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Karst systems represent the main drinking water source for 20-25% of world’s population, although covering only 7-10% of the global land surface (Ford & Williams, 2007). Karst aquifers are highly vulnerable to external pollution, so their protection and management is of critical importance to sustain water resources. In Greece, starting from the 1970’s, water demands for agricultural, domestic and industrial use increased significantly, mainly in coastal areas (Daskalaki & Voudouris, 2008). The main Hellenic aquifers are hosted in alluvial deposits, in Neogene deposits and in carbonate rocks. The latter cover about 35% of the country and are located in Western, Central and Southern Greece (Daskalaki & Voudouris, 2008). Karst aquifers are developed in limestones and dolomites (Triassic – Cretaceous), and in marbles (Paleozoic – Mesozoic). Their hydrogeological behaviour is controlled by tectonic deformation. About 45% of them is located inland, while the rest is in coastal areas (Voudouris & Kazakis, 2018). During several field sampling campaigns from 2016 to 2020, 126 karst water samples were collected in Greece. Physicochemical parameters (temperature, pH, electric conductivity and redox potential) were measured in situ. Analyses of major ions and trace elements were performed at the laboratories of INGVPalermo. Results were compared with the limits set by the Directive 98/83/EC that fixes quality standards for drinking water. Temperatures of sampled waters ranged from 8.7 to 31 °C, pH from 6.5 to 8.4, whilst Total Dissolved Solids from 206 to 25,617 mg L-1. Most of the samples showed a typical alkaline-earth bicarbonate composition, whilst those sited along the coastline presented elevated concentrations of Na+ (up to 7,680 mg L-1), Cl- (up to 14,200 mg L-1) and SO4 2- (up to 1,940 mg L-1), sometimes exceeding the EC limits, suggesting a seawater contamination. Furthermore, karst springs contaminated by seawater, displayed high concentrations of B (up to 3,870 μg L-1) and Sr (up to 7,080 μg L-1). Nitrate concentrations were always below the EC limit (50 mg L-1), indicating a low contamination from fertilizers. Few low chloride waters showed a metal enrichment, such as Tempi springs (Thessaly) that presented enrichments in Sr (up to 242 μg L-1), Mo (up to 2.27 μg L-1), Cs (up to 1.57 μg L-1) and As (up to 17 μg L-1). Such enrichments could be attributed to the local petrological environment. Generally, karst water samples can be considered suitable for human consumption. Water quality degradation of Hellenic karst springs is mainly due to seawater intrusion or to local geogenic contamination.

Identification of transfer of mantle-derived fluids (e.g. CO2, N2, noble gases) in continental regions is critical for developing exploration strategies of natural resources (i.e., hydrocarbons, ore deposits, heat sources) and also to investigate the processes that control the deep and shallow evolution of Earth such as subduction, volcanism, natural degassing vs. active tectonic and earthquakes (e.g., O’Nions & Oxburgh, 1988; Caracausi et al., 2013; Labidi et al., 2020). Recently the outgassing of deep-mantle volatiles has been verified in different crustal segments of central-western Europe, but the geological and tectonic controls on migration of these deep fluids remain to be fully understood. To figure out the source of these volatiles can furnish new elements to the understanding of the complex regional geodynamic evolution and for the exploitation of natural resources. Furthermore, that region is also characterized by an high heat flow (< 150 mW/m2) that highlights an high geothermal energy potential that is coupled to seismicity trough the overall crust (Horwarth et al., 2015). Here, we report on the results of an extensive geochemical survey of gas manifestations in the Serbian part of the Vardar zone, a mega-suture zone between Eurasia and Africa plates. Based on their chemical compositions (C, He, Ne, Ar), the studied gases are clustered into three distinct groups (CO2-, N2- and CH4-dominated). The He isotope ratios identify a weak (

