ALBERT

Beschreibung: The Amik Basin is an asymmetrical composite transtensional basin developed between the seismically active left-lateral Dead Sea Fault (DSF) splays and the left-lateral oblique-slip Karasu Fault segment during neotectonic period. The relationship between the DSF and the East Anatolian Fault Zone is important as it represents a triple junction between Arabian Plate, African Plate and Anatolian Block in which the Amik Basin developed. The basin was formed on a pre-Miocene basement consisting of two rock series: Paleozoic crustal units with a Mesozoic allochthonous ophiolitic complex and ~1300 m thick Upper Miocene-Lower Pliocene sedimentary sequence. Plio-Quaternary sediments and Quaternary volcanics unconformably overlie the deformed and folded Miocene beds. Quaternary alkali-basaltic volcanism, derived from a metasomatized asthenospheric or lithospheric mantle, is most probably related to the syn-collisional transtensional strike-slip deformation in the area. Active faults in the region have the potential to generate catastrophic earthquakes (M〉7). Nineteen samples of cold and thermal groundwaters have been collected over the Amik Basin area for dissolved gas analyses as well as two samples from the gas seeps, and one bubbling gas from a thermal spring Samples were analysed for their chemical and isotopic (He, C) composition. On the basis of their chemical composition, three main groups can be recognized. Most of the dissolved gases (16; Group I) collected from springs or shallow wells (〈 150 m depth), contain mainly atmospheric gasses with very limited H2 (〈 80 ppm) and CH4 (1– 2700 ppm) contents and minor concentrations of CO2 (0.5–11.2 %). The isotopic composition of Total Dissolved Carbon evidences a prevailing organic contribution with possible dissolution of carbonate rocks. However the CO2-richest sample shows a small but significant deep (probably mantle) contribution which is also evidenced by its He isotopic composition. Further three samples, taken from the northern part of the basin close to Quaternary volcanic outcrops and main tectonic structures, also exhibit a small mantle He contribution (Fig. 1). The two dissolved gases (Group II) collected from deep boreholes (〉 1200 m depth) are typical of hydrocarbon reservoirs being very rich in CH4 (〉 78 %) and N2 (〉 13%). The water composition of these samples is also distinctive of saline connate waters (Cl- and B-rich, SO4-poor). Isotopic composition of methane (δ13C ~ -65‰) indicates a biogenic origin while He-isotopic composition points to a prevailing crustal signature for one (R/Ra 0.16) of the sites and a small mantle contribution for the other (R/Ra 0.98) (Fig. 1). The three free gas samples (Group III), taken at two sites within the ophiolitic basement west of the basin, have the typical composition of gas generated by low temperature serpentinisation processes with high hydrogen (37–50 %) and methane (10–61 %) concentrations. While all three gases show an almost identical δD-H2 of ~ -750‰, two of them display an isotopic composition of methane (δ13C ~ -5‰; δD ~ -105‰) and a C1/[C2+C3] ratio (~100) typical of abiogenic hydrocarbons and a significant contribution of mantle-type helium (R/Ra: 1.33). The composition of these two gasses is comparable to that of the gasses issuing in similar geologic conditions (Chimera-Turkey, Zambales-Philippine and Oman ophiolites). The gas composition of the other site evidences a contribution of a crustal (thermogenic) component (δ13C-CH4 ~ -30‰; δD-CH4 ~ -325‰; C1/[C2+C3] ~ 3000). Such crustal contribution is also supported by higher N2 contents (40% instead of 2%) and lower He-isotopic composition (R/Ra 0.07) (Fig. 1). These first results highlight contributions of mantle-derived volatiles possibly drained towards shallow levels by the DSF and other parallel structures crossing the basin showing a tectonic control of the fluids circulating within the Basin .

Beschreibung: Published

Beschreibung: Patras, Greece

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

Beschreibung: open

Beschreibung: 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.

Beschreibung: Published

Beschreibung: Patras, Greece

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

Beschreibung: open

Beschreibung: 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.

