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The INGV monitoring system operating in the volcano Island since three decades, recorded a new phase of unrest at the La Fossa volcano since September 2021. The main set of the crisis was the central hydrothermal system, deeply affected by the input of heat and chemicals from the magmatic source. The Levante Bay, located northwest of the La Fossa edifice, is a thermal area, where the vapor, coming from a local hydrothermal aquifer, is emitted from several low temperature (100°C) fumaroles along the beach and in the near off shore. The composition of the gas is typical of hydrothermal systems, and indicates equilibrium at temperature close to 200°C. By the onset of the crisis, in September 2021, the composition of the gas emitted from these fumaroles showed a smooth trend of increasing contribution of the magmatic gas. In May 2022, a sudden release of gas occurred in the Levante Bay, which was testified by the whitening of the seawater in the bay, due the formation of sulfur flakes, and by the appearance of typical pockmark structures on the seafloor. The drastic increase of the gas flux from the underwater gas vents, coupled to the presence of the pockmarks, suggested that an explosive emission of gas occurred in May 2022. The chemical and isotopic composition (He and C isotopes) of the gas emitted from the fumaroles revealed the prevailing presence of the magmatic component, closely approaching the composition of the gas emitted from crater fumaroles. This episode drove the attention of the scientific community to this area, currently affected by a significant input of the magmatic vapor, because of the risk related to the huge gas emission and the eventual overpressurization of the local hydrothermal aquifer.

In September 2021, the La Fossa volcano entered a new phase of unrest. The monitoring system, operating in the island since late ‘80s, recorded a sudden variation in seismicity, ground deformation, fumarole temperatures, soil and plume degassing. These variations were interpreted as due to the fast vaporization and expansion of the hydrothermal system (Federico et al., submitted), hypothesized at depth > 1.5 km bsl. At the same time, fumarole chemistry showed clear-cut variations, related to the dominant contribution of the magmatic gas over the hydrothermal one. The CO2 content and the helium isotope composition of the magmatic source revealed the appearance of a more primitive magma, compared to that feeding the fumaroles in the previous period, during the climax of the unrest. The signs of the enhanced contribution of magmatic gases in the fumarolic gases was already evident since 2018, so the 2021 unrest appears to have been the outcome of a long lasting preparatory phase. The systematics of gas species together with C and He isotopes, emitted from fumaroles after the first months of the unrest, revealed the appearance of a different magmatic component, poorer in N2, 3He and richer in He, S and 13C. The magmatic contribution is persistently overwhelming the hydrothermal one by the time of this communication.

Greece belongs to the most geodynamically active regions of the world and as such, it has to be considered an area of intense geogenic degassing. In terms of carbon, the territory is characterized by the high hydrothermal and volcanic activity of the South Aegean Active Volcanic Arc (SAAVA), and by widespread geological seeps of buried carbon dioxide and methane. In the present work, we investigate the island of Gyali located in the volcanic system Kos-Gyali-Nisyros. Nine gas samples have been collected on the island of Gyali in areas found both on land, in a small lake (∼2000 m2) along its beach, and in the sea close to the shore at shallow depths (

This study presents the first hydrogeochemical model of the hydrothermal systems of Turrialba and Irazú volcanoes in central Costa Rica, manifested as thermal springs, summit crater lakes, and fumarolic degassing at both volcanoes. Our period of observations (2007-2012) coincides with the pre- and early syn-phreatic eruption stages of Turrialba volcano that resumed volcanic unrest since 2004, after almost 140 years of quiescence. Peculiarly, the generally stable Irazú crater lake dropped its level during this reawakening of Turrialba. The isotopic composition of discharged fluids reveals the Caribbean meteoric origin; a contribution of “andesitic water” for Turrialba fumaroles up to ~50% is suggested. Four groups of thermal springs drain the northern flanks of Turrialba and Irazú volcanoes into two main rivers. Río Sucio (i.e. “dirty river”) is a major rock remover on the North flank of Irazú, mainly fed by the San Cayetano spring group. Instead, one group of thermal springs discharges towards the south of Irazú. All thermal spring waters are of SO4-type (i.e. steam heated waters), although none of the springs has a common hydrothermal end-member. A water mass budget for thermal springs results in an estimated total output flux of 187 ± 37 L/s, with 100 ± 20 L/s accounted for by the San Cayetano springs. Thermal energy release is estimated at 110 ± 22 MW (83.9 ± 16.8 MW by San Cayetano), whereas the total rock mass removal rate by chemical leaching is ~3,000 m3/y (~2,400 m3/y by San Cayetano-Río Sucio). Despite Irazú being the currently less active volcano, it is a highly efficient rock remover, which, on the long term can have effects on the stability of the volcanic edifice with potentially hazardous consequences (e.g. flank collapse, phreatic eruptions). Moreover, the vapor output flux from the Turrialba fumaroles after the onset of phreatic eruptions on 5 January 2010 showed an increase of at least ~260 L/s above pre-eruptive background fumarolic vapor fluxes. This extra vapor loss implies that the drying of the summit hydrothermal system of Turrialba could tap deeper than previously thought, and could explain the coincidental disappearance of Irazú’s crater lake in April 2010.