Karst aquifers are considered to be one of the most important aquifer types, as they constitute the main drinking water resource for the majority of the global population (Ford et al., 2007). They are generated from the dissolution of carbonate rocks (e.g. limestone, dolomite, marble etc.), a phenomenon commonly known as “karstification”. This process is mainly caused by the acidity of water enriched in dissolved CO2, with the concentration of the latter being dependent on both the temperature and the CO2 partial pressure of the atmosphere in contact with the water (Bakalowicz, 2005). Carbonate rocks cover about 35% of the land surface of Greece and are mainly located in the western, central and southern parts of the country (Daskalaki et al., 2008). The Hellenic karst aquifer resources are more abundant in the western part of Greece, which receives the highest amount of precipitation (1800 mm/a) (Mimikou, 2005). The karst system constitutes a strategic resource of water in the region and preserving its quantity and quality is of the utmost importance for the sustainability of the area. Seventy samples of natural water were collected from karst springs in the northern (Macedonia-Thrace) and in the central parts of Greece, during 3 campaigns from 2016 to 2018. Sampling sites were selected on the basis of the springs flow rates (> 50 L/s). Water temperature, pH, Eh and electric conductivity were measured in situ with portable instruments; major ions were determined by Ionic Chromatography (IC) on filtered (anions) or filtered and acidified (cations) samples, whereas trace elements were determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) on filtered and acidified samples. All analyses were performed at the laboratories of INGV of Palermo. Chemical compositions were compared with the limits fixed by the Directive 98/83/EC, which is the most recent EU legislation that sets quality standards for drinking water. Regulations concerning the quality of drinking water as established by the Directive allow Member States to adapt the monitoring of water quality to local conditions (Karavoltsos et al., 2008). Temperatures of the sampled waters ranged from 8 to 25 °C, pH from 6.5 to 8.4, whilst Total Dissolved Solids (TDS) from 206 to 15,418 mg/L. The highest concentrations of sodium, potassium, chloride and sulfate were found in the karst springs of Central Greece (26.6-5610 mg/L; 1.56-204 mg/L; 81.06-9467 mg/L; 15-2420 mg/L, respectively), where values had sometimes exceeded the limits set by the Directive 98/83/EC, indicating a contamination due to sea water intrusion. Based on the chloride concentrations, samples were subdivided into low (Cl- < 100 mg/L) and high (Cl- > 100 mg/L) chloride karst waters. All water samples were plotted in a Langelier Ludwig diagram (Fig. 1) with the low chloride waters presenting a typical alkaline-earth bicarbonate composition. Exception is the samples of Kaliakuda, Sidirokastro and Koromilia that display enrichment in alkalis possibly due to hydrothermal activity. On the other hand, the most chloride-rich waters plot close to the sea water composition point while two samples (Rema, Mylos Kokkosi) are aligned along the seawater-groundwater mixing line (Fig. 1). Concentration ranges of major and trace elements for all waters are presented in Fig. 2, with low and high chloride samples being plotted with different symbols. High chloride group displays much higher values for Mg, SO4, Cl, Na, K, Sr, B, Li, Rb and Cs with respect to low chloride, with differences in the median values between two and three orders of magnitude. Species deriving from carbonate dissolution (Ca and HCO3) show the lowest range of concentrations both for low and high chloride waters (Fig. 2). Low chloride waters show a wide range of concentrations (three to four orders of magnitude) for trace elements such as Li, Fe, Rb, As, Mn, Cu and Cs. Trace elements were above the legislation limits (Directive 98/83/EC) mostly in the case of high chloride karst springs, showing elevated concentrations of Boron (up to 1861 μg/L), Strontium (up to 5026 μg/L) and Arsenic (up to 12.1 μg/L). In terms of Boron and Strontium, the exceeding values seem to be generally related to the intrusion of sea water. On the other hand, Arsenic, whose maximum admissible level is 10 μg/L, was above limit also in the low chloride water (17 μg/L) of Tempi, Thessalia. Few low chloride waters show a metal enrichment, such as Tempi (Sr = 242 μg/L, Mo = 2.27 μg/L, and Cs = 1.57 μg/L) and Kaliakuda (V = 3.89 μg/L, Mn = 3.65 μg/L, Fe = 71.26 μg/L, Cu = 11.55 μg/L, Zn = 22.61 μg/L, Rb = 54.7 μg/L), whilst nitrate concentrations that could indicate contamination from fertilizers or from septic tanks, are always below the maximum admissible value (50 mg/L). Most of the analyzed waters can be considered suitable for human consumption. Water quality deterioration of Hellenic karst springs is mainly due to sea water intrusion, whilst only few low chloride waters show significant enrichments in trace metals that rarely exceeds the drinking water standards. These higher contents are probably of natural origin due to local geological setting.