Beschreibung: Published

Beschreibung: Vienna, Austria

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

Beschreibung: open

Beschreibung: 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.

Beschreibung: Published

Beschreibung: Vienna, Austria

Beschreibung: 4.4. Scenari e mitigazione del rischio ambientale

Beschreibung: open

Beschreibung: Volcanoes represent an important natural source of several trace elements to the atmosphere. For some species (e.g., As, Cd, Pb and Se) they may be the main natural source and thereby strongly influencing geochemical cycles from the local to the global scale. Mount Etna is one of the most actively degassing volcanoes in the world, and it is considered to be, on the long-term average, the major atmospheric point source of many environmental harmful compounds. Their emission occurs either through continuous passive degassing from open-conduit activity or through sporadic paroxysmal eruptive activity, in the form of gases, aerosols or particulate. To estimate the environmental impact of magma-derived trace metals and their depositions processes, rainwater and snow samples were collected at Mount Etna area. Five bulk collectors have been deployed at various altitudes on the upper flanks around the summit craters of the volcano; samples were collected every two 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. Chemical analysis of rainwater clearly shows that the volcanic contribution is always prevailing in the sampling site closest to the summit crater (about 1.5 km). In the distal sites (5.5-10 km from the summit) and 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. About 30 samples of fresh snow were collected in the upper part of the volcano, during the winters 2006 and 2007 to estimate deposition processes at high altitude during cold periods. Some of the samples were collected immediately after a major explosive event from the summit craters to understand the interaction between snow and fresh erupted ash. Sulphur, Chlorine and Fluorine, are the major elements that prevailingly characterize the volcanic contribution in atmospheric precipitation on Mount Etna, but high concentrations of many trace elements are also detected in the studied samples. In particular, bulk deposition samples display high concentration of Al, Fe, Ti, Cu, As, Rb, Pb, Tl, Cd, Cr, U and Ag, in the site most exposed to the volcanic emissions: median concentration values are about two orders of magnitude higher than those measured in our background site. Also in the snow samples the volcanic signature is clearly detectable and decreases with distance from the summit craters. 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.

Beschreibung: Published

Beschreibung: Vienna, Austria

Beschreibung: 4.5. Degassamento naturale

Beschreibung: open

Beschreibung: 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 ~10km 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.

Beschreibung: Published

Beschreibung: 1441-1450

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

Beschreibung: 4.5. Degassamento naturale

Beschreibung: JCR Journal

Beschreibung: open

Beschreibung: Emissions of volcanoes and their depositions do have an immediate impact on their surrounding environment. In the present study, emissions and depositions of the active volcanic and geothermal system Vulcano (Italy) were investigated by active moss biomonitoring (Fig. 1) in the spring of 2012. Sphagnum moss bags were exposed for periods of 3 days, 3, 6 and 9 weeks. Soil and rainwater samples as well as meteorological data were also collected. After exposure, mosses were oven-dried, grinded and each sample was extracted either in deionized water or HNO3 (with H2O2). Extraction solutions were analyzed by ICP-MS for total concentrations of Li, Mg, Sr, Ba, Cr, Mn, S, Fe, Co, Cu, Zn, Mo, W, Tl, As, Sb, Bi, I, and Se. Soil and rain water samples were analyzed for the same trace elements. For elements such as As and Tl, deionized water extracts showed comparable concentrations to HNO3 extracts, indicating either the absence of particles or the presence of water-soluble particles. Elements such as Pb, Ba, Se and Sr were only dissolved to about 10 % or less in deionized water, indicating a significant share of water-insoluble particle formation. Distribution patterns of emissions and depositions over the whole island of Vulcano allowed classifying all investigated elements into four groups based on their origin (Fig. 2). Lithium was found ubiquitously on the island thus likely is of either marine or geogenic origin (group a in Fig. 2). The elements Mg, Fe, Sr, Mn, Zn, Co, and W were found predominantly on the crater where bare soil was present, and were grouped as “soilborne elements” (group b). These elements are characterized by deposition close to their source of origin. Elements with higher concentrations at the fumarolic field were grouped according to their transport characteristics. The elements I, Se, Tl, Bi, Sb, As, and S were considered as true volatiles (group c) being found also further away from the fumarolic field than Pb, Cr, Mo, and Ba which were interpreted to be predominantly emitted as particles (group d). Moss-bag biomonitoring proved to be an effective tool for the study of emission and deposition processes in active volcanic areas which also allows a classification of elements accumulated on the moss by their origin and distribution patterns.