Since 1978 water chemistry of the Laguna Caliente crater lake has been used to monitor volcanic activity at Poas, Costa Rica, making it arguably the best studied hyper-acidic crater lake on Earth. During these 39 years, three phases of unrest occurred, manifested through frequent phreatic eruptions, with each a duration of several years to over a decade (1978–1980, 1986–1996, 2006–2016). We here present a novel technique to deal with the long time series of the chemical composition of water of Laguna Caliente, independent on previous deterministic research and resulting conceptual models. Common patterns of chemical parameters in relation with phreatic eruptive activity for the period 1978–September 2014 are sought, applying the objective statistical method of Pattern Recognition. This resulted in the definition of the strongest precursory signals and their respective thresholds. Numerical outcomes often confirm findings based on geochemical models (e.g. SO4, SO4/Cl and pH are strong monitoring parameters). However, some surprising parameters (opposite behavior of Mg/Cl ratios, decreases in Ca and Mg concentrations, increasing Al/Mg ratios) still need a geochemical explanation and should be a focus for future research strategies. The obtained parameters and thresholds were retrospectively applied for the “test period” of the Pattern Recognition method (November 2014–February 2016). This test provided hints that suggested that eruptive activity at Poas was not yet over, despite apparent quiescence in early 2016. Indeed, after new phreatic eruptions since May 2016, the 2006–2016 phreatic eruptive cycle culminated in phreatomagmatic activity in April 2017. We conclude that evaluating time series of chemical composition of crater lakes framed in the Pattern Recognition method can be a useful monitoring approach. Moreover, increased sampling frequency can provide more details and more adequate prediction of phreatic activity at Poas. Comparing Laguna Caliente with other two well monitored acidic crater lakes (Ruapehu Crater Lake, New Zealand and Yugama, Kusatsu-Shirane, Japan) Poas results unique in many ways and undoubtedly the most active crater lake of the three during the past four decades.

La Caldera Cerro Blanco (CBC) es el sistema de calderas colapsadas más joven de los Andes Centrales Sur (Puna Sur, Argentina). El CBC está disminuyendo a una velocidad promedio de 0,87 cm / año y alberga un sistema geotérmico activo. Se realizó una caracterización geoquímica de los fluidos emitidos a partir de las composiciones químicas e isotópicas de fumarolas y manantiales térmicos y fríos vertidos en esta zona volcánica con el objetivo de construir el primer modelo conceptual hidrogeoquímico y realizar una estimación preliminar del potencial geotérmico. El reservorio hidrotermal principal, probablemente alojado dentro de las rocas del basamento pre-caldera, tiene un Na + -Cl ˉ (HCO 3 ) ˉcomposición con temperaturas estimadas ≥135 ° C. La ignimbrita de Cerro Blanco no consolidada y de grano fino probablemente actúa como la capa de roca del sistema hidrotermal. La presencia de brechas de erupción freática en el área circundante de las fumarolas geotérmicas respalda la efectividad del depósito piroclástico como rocas de sellado. Los datos isotópicos del agua (δ 18O y δD) indican una recarga meteórica del embalse hidrotermal, sugiriendo como áreas de recarga los sectores aledaños al CBC, principalmente hacia el W y NW donde existen grandes afloramientos del basamento precaldera. Se propone una conexión hidráulica controlada por falla entre las aguas termales y el embalse hidrotermal para el área de Los Hornitos. Las fumarolas muestran las características compositivas típicas de los fluidos hidrotermales, estando dominadas por el vapor de agua con concentraciones significativas de H 2 S, CH 4 y H 2. Teniendo en cuenta el alto gradiente geotérmico de esta área (∼104 ​​° C / km) y la fracción relativamente alta de He del manto (∼39%) calculada sobre la base de los valores R / Ra medidos, el acuífero hidrotermal probablemente reciba aportes de fluidos magmáticos. de la cámara de magma de desgasificación. El potencial geotérmico preliminar en CBC se evaluó con el Método de Volumen, calculando hasta E = 11.4 * 10 18 J. Tanto la escasa presencia de manifestaciones térmicas superficiales como la ocurrencia de una capa de roca eficiente probablemente contribuyan a minimizar la pérdida de energía térmica del reservorio. Los resultados aquí presentados constituyen la base de conocimiento necesaria para una evaluación más precisa del potencial geotérmico y, en última instancia, la implementación del recurso geotérmico como una alternativa energética viable para pequeñas localidades o instalaciones mineras aisladas del Sistema Interconectado Nacional debido a su localización remota. Fil: Chiodi, Agostina Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina Fil: Tassi, Franco. Università degli Studi di Firenze; Italia. Institute of Geosciences and Earth Resource; Italia Fil: Báez, Walter Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina Fil: Filipovich, Ruben Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina Fil: Bustos, Emilce. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina Fil: Glok Galli, Melisa. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Tandil. Sede Tandil del Centro de Investigaciones En Fisica E Ingenieria del Centro de la Provincia de Buenos Aires.; Argentina Fil: Suzaño, Nestor Omar. Universidad Nacional de Jujuy; Argentina Fil: Ahumada, Maria Florencia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina Fil: Viramonte, Jose German. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Salta. Instituto de Bio y Geociencias del NOA. Universidad Nacional de Salta. Facultad de Ciencias Naturales. Museo de Ciencias Naturales. Instituto de Bio y Geociencias del NOA; Argentina Fil: Giordano, Guido. Università Roma Tre Iii.; Italia. Consiglio Nazionale delle Ricerche; Italia Fil: Pecoraino, Giovannella. Istituto Nazionale di Geofisica e Vulcanologia; Italia Fil: Vaselli, Orlando. Istituto Di Geoscienze e Georisorse; Italia. Consiglio Nazionale delle Ricerche; Italia

