ALBERT

Description: No abstract

Description: Published

Description: 92-117

Description: 4V. Vulcani e ambiente

Description: restricted

Description: Real-time measurements of GEM and H2S discharged fromnatural 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 ofMt. Amiata (a 200,000 years 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 GEMand 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 77 ng/m3, respectively, whilst at Solfatara Crater were up to 690 and 3392 μg/m3, respectively. Although the GEM concentrations at Piancastagnaio were lower than the limit value recommended by local regulations for outdoor environment (300 ng/m3), they were almost one order of magnitude higher than the GEM background both in Tuscany (~3.5 ng/m3) and Mt. Amiata (3–5 ng/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 150 μg/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 thatwere 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/GEMratio, 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.

Description: Published

Description: 48-58

Description: 4V. Vulcani e ambiente

Description: JCR Journal

Description: restricted

Description: Istituto Nazionale di Geofisica e Vulcanologia - Sezione di Napoli Osservatorio Vesuviano

Description: Published

Description: 2.6. TTC - Laboratorio di gravimetria, magnetismo ed elettromagnetismo in aree attive

Description: open

Description: 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 10 1e103 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 〈30 mg/m3. To test the reproducibility of the Radiello® traps, 8 passive/diffusive samplers were contemporaneously deployed within an 0.2 m2 area in an H2S-contaminated site at Mt. Amiata (Tuscany, Italy), revealing that the precision of the H2SR values was ±49%. This large uncertainty, whose cause was not recognizable, is to be added to that related to the environmental conditions (wind speed and direction, humidity, temperature), which are known to strongly affect passive measurements. The Thermo® 450i analyzer measurements highlighted the occurrence of short-term temporal variations of the H2S concentrations, with peak values (up to 5732 mg/m3) potentially harmful to the human health. The Radiello® traps were not able to detect such temporal variability due to their large exposure time. The disagreement between the H2SR and H2STa values poses severe concerns for the selection of an appropriate methodological approach aimed to provide an accurate measurement of this highly toxic air pollutant in compliance with the WHO air quality guidelines. Although passive samplers may offer the opportunity to carry out low-cost preliminary surveys, the use of the high-frequency H2S analyzer is preferred when an accurate assessment of air quality is required. In fact, the latter provides precise real-time measurements for a reliable estimation of the effective exposure to hazardous H2S concentrations, giving insights into the mechanisms regulating the dispersion of this air pollutant in relation to the meteorological parameters.

Description: Published

Description: 51-58

Description: 4V. Vulcani e ambiente

Description: JCR Journal

Description: restricted

Description: Methane plays an important role in the Earth’s atmospheric chemistry and radiative balance being the most important greenhouse gas after carbon dioxide. It has recently been established that geogenic gases contribute significantly to the natural CH4 flux to the atmosphere (Etiope et al., 2008). Volcanic/geothermal areas contribute to this flux, being the site of widespread diffuse degassing of endogenous gases (Chiodini et al., 2005). In such an environment soils are a source rather than a sink for atmospheric CH4 (Cardellini et al., 2003; Castaldi and Tedesco, 2005; D’Alessandro et al., 2009; 2011; 2013). Due to the fact that methane soil flux measurements are laboratory intensive, very few data have been collected until now in these areas. Preliminary studies (Etiope et al., 2007) estimated a total CH4 emission from European geothermal and volcanic systems in the range 4-16 kt a-1. This estimate was obtained indirectly from CO2 or H2O output data and from CO2/CH4 or H2O/CH4 values measured in the main gaseous manifestations. Such methods, although acceptable to obtain order-of-magnitude estimates, completely disregard possible methanotrophic activity within the soil. At the global scale, microbial oxidation in soils contributes for about 3-9% to the total removal of methane from the atmosphere. But the importance of methanotrophic organisms is even larger because they oxidise the greatest part of the methane produced in the soil and in the subsoil before its emission to the atmosphere. Environmental conditions in the soils of volcanic/geothermal areas (i.e. low oxygen content, high temperature and proton activity, etc.) have been considered inadequate for methanotrophic microrganisms. But recently, it has been demonstrated that methanotrophic consumption in soils occurs also under such harsh conditions due to the presence of acidophilic and thermophilic Verrucomicrobia. These organisms were found in Italy at the Solfatara di Pozzuoli (Pol et al., 2007), in New Zealand at Hell’s Gate (Dunfield et al., 2007) and in Kamchatka, Russia (Islam et al., 2008). Both the Italian and the Hellenic territories are geodynamically very active with many active volcanic and geothermal areas. Here we report on methane flux measurements made at Pantelleria (Italy) and at Sousaki and Nisyros (Greece). The total methane output of these three systems is about 10, 19 and 1 t a-1, respectively (D’Alessandro et al., 2009; 2011; 2013). The total emissions obtained from methane flux measurements are up to one order of magnitude lower than those obtained through indirect estimations. Clues of methanotrophic activity within the soils of these areas can be found in the CH4/CO2 ratio of the flux measurements which is always lower than that of the respective fumarolic manifestations, indicating a loss of CH4 during the travel of the gases towards earth’s surface. Furthermore laboratory methane consumption experiments made on soils collected at Pantelleria and Sousaki revealed, for most samples, CH4 consumption rates up to 9.50 µg h-1 and 0.52 µg h-1 respectively for each gram of soil (dry weight). Only few soil samples displayed no methane consumption activity. Finally, microbiological and molecular investigations allowed us to identify the presence of methanotrophic bacteria belonging to the Verrucomicrobia and to the Alpha- and Gamma-Proteobacteria in the soils of the geothermal area of Favara Grande at Pantelleria. While the presence of the former was not unexpected due to the fact that they include acidophilic and thermophilic organisms that were previously found in other geothermal environments, the latter are generally considered not adapted to live in harsh geothermal environments. Their presence in the soils of Pantelleria could be explained by the fact that these soils do not have extremely low pH values (〉5). Indeed thermotollerant methanotrophic Gamma-proteobacteria, have been previously found in the sediments of thermal springs in Kamchatka (Kizilova et al., 2012). Such species could find their niches in the shallowest part of the soils of Favara Grande were the temperatures are not so high and they thrive on the abundant upraising hydrothermal methane.

