption coefficients (1.4 vs. 5.5% after 24 h) and compressive strength of the particles (2.9 vs. 0.6 MPa). Differences in pore shape, dimension, abundance and spatial distribution were observed by SEM between the two sets. The technical features of these LEAs were comparable to some expanded clays, with similar grain size, commercialised in Italy. These results are worth interesting as they reveal new perspectives of application both for a rock characterized by a low exploitation cost and widely available in central-southern Italy, as well as for an industrial waste produced in high amount but not recycled at all.

This paper reports novel data concerning the volcanic formation of the Piperno, a stone that has been used for a long time in the monumental architecture of Naples and the Campanian region (Southern Italy). A careful field survey of the outcrops or underground sites so far accessible allowed us to draw a lithostratigraphic reconstruction of the formation and enabled the recognition of the three main layers exploited in past centuries and which provided dimension stones for architectural and structural purposes. Petrophysical and mineralogical characterization also enabled us to discriminate the same layers previously identified. Different scoriae/matrix ratio, scoriae dimension and welding degree are the most peculiar features of these horizons. The combination of these three parameters, even though they did not affect the use of Piperno as dimension stone, somehow determined its variable susceptibility to the weathering agents. However, a linear relationship between the exposure time and the decay of the stone itself, at a parity of weathering intensity, was not observed. This assumption was proved by verifying that the specific layers of the volcanic sequence controlled the weathering degree of Piperno from monuments disregarding their age of emplacement.

The study proposes a model by which a thick succession of volcanic tuffs can be zeolitized by alteration of pyroclastic material in the presence of sufficient eruptive water and at temperatures close to water vapour condensation. In the case of phreatomagmatic products, the model simplifies interpretation of problematic deposits that exhibit pronounced vertical and lateral variation in lithification grade. A major feature of the model is that thick zeolitized tuffs can be formed during emplacement of pyroclastic products, in marked contrast to later alteration in an open hydrologic system. Geological, volcanological and mineralogical data for the Neapolitan Yellow Tuff, a widespread trachytic pyroclastic deposit outcropping around Campi Flegrei (Southern Italy), have been used to infer the physico-chemical conditions that determined mineral genesis. This tuff shows a reduction in lithification grade towards the base, top and with distance from the vent and very variable zeolitization within the lithified portion. We suggest that during initial emplacement the erupted products chilled against the ground, inhibiting zeolite crystallization. During rapid deposition of the thick, wet succession thermal insulation allowed the persistence of elevated temperatures for a time sufficient for enhancement of hydration-dissolution processes in the volcanic glass. The highly reactive alkali-trachytic glass quickly buffered the acid pH of the system, favouring phillipsite crystallization followed by chabazite nucleation. The variable zeolite content reflects fluctuating emplacement conditions (e.g. changes in water content and temperature). Cooling of the upper and relatively thin distal deposits inhibited the zeolitization process, thereby preserving the primary unlithified deposit.

The possibility of using Italian zeolitized volcanoclastites for the production of lightweight aggregates in the building industry has been tested. The present paper definitely demonstrates the good attitude of the Neapolitan Yellow Tuff (NYT) for the production of lightweight expanded aggregates (LEA) with bulk densities ranging between 0.9 and 1.1 g/cm 3 . LEAs showing these features, usually manufactured with clays, are mainly used in the production of lightweight structural concretes (LSC). The physical characterization of LEAs was carried out by means of: grain size analysis, loose weight, mean density of the single grain, water absorption after 30 min and 24 h, and strength of particles (UNI-7549). Afterwards, LEAs were mixed with sand, cement and water to prepare cubic concrete blocks following the UNI specifications (UNI-7549-12). On these specimens, the unit weight and uniaxial compressive strength after 28 days were determined. The investigated parameters measured both on LEAs and concretes, are comparable with those measured on materials commonly traded in Italy. The obtained results foresee interesting potential applications of a raw material characterized by a low exploitation cost and a widespread availability on the Italian territory.

Low-cost zeolitic rocks are promising substitutes for feldspathic fluxes in ceramic bodies, since their fusibility, modest hardness and high cation exchange capacity (CEC) should improve grinding and sintering. Five large-scale Italian deposits of natural zeolites with different mineralogy were characterised and tested in porcelain stoneware bodies. Their behaviour during processing was appraised and compared with that of zeolite-free bodies. Zeolites increased the slip viscosity during wet grinding, causing a coarser grain size distribution and consequently some drawbacks in both unfired and fired tiles. After overcoming this hindrance by dry grinding of zeolite rocks, the technological behaviour of zeolite-bearing tiles appear to be similar to that of current porcelain stoneware, though with larger firing shrinkage and residual closed porosity.