The shallow vertical temperature profile has been measured in the proximity of an eruptive fissure far about 4 km north-northeast from Mt. Etna central craters. The monitoring site was a steam-heated soil lying between a group of flank fractures on the upper northeast flank of Mt. Etna (Italy), i.e., on the northeast rift. We chose this area because it was close to an eruptive fissure, that opened in 2002 and extended from about 2500 to about 1500 m a.s.l., with our aim being to determine a connection between this fracture system and the ongoing volcanic activity. Heat flux anomalies from the ground from September 2009 to September 2012 were evaluated. Changes in the hydrothermal release—which can be related to variations in volcanic activity—are discussed and compared to the published geophysical data. The heat flux ranges varied during the pre-eruptive (from about 7 to 38 W × m−2), syn-eruptive (from about 3 to 49 W × m−2), and post-eruptive phases, with the heat released being lowest at the latter phase (from about 1 to 20 W × m−2). Moreover, the heat flux time variation was strongly correlated with the eruption rate from the new southeast crater between January 2011 and April 2012. The migration of magma through active conduits acts as a changing heating source for steam-heated soils located above the active fractures. Our findings suggest that tracking the heat flux above active fractures constitutes a useful investigation field for low-cost thermal monitoring of volcanic activity. Time variations in their emissions could highlight the relationship between a hydrothermal circuit and the local network of fractures, possibly indicating variation in the structural weakness of a volcanic edifice. Continuous monitoring of heat flux, combined with a realistic model, would contribute to multidisciplinary investigations aimed at evaluating changes in volcano dynamics.

project CGL2005-07509/CLI, Ministry of Education and Science of Spain; DPC-INGV project FLANK; Istituto Nazionale di Geofisica e Vulcanologia — Osservatorio Etneo, Sezione di Catania

In the period July 2005-October 2006 several soil gas prospections were performed on the island of Pantelleria, an active volcanic/geothermal system at present in a quiescent state. Measured parameters were CO2 concentrations and Rn-220 and Rn-222 activities at 50 cm depth and CO2 fluxes from the soil. The whole island was covered with a measurement density of 3.5 points/km(2) for CO2 (flux and concentration) and 1.6 points/km(2) for Rn. Further three main and seven minor areas of previously ascertained or expected exhalative activity were covered with a measurement density up to 100 points/km(2). The obtained results ranged from 0.038 to 95%vol for CO2 concentration, from 10 Bq/m(3) to 164,0008 Bq/m(3) from 10 Bq/m(3) to 750,000 Bq/m(3) for Rn-220 and Rn-222 activities, respectively and from

This study presents the chemical and isotopic compositions of hydrothermal gases from fumaroles discharging around Copahue volcano (Argentina). Gas samples, including those from two fumaroles at the active summit crater, were collected during 13 surveys carried out by different research teams from 1976 to February 2016. The time-series of H2, CO and light hydrocarbons showed episodic increases related to the main events of the last eruptive cycle that started on 19 July 2012. Concentration peaks were likely caused by enhanced input of hot magmatic fluids affecting the hydrothermal reservoir. These data contrast with the temporal variations shown by Rc/Ra and δ13C-CO2 values in 2012–2014, which indicated an increasing input from a crustal fluid source. In 2015–2016, however, these isotopic parameters showed opposite trends; their composition became closer to that of the two summit fumaroles, which possibly corresponds to that of the deep magmatic-related end-member. The delayed and reduced compositional changes in the peripheral hydrothermal fluid discharge in response to the 2012–2016 eruptive events suggest that geochemical surveys of these emissions are unlikely to provide premonitory signals of volcanic unrest if the volcanic activity remains centered in the main crater. Instead, an instrument which is able to provide measurements of volcanic gases in the air (e.g. MultiGAS) may be used to detect changes at the summit crater. Otherwise, monitoring of seismic activity and ground deformation, as well as the periodic measurement of the chemistry of the water in the Rio Agrio, which is fed by thermal discharge from the summit crater, seem to represent the most reliable means of monitoring at Copahue. However, the relative compositional stability of the hydrothermal reservoir is a great advantage in terms of geothermal resource exploitation and could encourage new investments in the Copahue geothermal project which was abandoned in the 1990s. Fil: Tassi, F.. Consiglio Nazionale delle Ricerche; Italia. Università degli Studi di Firenze; Italia Fil: Agusto, Mariano Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Estudios Andinos "Don Pablo Groeber". Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Estudios Andinos "Don Pablo Groeber"; Argentina Fil: Lamberti, María Clara Isabel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Estudios Andinos "Don Pablo Groeber". Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Estudios Andinos "Don Pablo Groeber"; Argentina Fil: Caselli, Alberto Tomás. Universidad Nacional de Río Negro; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Pecoraino, G.. Istituto Nazionale Di Geofisica E Vulcanologia; Italia Fil: Caponio, Cecilia. Università degli Studi di Firenze; Italia Fil: Szentivanyi, Juliana Maria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Estudios Andinos "Don Pablo Groeber". Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Estudios Andinos "Don Pablo Groeber"; Argentina Fil: Venturi, S.. Consiglio Nazionale delle Ricerche; Italia. Università degli Studi di Firenze; Italia Fil: Vaselli, O.. Consiglio Nazionale delle Ricerche; Italia. Università degli Studi di Firenze; Italia

