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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 (>1000 μg m−3). H2S 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 SO2 concentrations via a cableway and off-road vehicles.

Ischia Island is the emergent portion of a large volcanic complex on the Gulf of Naples (Southern Italy). Ischia volcano has undertaken a complex evolution since 150 ka b.p., with prolonged cycles of effusive and explosive eruptions alternated with quiescence periods (the most recent of which started after the 1302 A.D. Arso eruption). Currently, hot springs (with discharge temperature up to 90 C), fumarolic gas emissions with CO2 up to 97%, and diffuse soil degassing testify a persistent activity state of the Ischia volcano. Ischia Island is a very good example of an active volcano hosting a large hydrothermal system and, in particular, its south-western sector has long been known to be the most-actively degassing area, characterized by a pervasive hydrothermal circulation. Di Napoli et al. (2009) have recently suggested that thermal manifestations in this sector of the island are fed by a shallow hydrothermal reservoir located at 150–300 m of deep with equilibrium temperatures 150 C. The presence of a relative shallow depth thermal aquifer represent a threat to populations living in the surroundings of volcanoes. Indeed, the supply of volatiles and thermal energy from the deep-seated magmatic reservoirs may prompt pressurization of hydrothermal aquifer, increasing the probability of phreatic explosions Here, we report the results an integrated multidisciplinary (geological, geochemical and geophysical) investigation aimed at a comprehensive characterisation of the hydrothermal setting in the south-western sector of Ischia. Geological investigations, hydrogeochemical determinations (with a focus on dissolved gases) and soil diffuse CO2 fluxes surveys, and electrical resistivity tomography and TEM soundings, have simultaneously been carried out and interpreted, with the ultimate objective of building up a model of fluid circulation in the shallowest (< 0.5 km) part of the hydrothermal system. Results show that fluids circulation, in the investigated area, is governed by a very complex structural setting schematised in three main sectors: extra caldera, caldera floor, and resurgent caldera. In particular, the caldera floor sector is the portion of the study area to which gas-rich fluids can be transferred from underlying deeper and hotter hydrothermal reservoirs. Indeed, the aquifer geometry, and the dense network of faults and fractures, force hot and gas-rich fluids to preferentially flow towards (and thus accumulate within) this sector of the volcano. Our model of fluid circulation may serve as a basis for interpreting changes in the hydrothermal regime associated with any future unrest that could potentially escalate towards an eruption in this densely populated island

Biomonitoring may be defined as the use of organisms and biomaterials (biomonitors) to obtain informations on certain characteristics of a particular medium (atmosphere, hydrosphere etc.). In particular, mosses accumulate large amounts of trace metals, making them good bioaccumulators to estimate atmospheric pollution. The moss-bags technique, introduced in the early 1970’, has become very popular. Such active biomonitoring technique is particularly useful in highly polluted areas and has been extensively used in industrial and/or urban areas to examine deposition patterns and to recognize point sources of pollution. The main objective of this study, which represents the first application of the moss-bags technique in an active volcanic area, was to test its efficacy in such environment. Complementary objectives were: to determine the different behavior and the geographic dispersion of volcanogenic elements emitted from Mt. Etna; to check the usefulness of a simpler analytical techniques (leaching instead of mineralization of the moss samples). A mixture of Sphagnum species was picked in a clean area, treated in laboratory (washed, dried and packed)and exposed in field for 1 month. Sites were chosen considering the prevailing wind at Mt. Etna’s summit. Milled samples were analyses for major and trace elements concentrations, after microwave digestion (HNO3 + H2O2), by ICP-MS and ICP-OES techniques. The same elements were also analyzed after simple leaching with deionized water (1/50 weight ratio for 4 hours). Leaching solutions were also analyzed by IC for F, Cl and SO4. Analyses clearly showed the efficacy of the moss-bags technique also in this peculiar environment. Several elements were strongly enriched in the mosses exposed to the volcanic missions. The highest enrichment was measured on the rim of the summit craters, but evidences of metals bioaccumulation were also found in down wind sites, at several km from the volcanic source. The accumulation factor (exposed/unexposed moss) allowed us to distinguish a group of elements (Tl, Bi, Se, Cu, As, Cd, S), which are highly mobile in the high temperature volcanic environment. Also alkali metals showed a significant increase in their concentrations, probably because of their affinity for the halide species carried by the volcanic plume. Also the simple and cheap leaching technique gave important indications on the plume dispersion pattern, especially for highly volatile elements (F, Cl, S, Tl).

