A PTFE membrane for the in situ extraction of dissolved gases in natural waters: Theory and applications

A new method for extracting dissolved gases in natural waters has been developed and tested, both in the laboratory and in the field. The sampling device consists of a polytetrafluroethylene (PTFE) tube (waterproof and gas permeable) sealed at one end and connected to a glass sample holder at the other end. The device is pre-evacuated and subsequently dipped in water, where the dissolved gases permeate through the PTFE tube until the pressure inside the system reaches equilibrium. A theoretical model describing the time variation in partial gas pressure inside a sampling device has been elaborated, combining the mass balance and "Solution-Diffusion Model" (which describes the gas permeation process through a PTFE membrane). This theoretical model was used to predict the temporal evolution of the partial pressure of each gas species in the sampling device. The model was validated by numerous laboratory tests. The method was applied to the groundwater of Vulcano Island (southern Italy). The results suggest that the new sampling device could easily extract the dissolved gases from water in order to determine their chemical and isotopic composition

Continuous monitoring of hydrogen and carbon dioxide at Mt Etna

This study assessed the use of an H2 fuel cell as an H2-selective sensor for volcano monitoring. The resolution, repeatability, and cross-sensitivity of the sensor were investigated and evaluated under known laboratory conditions. A tailor-made device was developed and used for continuously monitoring H2 and CO2 at Mt Etna throughout 2009 and 2010. The temporal variations of both parameters were strongly correlated with the evolution of the volcanic activity during the monitoring period. In particular, the CO2 flux exhibited long-term variations, while H2 exhibited pulses immediately before the explosive activity that occurred at Mt Etna during 2010

Quantitative models of hydrothermal fluid–mineral reaction:The Ischia case

The intricate pathways of fluid–mineral reactions occurring underneath active hydrothermal systems are explored in this study by applying reaction path modelling to the Ischia case study. Ischia Island, in Southern Italy, hosts a well-developed and structurally complex hydrothermal system which, because of its heterogeneity in chemical and physical properties, is an ideal test sites for evaluating potentialities/limitations of quantitative geochemical models of hydrothermal reactions. We used the EQ3/6 software package, version 7.2b, to model reaction of infiltrating waters (mixtures of meteoric water and seawater in variable proportions) with Ischia’s reservoir rocks (the Mount Epomeo Green Tuff units; MEGT). The mineral assemblage and composition of such MEGT units were initially characterised by ad hoc designed optical microscopy and electron microprobe analysis, showing that phenocrysts (dominantly alkali–feldspars and plagioclase) are set in a pervasively altered (with abundant clay minerals and zeolites) groundmass. Reaction of infiltrating waters with MEGT minerals was simulated over a range of realistic (for Ischia) temperatures (95–260° C) and CO2 fugacities (10 ^-0.2 to 10^0.5) bar. During the model runs, a set of secondary minerals (selected based on independent information from alteration minerals’ studies) was allowed to precipitate from model solutions, when saturation was achieved. The compositional evolution of model solutions obtained in the 95–260°C runs were finally compared with compositions of Ischia’s thermal groundwaters, demonstrating an overall agreement. Our simulations, in particular, well reproduce the Mg-depleting maturation path of hydrothermal solutions, and have end-of-run model solutions whose Na–K–Mg compositions well reflect attainment of full-equilibrium conditions at run temperature. High-temperature (180–260° C) model runs are those best matching the Na–K–Mg compositions of Ischia’s most chemically mature water samples, supporting quenching of deep-reservoir conditions for these surface manifestations; whilst Fe, SiO2 and, to a lesser extent, SO4 contents of natural samples are better reproduced in low-temperature (95°C) runs, suggesting that these species reflect conditions of water–rock interaction in the shallow hydrothermal environment. The ability of model runs to reproduce the compositional features of Ischia’s thermal manifestations, demonstrated here, adds supplementary confidence on reaction path modelling as a realistic and insightful representation of mineral–fluid hydrothermal reactions. Our results, in particular, demonstrate the significant impact of host rock minerals’ assemblage in governing the paths and trends of hydrothermal fluids’ maturation

Numerical modelling of gas-water-rock interactions in volcanic-hydrothermal environment: the Ischia Island (Southern Italy) case study.