Herein we report on the chemical and isotopic (C, H, O, and He) compositions of the fluids from La Fossa crater fumaroles of Vulcano from 1999 to 2010. Consistent with records obtained since the end of the 1980s, our data show that the geochemical features of the fumarole system have experienced several episodes of remarkable change, each lasting no more than a few months. Typical signatures of these short-term anomalies are large increments in CO 2 , N 2 , and He concentrations, coupled to increased 13 C/ 12 C isotopic ratios, but their meaning remains widely debated. Within a model of fumarolic fluids based on mixing between hydrothermal and magmatic endmembers, we have developed a novel approach to constrain chemical (He/CO 2 and N 2 /He) and isotopic ( 13 C/ 12 C, D/H, and 3 He/ 4 He) ratios of the magmatic endmember during the short-term anomalies. Although much of the geochemical variability in fumaroles results from changes in mixing proportions, the magmatic fluid unquestionably shows significant variations in time. The magmatic He/CO 2 , N 2 /He, 13 C/ 12 C, and 3 He/ 4 He values throughout 1988–1996 differed from those feeding the anomaly at the end of 2004. Early clues of the new magmatic fluid appeared in 1998–1999, far from any short-term anomaly, whereas new and old magmatic fluids coexisted after 2004. We quantitatively prove that the detected geochemical changes are consistent with the degassing path of a magma having a latitic composition, and suggest the presence of two magma ponding levels at slightly different pressures, where bubble–melt decoupling can occur. The different He-isotope compositions at these levels suggest low hydraulic connectivity typical of a complex reservoir with dike and sill structures. In this framework, the short-term geochemical anomalies are probably due to gas accumulation at the top of magma bodies followed by massive escape, or activation of new degassing levels in the reservoir, for which the stress field almost certainly plays a key role. Such a scenario explains the observed increases in both fumarole output and shallow high-frequency seismicity (due to increased pore pressure) during the anomalies, while being consistent with the concomitant absence of any deep seismicity or ground deformation, eventually related to magma movement.

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below the legal threshold. Overall, the Fl/Fl + Py diagnostic ratio revealed that PAHs had a petrogenic origin. VOC levels, except for two notable exceptions near Palermo landfill, were always below the legal limit. As concerns PCB levels, several samples were found positive with levels exceeding the legal limits. It is worth noting that the % PCB distribution differs from that of commercial compositions. In parallel, some samples of groundwater containing PCDDs and PCDFs exceeding the legal threshold were also found. Among the 17 congeners monitored, the most abundant were the highest molecular weight ones.

The Domuyo volcanic complex (Neuquén Province, Argentina) hosts one of the most promising geothermal systems of Patagonia, giving rise to thermal manifestations discharging hot and Cl−-rich fluids. This study reports a complete geochemical dataset of gas and water samples collected in three years (2013, 2014 and 2015) from the main fluid discharges of this area. The chemical and isotopic composition (δD-H2O and δ18O-H2O) of waters indicates that rainwater and snow melting are the primary recharge of a hydrothermal reservoir located at relative shallow depth (400–600 m) possibly connected to a second deeper (2–3 km) reservoir. Reactive magmatic gases are completely scrubbed by the hydrothermal aquifer(s), whereas interaction of meteoric waters at the surface causes a significant air contamination and dilution of the fluid discharges located along the creeks at the foothill of the Cerro Domuyo edifice. Thermal discharges located at relatively high altitude (~ 3150 m a.s.l.), namely Bramadora, are less affected by this process, as also shown by their relatively high R/Ra values (up to 6.91) pointing to the occurrence of an actively degassing magma batch located at an unknown depth. Gas and solute geothermometry suggests equilibrium temperatures up to 220–240 °C likely referred to the shallower hydrothermal reservoir. These results, confirming the promising indications of the preliminary surveys carried out in the 1980′s, provide useful information for a reliable estimation of the geothermal potential of this extinct volcanic system, although a detailed geophysical measurements is required for the correct estimation of depth and dimensions of the fluid reservoir(s). Fil: Tassi, F.. Consiglio Nazionale delle Ricerche; Italia. Università degli Studi di Firenze; Italia Fil: Liccioli, Caterina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Estudios Andinos ; Argentina. Universidad de Buenos Aires. Facultad de Cs.exactas y Naturales. Departamento de Ciencias Geológicas. Grupo de Estudio y Seguimiento de Volcanes Activos; Argentina Fil: Agusto, Mariano Roberto. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina Fil: Chiodini, Giovanni. Istituto Nazionale Di Geofisica E Vulcanologia; Italia Fil: Vaselli, O.. Università degli Studi di Firenze; Italia Fil: Calabrese, S.. Istituto Nazionale Di Geofisica E Vulcanologia; Italia Fil: Pecoraino, G.. Università degli Studi di Firenze; Italia Fil: Tempesti, L.. Università degli Studi di Firenze; Italia Fil: Caponio, Cecilia. Istituto Nazionale Di Geofisica E Vulcanologia; Italia Fil: Fiebig, J.. Università degli Studi di Firenze; Italia Fil: Caliro, S.. Università degli Studi di Firenze; Italia Fil: Caselli, Alberto Tomás. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte. Instituto de Investigación en Paleobiología y Geología; Argentina

