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Fil: Chiodini, Giovanni. Istituto Nazionale Di Geofisica E Vulcanologia. Italia. Fil: Liccioli, Caterina. Universidad Nacional de Rio Negro. Instituto de Investigaciones en Paleobiologia y Geologia; Argentina. Río Negro, Argentina Fil: Vaselli, Orlando. Universita Degli Studi Di Firenze; Italia Fil: Calabrese, Sergio. Università di Palermo; Italia Fil: Tassi, Franco. Universita Degli Studi Di Firenze; Italia Fil: Caliro, Stefano. Istituto Nazionale Di Geofisica E Vulcanologia; Italia Fil: Caselli, Alberto Tomás Universidad Nacional de Rio Negro. Instituto de Investigaciones en Paleobiologia y Geologia; Argentina. Río Negro, Argentina Fil: Agusto, Mariano R. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: D'alessandro, Walter. Istituto Nazionale Di Geofisica E Vulcanologia; Italia Fil: Liccioli, Caterina. Consejo Nacional de Investigaciones Científicas y Técnicas. Río Negro, Argentina. Fil: Caselli, Alberto Tomás Consejo Nacional de Investigaciones Científicas y Técnicas. Río Negro, Argentina. A geochemical survey of the main thermal waters discharging in the southwestern part of the Domuyo volcanic complex (Argentina), where the latest volcanic activity dates to 0.11 Ma, has highlighted the extraordinarily high heat loss from this remote site in Patagonia. The thermal water discharges are mostly Na-Cl in composition and have TDS values up to 3.78 g L− 1 (El Humazo). A simple hydrogeochemical approach shows that 1,100 to 1,300 kg s− 1 of boiling waters, which have been affected by shallow steam separation, flow into the main drainage of the area (Rio Varvarco). A dramatic increase of the most conservative species such as Na, Cl and Li from the Rio Varvarco from upstream to downstream was observed and related solely to the contribution of hydrothermal fluids. The equilibrium temperatures of the discharging thermal fluids, calculated on the basis of the Na-K-Mg geothermometer, are between 190 °C and 230 °C. If we refer to a liquid originally at 220 °C (enthalpy = 944 J g− 1), the thermal energy release can be estimated as high as 1.1 ± 0.2 GW, a value that is much higher than the natural release of heat in other important geothermal fields worldwide, e.g., Mutnovsky (Russia), Wairakei (New Zealand) and Lassen Peak (USA). This value is the second highest measured advective heat flux from any hydrothermal system on Earth after Yellowstone. A geochemical survey of the main thermal waters discharging in the southwestern part of the Domuyo volcanic complex (Argentina), where the latest volcanic activity dates to 0.11 Ma, has highlighted the extraordinarily high heat loss from this remote site in Patagonia. The thermal water discharges are mostly Na-Cl in composition and have TDS values up to 3.78 g L− 1 (El Humazo). A simple hydrogeochemical approach shows that 1,100 to 1,300 kg s− 1 of boiling waters, which have been affected by shallow steam separation, flow into the main drainage of the area (Rio Varvarco). A dramatic increase of the most conservative species such as Na, Cl and Li from the Rio Varvarco from upstream to downstream was observed and related solely to the contribution of hydrothermal fluids. The equilibrium temperatures of the discharging thermal fluids, calculated on the basis of the Na-K-Mg geothermometer, are between 190 °C and 230 °C. If we refer to a liquid originally at 220 °C (enthalpy = 944 J g− 1), the thermal energy release can be estimated as high as 1.1 ± 0.2 GW, a value that is much higher than the natural release of heat in other important geothermal fields worldwide, e.g., Mutnovsky (Russia), Wairakei (New Zealand) and Lassen Peak (USA). This value is the second highest measured advective heat flux from any hydrothermal system on Earth after Yellowstone.