Earthquakes and volcanic eruptions represent a hazard. However, the impact of gases released in geodynamically active areas should not be underestimated. It is commonly known that geogenic sources release great amounts of gases, which, apart from having an important influence on the global climate, can also have a strong impact on human health causing both acute and chronic effects. In particular, CO2 and sulphur gases (mainly H2S and SO2) are the main compounds responsible for acute mortality due to their asphyxiating and/or toxic properties. One of the most known and also worst episodes occurred, took place on the 21th of August 1986 at Lake Nyos, Cameroon, when about 1700 people were killed and 850 injured by a massive CO2 release (D’Alessandro, 2006). Like other geodynamically active areas, Greece is also affected by a large number of geogenic gas manifestations (Daskalopoulou et al., 2018a). These occur either in the form of point sources (fumaroles, mofettes, bubbling gases) or of diffuse soil gas emanations (Daskalopoulou et al., 2018b). D’Alessandro and Kyriakopoulos (2013) made a preliminary estimation of the risk related to geogenic gases in Greece for the time period of 1992-2011; the whole population of the country was considered. In that period, at least two fatal episodes with a total of three victims took place, likely caused to the 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 many other natural or anthropogenic risks. Since deaths due to natural gases are often wrongly attributed, it cannot be excluded that some fatal episode has not been recognized and thus that the risk is somewhat higher than assessed. Although very low, this risk should not be neglected, not only because it is possibly underestimated, but also because simple countermeasures could be adopted for risk reduction. Dangerous areas could be easily identified and delimited by geochemical prospecting and their hazards properly highlighted. Apart from the sites where fatal episodes occurred, many other hazardous sites have been recognized in Greece. Here we present data collected at Loutra Ypatis (central Greece). Study area Sperchios Basin – Evoikos Gulf Graben is a 130 km long actively spreading graben in Central Greece (1 cm/a). The high geothermal gradient of the area is evident by the presence of many thermal springs with temperatures that vary from 24 to 82 °C. In the waters of these springs, discharging along the normal faults bordering the graben, an abundant gas phase is bubbling. Loutra Ypatis is one of the emerging springs and its waters (31 °C) are exploited by a spa. The water is currently drained by a gallery and therefore the water level is about 5 m below ground at the bottom of a funnel-like hole (Fig. 1 left). For safety reasons the hole was covered by a closed building (Fig. 1 left and center). The gas, which is vigorously bubbling in the spring, is mostly (> 96%) composed of CO2 (D’Alessandro et al., 2014). The walls of the hole are covered of sulfur that derives from the partial oxidation of the H2S (2500 ppm) contained in the released gas (D’Alessandro et al., 2014). Methods In October 2015 atmospheric concentrations of CO2 were measured with a Licor LI820 NDIR spectrometer (range 0 to 20,000 ppm, accuracy of 2%), whilst in April 2016, the atmospheric concentrations of CO2 and H2S were measured with a Multi-GAS analyser manufactured by INGV-Palermo equipped with Licor LI-840 NDIR spectrometer (CO2 0-20,000 ppm) and an EZ3H electrochemical sensor by City Technology Ltd. (H2S 0–100 ppm). Simultaneous CO2, CH4 (both 0- 100%), CO, H2S (both 0-500 ppm) and O2 (0 – 25%) concentrations within the building were measured with a portable gas analyser GA2000 (Geotechnical Instruments). Results and discussion Due to the fact that a building covers the thermal spring, the intense bubbling activity of its waters creates a strong gas accumulation inside. The main component of the released gases is CO2, which has a higher density with respect to atmospheric air, thus creating the conditions for gas accumulation. About 2 m above the water level, CO2 concentrations of >95% and non-detectable O2 concentrations were measured. At higher levels above the water, CO2 concentrations were decreased but never below 50%. Such concentrations within the building are lethal for both