The geochemical behaviour of Rare Earth Elements, Zr and Hf was investigated in the thermal waters of Nevado del Ruiz volcano system. A wide range of pH, between 1.0 and 8.8, characterizes these fluids. The acidicwaters are sulphate dominatedwith different Cl/SO4 ratios. The important role of the pH and the ionic complexes for the distribution of REE, Zr a nd Hf in the aqueous phase was evidenced. The pH rules the precipitation of authigenic Fe and Al oxyhydroxides producing changes in REE, Zr, Hf amounts and strong anomalies of Cerium. The precipitation of alunite and jarosite removes LREE from the solution, changing the REE distribution in acidic waters. Y-Ho and Zr-Hf (twin pairs) have a different behaviour in strong acidic waterswith respect to the water with pH near-neutral. Yttrium and Ho behave as Zr and Hf in waters with pH near neutral-to-neutral, showing superchondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate (Fe-, Al-oxyhydroxides), suggesting an enhanced scavenging of Ho and Hf with respect to Y and Zr, leading to superchondritic values. In acidic waters, a different behaviour of twin pairs occurs with chondritic Y/Ho ratios and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf were investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anion chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH < 3.6. In strong acidic waters the fractionation of Zr and Hf was recognized as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.

Chemical and isotopic analyses of the main gas manifestations of the island of Pantelleria (Italy) were used to gain insight on the origin of the released methane. Results indicate that the most probable origin is through abiogenic reactions within the hydrothermal system. Methane and CO 2 flux measurements from the soils were made with the accumulation chamber method in an area of about 0.015 km 2 within the main fumarolic area of the island (Favara Grande). The 23 measurements range from − 34 to 3550 mg m −2 d − 1 for CH 4 and from 0.6 to 379 g m − 2 d − 1 for CO 2 . The relationships between CH 4 and CO 2 fluxes and the CH 4 /CO 2 ratios in the gases collected between the depths of 25 and 100 cm provide evidence for methanotrophic processes within the soils. Methane output for the surveyed area was calculated to be 2.5 t a − 1 and extrapolated to about 5–10 t a − 1 for the entire volcanic/hydrothermal system of the island. Previous higher estimates of the CH 4 output at Pantelleria (Etiope et al., 2007, J. Volcanol. Geotherm. Res., 165, 76–86) were based on soil CO 2 output and CH 4 /CO 2 ratios in fumarolic gases; the present work provides the first direct CH 4 flux data and it suggests that methanotrophic activity in the soil could be substantial in reducing the CH 4 emission to the atmosphere.

Alkaline lakes like the hydrothermally affected lake Specchio di Venere (Pantelleria Island, Central Mediterranean) are typical geological settings harbouring calcified microbial mats. The present work is focused on the discrimination between biotic and abiotic processes driving carbonate precipitation in this lake, using hydrochemical, mineralogical and isotopic data. Hydrochemical analyses demonstrate that the lake is nearly 10−fold supersaturated with regard to aragonite and seasonally reaches hydromagnesite supersaturation. Microscopic observations depict organosedimentary laminated structures consisting of microbial communities and aragonitic precipitates, which are rather disseminated in pores than directly linked to microorganisms. Oxygen isotopic data indicate that authigenic carbonate crystallisation from evaporating water is the dominant precipitation process, further suggested by the absence of textural evidence of diagenetic processes. Conversely, the observed δ13C values reflect an influence of extracellular polymeric substances (EPS) on carbon fractionation during the precipitation process, due to the selective sequestration of 12C in the biomass. The above considerations suggest that at lake Specchio di Venere the carbonate precipitation is mainly of inorganic nature, but a minor role played by biologically influenced processes in microbial mats is not excluded.

Volcanic emissions represent one of the most relevant natural sources of trace elements to the troposphere. Due to their potential toxicity, they may have important environmental impacts from local to global scale. They can also severely affect the atmospheric and terrestrial environment at timescales ranging from a few to millions of years. Mt. Etna volcano is known as one of the largest global contributors of magmatic gases (CO2, SO2 and halogens) and particulate matter, including some toxic trace elements. The aim of this study is to characterize the chemical composition and the mineralogical features of the volcanogenic aerosol passively emitted from Mt. Etna. Twenty-five samples were collected by filtration technique from different sites between 2008 and 2014. Chemical and mineralogical analyses allowed to discriminate two main constituents: the first is mainly referable to the silicate component in the volcanic plume, like lithic, juvenile fragments or glass shards and crystals (e.g. plagioclases, pyroxenes, oxides); the second constituent consists of soluble compounds like sulphosalts or halide minerals (sulphates, chlorides and fluorides). Fluxes of major and trace metals emitted in the atmosphere have been estimated. By comparing the Etnean trace elements with those from European anthropic emissions, we conclude that Mt. Etna is the main persistent point source of major and trace metals in the Mediterranean region. Results gathered from this investigation is of fundamental importance due to the exposure and potential impact of harmful chemical compounds for hundred thousand tourist visits each year to the summit of Mt. Etna.

