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The encapsulation and delivery of drugs often involves the use of expensive microporous materials, and we have investigated the potential for natural zeolites from the widespread volcanic formations of southern Italy as alternatives to these carriers. Surface-modified natural zeolites (SMNZs) with diverse micellar structures (patchy and complete bilayers) were obtained by using different cationic surfactants [cetylpyridinium chloride (CP-Cl), benzalkonium chloride (BC-Cl), hexadecyltrimethylammonium chloride (HDTMA-Cl), and bromide (HDTMA-Br) with phillipsite-rich tuff from the Campania region (southern Italy)]. Loading and release kinetics tests of sodium ibuprofen (IBU) were carried out with organo-phillipsite composites using Fourier transform infrared spectroscopy (FTIR) and thermal analysis coupled with evolved gas analysis (EGA). Results from these tests were mathematically modeled to evaluate IBU adsorption and release mechanisms. The maximum loaded amount of IBU was attained for organo-phillipsite modified with HDTMA-Br (PHB), which showed a complete bilayer micellar structure. Whenever a patchy bilayer micellar structure formed, the lowest adsorptions of IBU were observed. Equilibrium adsorption results were fit using Langmuir, Sips, and Toth models. Pseudo-first-order and pseudo-second-order fits to the loading kinetic data provided significant goodness of fit. Good fits to the release kinetic data were obtained using first-order and Weibull equations, shedding new light on the release mechanism of IBU from phillipsite. The active amount of IBU on the modified zeolite surface was almost totally available for pharmaceutical purposes.

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.

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

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.

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.

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.

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.

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.

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.

Zeolites were first described from vugs and fissures in basaltic flows in the mid-eighteenth century (Cronstedt 1756), and they are now known to be widespread in a variety of geological environments. More zeolite species occur in vesicles and fractures of basaltic rocks than in any other geologic setting. However, zeolites from sedimentary rocks, in particular, represent the most important occurrences both in terms of aerial extent of deposits and in terms of the abundance of certain zeolite species. The introduction of new analytical techniques in the latter part of the 20th century provided a significant stimulus to zeolite research; these techniques allowed identification of large quantities of zeolites in widespread deposits of sedimentary rocks and, in particular, in sediments from saline, alkaline lakes of the western United States (Sheppard and Gude 1968, 1969a, 1973). Based on geological and hydrologic environments, zeolite occurrences in sedimentary rocks can be classified in the following framework: (a) saline, alkaline lakes; (b) alkaline soils and land surfaces; (c) deep-sea sediments; (d) open hydrologic systems; (e) as products of hydrothermal alteration; and (f) burial diagenetic or low-metamorphic environments. From a broader perspective, zeolite deposits can be classified into two main groups, namely closed hydrologic systems and open hydrologic systems. The work of Sheppard and Gude (1968, 1969a, 1973) and later Surdam (1977), discussing not only the mineralogy of the deposits but also the geology, hydrology, and chemistry of the depositional basins, represent milestones in the study of closed hydrologic system formation of zeolites. Surdam (1977) considered closed hydrologic basins in two different tectonic settings: (a) block-faulted regions in arid and semiarid regions; and (b) trough valleys associated with rifting. Examples of the first setting are the closed lakes of the Basin and Range province of the western United States whereas the …

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.

Industrial minerals represent an important resource for the Italian economy, both in terms of exploitation and transformation, especially in those sectors for which Italy holds a leadership such as ceramics and glass. Among Italian regions Campania is one of the poorest of such kind of resources although some geological formations could be advantageously exploited. An important role is played by the deposits of sedimentary zeolites linked to the activity of different volcanic districts occurring on the Neapolitan territory such as the Campanian Ignimbrite, the most important volcanic episode of the Campi Flegrei (Southern Italy), which blankets a wide area of the Campanian region. The Campanian Ignimbrite has been thoroughly investigated from a volcanological and petrographic point of view. However, little attention was devoted to the attainment of those information useful to verify the potential of the deposit as well as the interpretation of post-depositional mineral-forming processes that have affected this deposit and have led to the formation of several facies, among which the most important are characterized by intense feldspathization (grey facies) and remarkable zeolitization (yellow facies). X-ray diffraction, X-ray fluorescence, inductively coupled plasma emission spectrometry and scanning electron microscopy methods were used to thoroughly characterize the entire set of samples collected from 31 outcrops. Data so far acquired enabled to define the role played by several parameters (i.e., temperature, alkaline and alkaline-earth cations, etc.) in influencing the zeolitization process and the consequent crystallization of phillipsite, chabazite, and analcime. Feldspathization appears to have been controlled mainly by the emplacement temperature of the deposits. The proposed genetic model involves emplacement of the pyroclastic flow in a single episode, producing a deposit with an upward-decreasing temperature gradient. In this model, the central portion had a temperature insufficient to cause significant feldspathization, and the upper portion of the formation was affected by water percolation while still hot, producing progressive zeolitization. Volcano-stratigraphical parameters suggest some constrains on the maximum temperatures affecting the central portion of WGI. Thermodynamic data on zeolites constrain the maximum temperatures of the LYT unit which likely decrease upwards in the unit up to ambient conditions in CPF.