Description: Published

Description: Patras, Greece

Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi

Description: open

Description: Volcanic and geothermal systems emit endogenous gases by widespread degassing from soils, including CH4, a greenhouse gas twenty-five times as potent as CO2. Recently, it has been demonstrated that volcanic or geothermal soils are not only a source of methane, but are also sites of methanotrophic activity. Methanotrophs are able to consume 10–40 Tg of CH4 a−1 and to trap more than 50% of the methane degassing through the soils. We report on methane microbial oxidation in the geothermally most active site of Pantelleria (Italy), Favara Grande, whose total methane emission was previously estimated at about 2.5Mga−1 (t a−1). Laboratory incubation experiments with three top-soil samples from Favara Grande indicated methane consumption values of up to 59.2 nmol g−1 soil d.w. h−1. One of the three sites, FAV2, where the highest oxidation rate was detected, was further analysed on a vertical soil profile, the maximum methane consumption was measured in the topsoil layer, and values greater than 6.23 nmol g−1 h−1 were still detected up to a depth of 13 cm. The highest consumption rate was measured at 37 C, but a still detectable consumption at 80 C (〉1.25 nmol g−1 h−1) was recorded. The soil total DNA extracted from the three samples was probed by Polymerase Chain Reaction (PCR) using standard proteobacterial primers and newly designed verrucomicrobial primers, targeting the unique methane monooxygenase gene pmoA; the presence of methanotrophs was detected at sites FAV2 and FAV3, but not at FAV1, where harsher chemical–physical conditions and negligible methane oxidation were detected. The pmoA gene libraries from the most active site (FAV2) pointed to a high diversity of gammaproteobacterial methanotrophs, distantly related to Methylocaldum-Metylococcus genera, and the presence of the newly discovered acido-thermophilic Verrucomicrobia methanotrophs. Alphaproteobacteria of the genus Methylocystis were isolated from enrichment cultures under a methane-containing atmosphere at 37 C. The isolates grow at a pH range of 3.5 to 8 and temperatures of 18–45 C, and consume 160 nmol of CH4 h−1 mL−1 of culture. Soils from Favara Grande showed the largest diversity of methanotrophic bacteria detected until now in a geothermal soil. While methanotrophic Verrucomicrobia are reported as dominating highly acidic geothermal sites, our results suggest that slightly acidic soils, in high-enthalpy geothermal systems, host a more diverse group of both culturable and uncultivated methanotrophs.