This paper documents arsenic concentrations in 157 groundwater samples from the island of Ischia and the Phlegrean Fields, two of the most active volcano-hosted hydrothermal systems from the Campanian Volcanic Province (Southern Italy), in an attempt to identify the environmental conditions and mineral-solution reactions governing arsenic aqueous cycling. On Ischia and in the Phlegrean Fields, groundwaters range in composition from NaCl brines, which we interpret as the surface discharge of deep reservoir fluids, to shallow-depth circulating fluids, the latter ranging from acid-sulphate steam-heated to hypothermal, cold, bicarbonate groundwaters. Arsenic concentrations range from 1.6 to 6900 μg·l- 1 and from 2.6 to 3800 μg·l- 1 in the Phlegrean Fields and on Ischia, respectively. They increase with increasing water temperature and chlorine contents, and in the sequence bicarbonate groundwaters < steam-heated groundwaters < NaCl brines. According to thermochemical modeling, we propose that high As concentrations in NaCl brines form after prolonged water-rock interactions at reservoir T, fO2 and fH2S conditions, and under the buffering action of an arsenopyrite + pyrite + pyrrhotite rock assemblage. On their ascent toward the surface, NaCl brines become diluted by As-depleted meteoric-derived bicarbonate groundwaters, giving rise to hybrid water types with intermediate to low As contents. Steam-heated groundwaters give their intermediate to high As concentrations to extensive rock leaching promoted by interaction with As-bearing hydrothermal steam. © 2005 Elsevier B.V. All rights reserved.

The total amount of CO2 released at Ischia Island has been estimated from soil gas flux measurements and from chemical composition of the gases released by fumaroles or dissolved in groundwaters. The preliminary results indicate an overall CO2 output of about 15 kg s-1 from the entire island (46 km2). The main contribution to the total output from diffuse soil degassing is about 14.8 kg s-1, followed by dissolved CO2 of about 0.3 kg s-1. The contribution of fumaroles to the total output was found to be negligible (about 0.03 kg s-1). Ischia's output, although being considerably less than that of open conduit volcanoes, is higher than many other volcanic systems, especially those related to volcanic arcs. The recent tensile tectonic regime of the area allows probably an easier upflow of CO2 from the mantle sustaining the diffuse degassing of the island.

Among surface waters, lakes in volcanic areas display the greatest range in pH values: from negative values up to about 12. The present chapter is a short review of the main features of alkaline lakes, which belong to the high-pH part of this range. They are characterised by saline or hypersaline waters, pH values higher than 9 and high Na+, HCO3 − and CO3 2− and low Ca2+ concentrations. Alkaline lakes are found in quiescent or recently extinct volcanic areas where neither water vapour nor acidic magmatic gases can reach surface waters. Their occurrence depends on peculiar climatic and geological conditions that allow evaporative concentration of the water (potentially evaporation much higher than water inputs and in endorheic basins) and on geochemical factors that favour a chemical evolution towards an alkaline environment (composition of the dilute input waters characterised by a ratio between total dissolved inorganic carbon and earth-alkaline elements much higher than 1). Such initial composition, due to evaporative concentration, after the deposition of earth-alkaline carbonate minerals, will lead to the above-mentioned typical composition. Alkaline lakes also host microbial communities sometimes characterised by extremely high productivity. These microbial communities are scientifically remarkable because they comprise some interesting extremophiles, which can grow not only at very high pH and salinity conditions but also in the presence of elevated concentrations of toxic elements (e.g. As, Se, Te).

Total CO2 output from fumaroles, bubbling and water dissolved gases and soil gases was investigated at Pantelleria Island volcano, Italy. The preliminary results indicate an overall output of 0.39 Mt a−1 of CO2 from the island. The main contribution to the total output was from diffuse soil degassing (about 0.32 Mt a−1), followed by dissolved CO2 (0.034 Mt a−1), focussed soil degassing (0.028 Mt a−1) and bubbling CO2 (0.013 Mt a−1). The contribution of CO2 from fumarole gases was found to be negligible (1.4×10−6 Mt a−1). Carbon-13 values for CO2 coupled with those for associated He in gases from fumaroles and sites of focussed soil degassing clearly rule out any significant organic CO2 component and suggest a common mantle origin for these gas species. The inferred mantle source beneath Pantelleria would seem to have peculiar geochemical characteristics, quite distinct from those of mantle producing MORB but compatible with those of magmatic sources of central Mediterranean and central European volcanoes. These findings indicate that the Pantelleria volcanic complex is a site of active mantle degassing that is worthy of attention for future geochemical surveillance of the island.

Between 1994 and 1995, gas samples from fumaroles and thermal waters were collected on Ischia Island. The chemical composition of the shallow and deep natural hydrothermal fluids discharged is related to the main hydrological and lithological characteristics of the rock formations present in the reservoir. A biphase reservoir (liquid+gas) is identified, where the dominant liquid has a temperature of about 280°C. On the basis of δ13CTDC values it was possible to hypothesize a deep source characterised by carbon isotopic values varying from 0 to −3δ‰. These values are noticeably more positive with respect to those attributed to magmatic CO2 (δ 13 C CO 2 ranging from −5 to −8δ‰), thus suggesting a magmatic source modified by crustal contamination. This hypothesis is supported by the carbon isotopic composition of CO2 in sampled gases, which varied from 0 to −5δ‰. The inferred isotopic value of carbon of magmatic CO2 would then be about −2δ‰. The observed differences in C isotopic composition between fumarolic and magmatic gases would be caused by kinetic and/or equilibrium fractionation processes. These processes would cause a fractionation of δ13C of deep CO2 towards more negative values (down to −5‰). Actually, CO2 removal or addition processes caused by the interaction between deep gases and shallow hydrothermal waters are likely to be responsible for the different chemical and isotopic compositions of gaseous emissions. For these reasons, and on the basis of the homogeneity of geothermometric values, the existence of a single, large reservoir that feeds all of the fluids discharged at Ischia Island can be hypothesised. Based on acquired data, a new geochemical model of the geothermal system of Ischia Island is proposed.