animals and human beings. Of course, access is forbidden, but as the building is not perfectly sealed, the gases permeate to the outside through fissures and cracks. Figure 2 shows the CO2 concentrations measured in the air on October 2015 at 1.5 m height while walking around the walls of the edifice at about 2 m distance. Leaking of CO2 from the edifice is made evident by concentrations reaching values of more than 6000 ppm. The highest values were measured close to the entrance of the edifice were fissures and cracks are concentrated. Due to the tendency of CO2 to accumulate at lower levels, in this place, close to the ground, CO2 levels lethal to small animal can be reached. This was made evident by a dead bird found in that occasion (Fig. 1). In April 2016, due to the much windier conditions, CO2 concentrations at the same places reached values never exceeding 1000 ppm while H2S was always below 1 ppm. These values sharply increased getting closer to the fissures around the main entrance of the building and reached saturation of the sensors (CO2 > 20,000 ppm and H2S > 100 ppm) at a distance of few centimeters. The intense CO2 degassing observed at Loutra Ypatis may be responsible for elevated levels that can have an impact on human beings. It is worth noting that values measured in the atmosphere close to the building exceed the Occupational Recommended Exposure Limit of 5000 ppm (NIOSH, 2005). In closed spaces lethal levels can be easily reached. An older inhabitant of the close by village told us that in his childhood a playmate died by going inside the gallery that drains the thermal water out of the spa due to the high CO2 levels. Such episode underscores the need not to disregard the gas hazard created by intense natural gas manifestations like the thermal spring of Loutra Ypatis.

Areas located at plate boundaries are characterized by the presence of seismic, volcanic, and geothermal activity, as well as ore deposition. Such processes are enhanced by the circulation of hydrothermal fluids in the crust transporting volatiles from either the deep crust or the mantle to the surface. Intense geodynamic activity is also taking place in Greece giving rise to: (i) the highest seismicity in Europe, (ii) the presence of an active volcanic arc and numerous areas of anomalously high geothermal gradient, and (iii) a widespread occurrence of thermal springs. Elevated heat flow values are concentrated in Sperchios basin, an area characterised by a system of deeply rooted extensional faults and quaternary volcanic activity. This regime favoured the formation of hydrothermal systems, the surface expression of which are thermal springs with intense bubbling of CO2-rich gases. Flux measurements in the bubbling pools were made with the floating chamber method. The highest bubbling CO2 output is found in Thermopyles and Psoroneria (1 and 2 t/d, respectively). The outgoing channels of these springs have an elevated flow (>250 l/s) of gas-charged water (>15 mmol/l of CO2). Although no bubbling is noticed along the stream, the CO2 content decreases by an order of magnitude after few hundreds of metres, indicating an intense degassing from the water. Taking into account the water flow and the amount of CO2 lost to the atmosphere, the CO2 output of the outgoing channels is quantified in >10 t/d for Thermopyles and 9 t/d for Psoroneria. An estimation is also made at Ypati, Kamena Vourla, Koniavitis and Edipsos, where the mean values reach 1 t/d of CO2 for each spring. The obtained values are always higher respect to the estimated outputs from visible bubbling, suggesting that most of the degassing is “hidden”. Furthermore, the loss of CO2 from the water determines a shift in dissolved carbonate species as demonstrated by the pH increase along the channel that leads eventually to an oversaturation in carbonate minerals and therefore travertine deposition. To sum up, the total CO2 output of the study area is estimated at 30 t/d, with the major contribution deriving from the degassing along the outflow channels of the thermal springs. Such output is comparable to that of the single active volcanic systems along the South Aegean Volcanic Arc (Sousaki, Methana, Milos, Santorini, Kos and Nisyros) and highlights the importance of “hidden” degassing along CO2-oversaturated streams.