This paper presents the preliminary results of a biomonitoring study based on the use of moss bags exposed at 24 sites on Etna volcano. Sphagnum mosses were used to study bioaccumulation originating from atmospheric deposition, by measuring the tissue contents of major and a large suite of trace elements. Elements, such as Tl, Bi, As, Se, Cu and Cd, display high concentrations in the exposed samples close to the active vents. This study confirms the effectiveness of the moss bags technique also in active volcanic areas.

Biomonitoring may be defined as the use of organisms and biomaterials (biomonitors) to obtain information on certain characteristics of a particular medium (atmosphere, hydrosphere etc.). In particular, mosses accumulate large amounts of trace metals, making them good bioaccumulators to estimate atmospheric pollution. The moss-bags technique, introduced in the early 1970’, has become very popular. Such active biomonitoring technique is particularly useful in highly polluted areas and has been extensively used in industrial and/or urban areas to examine deposition patterns and to recognize point sources of pollution. The main objective of this study, which represents the first application of the moss-bags technique in an active volcanic area, was to test its efficacy in such environment. Complementary objectives were: to determine the different behaviour and the areal dispersion of volcanogenic elements emitted from Mt. Etna; to characterize the morphology and mineralogy of particles transported in the plume-system, basing on microscopy investigation. A mixture of Sphagnum species was picked in a clean area, treated in laboratory (rinsed, dried and packed) and exposed in field for 1 month. Sites were chosen considering the prevailing wind at Mt. Etna’s summit. Milled samples were analyses for major and trace elements concentrations, after microwave digestion (HNO3 + H2O2), by ICP-MS and ICP-OES techniques. Morphology and mineralogy of volcanic particulate were investigated by using a SEM with EDS. Analyses clearly showed the efficacy of the moss-bags technique also in this peculiar environment. Several elements were strongly enriched in the mosses exposed to the volcanic emissions. The highest enrichment was measured close to the summit crater, but evidences of metals bioaccumulation were also found in down wind sites, at several km from the volcanic source. The accumulation factor (exposed/unexposed moss) allowed us to distinguish a group of elements (Tl, Bi, Se, Cu, As, Cd, S), which are highly mobile in the high temperature volcanic environment. Also alkali metals showed a significant increase in their concentrations, probably because of their affinity for the halide species carried by the volcanic plume. Microscopic observations evidenced sulphate and halide crystals on particles trapped by the mosses. Mosses exposed at sites directly fumigated by the volcanic plume showed crystal growth also directly on the moss surface.

8. A biomonitoring survey using leaves of tree (Betulla aethnensis, Pinus nigra and Populus tremula) and two endemic species (Senecio aethnensis and Rumex aethnensis) above treeline level, was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (800-3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analyzed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted by volcanic emissions. Leaves collected along two radial transects from the active vents on the eastern flank, highlight that the levels of metals decrease one or two orders of magnitude with the distance from the source. This variability is higher for volatile elements (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The different species of plants show significant differences in the bioaccumulation of most of the analyzed elements, in particular lanthanides, which are systematically enriched in Rumex leaves. The high concentrations of many toxic elements in the two endemic species allow us to consider these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches.

A biomonitoring survey, above tree line level, using two endemic species (Senecio aethnensis and Rumex aethnensis)was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic atmospheric emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (1500-3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analyzed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted by volcanic emissions. Leaves collected along two radial transects from the active vents on the eastern flank, highlight that the levels of metals decrease one or two orders of magnitude with increasing distance from the source. This variability is higher for volatile elements (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The two different species of plants do not show significant differences in the bioaccumulation of most of the analyzed elements, except for lanthanides, which are systematically enriched in Rumex leaves. The high concentrations of many toxic elements in the leaves allow us to consider these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches in the Mt. Etna area.