Hydrothermal systems hosted within active volcanic systems represent an excellent opportunity to investigate the interactions between aquifer rocks, infiltrating waters and deep-rising magmatic fluids, and thus allow deriving information on the activity state of dormant volcanoes. From a thermodynamic perspective, gas-water-rock interaction processes are normally far from equilibrium, but can be represented by an array of chemical reactions, in which irreversible mass transfer occurs from host rock minerals to leaching solutions, and then to secondary hydrothermal minerals. While initially developed to investigate interactions in near-surface groundwater environments, the reaction path modeling approach of Helgeson and co-workers can also be applied to quantitative investigation of reactions in high T-P environments. Ischia volcano, being the site of diffuse hydrothermal circulation, is an ideal place where to test the application of reaction-path modeling. Since its last eruption in 1302 AD, Ischia has shown a variety of hydrothermal features, including fumarolic emissions, diffuse soil degassing and hot waters discharges. These are the superficial manifestation of an intense hydrothermal circulation at depth. A recent work has shown the existence of several superposed aquifers; the shallowest (near to boiling) feeds the numerous surface thermal discharges, and is recharged by both superficial waters and deeper and hotter (150-260° C) hydrothermal reservoir fluids. Here, we use reaction path modelling (performed by using the code EQ3/6) to quantitatively constrain the compositional evolution of Ischia thermal fluids during their hydrothermal flow. Simulations suggest that compositions of Ischia groundwaters are buffered by interactions between reservoir rocks and recharge waters (meteoric fluids variably mixed - from 2 to 80% - with seawater) at shallow aquifer conditions. A CO2 rich gaseous phase is also involved in the interaction processes (fCO2 = 0.4-0.6 bar). Overall, our model calculations satisfactorily reproduce the main chemical features of Ischia groundwaters. In the model runs, attainment of partial to complete equilibrium with albite and K-feldspar fixes the Na/K ratios of the model solutions at values closely matching those of natural samples. Precipitation of secondary phases, mainly clay minerals (smectite and saponite) and zeolites (clinoptilolite), during the reaction path is able to well explain the large Mg-depletions which characterise Ischia thermal groundwaters; while pyrite and troilite are shown to control sulphur abundance in aqueous solutions. SiO2(aq) contents in model simulations fit those measured in groundwaters and are being buffered by the formation of quartz polymorphs and Si-bearing minerals. Finally, our simulations are able to reproduce redox conditions and Fe-depletion trends of natural samples. We conclude that reaction path modelling is an useful tool for quantitative exploration of chemical process within volcano-hosted hydrothermal systems

DEEP RESERVOIR TEMPERATURES OF LOW-ENTHALPY GEOTHERMAL SYSTEMS IN TUNISIA: NEW CONSTRAINTS FROM CHEMISTRY OF THERMAL WATERS

Tunisia is characterized by hot and warm groundwaters (temperature up to 75 °C) which represent the surface manifestation of geothermal systems hosted in carbonate-evaporite rock sequences. The T-conditions of Tunisia deep thermal reservoirs are here evaluated for the first time at the regional scale. The results here shown clearly highlight the limitations inherent in the application of common geothermometric methods in the estimation of equilibrium temperatures in sedimentary environments. The modeling approach proposed by Chiodini et alii (1995), which makes use of the ratios between dissolved HCO3, SO4 and F, provides the most reliable results, and allows us to derive equilibrium temperatures up to 200 °C for the Tunisian thermal reservoirs. Very high equilibrium pCO2 (100 bar) values are also estimated, likely indicative of the confined aquifer conditions

Real vs. immersive-virtual emotional experience: Analysis of psycho-physiological patterns in a free exploration of an art museum

