Advanced argillic alteration at Cave di Caolino, Lipari, Aeolian Islands (Italy): Implications for the mitigation of volcanic risks and the exploitation of geothermal resources.

Four sites in the western sector of Lipari Island with still active hydrothermal activity are here considered. The petrography (mesoscopic observations and XRPD) and geochemistry (major, minor and trace elements chemistry) of ten representative and extremely altered volcanic rocks were characterized. Two types of parageneses of altered rocks are discriminable, one rich in silicate phases (opal/cristobalite, montmorillonite, kaolinite, alunite and hematite) and one in sulphates (gypsum, plus minor amounts of anhydrite or bassanite). The altered silicate-rich rocks are rich in SiO2, Al2O3, Fe2O3 and H2O, and depleted in CaO, MgO, K2O and Na2O, while the sulphate-rich ones are extremely enriched in CaO and SO4 in comparison with local unaltered volcanic rocks. The content of many incompatible elements is similar in altered silicate-rich rocks and lower in sulphate-rich ones with respect to the pristine volcanic rocks; conversely, almost all REEs are markedly enriched in silicate-rich rocks and heavy REEs are enriched in sulphate-rich altered rocks compared to unaltered volcanic rocks. Reaction path modelling of basaltic andesite dissolution in local steam condensate predicts the production of amorphous-silica, anhydrite, goethite, and kaolinite (or smectites and saponites) as stable secondary minerals and alunite, jarosite, and jurbanite as ephemeral minerals. Considering possible post-depositional reactions and admitting that the presence of two distinct parageneses is apparent, since gypsum is prone to form large crystals, it can be concluded that there is an excellent agreement between the alteration minerals occurring in nature and those predicted by geochemical modelling. Consequently, the modelled process is the main responsible for the production of the advanced argillic alteration assemblage of "Cave di Caolino" on Lipari Island. Since rock alteration is sustained by the H2SO4 solution produced by hydrothermal steam condensation, there is no need to invoke the involvement of SO2-HCl-HF-bearing magmatic fluids, in line with the absence of fluoride minerals.

Physico-Mechanical Performances of Mortars Prepared with Sorted Earthquake Rubble: The Role of CDW Type and Contained Crystalline Phases.

Construction and demolition waste (CDW) from earthquake rubbles was used here as recycled aggregates (RA) in cementitious binders. The materials were sorted in six groups: concrete (CO), natural stone (NS), tile (TI), brick (BR), perforated brick (PF) and roof tile (RT). The abundance (wt.%) of crystalline phases in each RA type was determined by X-ray Powder Diffraction (XRPD). Each group of RAs was used alone (100 wt.% of RA) and mixed with quartz-rich virgin aggregates (VA) to prepare 13 types of mortars (12 specimens per type): one reference mortar (RM) with only VA, six recycled aggregate mortars (RAM) and six recycled-plus-virgin aggregate mortars (RVAM). The physical and mechanical properties of aggregates and mortars reflect the type and abundance of crystalline phases in each CDW group. Recycled mortars rich in concrete, natural stones and tiles have better mechanical performance than mortars prepared with recycled bricks, perforated bricks and roof tiles. For each RA, RVAMs have superior mechanical characteristics than the corresponding RAM. Since the type and amount of phases contained in recycled aggregates strongly control the mechanical performance of new construction materials, they should be routinely quantified as reported here, in addition to other physical features (water absorption, density, etc.). The separation of heterogeneous CDW into homogeneous RA groups is necessary for the production of new construction materials with stable and predictable performances to ensure CDW recycling, especially in areas hit by major adverse events, where large amounts of still valuable materials could be used for reconstruction processes.

Provenance and deposition of a lithified volcanic-rich layer (VRL-5.5) at 5.5 Ma from Central Apennines (Italy).

Two slightly lithified volcanic rich layers (VRL) (former tephra) SVT-2 (San Vittorino) and CAC (Castiglione a Casauria) were sampled from two distinct post-evaporitic Messinian stratigraphic sections (Abruzzo, Central Italy). They crop only few tens of km apart and are predominantly massive, although some specimens show sedimentary structures. Both VRLs were investigated for the first time by field, mesoscopic, X-ray powder diffraction (XRPD), transmission optical microscopy (TOM), scanning electron microscopy (SEM), bulk composition, electron-microprobe analysis (EMPA) and quantitative textural attributes by image analysis. The XRPD analysis detects the presence of a glass phase, plus few (< 2 area %) magmatic-like feldspars, clinopyroxene and biotite and stratigraphically variable sedimentary minerals such as calcite, dolomite, illite and montmorillonite (from 0 to 40 area %). The 2D image analysis performed on SEM microphotographs reveals that both sections are composed of very fine glass shards, magmatic minerals are never isolated, whilst the carbonate crystals mainly fill voids among volcanic particles. Both these VRLs have identical rhyolitic glass compositions that closely overlap with those of previously-studied coeval and stratigraphically related sections occurring in the northern Apennine region and dated as 5.5 Ma. The 2D textural features of glassy particles (length, width, aspect ratio, grain-size distribution, MZ , σi, SKi, KG and roundness) in both SVT-2 and CAC sections are very similar and also close to the northern section of Camporotondo (Marche region). The outcomes provided here indicate that SVT-2 and CAC sections represent the southernmost distal deposits of the same large eruption that occurred about 5.5 Ma (VRL-5.5). They result from distal fallout of tephra through seawater, occasionally remobilised under low energy and localised conditions, especially in the uppermost part of the CAC section. All the VRL-5.5 rocks are probably related to a very large eruption that occurred in the Carpathian-Pannonian magmatic district. The analytical protocols used in this study can be useful to investigate other ancient volcanic-rich layers, corresponding to lithified tephra.