The zeolitic minerals have been observed in volcanic sequences of recent geologic age (Pliocene–Miocene) that have been located around the Laguna de Cuitzeo and near Morelia (Capital of the State of Michoacan, Mexico). The zeolites of the Cuitzeo area were studied by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), X-ray fluorescence (XRF), FTIR and Raman spectroscopy in combination with thermoanalytical methods (thermogravimetric analysis — TG/DTG — and differential thermal analysis — DTA). The main mineral constituent is an intermediate type of the isomorfous series heulandite–clinoptilolite end members. Trace of feldspars, biotite, and smectite (and an amorphous fraction) were also detected. Chemical composition (Ca 1.44–2.00 K 1.44–0.74 Na 0.05–0.53 Mg 0.67–0.92 Fe 0.02–0.10 )[Si 29.04–29.85 Al 6.31–7.04 O 72 ] 13.5 H 2 O and some chemical features (Γ = 0.96–1.08), (Si/Al ratio 4.47; Al + Fe 3 + of 6.36 to 7.13) with 2.38 (Mg + Ca) > 1.43 (Na + K) correspond to the intermediate member of the clinoptilolite–heulandite isomorphous series. The dehydration rate of the Cuitzeo zeolites, especially in the range from 150 to 400 °C, as well as spectroscopic features (FTIR and Raman), external cation exchange capacity (135 meq kg − 1 ) and porosimetric data are also characteristic for this intermediate clinoptilolite–heulandite member. The value of the BET specific surface area (20.3 m 2 /g) is about 1.5 times higher than that relative to clinoptilolite-rich tuff powders of different geographic origin and previously characterized. Cuitzeo zeolite deposit is of a great economic interest, considering that it is the unique and richest among the zeolite formations in Southwestern Mexico with zeolite content higher than 70 wt.%. This value is relatively high: most of the exploited zeolitic tuffs from the Oaxaca State (the most studied and well known deposits of natural zeolites in the south of Mexico) have been estimated to contain less than 60 wt.% zeolite minerals. Based on the above properties the zeolite from Cuitzeo area could be a very effective tool for technological application (such as agricultural use, decontamination of water and soils, cement industry, etc.), particularly due so far of the complete absence of zeolitic deposits in the central region of Mexico.

The crystal structure, crystal chemistry, and low-temperature structural evolution of natural thomsonite from Terzigno, Somma-Vesuvius volcanic complex, Naples Province, Italy, have been investigated by means of in situ single-crystal X-ray diffraction, electron microprobe analysis in the wavelength dispersive mode, and Raman spectroscopy. Six structure refinements have been obtained at different temperatures: 295.5, 248.0, 198.0, 148.0, 98.0, and 296.0 K (after the low- T experiments). The reflection conditions and the structure refinements prove that the crystal of thomsonite here investigated is orthorhombic with a = 13.0809(3), b = 13.0597(3), c = 6.6051(1) A, V = 1128.37(14) A 3 , and space group Pbmn , which differs from thomsonite from different localities reported in previous studies (with a ~ 13.1, b ~ 13.06, c ~ 13.2 A, and space group Pncn ). The refined bond distances suggest that the Si/Al-distribution in the tetrahedral framework is fully “disordered,” giving rise to the halving of the c axis relative to that found in “ordered” thomsonites. The extra-framework population consists of: (1) one site about 50% occupied by Ca (labeled as “Ca”); (2) one site occupied by Na (~70%) and Ca (~30%) (labeled as “Na”); and (3) three water molecule sites (“W1,” “W2,” “W3”). The structure refinements allowed the location of all the proton sites, and the hydrogen-bonding scheme in the structure is provided. The low-temperature refinements show no significant change in the structure within the T -range investigated. The evolution of the unit-cell volume with T exhibits a continuous and linear trend, without any evident thermo-elastic anomaly, with thermal expansion coefficients α V = V −1 ·∂ V /∂ T = 20(2)·10 −6 K −1 (between 98.0 and 295.5 K). A list with the principal Raman active modes is provided and a comparison with the vibrational modes previously found for “ordered” thomsonite is carried out.