Humans are attracted by the fertile properties of volcanic soils. Currently around 10% of the world population lives within active volcanic areas. Volcanoes emit enormous amounts of potentially toxic elements, even in the absence of obvious volcanic activity. Selenium is particularly interesting due to it geochemical similarities with sulphur, a major compound in volcanic gasses. Although selenium (Se) is an essential element for humans, ingestion of an excess amount of Se can produce adverse effects. Mt. Etna, the biggest volcano in Europe, is persistently active for the last 200,000 years. It is one of the most intensely monitored volcanoes. In the area, volcanic gasses, rainwater and groundwater are enriched in selenium. Although soils play an important role in the Se level in food and water and thereby human health, the behaviour of S! e in Etnean soils is currently unknown. We studied the Se sorption during rainwater-soil interaction in batch experiments with soils and synthetic rainwater with different pHs. Our results show spatial trends with soil sample location. Trace element deposition from the plume cannot explain the observed elemental patterns. Moreover, Fe oxides do not control the geochemical Se cycle in this environment. However, the stage of soil development and especially the presence of Al compounds and organic matter play an important role in the behaviour of Se. These results have implications for the chemical composition of the aquifer. In addition, the mobility of Se influences the bioavailability and potential toxicity through agricultural activities, essential to the local economy.

Humans are attracted by the fertile properties of volcanic soils and currently around 10% of the world population lives within active volcanic areas. Volcanoes emit significantly amounts of potentially toxic elements such as selenium (Se), even in the absence of obvious volcanic activity. Although Se is an essential element for humans, ingestion of an excess amount of Se can produce adverse effects. Mt. Etna, the biggest volcano in Europe, is persistently active for the last 200,000 years and one of the most intensely monitored volcanoes. We have studied selenium in rainwater and soils from Mt Etna volcano. Bulk depositions were collected from April 2006 to December 2007, using a network of five rain gauges, located at various altitudes around the summit craters. Highest Se concentrations (up to 13 µg/L) have been found close to the emission vent, confirming the prevailing volcanic contribution to rainwater composition close to the summit craters. The deposition rate for Se was estimated to be 1.7 µg m-2 day-1 nearby to the summit vents, to 0.5 µg m-2 day-1 at the local background site on the upwind western sector. Thirty soils collected at the flanks of the volcano show total concentrations between 0.1 and 2.2 ppm. Lab-controlled experiments with these soils and synthetic rainwater show that up to 5% of the Se is mobilized during soil-rain water interaction. The trace element deposition of the plume cannot explain the observed spatial trends. However, the stage of soil development plays an important role in the behaviour of Se within the soils. Our results have implications for the chemical composition of the Etnean aquifer. Additional, the mobility of soil Se influences the bioavailability and potential toxicity through agricultural activities, essential to the local economy.

Fumarolic alteration crusts and efflorescences have been sampled at the Sousaki solfataric field. Samples have been analysed for mineralogical (XRD) and chemical composition (HNO3 digestion and leaching with distilled water). Results show that mineralogical and chemical compositions (major, minor and trace metals) are controlled by microenvironmental conditions. The sample collected in the anoxic part of a cave is composed almost exclusively by native sulfur. The samples collected in the oxidizing part of the cave and outside in relatively sheltered position are mainly composed by very soluble sulfates. Chemical composition evidence strong enrichments in Al, Ca, Cr, Fe, Mg and Ni which are present in highly soluble form and derive from the fumarolic alteration of the outcropping rocks (Marls and peridotites). One sample collected outside the cave, well exposed to atmospheric agents, is composed almost exclusively of gypsum and the chemical composition reveals, with respect to the previous samples, a relative enrichment of elements (Ba, Ca, K, Pb and Sr) forming less soluble sulfates. The presence of toxic metals like Al, Cr and Ni in high concentrations and highly soluble form evidences the potential impact of the fumarolic activity on the local environment.