Florina Basin is located in northern Greece, close to Mount Voras where the volcanic activity of Late Messinian age began. In the area, many CO2-rich gas emissions are present as a bubbling free-phase in groundwater (both springs and wells) and soil gases. Volcanism along with the geological and geodynamic regime of the basin, created the ideal conditions for CO2 accumulation in vertically stacked reservoirs. One of these, industrially exploited by the company Air Liquide Greece, produces 30,000 t/a of CO2. Results show that CO2 concentrations in the gases of Florina can arrive up to 99.8% and are mostly above 90%. Moreover, C-isotope composition (-2.1 to + 0.3 h vs. VPDB) indicates a mixed mantle-limestone origin for CO2, while He isotope composition (R/RA from 0.21 to 1.20) shows a prevailing crustal origin with an up to 15% mantle contribution. Helium and methane, with concentrations spanning over three orders of magnitude, show a positive correlation and a consequent high variability of He/CO2 and CH4/CO2 ratios. This variability can be attributed to the interaction of the uprising gases with groundwater that chemically fractionates them due to their different solubility. Based on the CO2, CH4 and He concentrations, gas samples collected in the basin can be divided in 3 groups: a) deep reservoir gases, b) enriched in less soluble gases and c) depleted in less soluble gases. The first group consists of gas samples collected at the Air Liquide extraction wells, which tap a 300m deep reservoir. This group can be considered as the least affected by fractionation processes due to interaction with groundwater. The gases of the second group due to their interaction with shallower unsaturated aquifers, become progressively enriched in less soluble gases (He and CH4). Finally, the third group represents residual gas phases after extensive degassing of the groundwater during its hydrological pathway.

Volatiles are transported from the deep crust or mantle to the surface in geodynamically active areas where seismic, volcanic and geothermal activity is present; the circulation of hydrothermal fluids in the crust is enhanced. In such areas, faults may act as preferential pathways for advective gas-carrying fluid transport. Towards the surface, pressure decrease allows the gases to escape from the fluids into soil gas and eventually into the atmosphere (King, 1986). The migration of carbon-bearing crustal and mantle fluids contributes to Earth’s carbon cycle (Berner & Kothavala 2001). However, till now, the mechanisms, magnitudes and time variations of carbon transfer from depth to the surface remain the least understood parts of the global carbon budget. Carbon dioxide and methane are the main contributors of the total amount of C-degassing from geological (volcanic and non-volcanic) sources. From the beginning of the last century, high attention has been paid to the reservoirs of CO2 and CH4 in the atmosphere because they represent the most dangerous species in terms of global warning. The increased amount of carbon dioxide and methane in the atmosphere has important implications for the energy balance and the chemical composition of the atmosphere. Mörner and Etiope (2002) calculated that 102-103 Mt of CO2 are presumably involved in the carbon cycle every year. This estimation though, is affected by high uncertainty as a number of sources and C-degassing environments that account for this high leakage were not taken into consideration. Greece belongs to the most geodynamically active regions of the world and as such, it has to be considered an area of intense geogenic degassing. Regarding carbon, the territory is characterized by the high hydrothermal and volcanic activity of the South Aegean Active Volcanic Arc (SAAVA), and by widespread geological seeps of buried carbon dioxide and methane. In the present work, we present more than 700 literature data of free gases spread along the whole Hellenic territory to get insight on geographic distribution and composition of the released fluids. Moreover, we review all the published studies on CO2 and/or CH4 output of high degassing areas of Greece that are mainly concentrated along the SAAVA in a first attempt to estimate the total geologic output of the nation. Helium isotope data propose that the highest mantle contribution (50 to 90%) is found along the SAAVA, whereas the lowest in continental Greece (0-20%), with the atmospheric contribution being mostly negligible. Based on the geographical