A new approach to deposit homogeneous samples of asbestos fibres for toxicological tests in vitro.

In this paper we describe the results obtained with a novel method to prepare depositions of asbestos fibres for toxicological tests in vitro. The technique is based on a micro-dispenser, working as an inkjet printer, able to deposit micro-sized droplets from a suspension of fibres in a liquid medium; we used here a highly evaporating liquid (ethanol) to reduce the experimental time, however other solvents could be used. Both the amount and spatial distribution of fibres on the substrate can be controlled by adjusting the parameters of the micro-dispenser such as deposition area, deposition time, uniformity and volume of the deposited liquid. Statistical analysis of images obtained by optical and scanning electron microscopy shows that this technique produces an extremely homogeneous distribution of fibers. Specifically, the number of deposited single fibres is maximized (up to 20 times), a feature that is essential when performing viability tests where agglomerated or untangled fibrous particles need to be avoided.

Structure and Properties of Electrochemically Synthesized Silver Nanoparticles in Aqueous Solution by High-Resolution Techniques.

The aim of this work was to deeply investigate the structure and properties of electrochemically synthesized silver nanoparticles (AgNPs) through high-resolution techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), Zeta Potential measurements, and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). Strong brightness, tendency to generate nanoclusters containing an odd number of atoms, and absence of the free silver ions in solution were observed. The research also highlighted that the chemical and physical properties of the AgNPs seemed to be related to their peculiar oxidative state as suggested by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRPD) analyses. Finally, the MTT assay tested the low cytotoxicity of the investigated AgNPs.

Carrier and dilution effects of CO2 on thoron emissions from a zeolitized tuff exposed to subvolcanic temperatures.

Radon (222Rn) and thoron (220Rn) are two isotopes belonging to the noble gas radon (sensu lato) that is frequently employed for the geochemical surveillance of active volcanoes. Temperature gradients operating at subvolcanic conditions may induce chemical and structural modifications in rock-forming minerals and their related 222Rn-220Rn emissions. Additionally, CO2 fluxes may also contribute enormously to the transport of radionuclides through the microcracks and pores of subvolcanic rocks. In view of these articulated phenomena, we have experimentally quantified the changes of 220Rn signal caused by dehydration of a zeolitized tuff exposed to variable CO2 fluxes. Results indicate that, at low CO2 fluxes, water molecules and hydroxyl groups adsorbed on the glassy surface of macro- and micropores are physically removed by an intermolecular proton transfer mechanism, leading to an increase of the 220Rn signal. By contrast, at high CO2 fluxes, 220Rn emissions dramatically decrease because of the strong dilution capacity of CO2 that overprints the advective effect of carrier fluids. We conclude that the sign and magnitude of radon (sensu lato) changes observed in volcanic settings depend on the flux rate of carrier fluids and the rival effects between advective transport and radionuclide dilution.

Deep sea explosive eruptions may be not so different from subaerial eruptions.

The dynamics of deep sea explosive eruptions, the dispersion of the pyroclasts, and how submarine eruptions differ from the subaerial ones are still poorly known due to the limited access to sea environments. Here, we analyze two ash layers representative of the proximal and distal deposits of two submarine eruptions from a 500 to 800 m deep cones of the Marsili Seamount (Italy). Fall deposits occur at a distance of more than 1.5 km from the vent, while volcanoclastic flows are close to the flanks of the cone. Ash shows textures indicative of poor magma-water interaction and a gas-rich environment. X-ray microtomography data on ash morphology and bubbles, along with gas solubility and ash dispersion models suggest 200-400 m high eruptive columns and a sea current velocity <5 cm/s. In deep sea environments, Strombolian-like eruptions are similar to the subaerial ones provided that a gas cloud occurs around the vent.

Transient to stationary radon (220Rn) emissions from a phonolitic rock exposed to subvolcanic temperatures.