We have analyzed the carbon isotopic composition of CO 2 , methane, ethane, propane and n-butane, the hydrogen isotopic composition of methane as well as total concentrations of gas constituents contained in the Mediterranean volcanic–hydrothermal discharges of Nisyros (Greece), Vesuvio, La Solfatara, Ischia and Pantelleria (all Italy) to determine the origin of the hydrocarbons. Isotopic criteria conventionally used for hydrocarbon classification suggest thermogenic origins, except for Pantelleria, for which an abiogenic origin is indicated. These findings would imply that thermogenic sources can provide methane/(ethane + propane) concentration ratios as high as those usually observed for microbial hydrocarbons. However, additional consideration of gas concentration data challenges the suitability of conventional criteria for the classification of hydrocarbons emanating from hydrothermal environments. Methane seems to be in close equilibrium with co-occurring CO 2 , whereas its higher chain homologues are not. Therefore, it cannot be excluded that methane on the one hand and ethane, propane and n-butane on the other hand have distinct origins. The carbon isotopic composition of methane might be controlled by the carbon isotopic composition of co-occurring inorganic CO 2 and by hydrothermal temperatures whereas the carbon isotopic composition of the higher n-alkanes could correspond to the maturity of organic matter and/or to the residence time of the gasses in the source system.

International audience; Along the Jordan Valley-Dead Sea Fault area several natural waters in springs, wells, and catchments occur. The chemical-physical characters of the studied waters allowed for the first time the investigation of the Zr and Hf geochemical behavior, apart from REE, extended to a wide range of Eh, temperature, salinity, and pH conditions. The results of this study indicate that the dissolved Zr and Hf distribution in natural waters is strongly influenced by redox conditions since these in turn drive the deposition of Fe-oxyhydroxides or pyrite. In oxidizing waters saturated or oversaturated in Fe-oxyhydroxides (Group 1), superchondritic Zr/Hf values are measured. On the contrary, in waters where Eh < 0 values occur (Group 2), chondritic Zr/Hf values are found. Superchondritic Zr/Hf values are produced by the preferential Hf scavenging onto Fe-oxyhydroxides that is inhibited under reducing conditions consistent with the water oversaturation relative to pyrite. Redox conditions also influence the amplitude of Ce and Eu anomalies. Oxidized Group-1 waters show negative Ce anomalies related to the oxidative Ce scavenging as CeO2 onto Fe-oxyhydroxide. Reduced Group-2 waters show positive Eu anomaly values consistent with the larger Eu2+ concentration relative to Eu3+ in these waters suggested by model calculations. The higher stability of Eu2+ with respect to its trivalent neighbors along the REE series can explain the above mentioned positive Eu anomaly values. The middle-REE enrichment observed in shale-normalized REE patterns of studied waters can be ascribed to carbonate and/or gypsum dissolution.

Real-time measurements of GEM and H2S discharged from natural and anthropogenic sources are a valuable tool to investigate the dispersion dynamics of these contaminants in air. In this study, a new approach to measure GEM and H2S concentrations in air, carried out by coupling a portable Zeeman atomic absorption spectrometer with high frequency modulation of light polarization (Lumex RA-915M) and a pulsed fluorescence gas analyzer (Thermo Scientific Model 450i), was applied to two distinct areas: (i) in the surroundings of Piancastagnaio (Siena, Central Italy), located in the eastern flanks of Mt. Amiata (a 200,000Âyears old volcano), where three geothermal plants are operating and whose exhaust gases are dispersed in the atmosphere after passing through the turbines and an abatement system to mitigate the environmental impact on air, and (ii) at Solfatara Crater (Campi Flegrei, Southern Italy), a volcanic apparatus characterized by intense hydrothermal activity. In 2014, seven GEM and H2S surveys were carried out in the two areas along pre-defined pathways performed by car at both the study sites. The lowest and highest recorded GEM and H2S concentrations at Piancastagnaio were up to 194 and 77Âng/m3, respectively, whilst at Solfatara Crater were up to 690 and 3392Âμg/m3, respectively. Although the GEM concentrations at Piancastagnaio were lower than the limit value recommended by local regulations for outdoor environment (300Âng/m3), they were almost one order of magnitude higher than the GEM background both in Tuscany (~Â3.5Âng/m3) and Mt. Amiata (3–5Âng/m3), suggesting that the main source of GEM was likely related to the geothermal plants. At Solfatara Crater, the highest GEM values were recognized in proximity of the main fumarolic gas discharges. As far as the H2S concentrations are concerned, the guideline value of 150Âμg/m3, recommended by WHO (2000), was frequently overcome in the study areas. Dot (in the surroundings of Piancastagnaio) and contour (at Solfatara Crater) maps for GEM and H2S concentrations built for each survey highlighted the important effects played by the meteorological parameters, the latter being measured by a Davis® Vantage Vue weather station. In particular, the GEM and H2S plumes were strongly affected by the wind speed and direction that were able to modify the dispersion of the two parameters in air in a matter of hours, indicating that the proposed analytical approach is able to produce a more realistic picture of the distribution of these air pollutants than that provided by using passive traps. Finally, the H2S/GEM ratio, calculated by normalizing the measured GEM and H2S concentrations to their highest values (nH2S/GEM), was used as a good proxy for the chemical-physical processes that these two gas species can suffer once emitted in the air. In particular, H2S resulted to be more affected by secondary processes than GEM, possibly related to photochemical oxidation reactions.