[EN] Virtual reality is a powerful tool in human behaviour research. However, few studies compare its capacity to evoke the same emotional responses as in real scenarios. This study investigates psycho-physiological patterns evoked during the free exploration of an art museum and the museum virtualized through a 3D immersive virtual environment (IVE). An exploratory study involving 60 participants was performed, recording electroencephalographic and electrocardiographic signals using wearable devices. The real vs. virtual psychological comparison was performed using self-assessment emotional response tests, whereas the physiological comparison was performed through Support Vector Machine algorithms, endowed with an effective feature selection procedure for a set of state-of-the-art metrics quantifying cardiovascular and brain linear and nonlinear dynamics. We included an initial calibration phase, using standardized 2D and 360 degrees emotional stimuli, to increase the accuracy of the model. The self-assessments of the physical and virtual museum support the use of IVEs in emotion research. The 2-class (high/low) system accuracy was 71.52% and 77.08% along the arousal and valence dimension, respectively, in the physical museum, and 75.00% and 71.08% in the virtual museum. The previously presented 360 degrees stimuli contributed to increasing the accuracy in the virtual museum. Also, the real vs. virtual classifier accuracy was 95.27%, using only EEG mean phase coherency features, which demonstrates the high involvement of brain synchronization in emotional virtual reality processes. These findings provide an important contribution at a methodological level and to scientific knowledge, which will effectively guide future emotion elicitation and recognition systems using virtual reality.This work was supported by Ministerio de Economia y Competitividad de Espana (URL: http://www.mineco.gob.es/; Project TIN201345736-R and DPI2016-77396-R); Direccion General de Trafico, Ministerio Del Interior de Espana (URL: http://www.dgt.es/es/; Project SPIP2017-02220); and the Institut Valencia d'Art Modern (URL: https://www.ivam.es/).The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.Marín-Morales, J.; Higuera-Trujillo, JL.; Greco, A.; Guixeres, J.; Llinares Millán, MDC.; Gentili, C.; Scilingo, EP.... (2019). Real vs. immersive-virtual emotional experience: Analysis of psycho-physiological patterns in a free exploration of an art museum. 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Isotopic composition of the precipitations in the central Mediterranean: Origin marks and orographic precipitation effects

The isotopic composition of the rainfall in northwestern Sicily (Italy, central Mediterranean) was investigated in the period February 2002 to March 2003. A rain gauge network was installed and sampled monthly. The monthly values of the D and 18O ratios showed a wide range that reflected seasonal climatic variations. Mean weighted values were used to define an isotopic model of precipitation. Temporal variations in deuterium excess were also investigated. Using mean volume weighted values, the Local Meteoric Water Line (LMWL) can be represented by the equation: \u3b4D = 4.7\u3b418O - 8.2 (r2 = 0.96). Deuterium excess (d = \u3b4D - 8\u3b418O) was found to be strongly related to orography. The coastline samples were characterized by mean weighted deuterium excess values close to 12.5\u2030 samples from inland areas showed values of 169\u2030, while samples taken from the main reliefs showed values close to 19%\ub7 In inland areas, isotopic exchange between raindrops and moisture could shift the deuterium excess values slightly. On the higher reliefs, the interaction between falling raindrops and orographic clouds could shift the deuterium excess values significantly. The low slope of the LMWL could be referred to the high deuterium excess values of the higher sites and is related to orographic precipitation rather than to evaporation processes during the fall of the raindrops. The results obtained suggest that local orographic features may significantly change the isotopic composition of precipitation. Copyright 2006 by the American Geophysical Union

A New Web-Based Catalog of Earth Degassing Sites in Italy

Italy is a region characterized by intense and widespread processes of Earth degassing. High-temperature gases are released by crater plumes and fumaroles in volcanic environments throughout Italy. Also prevalent are numerous low-temperature gas emissions rich in carbon dioxide (CO2). These low-temperature emissions are located in a large area, mainly in the western sector of central and southern Ital