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Abstract 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 CO 2 concentrations and 220Rn and 222Rn activities at 50 cm depth and CO 2 fluxes from the soil. The whole island was covered with a measurement density of 3.5 points/km2 for CO 2 (flux and concentration) and 1.6 points/km2 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/km2. The obtained results ranged from 0.038 to 95%vol for CO 2 concentration, from 10 Bq/m3 to 164,000 Bq/m3 from 10 Bq/m3 to 750,000 Bq/m3 for 220Rn and 222Rn activities, respectively and from <0.1 to 4700 g/m2 day for CO 2 fluxes. Probability plots evidenced for all measured parameters the presence of three populations (background, mixed and hydrothermal). All anomalous values were found in the central part of the island within the youngest caldera. Flux data allowed us to estimate a total CO 2 output of the volcanic/geothermal system of Pantelleria in 24.2 tons per day. Some new exhaling area, significantly contributing to the total output and characterised by stunted or absent vegetation, were evidenced on the southern flank of Mt. Grande. At one of these areas the relationships between the measured parameters and vegetation cover were studied in detail along a 140 m long transect of 15 points. Finally, a first evaluation of the gas hazard related to the geogenic degassing evidenced some high risk area at the mofette along the shores of the Lake Specchio di Venere (CO 2) and in the village of Rekale (CO 2 and Rn). [ABSTRACT FROM AUTHOR]

Abstract: Passive samplers were used to measure the atmospheric concentrations of SO2 naturally emitted at three volcanoes in Italy (Etna, Vulcano and Stromboli) and of H2S 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, SO2 concentrations reach values that are dangerous to people affected by bronchial asthma or lung diseases (>1000μgm−3). H2S values measured at Nisyros also exceed the limit considered safe for the same group of people (>3000μgm−3). The data obtained using passive samplers represent time-averaged values over periods from a few days up to 1month, 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 SO2 concentrations via a cableway and off-road vehicles. [Copyright &y& Elsevier]

Abstract: 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 CO2 flux measurements from the soils were made with the accumulation chamber method in an area of about 0.015km2 within the main fumarolic area of the island (Favara Grande). The 23 measurements range from −34 to 3550mgm−2 d−1 for CH4 and from 0.6 to 379gm−2 d−1 for CO2. The relationships between CH4 and CO2 fluxes and the CH4/CO2 ratios in the gases collected between the depths of 25 and 100cm provide evidence for methanotrophic processes within the soils. Methane output for the surveyed area was calculated to be 2.5ta−1 and extrapolated to about 5–10ta−1 for the entire volcanic/hydrothermal system of the island. Previous higher estimates of the CH4 output at Pantelleria (Etiope et al., 2007, J. Volcanol. Geotherm. Res., 165, 76–86) were based on soil CO2 output and CH4/CO2 ratios in fumarolic gases; the present work provides the first direct CH4 flux data and it suggests that methanotrophic activity in the soil could be substantial in reducing the CH4 emission to the atmosphere. [Copyright &y& Elsevier]

Hydrological and geochemical studies performed on Lake Specchio di Venere on Pantelleria island (Italy) indicate that this endorheic basin has been formed through upwelling of the water table, and that it is continuously fed by the thermal springs situated on its shores. The lake is periodically stratified both thermally and in salinity, albeit this stratification is rather unstable over time, since meteorological events such as strong rain or wind can determine the mixing of its waters. Periodical analyses of the lake water chemistry show large variations of the salt content due to the yearly evaporation-rain dilution cycle. These processes are also responsible for the saline stratification during steady meteorological conditions. The mineralogical characterisation of the bottom sediments shows the almost exclusive presence of neoformation minerals, mainly carbonates, formed in response to the pH gradient between spring- (pH ≈ 6) and lake-waters (pH ≈ 9). Finally, the CO2 partial pressures in the lake water slightly exceeding the atmospheric one, are due to the large amounts of CO2 brought to the lake through the bubbling free gas phase of the thermal springs. Nevertheless the high pH value of the lake water, its small volume and its periodical mixing prevent dangerous built up of this gas. [ABSTRACT FROM AUTHOR]