Duvalo “volcano” is a site of anomalous geogenic degassing close to Ohrid (North Macedonia) not related to volcanic activity, despite its name. CO2 flux measurements made with the accumulation chamber (321 sites over ∼50,000 m2) showed fluxes up to nearly 60,000 g m-2 d-1, sustaining a total output of ∼67 t d-1. Soil gas samples were taken at 50 cm depth from sites with high CO2 fluxes and analyzed for their chemical and isotope composition. The gas is mainly composed by CO2 (> 90%) with significant concentrations of H2S (up to 0.55 %) and CH4 (up to 0.32 %). The isotope compositions of He (R/RA 0.10) and of CO2 (δ13C ∼0‰) exclude significant mantle contribution, while δ13C-CH4 (∼ -35‰) and δ2H-CH4 (∼ -170‰) suggest a thermogenic origin for CH4. The area is characterized by intense seismic activity and Duvalo corresponds to an active tectonic structure bordering the Ohrid graben. The production of H2S within the stratigraphic sequence may be explained by thermochemical reduction of sulfate. The uprising H2S is partially oxidized to sulfuric acid that, reacting with carbonate rocks, releases CO2. The tectonic structure of the area favors fluid circulation, sustaining H2S production and oxidation, CO2 production and allowing the escape of the gases to the atmosphere. In the end, Duvalo represents a tectonic-related CO2 degassing area whose gases originate mostly, if not exclusively, in the shallowest part of the crust ( 1000 t km-2 d-1).

Geothermal areas of Greece are located in regions affected by recent volcanism and in continental basins characterised by elevated heat flow. Many of them are found along the coast, and thus, water is often saline due to marine intrusion. In the current study, we present about 300 unpublished and literature data from thermal and cold mineral waters collected along Greece. Samples were analysed for major ions, Li, SiO2 and isotopes in water. Measured temperatures range from 6.5 to 98 °C, pH from 1.96 to 11.98, while Total Dissolved Solutes (TDS) from 0.22 to 51 g/L. Waters were subdivided into four main groups: (1) thermal; (2) cold; (3) acidic (pH 11). On statistical basis, thermal waters were subdivided into subgroups according to both their temperature [warm ( 75 °C)] and TDS [low salinity ( 30 g/L)]. Cold waters were subdivided based on their pCO2 [low ( 0.85 atm)]. δ18O–H2O ranges from − 12.7 to + 2.7‰ versus SMOW, while δ2H–H2O from − 91 to + 12‰ versus SMOW being generally comprised between the Global Meteoric Water Line and the East Mediterranean Meteoric Water Line. Positive δ18O shifts with respect to the former are mostly related to mixing with seawater, while only for a few samples these shifts point to high-temperature water–rock interaction processes. Only a few thermal waters gave reliable geothermometric estimates, suggesting reservoir temperatures between 80 and 260 °C.