Volcanic emissions represent one of the major natural source for several trace metals (Cd, Cu, As, Pb, Hg and Zn) into the atmosphere both as gaseous and aerosol forms. The Mediterranean Sea can be considered a large geochemical sink for these elements whose source are the huge amounts of aerosols of different origin. The industrialised areas located in the northern part of the basin represent a nearly constant source of the anthropogenic-dominated aerosol. By contrast, the arid and desert regions located at the southern and eastern parts of the Mediterranean, are the sources of frequent dust “pulses” perturbing the “steady-state” conditions of the local atmosphere through the input of several millions of tons of desert dust. In this context, Mount Etna, Stromboli and Vulcano represent the biggest volcanic point-sources in the Mediterranean area by introducing several thousands of tons of gases and particles per day in the troposphere, both during eruptive and passive degassing periods. Comparison between estimated annual metal fluxes from the three Italian active volcanoes and the local emissions (Environmental Protection Agency), evidences the significant contribution of the volcanogenic trace metals (Cu, Se, Cr, As, Hg and Cd) to the metropolitan area of Catania and the whole Sicily. On a regional scale, volcanic degassing plays also an important role accounting for about 1 to 10% for the total European anthropogenic emissions of As, Cd, Cr, Hg, Ni and Pb (European Monitoring and Evaluation Programme).

A biomonitoring survey, above treeline level, using two endemic species (Senecio aethnensis and Rumex aethnensis) was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (1500-3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analysed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted by volcanic emissions. Leaves collected along two radial transects from the active vents on the eastern flank, highlight that the levels of metals decreas one or two orders of magnitude with the distance from the source. This variability is higher for volatile elements (As, Bi, Cd, Cs, Pb, Sb, Tl) than for more refractory elements (Al, Ba, Sc, Si, Sr, Th, U). The two different species of plants do not show significant differences in the bioaccumulation of most of the analyzed elements, except for lanthanides, which are sistematically enriched in Rumex leaves. The high concentrations of many toxic elements in the leaves allow us to consider these plants as highly tolerant species to the volcanic emissions, and suitable for biomonitoring researches.

Volcanic volatiles and aerosol emitted into the atmosphere ultimately fall on the Earth’s surface as wet or dry deposition, and they can influence the environment and the ecosystems at local and regional scales. Therefore, atmospheric deposition plays a key-role in the geochemical cycles, redistributing volcanogenic elements to the ground. For this reason, estimating the volcanogenic trace element fluxes from the atmosphere to the surface is necessary for a better knowledge of the environmental impact of the volcanic emissions. Nevertheless, from a literature review, we have recognized the scarcity of investigation on trace element deposition in the surroundings of active volcanoes. Here, we present a chemical characterization of bulk deposition around Mt. Etna, Italy, including both major and many trace elements. Bulk depositions were collected approximately fortnightly, from April 2006 to December 2007, using a network of five rain gauges, located at various altitudes on the upper flanks around the summit craters of the volcano. For most elements highest concentrations have been found close to the emission vent, confirming the prevailing volcanic contribution to rainwater composition close to the summit craters. Comparison with contemporaneously collected plume emissions shows that deposition processes produce no evident element-to-element fractionation. By contrast, comparison with whole rock composition indicates a contrasting behaviour between volatile elements, which are highly-enriched in rainwater, and refractory elements, which have low rainwater/whole rock concentration ratios. Chemical concentrations in bulk deposition were used to estimate the deposition rates of a large suite of elements. Deposition rates for volatile trace elements like Se, As, and Cd range from 1.7, 1.2 and 0.9 µg m-2 day-1 nearby to the summit vents, to 0.5, 0.3, and 0.1 µg m-2 day-1 at the local background site on the upwind western sector.