Major ion content of 37 wet-only rainwater samples collected on the southern flank of Mount Etna volcano was investigated. Measured pH values range from 3.80 to 7.22 and display a positive correlation with Ca2 + and an inverse correlation with NO3-, suggesting that anthropogenic NOx are the most effective acidifying agents while Ca, likely as solid CaCO3, is the prevailing proton acceptor. Na/Cl ratios indicate a dominant marine origin for both species, while K, mg and Ca contents point to additional sources (soil dust, fertilisers etc.). Nitrate and sulphate concentrations display a nearly constant ratio indicating a common anthropogenic origin, and only a few samples are characterised by sulphate excess. The analysis of time series reveals a good correlation between the excess sulphate in rainwater and SO2 fluxes from the summit craters plume. Non sea salt chloride contents show also a significant correlation with volcanic activity indicating a magmatic sulphur and chloride contribution to rainwater. Meteoric flux estimations point to a prevailing magmatic origin for sulphur in the collected rainwaters while sea spray is the main source of chlorine. [ABSTRACT FROM AUTHOR]

Highlights: [•] Isotopic composition of precipitation and groundwater in Sicily (Italy). [•] Isotopic data processing for hydrogeological purpose. [•] GIS mapping of isotopic data. [Copyright &y& Elsevier]

Abstract: 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 2years, 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 (1.5–50μgm−3). Minor and trace element concentrations ranged from about 0.001 to 1μgm−3. From such analysis, we derived an aerosol mass flux ranging from 3000 to 8000ta−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 80ta−1 (Al, Fe, Si) to 0.01–0.1ta−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. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

Abstract: 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), δ 13CCO2 =−3.51±0.9‰, and helium isotopic ratio of about 3.5 Ra (3He/4He ratio normalized to the air ratio, R a), 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. [Copyright &y& Elsevier]

Abstract: Quantifying the contribution of volcanism to global mercury (Hg) emissions is important to understand the pathways and the mechanisms of Hg cycling through the Earth''s geochemical reservoirs and to assess its environmental impacts. While previous studies have suggested that degassing volcanoes might contribute importantly to the atmospheric budget of mercury, little is known about the amount and behaviour of Hg in volcanic aquifers. Here we report on detailed investigations of both the content and the speciation of mercury in aquifers of active volcanoes in Italy and Guadeloupe Island (Lesser Antilles). In the studied groundwaters, total Hg (THg) concentrations range from 10 to 500 ng/l and are lower than the 1000 ng/l threshold value for human health protection fixed by the World Health Organization [WHO (1993): WHO Guidelines for Drinking Water Quality- http://www.who.int/water_sanitation_health/GDWQ/index.htlm]. Positive co-variations of (THg) with sulphate indicate that Hg-SO4-rich acid groundwaters receive a direct input of magmatic/hydrothermal gases carrying mercury as Hg0 (gas). Increasing THg in a volcanic aquifer could thus be a sensitive tracer of magmatic gas input prior to an eruption. Since the complex behaviour and toxicity of mercury in waters depend on its chemical speciation, we carefully determined the different aqueous forms of this element in our samples. We find that dissolved elemental Hg0 (aq) and particulate-bound Hg (HgP) widely prevail in volcanic aquifers, in proportions that highlight the efficiency of Hg adsorption onto colloidal particles. Moreover, we observe that dissolved Hg0 aq and Hg(II) forms coexist in comparable amount in most of the waters, in stark contrast to the results of thermodynamic equilibrium modelling. Therefore, chemical equilibrium between dissolved mercury species in volcanic waters is either prevented by natural kinetic effects or not preserved in collected waters due to sampling/storage artefacts. Finally, we provide a first quantitative comparison of the relative intensity of aqueous transport and atmospheric emissions of mercury at Mount Etna, a very active basaltic volcano. [Copyright &y& Elsevier]