Twenty gas samples have been collected from the natural gas manifestations of Milos Island, the majority of which is found underwater along its coast. Furthermore, three anomalous degassing fumarolic areas (Kalamos, Paleochori and Adamas) have been recognized on-land. Almost all the gases are CO2-dominated with CO2 ranging from 88 to 99% vol for the samples taken underwater, while the on-land manifestations show a wider range (15–98%) due to air contamination. Methane reaches up to 1.0% vol, H2 up to 3.2% vol and H2S up to 3.5% vol indicating a hydrothermal origin of the gases. The isotope composition of He points out to mantle contributions up to 45%, while the C-isotope composition of CO2 (from −1.9 to +1.3‰ vs. V-PDB with most of the values around −0.5‰) suggests a prevailing limestone origin. Isotope composition of CH4, ranging from −18.4 to −5.0‰ vs. V-PDB for C and from −295 to +7‰ vs. V-SMOW for H, points to a geothermal origin with sometimes evident secondary oxidation processes. Additionally, CO2-flux measurements showed high values in the three fumarolic areas (up to 1100, 1500 and 8000 g/m2/d at Kalamos, Paleochori and Adamas respectively) with the highest CO2-flux values (up to about 23,000 g/m2/d) being measured in the sea at Kanavas with a floating chamber. The south-western part of the island was covered with a lower density prospection revealing only few anomalous CO2 flux values (up to 650 g/m2/d). The total output of the island (30.5 t/d) is typical of quiescent closed-conduit volcanoes and comparable to the other volcanic/geothermal systems of the south Aegean active volcanic arc (Nisyros, Kos, Nea Kameni, Methana and Sousaki).

A comprehensive hydrogeochemical study of the cold and thermal groundwaters of the presently quiescent volcanic system at Methana was undertaken that involved collecting 71 natural water samples. Methana is a peninsula in Peloponnesus, Greece whose arid climate and hydrological situation is similar to that of the nearby small islands of the Aegean Sea. Similarly, the chemical and isotopic compositions of its water are dominated by the mixing of seawater with meteoric water both through direct intrusion and meteoric recharge. However, the simple mixing trends at Methana are modified by water–rock interaction processes, enhanced by the dissolution of endogenous CO2, which lead to strong enrichments in alkalinity, Ca, Ba, Fe and Mn. The thermal waters show very high salinity that is sometimes close to that of seawater [total dissolved solids (TDS) = 8.5–40 g/l]. Although the cold groundwaters sometimes also show elevated TDS values (up to 6.3 g/l), their overall quality is acceptable due to the trace metal and nitrate contents mostly being below acceptable limits. While the saltiest groundwaters are not acceptable for human consumption, they are used for irrigation without exerting toxic effects on plants, which is probably due to the high permeability of the soils not supporting salt accumulation and salinity-resistant crops being cultivated.

Samples of efflorescences and encrustations of hydrothermal origin were collected at Sousaki (Greece) and analysed for their mineralogical (XRD) and chemical composition. Solutions obtained both from mineralization with HNO3 and from leaching with deionised water were analysed for major (ICP-OES), minor and trace metals (ICP-MS) and sulfate contents (IC). Results evidence the dependence of the chemical and mineralogical composition on micro-environmental conditions i.e. humidity, oxygen-rich or -poor environment, exposed or sheltered from meteoric agents. In fact, the presence of highly soluble sulfate minerals with elevated contents of many metals (e.g. Mg, Al, Fe, Mn, Cr, Ni, etc.) further underscores the important influence of hydrothermal activity on elements' mobility, whilst the sometimes very high concentrations in toxic elements like Al, Cr, Ni suggest also possible environmental impacts.