Geochemical comparison between some metals (As, Cd, Cu, Pb, Se, V, Zn) emissions from an active volcano (Mt. Etna) and a highly industrialized area (Šalek Valley) showed some interesting similarities: in general, most of the elements emitted into the atmosphere do not return to the Earth’s surface and are therefore dispersed into the environment. Exceptions for Šalek Valley are Cd, which probably derives in large part from rock leaching, and in part As and Pb, which fall mostly as ash. Also, Etna’s emissions are richer in Cd and Cu, whereas industrial emissions at Šalek Valley are richer in V and Zn. All other metals have similar fluxes in the two types of emissions.

Active volcanoes emit considerable amounts of contaminants such as As, Se and V. Mount Etna is the biggest volcano of Europe and an excellent geochemical site to study water-soil processes. Due to its volcanic activity, the rainwater has a strong compositional gradient, both in time and space. At present, the behaviour of trace elements in the soils around Mt Etna is poorly understood. To determine the influence of the rainwater pH on the potential mobilization of geogenic pollutants, batch experiments have been performed with synthetic rainwater for 25 soils collected along the flanks of the volcano. Our results show that: i) The maximum concentrations in the leaching solutions are higher for acid rain than for neutral rain (e.g. 7.7 vs 1.3 mg/L for Se). ii) With neutral rain conditions the soils upwind from the volcano have higher concentrations of Se than those downwind (up to 1.3 mg/L compared to ≤0.3 mg/L for the other samples). This trend is less clear for As and V. iii) For soils collected from 2 to 10 km downwind of the craters, Se concentrations in acid rain leachates decrease one order of magnitude with increasing distance. A similar pattern is also observed upwind from the volcano. For As and V no clear relationship between concentrations and location with respect to the volcanic craters is observed. Both i) and ii) result in a low pH dependence for samples upwind from the volcano. The biggest difference between acid and neutral leaching for As and V is observed for a sample 2 km downwind from the craters. The observed patterns are influenced by potential controlling factors, such as organic matter content, total concentrations, mineralogy, influence of the volcanic plume, etc. Our results have implications for the chemical composition of the Etnean aquifer, the only water resource to the one million inhabitants around Mt Etna, as well as for the bioavailability and potential toxicity through agricultural activities, essential to the local economy.

Recent evidence supports and reinforces the concept that environmental cues may reprogramme somatic cells and change their natural fate. In the present review, we concentrate on environmental reprogramming and fate potency of different epithelial cells. These include stratified epithelia, such as the epidermis, hair follicle, cornea and oesophagus, as well as the thymic epithelium, which stands alone among simple and stratified epithelia, and has been shown recently to contain stem cells. In addition, we briefly discuss the pancreas as an example of plasticity of intrinsic progenitors and even differentiated cells. Of relevance, examples of plasticity and fate change characterize pathologies such as oesophageal metaplasia, whose possible cell origin is still debated, but has important implications as a pre-neoplastic event. Although much work remains to be done in order to unravel the full potential and plasticity of epithelial cells, exploitation of this phenomenon has already entered the clinical arena, and might provide new avenues for future cell therapy of these tissues.

Active volcanoes emit considerable amounts of contaminants such as As, Se and V. Previous studies have shown that the volcanic activity at Mt Etna (Sicily) has a strong influence on local rainwater compositions. However to date, the behaviour of trace elements in the soils around Mt Etna is poorly understood. 4-hr batch experiments have been performed with 1:5 soil solutions of air-dried soil (fraction

This paper reports the use of diffusive tubes in determining HF, HCI, and SO2 in the volcanic plume of Mount Etna in an attempt to highlight the potential of this method in studying volcanoes. In a first application a network of 18 diffusive tubes was installed on Etna's flanks, aimed at evaluating the atmospheric dispersion of the volcanic plume on a local scale. Results showed a monotonic decrease in volatile air concentrations with distance from the craters (HF from 0.15 to