An attempt to correlate differnt facies of an important volcaniclastic formation of southern Italy, the Campanian Ignimbrite, with their zeolite content and physico-mechanical properties was carried out. The following parameters were measured: total zeolite content, solid unit weight (γ s ), porosity, and uniaxial compressive strength. Samples were formerly grouped on the basis of the displayed colour in four categories each of them characterized by a different zeolite grade. An increase of zeolite content determines a decrease of porosity and a good positive correlation with UCS values. The relationship existing between zeolite grade and UCS becomes less pronounced or even lost, when zeolite content reaches about 50% wt. Here, UCS values scatter in a quite wide range (3–6 MPa). It is hypothesized that the lithification of zeolite-bearing rocks is the result of two combined effects playing a different role during the zeolitization process: the transformation of the amorphous fraction in zeolite and the rock texture. In the first stage of the zeolitization process the role played by the rock texture (clasts/matrix ratio, pumice concentration, fractures, etc.) is totally masked by the overwhelming behaviour of zeolite itself up to that threshold value, above which the influence of these two leading parameters is inverted.

The present study reports the results of research on volcaniclastic products from Logudoro (northern Sardinia), a reconstructed stratigraphic succession some hundreds of meters thick, comprising two different ignimbritic units separated by an epiclastic layer (generally ˜10 m thick). Clinoptilolite is the most widely distributed authigenic phase in epiclastite and unwelded units, always associated with opal-CT and sometimes with smectite. An adularia-like feldspar, cristobalite and epigenetic quartz are typical phases of welded units. Within the zeolitized units (unwelded ignimbrite and epiclastic units) clinoptilolite and opal-CT constitute the cement deriving from the transformation of the precursor rhyolitic glass, in agreement with a single zeolitization process that developed after the deposition of the entire succession. Silica increases in zeolitized rocks with respect to the precursor material, leading to hypothesize that the secondary mineralization process was favored by mineralized hydrothermal fluids preferentially circulating through the fault system of the area. Quartz veins in welded subunit and K-feldspar (adularia-like) preferentially located near the faults are in agreement with this hypothesis. The interaction of these fluids with the glassy fraction favored its dissolution and the consequent crystallization of clinoptilolite. Furthermore, the pH increase and the silica supersaturation enhanced the contemporary or subsequent precipitation of opal-CT.

Publisher Summary In Campania region (Southern Italy), the large availability of volcanic products determined the utilization of these products for structural purposes. Neapolitan Yellow Tuff (NYT), Campanian Ignimbrite (CI), and Piperno (PI) were the most widely used volcanic products in historical architecture of Campania region.. This chapter describes the mineralogical and petrographical features of these materials and the research conducted to study the decay phenomena by means of laboratory simulations, which reproduce the aging processes of the stone. Mineralogical characterization was carried out by scanning electron microscopy (SEM) observations and by X-ray powder diffraction analysis (XRPD). Open porosity was calculated by He-pycnometer. Water absorption was measured by immersion test. Ageing tests, wet-dry and salt crystallization tests, were performed to study the decay phenomena. From the mineralogical analysis, a substantial difference was found out between the NYT on one side, and CI and PI on the other. The matrix of the former is mainly constituted by zeolites, amorphous phases, and volcanic glass; and the latter (CI and PI) have a matrix constituted by feldspars and minor amount of glass. The chapter provides table to illustrate variation of the physico-mechanical properties (porosity, water absorption, and uniaxial compressive strength) after aging tests. The overall results obtained show poorer durability of Neapolitan Yellow Tuff, when compared to other stones.

The Campi Flegrei volcanic field, Southern Italy, is composed of a large variety of pyroclastic deposits related to both magmatic and hydromagmatic activity. In spite of similarities of composition, grain size, age and pre-eruptive environment, the various deposits exhibit great differences in terms of degree and type of alteration of the juvenile components. In particular, detailed analyses of pyroclasts collected in the numerous monogenetic volcanic cones show the broad range of alteration, from fresh glass to complete replacement of the glass by the zeolites. The comparative analysis of 17 different deposits has allowed us to conclude that the eruptive and emplacement conditions were the major controls on the zeolitization processes. The relationships between volcanological features of deposits and secondary mineralization are consistent with the glass-fluid phase reaction in a near-closed post-depositional system. Eruptions characterised by separation of water vapour from the pyroclastic particles produce unaltered or poorly altered deposits. In contrast, eruptions characterised by mechanisms that permit the capture and retention of pore water and water vapour produce zeolitized deposits. According to these lines of evidence the zeolitization of pyroclastic products of Campi Flegrei took place immediately after emplacement, during the cooling of wet deposits.