In this study, hydrogen sulfide (H2S) measurements in air carried out using (a) passive/diffusive samplers (Radiello® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H2S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H2S generally varied over 5 orders of magnitude (from 101e103 mg/m3), the H2S values measured with the Radiello® traps (H2SR) being significantly higher than the average values measured by the Thermo® 450i during the trap exposure (H2STa), especially when H2S was

International audience; The Dead Sea Transform (DST) fault system, where a lateral displacement between the African and Arabian plates occurs, is characterised by anomalous heat flux in the Israeli area close to the border with Syria and Jordan. The concentration of He and CO2, and isotopic composition of He and total dissolved inorganic carbon were studied in cold and thermal waters collected along the DST, in order to investigate the source of volatiles and their relationship with the tectonic framework of the DST. The waters with higher temperature (up to 57.2 °C) are characterised by higher amounts of CO2 and helium (up to 55.72 and 1.91 * 10-2 cc l-1, respectively). Helium isotopic data (R/Ra from 0.11 to 2.14) and 4He/20Ne ratios (0.41-106.86) show the presence of deep-deriving fluids consisting of a variable mixture of mantle and crust end-members, with the former reaching up to 35%. Carbon isotope signature of total dissolved carbon from hot waters falls within the range of magmatic values, suggesting the delivery of deep-seated CO2. The geographical distribution of helium isotopic data and isotopic carbon (CO2) values coupled with (CO2/3He ratios) indicate a larger contribution of mantle-derived fluids affecting the northern part of the investigated area, where the waters reach the highest temperature. These evidences suggest the occurrence of a favourable tectonic framework, including a Moho discontinuity up-rise and/or the presence of a deep fault system coupled with the recent magmatic activity recognised in the northern part of Israel.

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.

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.

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.

International audience; 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 acidic waters are sulphate dominated with different Cl/SO4 ratios. The important role of the pH and the ionic complexes for the distribution of REE, Zr and 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 waters with 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 super-chondritic 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.

Volatile metal(loid)s are known to be emitted from volcanoes worldwide. We tested the suitability of active moss monitoring for tracking volatile metal(loid)s released from the fumarolic field on Vulcano Island, Italy, and differentiated fumaroles from other sources of gaseous and particulate trace elements such as sea spray and soil. Metal(loid) accumulation on the mosses per day did depend neither on the state of the exposed moss (dead or living) nor exposure time (3, 6, or 9 weeks). After collection, mosses were digested with either HNO3/H2O2 or deionized water and analyzed by ICP-MS. While for most elements both extraction methods yielded similar concentrations, higher concentrations were observed e.g. for Pb in the stronger HNO3/H2O2 extracts, indicating the presence of particles, which were not digested and removed by filtration in deionized water extracts. Due to their ubiquitous detection in comparable concentrations at all 23 moss monitoring stations all over the island, Li, Mg and Sr were attributed to sea spray origin. Iron, Co, W, V, Pb, Cr, Mo, and Ba occurred predominantly at the crater, where the soil was not covered by vegetation, and thus likely represent soil-borne particulate transport. Arsenic, Sb, S, Se, Tl, Bi, and I showed a clear concentration maximum within the fumarolic field. Concentrations gradually decreased along a transect in wind direction from the fumaroles, which confirms their volcanic origin. Active moss monitoring thus proved to be an inexpensive and easy-to-apply tool for investigations of volcanic metal(loid) emissions and distributions enabling differentiation of trapped elements by their source of origin.

Passive samplers were used to measure the atmospheric concentrations of SO 2 naturally emitted at three volcanoes in Italy (Etna, Vulcano and Stromboli) and of H 2 S naturally emitted at three volcanic/geothermal areas in Greece (Milos, Santorini and Nisyros). The measured concentrations and dispersion patterns varied with the strength of the source (open conduits or fumaroles), the meteorological conditions and the area topography. At Etna, Vulcano and Stromboli, SO 2 concentrations reach values that are dangerous to people affected by bronchial asthma or lung diseases (> 1000 μg m − 3 ). H 2 S values measured at Nisyros also exceed the limit considered safe for the same group of people (> 3000 μg m − 3 ). The data obtained using passive samplers represent time-averaged values over periods from a few days up to 1 month, and hence concentrations probably reached much higher peak values that were potentially also dangerous to healthy people. The present study provides evidence of a peculiar volcanic risk associated with tourist exploitation of active volcanic areas. This risk is particularly high at Mt. Etna, where the elderly and people in less-than-perfect health can easily reach areas with dangerous SO 2 concentrations via a cableway and off-road vehicles.