The results from measurements of extensive parameters (steam output and exhaling surface area) taken at the crater fumarolic field of Vulcano Island (Aeolian arc, southern Italy) are reported along with a detailed description of the measuring method. The steam emission rate increased by 1 order of magnitude during the observation time (1983–1995), while its concentration in the released gases was only slightly changed. During the same period the total exhaling surface expanded from 50 m2 to more than 2400 m2 and evolved following preferential trends that coincide with the main tectonic structures of the island. The observed peaks in steam output show a positive correlation with episodes of volcanic activity unrest. The temporal increase of steam output and the observed development in the exhaling surface areas are consistent with a volcano-tectonic triggering of the exhaling activity. Particularly, the peaks in the steam output are interpreted as a consequence of degassing from an active magma, slowly moving toward the surface.

[1] In this paper, fluid source(s) and processes controlling the chemical composition of volatile organic compounds (VOCs) in gas discharges from Mt. Etna and Vulcano Island (Sicily, Italy) were investigated. The main composition of the Etnean and Volcano gas emissions is produced by mixing, to various degrees, of magmatic and hydrothermal components. VOCs are dominated by alkanes, alkenes and aromatics, with minor, though significant, concentrations of O-, S- and Cl(F)-substituted compounds. The main mechanism for the production of alkanes is likely related to pyrolysis of organic-matter-bearing sediments that interact with the ascending magmatic fluids. Alkanes are then converted to alkene and aromatic compounds via catalytic reactions (dehydrogenation and dehydroaromatization, respectively). Nevertheless, an abiogenic origin for the light hydrocarbons cannot be ruled out. Oxidative processes of hydrocarbons at relatively high temperatures and oxidizing conditions, typical of these volcanic-hydrothermal fluids, may explain the production of alcohols, esters, aldehydes, as well as O- and S-bearing heterocycles. By comparing the concentrations of hydrochlorofluorocarbons (HCFCs) in the fumarolic discharges with respect to those of background air, it is possible to highlight that they have a geogenic origin likely due to halogenation of both methane and alkenes. Finally, chlorofluorocarbon (CFC) abundances appear to be consistent with background air, although the strong air contamination that affects the Mt. Etna fumaroles may mask a possible geogenic contribution for these compounds. On the other hand, no CFCs were detected in the Vulcano gases, which are characterized by low air contribution. Nevertheless, a geogenic source for these compounds cannot be excluded on the basis of the present data.

The present study illustrates the procedures applied for the coordinate system conversion of the historical fumarole positions at La Fossa crater, to allow their comparison with newly acquired global positioning system (GPS) data. Due to the absence of ground control points in the field and on both the old Gauss Boaga and the new UTM WGS 1984 maps, we had to model the transformation errors between the two systems using differential GPS techniques. Once corrected, the maps show a residual Easting shifting, due to erroneous georeferencing of the original base maps; this is corrected by morphological comparative methods. The good correspondence between the corrected positions of the historical data and the results of the new GPS survey that was carried out in 2009 highlights the good quality of the old surveys, although they were carried out without the use of accurate topographical instruments.

The complexity of volcano-hosted hydrothermal systems is such that thorough characterization requires extensive and interdisciplinary work. We use here an integrated multidisciplinary approach, combining geological investigations with hydrogeochemical and soil degassing prospecting, and resistivity surveys, to provide a comprehensive characterization of the shallow structure of the southwestern Ischia's hydrothermal system. We show that the investigated area is characterized by a structural setting that, although very complex, can be schematized in three sectors, namely, the extra caldera sector (ECS), caldera floor sector (CFS), and resurgent caldera sector (RCS). This contrasted structural setting governs fluid circulation. Geochemical prospecting shows, in fact, that the caldera floor sector, a structural and topographic low, is the area where CO2-rich (>40 cm3/l) hydrothermally mature (log Mg/Na ratios 150 g m−2 d−1), is clearly captured by electrical resistivity tomography (ERT) and transient electromagnetic (TEM) surveys as a highly conductive (resistivity 10,000 mg/l) and poorly conductive meteoric-derived (TDS < 4,000 mg/l) waters are observed, respectively. We finally integrate our observations to build a general model for fluid circulation in the shallowest (

Ischia volcano, in Central Italy, has long been known for its copious surface hydrothermal manifestations, signs of a pervasive circulation of hot fluids in the subsurface. Because of the significant chemical heterogeneity of fumarolic gas discharges and hot spring discharges, evidences of a complex hydrothermal setting, a definite model of fluid circulation at depth is currently unavailable, in spite of the several previous efforts. Here, we report on the chemical and isotopic composition of 120 groundwater samples, collected during several sampling surveys from 2002 to 2007. The acquired data suggest that the composition of surface manifestations reflect contributions from meteoric water, sea water, and thermal fluids rising from two distinct hydrothermal reservoir, with equilibrium temperatures of respectively ~ 150 °C and ~ 270 °C, and depths of 150–300 m and > 300 m (but possibly > 1000 m). We also make use of an isotopic characterization of the dissolved gas phase in thermal waters to demonstrate that the Ischia hydrothermal system is currently supplied by a deep-rising gas component (DGC), characterized by CO2 ~ 97.7 ± 1.2 vol.% (on a water-free basis), δ13CCO2 = − 3.51 ± 0.9‰, and helium isotopic ratio of about 3.5 Ra (3He/4He ratio normalized to the air ratio, Ra), likely magmatic in origin. An assessment of the thermal budget for Ischia hydrothermal system is also presented, in the attempt to derive a first estimate of the size and rate of degassing of the magmatic reservoir feeding the gas emissions. We calculate that a heat flow of about 153–222 MW presently drives hydrothermal circulation on the island, which we suggest is supplied in convective form (e.g., by the ascent of a high-T magmatic vapour phase) by complete degassing of 2.2–3.3 · 107 m3 yr− 1 of trachytic magma (with ~ 2.1 wt.% dissolved H2O content). If extrapolated to entire period of quiescence lasting since the Arso eruption in 1302 A.D., this volume corresponds to 1.6–2.3·1010 m3 of magma degassed in about 700 years of quiescent activity.