Beschreibung: Published

Beschreibung: Patras, Greece

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

Beschreibung: open

Beschreibung: The study area is a 130 km long fast spreading graben in Central Greece bordered by active faults. Its complex geodynamical setting includes the presence at depth of a subduction slab responsible for the recent (Quaternary) volcanic activity in the area which possibly represents the northward continuation of the South Aegean active volcanic arc. To the area belongs also the western termination of the North-Anatolian fault a tectonic lineament of regional importance. The high geothermal gradient of the area is evidenced by the presence of many thermal springs with temperatures from 19 to 82 °C, issuing along the normal faults bordering the graben. In the period 2004-2012 more than 60 gas and water samples have been collected and their chemical and isotopic analysis revealed a wide range of compositions. Going from west to east the gas composition changes (Fig. 1) from CH4- to CO2-dominated passing through mixed N2-CH4 and N2-CO2 compositions, while at the same time the He isotopic composition goes from typical crustal values (0.02 R/Ra) up to 0.87 R/Ra (corrected for air contamination), showing in the easternmost sites a small but significant mantle input (up to ~ 10%). Isotopic composition of CH4-C indicates a thermogenic origin for the CH4-rich samples (δ13C from -50 to -37 ‰) and hydrothermal origin for the remaining samples (〉 -25‰). Positive δ15N values (around +2 ‰) indicate a contribution of crustal derived nitrogen for the N2-rich samples. The most pristine values of δ13C(CO2) refer to the most CO2-rich samples. These values (~ -3 ‰) point to a mixed mantle-marine carbonate source. Lower δ13C values (-10 ÷ -5 ‰) of the other sites can be explained by loss of CO2 due to dissolution processes. Also temperature and salinity of the waters shows differences along the graben increasing from west to east (Fig. 2). Two main groups can be separated on the basis of the total dissolved salts (TDS). The first, represented by dilute waters (TDS 〈 500 mg/l), is found in the westernmost sites characterised by the presence of CH4-rich and mixed N2-CH4 gases. The remaining waters display higher salinities (TDS from 9 to 35 g/l) due to the mixing with high salinity waters. The water composition can be explained by mixing of two end-members, one with low salinity of meteoric origin and the other with high salinity of marine origin. The mixing can be evidenced in Fig. 2. Low salinity waters show low chloride contents and their light water isotope composition overlaps the field of the cold groundwaters of the area confirming their meteoric origin. High salinity waters are aligned along the mixing line between the cold groundwaters and the seawater confirming the contribution of marine component. Most of the water compositions in the triangular graph of Giggenbach fall in the field of the non equilibrated waters being therefore unsuitable for geothermometric estimations. Only the easternmost sites (Gialtra, Ilion and Edipsos) falling the field of the partially equilibrated waters yield estimated temperatures in the range 150-170 °C. Silica geothermometers confirm these estimations. This study revealed that the complex geodynamic setting of the area is clearly reflected in the wide compositional range of the gases collected in the area that evidence contributions from different end-members (atmosphere, crust, mantle and hydrothermal systems). Water chemistry can be explained mainly from the mixing of a meteoric low-salinity end-member with a high-salinity marine end-member partially modified by hydrothermal water-rock interactions. The highest estimated temperatures in the hydrothermal reservoirs are in the range 150-170 °C.

Beschreibung: Published

Beschreibung: Patras, Greece

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

Beschreibung: open