International audience; The significant amounts of selenium (Se) emitted by volcanoes may have important impact on human health due to the narrow range between nutrition requirement and toxic effects for living organisms upon Se exposure. Although soils play a key role in determining the level in food and water and thereby human health, little is known about the behaviour of Se in volcanic soils. In this work we evaluated the Se release during rainwater–soil interaction under controlled conditions using soils collected on the flanks of Etna volcano and synthetic rain. Selenium concentrations in soil leachate solutions displayed a spatial distribution, which cannot be explained by plume deposition, total Se soil concentrations or the presence of Fe oxides. Instead, Al compounds and to a minor extent SOM were identified as the active phases controlling the selenate mobilization during interaction with sulphate-containing rainwater. This shows the importance of soils as reactive interfaces. Selenium is mobilized when volcanic-derived acid rain interacts with poorly developed soils close to the crater. This geogenic process might influence the chemical composition of groundwater and as a result, human health.

This study reports on the first quantitative assessment of the geochemical cycling of volcanogenic elements, from their atmospheric release to their deposition back to the ground. Etna’s emissions and atmospheric depositions were characterised for more than 2 years, providing data on major and trace element abundance in both volcanic aerosols and bulk depositions. Volcanic aerosols were collected from 2004 to 2007, at the summit vents by conventional filtration techniques. Precipitation was collected, from 2006 to 2007, in five rain gauges, at various altitudes around the summit craters. Analytical results for volcanic aerosols showed that the dominant anions were S, Cl, and F, and that the most abundant metals were K, Ca, Mg, Al, Fe, and Ti (1.5–50 μg m−3). Minor and trace element concentrations ranged from about 0.001 to 1 μg m−3. From such analysis, we derived an aerosol mass flux ranging from 3000 to 8000 t a−1. Most analysed elements had higher concentrations close to the emission vent, confirming the prevailing volcanic contribution to bulk deposition. Calculated deposition rates were integrated over the whole Etna area, to provide a first estimate of the total deposition fluxes for several major and trace elements. These calculated deposition fluxes ranged from 20 to 80 t a−1 (Al, Fe, Si) to 0.01–0.1 t a−1 (Bi, Cs, Sc, Th, Tl, and U). Comparison between volcanic emissions and atmospheric deposition showed that the amount of trace elements scavenged from the plume in the surrounding of the volcano ranged from 0.1% to 1% for volatile elements such as As, Bi, Cd, Cs, Cu, Tl, and from 1% to 5% for refractory elements such as Al, Ba, Co, Fe, Ti, Th, U, and V. Consequently, more than 90% of volcanogenic trace elements were dispersed further away, and may cause a regional scale impact. Such a large difference between deposition and emission fluxes at Mt. Etna pointed to relatively high stability and long residence time of aerosols in the plume.

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.

The S, halogen and NO 3 contents of rainwater samples from the Etnean area were studied in order to define the environmental impact of plume emissions on the local environment. Samples, collected on a network of 11 bulk rain gauges, show significant variability in anion content, which can be ascribed to different meteorological and environmental conditions at each sampling site and to a variable distance from the different source areas. Data analysis suggests that S, F, Cl and Br are mainly magma-derived, whereas NO 3 mainly originates from anthropogenic sources. Samples collected from sites close to craters display considerable temporal variability, with increased anion concentrations being recorded during periods of intense plume degassing. Variations in precipitation also induce significant modifications in the chemistry of the meteoric-derived Etnean groundwaters.

The aim of this work is to study the interactions processes between the fluids of deep origin and the shallow groundwaters of the Vulcano Porto area. During 1995, 13 well waters were sampled three times (May, July and November) and analysed for major and some minor elements (B, Br and NH4) and for dissolved gases. The close relationship of these waters with the deep magmatic source is highlighted by the composition of the dissolved gases. Furthermore, the areal distribution of dissolved species is controlled mainly by the gas fluxes from depth and by the presence of a deeper thermal aquifer. The distribution of major anomalies in the parameters measured in the groundwaters, in fact, overlaps the soil gas fluxes distribution that are related to the existence of preferential upflow routes of fumarolic fluids through weak structural lines in the volcanic edifice.