There is an urgent need to better constrain the global rates of mercury degassing from natural sources, including active volcanoes. Hitherto, estimates of volcanic fluxes have been limited by the poorly determined speciation of Hg in volcanic emissions. Here, we present a systematic characterisation of mercury partitioning between gaseous (Hg(g)) and particulate (Hg(p)) forms in the volcanic plume of Mount Etna, the largest open-vent passively degassing volcano on Earth. We demonstrate that mercury transport is predominantly in the gas phase, with a mean Hg(p)/Hg(g) ratio of ∼0.01 by mass. We also present the first simultaneous measurement of divalent gaseous mercury () and total gaseous mercury (Hg(g)) in a volcanic plume, which suggests that is the prevalent form of mercury in this context. These data are supported by the results of model simulations, carried out with HSC thermodynamic software. Based on a mean “bulk plume” Hg/SO2 mass ratio of 8.7×10−6, and a contemporaneous volcanic SO2 flux of 0.8Mtyr−1, we estimate an Hg emission rate from Mt. Etna during passive degassing of 5.4tyr−1 (range, 1.1–10tyr−1). This corresponds to ∼0.6% of global volcanic Hg emissions, and about 5% of Hg released from industrial activities in the Mediterranean area. [Copyright &y& Elsevier]

Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO2 per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO2 leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in seawater carbonate chemistry that is well suited to studies of the effects of long-term increases in CO2 levels. This shoreline lacks toxic compounds (such as H2S) and has a gradient in carbonate saturation states., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

In this paper, in an attempt to reveal possible changes connected to natural or anthropogenic causes, the main results of hydrogeochemical monitoring carried out at Mount Etna are evaluated. We report on the salinity contents of the groundwaters that flow in fractured volcanics, which make up the flanks of the volcano. These waters, analyzed for major ion chemistry, were sampled regularly from 1994 to 2004. Basing on nonparametric Sen's slope estimator, time series of groundwater composition reveal that the salinity of most of the Etnean aquifers increased by 0.5% to 3.5% each year during this period. This change in the water chemistry is clearly referable to the overexploitation of the aquifers. This increasing trend needs to be inverted urgently; otherwise, it will cause a shortage of water in the near future, because the maximum admissible concentration of salinity for drinking water will be exceeded.

Radon levels were measured in 119 groundwater samples collected throughout the active volcanic area of Mt. Etna by means of a portable Lucas-type scintillation chamber. The measured activity values range from 1.8 to 52.7 Bq l(-1). About 40% of the samples exceed the maximum contaminant level of 11 Bq l(-1) proposed by the USEPA in 1991. The highest radon levels are measured in the eastern sector of the volcano, which is the seismically most active zone of the volcano. On the contrary the south-western sector, which is both seismically active and a site of intense magmatic degassing, display lower radon levels. This is probably due to the formation of a free gas phase (oversaturation of CO(2)) that strips the radon from the water. Comparison of the data gathered at Mt. Etna with those of other areas indicates that (222)Rn activity in groundwater is positively correlated with both the content of parent elements in the aquifer rocks and the temperature of the geothermal systems that interacts with the sampled aquifers.

Many studies have assessed the strong influence of volcanic activity on the surrounding environment. This is particularly true for strong gas emitters such as Mt. Etna and Stromboli volcanoes. Among volcanic gases, fluorine compounds are potentially very harmful. Fluorine cycling through rainwater in the above volcanic areas was studied analysing more than 400 monthly bulk samples. Data indicate that only approximately 1% of fluorine emission through the plume is deposited on the two volcanic areas by meteoric precipitations. Although measured bulk rainwater fluorine fluxes are comparable to and sometimes higher than in heavily polluted areas, their influence on the surrounding vegetation is limited. Only annual crops, in fact, show some damage that could be an effect of fluorine deposition, indicating that long-living endemic plant species or varieties have developed some kind of resistance., (Copyright 2002 Elsevier Science B.V.)