Description: Published

Description: 5865–5875

Description: 4V. Vulcani e ambiente

Description: JCR Journal

Description: open

Description: Improving the constraints on the atmospheric fate and depletion rates of acidic compounds persistently emitted by non-erupting (quiescent) volcanoes is important for quantitatively predicting the environmental impact of volcanic gas plumes. Here, we present new experimental data coupled with modelling studies to investigate the chemical processing of acidic volcanogenic species during tropospheric dispersion. Diffusive tube samplers were deployed at Mount Etna, a very active open-conduit basaltic volcano in eastern Sicily, and Vulcano Island, a closed-conduit quiescent volcano in the Aeolian Islands (northern Sicily). Sulphur dioxide (SO2), hydrogen sulphide (H2S), hydrogen chloride (HCl) and hydrogen fluoride (HF) concentrations in the volcanic plumes (typically several minutes to a few hours old) were repeatedly determined at distances from the summit vents ranging from 0.1 to 10 km, and under different environmental conditions. At both volcanoes, acidic gas concentrations were found to decrease exponentially with distance from the summit vents (e.g., SO2 decreases from 10 000 μg/m3 at 0.1 km from Etna’s vents down to 7 μg/m3 at 10 km distance), reflecting the atmospheric dilution of the plume within the acid gas-free background troposphere. Conversely, SO2/HCl, SO2/HF, and SO2/H2S ratios in the plume showed no systematic changes with plume aging, and fit source compositions within analytical error. Assuming that SO2 losses by reaction are small during short-range atmospheric transport within quiescent (ash-free) volcanic plumes, our observations suggest that, for these short transport distances, atmospheric reactions for H2S and halogens are also negligible. The one-dimensional model MISTRA was used to simulate quantitatively the evolution of halogen and sulphur compounds in the plume of Mt. Etna. Model predictions support the hypothesis of minor HCl chemical processing during plume transport, at least in cloud-free conditions. Larger variations in the modelled SO2/HCl ratios were predicted under cloudy conditions, due to heterogeneous chlorine cycling in the aerosol phase. The modelled evolution of the SO2/H2S ratios is found to be substantially dependent on whether or not the interactions of H2S with halogens are included in the model. In the former case, H2S is assumed to be oxidized in the atmosphere mainly by OH, which results in minor chemical loss for H2S during plume aging and produces a fair match between modelled and measured SO2/H2S ratios. In the latter case, fast oxidation of H2S by Cl leads to H2S chemical lifetimes in the early plume of a few seconds, and thus SO2 to H2S ratios that increase sharply during plume transport. This disagreement between modelled and observed plume compositions suggests that more in-detail kinetic investigations are required for a proper evaluation of H2S chemical processing in volcanic plumes.

Description: Published

Description: 11653–11680

Description: open

Description: Volcanoes contribute to atmospheric pollution by increasing the amount of reactive and greenhouse gases and aerosols, making volcanic emissions one of the major natural sources of several trace elements to the atmosphere. In particular, Mt. Etna is considered to be, on the long-term average, the major atmospheric point source of many environmental harmful compounds. Their emission occurs in the form of gases, aerosols or particulate, both through continuous passive degassing from open-conduit activity and through sporadic paroxysmal eruptive activity. To estimate the environmental impact of magma-derived trace metals and their depositions processes, five bulk collectors have been deployed at various altitudes on the upper flanks around the summit craters of the volcano. Samples were collected every second week for a period of one year and analyzed for the main chemical-physical parameters (electric conductivity and pH) and for major and trace elements concentrations. The first data obtained clearly show that the volcanic contribution is always prevailing in the sampling site closest to the summit craters (∼1.5 km). In the distal sites (5.5-10 km from the summit) downwind of the summit craters, the volcanic contribution is also detectable but often overwhelmed by anthropogenic or other natural (seawater spray, geogenic dust) contributions. Volcanic contribution may derive from both dry and wet deposition of gases and aerosols from the volcanic plume, but sometimes also from leaching of freshly emitted volcanic ashes. In fact, in our background site (7.5 km in the upwind direction,) volcanic contribution has been detected only following an ash deposition event. Fluorine, S and Cl, are the major elements that prevailingly characterize the volcanic contribution in bulk deposition on Mt. Etna, but high concentrations of many trace elements are also detected in the studied samples. In particular, Si, Al, Fe, Ti, Cu, As, Rb, Pb, Tl, Cd, Cr, U and Ag display, in the site most exposed to the volcanic emissions, median concentration values about two orders of magnitude higher than those measured in our background site. Furthermore some of the analysed elements display very high enrichment values with respect to the average crust and, in the closest site to the summit craters, also deposition values higher than those measured in polluted urban or industrial sites.