This work presents the results of an assessment of the existence and concentration of 13 volatile organic compounds (VOCs) in groundwaters from 14 hydrological basins in Sicily (25,710km (2)). On the basis of hydrological, hydrogeochemical and geological studies, 324 sampling points were selected. All groundwater sampled were collected twice, from October to December 2004 and from February to May 2005, and were analysed to determine the concentration and spatial distribution of the VOCs in the aquifers. The need to analyze a large number of samples in a short space of time so as to obtain quantitative analyses in trace concentration levels spurred us to create a new analytical method, both simple and sensitive, based on HS-SPME/GC/MS. The concentrations of VOCs measured in industrial and intensive agricultural unconfined aquifers were greater than those found in other aquifers. Tetrachloroethylene, chloroform, trichloroethylene and 1,2-dichloropropane were the most frequently detected VOCs. However, they exceeded the guideline values proposed by the EU in only three aquifers located near to industrial and intense agricultural areas.

This paper provides new data on sulfur, halogens, and minor and trace metal contents in airborne particulate matter from the Mt. Etna volcanic plume. Aerosol samples were collected by conventional filtration techniques before and during the summer 2001 eruption, in order to investigate relations between plume chemistry and volcano dynamics. Data analysis reveals that abundances of trace metals in the plume result from mixing of erosive and volatile components. The former is responsible for the contents of rare earth elements (REE), Ca, Ba, Sr, Ti, Sc, Y, Hf and Th; the latter contributes significantly to the abundance of Cs, Rb, Na and K, probably transported in the plume as metal halides, and Cd, Pb, Zn, Ge, Te, Mo, Re, Se, Sb, Sn, In, Bi, Tl, Cu and Au, associated with sulfur in plume particles. Enrichment factors show that plume particulate matter from the Monti Carcarazzi vent, which opened on the southern flank of the volcano in July 2001, is typically depleted in volatile trace elements with respect to the output from the summit crater, suggesting the secondary nature of the outpouring lavas. The decreasing trend observed throughout the eruption in the enrichment factors of most trace metals probably indicates a small-volume batch of magma with limited feed from depth.

] FiveyearsofgasmonitoringfromselectedsitessuggestthatMtEtna’splumbingsystemismuchmoreextensivethanpreviously reported. It extends at least 40 km SW from thevolcano’s boundary along the NE-SW regional fault, whereit discharges about 200 tons/day of gas, containing heliumwith mantle-type isotopic composition. Synchronousvariations of

[1] The recent eruption of Mount Etna (July 2001) offered the opportunity to analyze magma-derived volatiles emitted during pre- and syn-eruptive phases, and to verify whether their composition is affected by changes in volcanic dynamics. This paper presents the results of analyses of F, Cl and S in the volcanic plume collected by filter-packs, and interprets variations in the composition based on contrasting solubility in magmas. A Rayleigh-type degassing mechanism was used to fit the acquired data and to estimate Henry's solubility constant ratios in Etnean basalt. This model provided insights into the dynamics of the volcano. Abundances of sulfur and halogens in eruptive plumes may help predict the temporal evolution of an ongoing effusive eruption.

Several types of natural gas emissions (soil gas, low temperature fumaroles, gas bubbling in mud pools) were collected monthly on Mt. Etna volcano between July 2000 and July 2003 both from its summit and its flanks. Samples were analysed for the determination of the concentrations of CO2, CH4, He, H2, CO as well as the isotopic ratios of 13C/14C of CO2 (δ^13C) and He (R/Ra). The analysed gases were chemically divided into two groups: air-contaminated (from sites closer to the summit vents of Mt. Etna) and CO2-rich. Among the latter, samples from the lower SW flank of the volcano showed high contents of biogenic thermogenic and/or microbial CH4. Isotopic shift in the δ^13C values is caused by input of organic CO2 and/or by interaction between magmatic CO2 and shallow ground water as a function of water temperature and CO2 flux from depth. Based on a graphic method applied to δ^13C(subscript TDIC) of some ground water, the inferred isotopic composition of the pristine magmatic gas at Mt. Etna is characterised by δ^13C values ranging from -2 to -1‰. During the period July 2000-July 2003 significant variations were observed in many of the investigated parameters almost at all monitored sites. Seasonal influences were generally found to be negligible, with only a limited effect of air temperature changes on soil CO2 and ground temperature in only two of the air-contaminated sites. The largest chemical anomalies were observed in the air-contaminated sites, probably because of the strong buffering power of local ground water on gases released through the most peripheral areas where the CO2-rich sites are located. The anomalous changes observed during the study period can be explained in terms of progressive gas release from separate batches of magma that ascend towards the surface in a step-wise manner. Data relevant to the period following the 2002-03 eruption suggest that magma kept accumulating beneath the volcano, thus increasing the probability of a new large eruption at Mt. Etna.