Rock substrates beneath active volcanoes are frequently subjected to temperature changes caused by the input of new magma from the depth and/or the intrusion of magma bodies of variable thickness within the subvolcanic rocks. The primary effect of the influx of hot magma is the heating of surrounding host rocks with the consequent modification of their physical and chemical properties. To assess mobilization in subvolcanic thermal regimes, we have performed radon (220Rn) thermal experiments on a phonolitic lava exposed to temperatures in the range of 100-900°C. Results from these experiments indicate that transient Rn signals are not unequivocally related to substrate deformation caused by tectonic stresses, but rather to the temperature-dependent diffusion of radionuclides through the structural discontinuities of rocks which serve as preferential pathways for gas release. Intense heating/cooling cycles are accompanied by rapid expansion and contraction of minerals. Rapid thermal cycling produced both inter- and intra-crystal microfracturing, as well as the formation of macroscopic faults. The increased number of diffusion paths dramatically intensified Rn migration, leading to much higher emissions than temperature-dependent transient changes. This geochemical behaviour is analogous to positive anomalies recorded on active volcanoes where dyke injections produce thermal stress and deformation in the host rocks. An increased Rn signal far away from the location of a magmatic intrusion is also consistent with microfracturing of subsurface rocks over long distances via thermal stress propagation and the opening of new pathways.

Retrieving magma composition from TIR spectra: implications for terrestrial planets investigations.

Emissivity and reflectance spectra have been investigated on two series of silicate glasses, having compositions belonging to alkaline and subalkaline series, covering the most common terrestrial igneous rocks. Glasses were synthesized starting from natural end-members outcropping at Vulcano Island (Aeolian Islands, Italy) and on Snake River Plain (USA). Results show that the shift of the spectra, by taking Christiansen feature (CF) as a reference point, is correlated with SiO2 content, the SCFM factor and/or the degree of polymerization state via the NBO/T and temperature. The more evolved is the composition, the more polymerized the structure, the shorter the wavelength at which CF is observable. CF shift is also dependent on temperature. The shape of the spectra discriminates alkaline character, and it is related to the evolution of Qn structural units. Vulcano alkaline series show larger amount of Q4 and Q3 species even for mafic samples compared to the subalkaline Snake River Plain series. Our results provide new and robust insights for the geochemical characterization of volcanic rocks by remote sensing, with the outlook to infer origin of magmas both on Earth as well as on terrestrial planets or rocky bodies, from emissivity and reflectance spectra.

Infra Red Spectroscopy of the Regulated Asbestos Amphiboles.

Vibrational spectroscopies (Fourier Transform Infra Red, FTIR, and Raman) are exceptionally valuable tools for the identification and crystal-chemical study of fibrous minerals, and asbestos amphiboles in particular. Raman spectroscopy has been widely applied in toxicological studies and thus a large corpus of reference data on regulated species is found in the literature. However, FTIR spectroscopy has been mostly used in crystal-chemical studies and very few data are found on asbestos amphiboles. This paper is intended to fill this gap. We report new FTIR data collected on a suite of well-characterized samples of the five regulated amphibole species: anthophyllite, amosite, and crocidolite, provided by the Union for International Cancer Control (UICC) Organization, and tremolite and actinolite, from two well-known occurrences. The data from these reference samples have been augmented by results from additional specimens to clarify some aspects of their spectroscopic features. We show that the FTIR spectra in both the OH-stretching region and in the lattice modes region can be effective for rapid identification of the asbestos type.

Mineralogy and textures of riebeckitic asbestos (crocidolite): The role of single versus agglomerated fibres in toxicological experiments.

Asbestos may cause adverse effects, but relationship between mineralogy and texture of fibres versus toxicity is still lacking. Toxicological studies can be interpreted and compared only if quantitative features of fibres are determined. Here, riebeckitic ("crocidolite") amphibole fibres were analysed by XRPD, FTIR, SEM-EDS and EMP-WDS; only crystals with stochiometry A□BNa2C(Fe2+2.5Mg0.5)CFe3+2TSi8O22W(OH)2 are present in the starting material used for the experiments. Fibres deposited from solutions of 0.1, 1, 10, 25, 50, 75 and 100mg/L were counted by image analysis using SEM images. At 0.1 and 1mg/L the fibres are well separated, whereas between 1 and 10mg/L they start to agglomerate. In-vitro tests performed on fibres deposited at the same mg/L concentrations show that the toxic potential follows a curvilinear increasing trend with a decreasing rate. Since the range of sizes of single fibres and their mineralogy are constant, this decreasing rate can be only attributed to the increasing amount of agglomerated fibres. Hence, single versus agglomerated fibre population is a factor that cannot be neglected in defining the final adverse effects of asbestos. The analytical protocol proposed here is valuable for any aero-dispersed dust, in polluted environments, as well as in the interpretation of experimental studies.