Description: Unpublished

Description: Athens, Greece

Description: 4.5. Degassamento naturale

Description: open

Description: Volcanic activity is the main natural sources of sulphur dioxide (SO2) to the atmosphere. Although total anthropogenic sources are overwhelming greater, volcanoes like Mt. Etna and many others are considered to be among the biggest point sources of SO2 also during intereruptive periods. Apart from being one of the most impressive geodynamic expressions, volcanoes are also an important tourist attraction. During the summer season the number of tourists visiting the summit craters each day is on average many tens at Stromboli, hundreds at Vulcano and thousands at Mt. Etna. Of course touristic exploitation of active volcanic areas cannot exempt from warranting a reasonable security to the visiting persons. But while many risks in these areas have been since long time considered, gas hazard, a very subtle risk, is often disregarded. For healthy persons, about 1000 µg m-3 of sulphur dioxide is sensed by smell, 2000 to 4000 µg m-3 cause eye, nose and throat irritation, and 10,000 to 15,000 µg m-3 cause respiratory failure. For individuals with bronchial asthma or lung diseases, exposure to much lower doses could be fatal. Generally, a 700 µg m-3 level is considered to be a safe limit for such persons. The atmospheric concentrations of naturally emitted SO2 were measured at three volcanoes of southern Italy (Mt. Etna, Vulcano and Stromboli). Measurements were made with a network of passive samplers positioned at about 1.5 m above the ground, which gave time-integrated values for periods from few days to 1 month. Samplers were placed in zones of the volcanoes with high tourist frequentation. Measured concentrations reach values as high as 2700, 2400 and 10,000 µg m-3 for Etna, Vulcano and Stromboli respectively. Such values are absolutely dangerous to people affected by bronchial asthma or lung diseases. But considering that these are average values over periods from few days up to one month, SO2 concentrations could reach much higher peak values that could be dangerous also to healthy people. The present study evidences a peculiar volcanic risk connected to the touristic exploitation of active volcanic areas. Such risk is particularly enhanced at Mt.Etna where elderly and not perfectly healthy people can easily reach, with cableway and off-road vehicles, areas with dangerous SO2 concentrations.

Description: Published

Description: Bari, Italy

Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive

Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi

Description: open

Description: Methane plays an important role in the Earth’s atmospheric chemistry and radiative balance being the second most important greenhouse gas after carbon dioxide. Methane is released to the atmosphere by a wide number of sources, both natural and anthropogenic, with the latter being twice as large as the former (IPCC, 2007). It has recently been established that significant amounts of geological methane, produced within the Earth’s crust, are currently released naturally into the atmosphere (Etiope, 2004). Active or recent volcanic/geothermal areas represent one of these sources of geological methane. But due to the fact that methane flux measurements are laboratory intensive, very few data have been collected until now and the contribution of this source has been generally indirectly estimated (Etiope et al., 2007). The Greek territory is geodynamically very active and has many volcanic and geothermal areas. Here we report on methane flux measurements made at two volcanic/geothermal systems along the South Aegean volcanic arc: Sousaki and Nisyros. The former is an extinct volcanic area of Plio-Pleistocene age hosting nowadays a low enthalpy geothermal field. The latter is a currently quiescent active volcanic system with strong fumarolic activity due to the presence of a high enthalpy geothermal system. Both systems have gas manifestations that emit significant amounts of hydrothermal methane and display important diffuse carbon dioxide emissions from the soils. New data on methane isotopic composition and higher hydrocarbon contents point to an abiogenic origin of the hydrothermal methane in the studied systems. Measured methane flux values range from –48 to 29,000 (38 sites) and from –20 to 1100 mg/mˆ2/d (35 sites) at Sousaki and Nisyros respectively. At Sousaki measurement sites covered almost all the degassing area and the diffuse methane output can be estimated in about 20 t/a from a surface of about 10,000 mˆ2. At Nisyros measurements covered the Stephanos and Kaminakia areas, which represent only a part of the entire degassing area. The two areas show very different methane degassing pattern with latter showing much higher flux values. Methane output can be estimated in about 0.25 t/a from an area of about 30,000 mˆ2 at Stephanos and about 1 t/a from an area of about 20,000 mˆ2 at Kaminakia. The total output from the entire geothermal system of Nisyros probably should not exceed 2 t/a.

Description: Published

Description: Vienna, Austria

Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi

Description: open