The crystal-chemistry of a series of natural phillipsites [ideal unit formula: K2(Na,Ca0.5)3[Al5Si11O32]· 12H2O, Z = 1, with a ~ 9.96, b ~ 14.20, c ~ 8.71 A, and β ~ 24.97°, space group P 21/ m ] from the Neapolitan Yellow Tuff was investigated by electron-microprobe analysis in the energy dispersive mode and powder X-ray diffraction using an in-house conventional diffractometer. A significantly different population of the extra-framework cations ( i.e. , K, Na and Ca) and water molecules was observed for crystals from different localities. All phillipsites from NYT can be described as “K-rich phillipsites”, due to the significantly high amount of potassium among the extra-framework cations. Rietveld structure refinements have been performed. The refined unit-cell parameters of the phillipsite samples show a little, but significant, control of the crystal-chemistry. The unit-cell volumes range between ~ 1008.7 and ~ 1011.6 A 3. Samples with the highest amount of Na and the lowest amount of K show the largest unit-cell volume, whereas the smallest unit-cell volumes are observed for the samples with the lowest amount of Na and the highest amount of Ca. As to the unit-cell lengths, the longest c -axis with the highest distortion of the monoclinic unit-cell ( i.e. , with the highest β angle value) is observed for the samples with the lowest amount of Ca and the highest amount of K. The structure refinements performed in this study show a good general agreement with the complex configuration of the extra-framework population recently found on the basis of single-crystal data, with (1) one or two mutually exclusive K-rich sites, ~ 0–0.3 A apart ( i.e. , K1 and K2); (2) one site partially occupied by Ca + Na; (3) seven independent sites occupied by water molecules (W1, W2, W3, W4, W4′, W5 and W6).

The crystal-structure, crystal-chemistry, and low-temperature behavior of a natural phillipsite-Na from the “Newer Volcanic Suite,” Richmond, Melbourne district, Victoria, Australia [K 0.75 (Na 0.88 Ca 0.57 ) ∑1.45 (Al 2.96 Ti 0.01 Si 5.07 ) ∑8.04 O 16 · 6.2H 2 O ( Z = 2), a = 9.9238(6), b = 14.3145(5), c = 8.7416(5) A, β = 124.920(9)°, and V = 1018.20(9) A 3 , space group P 2 1 / m ], have been investigated by means of in situ single-crystal X-ray diffraction, thermogravimetric analysis, and electron microprobe analysis in the wavelength dispersive mode. Two accurate structural refinements have been obtained on the basis of single-crystal X-ray diffraction data collected at 298 and 100 K, with: R 1 ( F ) 298K = 0.035, 3678 unique reflections with F o > 4σ( F o ) and 195 parameters, and R 1 ( F ) 100K = 0.035, 3855 unique reflections, F o > 4σ( F o ) and 195 parameters. In both refinements, the residuals in the final difference Fourier maps are e − /A 3 . A configuration of the extra-framework population different from that reported in previous studies is found at room temperature, with two possible sites for potassium (K1 and K2), one sodium/calcium site (Ca), and seven independent sites partially occupied by water molecules (W1, W2, W3, W4, W4′, W5, and W6). The low-temperature refinement shows that the framework component of the phillipsite structure is maintained within the T -range investigated. However, a change in the configuration of the extra-framework content occurs at low temperature: the occupancy of site K2 drastically decreases, while that of site K1 increases, the Ca site is split into two sub-sites (Ca1 and Ca2) and the number of water molecule sites decreases to six (W1, W2, W3, W4, W5, and W6). The rearrangement of the extra-framework population at low temperature is likely due to the change in shape (and size) of the micropores by tetrahedral tilting. The evolution of the “free diameters” with temperature shows that an “inversion” of the ellipticity of the eight-membered ring channel along [010] occurs. The evolution of the unit-cell parameters with T (measured at 298, 250, 200, 150, and 100 K) shows a continuous and linear trend, without evident thermo-elastic anomalies. The axial and volume thermal expansion coefficients (α j = l j −1 ·∂ l j /∂ T , α V = V −1 ·∂ V /∂ T ) between 100 and 298 K, calculated by weighted linear regression, yield the following values: α a = 1.8(1) × 10 −5 , α b = 1.2(1) × 10 −5 , α c = 1.1(1) × 10 −5 , and α V = 3.7(1) × 10 −5 K −1 . The thermal expansion of phillipsite is significantly anisotropic (α a :α b :α c = 1.64:1.09:1).