Nisyros Island, Greece, is a stratovolcano known for its intense hydrothermal activity. On June 2013, during a multidisciplinary field campaign, soil samples were collected in the caldera area to determinate the main mineralogical assemblages and to investigate the distribution of trace element concentrations and the possible relationship to the contribution of fluids of deep origin. Soil samples were analysed with XRD and for the chemical composition of their leachable (deionized water) and pseudo total (microwave digestion) fraction both for major and trace elements. The results allow to divide the samples in 2 groups: Lakki Plain and Stefanos Crater. The latter, where a fumarolic area is located, shows a mineralogical assemblage dominated by phases typical of hydrothermal alteration. Their very low pH values (1.9 – 3.4) show the strong impact of fumarolic gases which are probably also the cause of strong enrichments in these soils of highly volatile elements like S, As, Se, Bi, Sb, Tl and Te. © 2014, Editrice Compositori s.r.l., All rights reserved.

The studied area is a 130km long fast spreading graben in Central Greece. Its complex geodynamical setting includes both the presence of a subduction slab at depth responsible for the recent (Quaternary) volcanic activity in the area and the western termination of a tectonic lineament of regional importance (the North-Anatolian fault). A high geothermal gradient is made evident by the presence of many thermal springs with temperatures from 19 to 82°C, that discharge along the normal faults bordering the graben. In the period 2004-2012, 58 gas and 69 water samples were collected and their chemical and isotopic analysis revealed a wide range of compositions.Two main groups of thermal waters can be distinguished on the basis of their chemical composition. The first, represented by dilute waters (E.C.

Like other geodynamically active areas, Greece is also affected by a large number of geogenic gas manifestations. These occur either in the form of point sources (fumaroles, mofettes, bubbling gases) or as diffuse soil gas emanations. Geogenic sources release huge amounts of gases, which, apart from having important influences on the global climate, could also have a strong impact on human health. Gases have both acute and chronic effects. Carbon dioxide (CO2) and hydrogen sulphide are the main gases responsible for acute mortality due to their asphyxiating and/or toxic properties. Methane instead represents a risk for its explosive properties. Gas hazards are often disregarded because in fatal episodes connected to geogenic gases, the cause of death is often not correctly identified. Due to the fact that geodynamically active areas can release geogenic gases for millions of years over wide areas, it is important to realistically estimate potential risks. The present work produced a first catalogue of the geogenic gas manifestations of the whole Greek territory including relevant literature data. A preliminary estimation of the correlated risk has been made for the time period of the last 20 years considering the whole population of Greece. In this period, at least two fatal episodes with a total of three victims are likely due to exposure to geogenic gases (specifically CO2). This would give a risk of 1.3 × 10-8 fatality from geogenic gas manifestations per annum. This value, although probably underestimated, is much lower than most other natural or anthropogenic risks. © 2013 Springer Science+Business Media Dordrecht.

The genetic relationship between carbon-bearing species (CO, CO2, CH4, C2H6, C3H8, C2H4 and C3H6) was investigated in volcanic-hydrothermal gases emitted from Nisyros (Greece), Vesuvio, La Solfatara (Campi Flegrei) and Pantelleria (all Italy). Apparent carbon isotopic temperatures of the CH4-CO2 system are similar to 360 degrees C at Nisyros, 420-460 degrees C at Vesuvio, similar to 450 degrees C at La Solfatara and similar to 540 degrees C at Pantelleria. These temperatures are confirmed by measured propene/propane and H-2/H2O concentration ratios. CH4 and CO2 equilibrate in the single liquid phase prior to the onset of boiling, whereas propene and propane attain equilibrium in the saturated water vapor phase. Boiling in these high-enthalpy hydrothermal systems might occur isothermally. Once vapor has been extracted from the parental liquid, CO/CO2 responds most sensitively to the temperature gradient encountered by the ascending gases. Our results imply that the CH4-CO2 isotopic geothermometer can provide reliable information about temperatures of deep hydrothermal liquids associated with volcanism. Propene/propane and H-2/H2O concentration ratios should be measured along with the carbon isotopic composition of CO2 and CH4 to provide independent constraints on the geological significance of the apparent carbon isotopic temperatures.

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. © 2012 Elsevier B.V.