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.

The aim of this research is to assess the possible use of Italian zeolitic rocks for the production of lightweight aggregates. In particular, both the expansion at high temperature and the technological features of fired products were investigated. Fifteen zeolite-bearing volcanoclastites from Northern Sardinia and three zeolitized tuffs from Campania and Tuscany (Sorano and Campanian ignimbrites and Neapolitan Yellow Tuff) were taken into account. The firing expansion turned out to be mainly dependent on the chemical composition (especially SiO 2 and fluxing oxides such as Fe 2 O 3 , Na 2 O, K 2 O, MgO and CaO) and the water content (largely related to the zeolite amount) of the raw materials. Other relevant parameters were the temperature of maximum expansion (ranging between 1350 and 1500 °C, without additives) and soaking time (between 2 and 5 min). Some products are highly impervious to water (water absorption below 1%) and exhibit a considerable firing expansion (>100% in volume), a low bulk density (0.5–0.7 g·cm −3 ) and fair technical properties (loose weight and strength of particles). These encouraging results make some of the investigated tuffs interesting raw materials for the production of lightweight aggregates.

¶This paper deals with the mineralogical features of the most important and widespread pyroclastic formation of Southern Italy: the Campanian Ignimbrite. This formation is characterized by four stratigraphic units, different in colour and mineralogical composition. The lowermost unit (USAF) is constituted by an incoherent, thin (few tens of cm) sequence of glass or feldspar-rich layers. The middle part of the succession is formed by two main units: a lower grey, welded unit (WGI) capped by a yellow and lithified unit (LYT) that differ in both volcanological features and mineralogical composition. Locally these units are found separately. An incoherent unit (max thickness about 2 m) mainly represented by fresh glass, forms the upper part of the succession. A detailed analysis has been carried out on six sections representative of the entire succession. The WGI is feldspathized by authigenic mineralization processes, and the feldspar content ranges between 30 and 90%. The LYT has been deeply affected by zeolitization processes and the total zeolite content often reaches 60%. Based on a comparative examination of both volcanological and mineralogical data, it is hypothesized that these two units were involved in different secondary mineralization processes. The portion of the succession characterized by the highest emplacement temperatures suffered welding and feldspathization and the result of these processes gave rise to the WGI unit. In contrast, the overlying lower-temperature and incoherent portion of the deposit was affected by circulation of meteoric water, thus enhancing zeolitization and lithification. The product of this process gave rise to the LYT unit.

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.

Experiments on zeolitization were conducted on four synthetic monocationic glasses (Na, K, Ca, or Mg-rich glass) with Si/Al molar ratios of 2.67, similar in acidity to many volcanic glasses of partially zeolitized Italian tuffs. The products of the hydrothermal treatment at 100, 150, and 200°C of single glasses or glass mixtures with deionized H2O or monosaline solutions (NaCl, KCl, CaCl2) were characterized by X-ray diffraction, thermal, microscopic and chemical analyses. Chemical analyses of mother liquors were also performed. Mineral assemblages, containing chabazite, phillipsite, analcime, and K-feldspar, very similar to those found in altered, volcaniclastic alkali-trachytic or trachytic glass deposits were produced. Potassium was essential to chabazite and phillipsite crystallization, although phillipsite was obtained also in Ca-Na mixed systems. Sodium was necessary for analcime formation. Calcium plays only a secondary role in zeolitization, and magnesium does not favor zeolite crystallization but promotes the formation of smectite. Glass composition determines the mineral assemblages obtained and hence in those commonly found in nature.

Two clinoptilolites from genetically different volcanoclastic formations have been studied. Both deposits are located in the Logudoro region (North-Western Sardinia, Italy) within epiclastic and pyroclastic formations related to calcalkaline volcanic activity. Chemical characterization performed by electron microprobe analysis on both samples showed a quite similar composition ([Si/(Si+Al)] = 0.81/0.82), with the exception of some extra-framework cations. In particular the epiclastic clinoptilolites turned out to be much higher in Mg content (0.72 vs. 0.26 a.f.u.) and considerably lower in K (1.10 vs. 2.37 a.f.u.) than the pyroclastic clinoptilolites. Previous investigations evidenced a different behaviour of the two clinoptilolite samples towards cation exchange processes and a substantial difference between the theoretical and experimental CEC. In this frame, Rietveld refinements based on synchrotron data allowed to define a different cationic population within the four exchangeable cation sites.