distribution of the gases, it is evident that the R/RA ratios and CO2 concentrations increase in areas characterized by: i) thin crust; ii) elevated heat flow values; iii) recent (Pleistocene-Quaternary) volcanic activity; and iv) deep routed extensional or transtensional regional faults. The highest values are therefore found along the SAAVA and the lowest in the western part of Greece where CH4 emission is prevailing. Furthermore, it was noticed that the majority of the samples present a prevailing limestone C component, whilst only few samples have a prevailing mantle C component (Sano and Marty, 1995). It seems barely possible though to distinguish CO2 deriving from crustal and slabrelated limestones. Additionally, due to the complex geodynamic history, the mantle C isotope composition could be affected by subduction-related metasomatism and, similarly to the nearby Italian area (Martelli et al., 2008), the C isotope composition could be more positive. In this case, the mantle contribution is probably underestimated. In terms of geogenic carbon degassing, the best studied and most exhaling area is the SAAVA, which releases 104,090 t/a of CO2 and 20.26 t/a of CH4. Continental Greece on the contrary, is much less studied but may release CO2 in the same order of magnitude in its eastern-central and northern part. The western and south-western parts of Greece are conversely the main area of methane and higher hydrocarbon degassing. Methane output of Greece is much less constrained but the presence on its territory of one of the biggest thermogenic gas seepages of Europe releasing about 200 t/a of CH4 to the atmosphere underscores its potentially high contribution. Approximately 114,310 t/a of CO2 and 221 t/a of CH4 are released from the whole Hellenic territory (Daskalopoulou et al., submitted). This estimation though, should be considered minimum as there are processes and sources that have not been taken into consideration yet. More specifically, in the submarine manifestations found at greater depths, gases cannot reach the sea surface due to the dissolution process that takes place along the water column; this is especially true for CO2 that is more soluble in water respect to other gases (eg. Milos - Dando et al., 1995; Kolumbo - Rizzo et al., 2016 etc). Moreover, the geological and geodynamic regime can contribute in the formation of CO2 reservoirs. This is the case of Florina Basin (Pearce et al., 2004) where more than one CO2 reservoirs were created, with one of them being exploited by the company Air Liquide Greece. It is worth noting that this reservoir, found at a depth of approximately 300 m, produces 30,000 t/a of CO2 (Pearce et al., 2004). Moreover, in the same area, water is also used for water supply and irrigation purposes. This water though contains a great amount of dissolved CO2 great part of which is released to the atmosphere when the water is pumped to the surface. Another source that should be underscored is the quantification of geogenic CO2 dissolved in big karstic aquifers. Chiodini et al. (1999, 2000) demonstrated that the relatively high solubility of CO2 in water plays an important role in the quantification of carbon. This approach was proved for central Italy and it might be the case for continental Greece due to the similar geodynamic history. Finally, in ophiolitic sequences where serpentinization takes place, if and when the conditions are adequate (i.e. presence of effective catalysts – Etiope and Ionescu, 2015) an abiogenic origin for CH4 seems to be favored even at low temperatures. Ophiolitic sequences crop out widely in Greece along two N-S trending belts, whilst more hyperalkaline springs or dry seeps may be present. However, their flux in generally is very low and therefore their contribution to the total natural CH4 output has probably to be considered negligible.

T he Duvalo locality is located in the SW of the Republic of North Macedonia, in the Ohrid region, near the village of Kosel. It is an area of strong soil degassing, called “volcano” by the local people despite volcanic activity has never been documented in the recent geologic history of the area [1]. A large area (thousands of sqm) shows signs of strong alteration and is devoid of vegetation. Until the 19thcentury sulphur was mined from this area [1]. In August 2019, a campaign of soil CO2 flux measurements and soil gas sampling was made. Duvalo is sometimes referred to as an active geothermal feature but no signs of enhanced geothermal gradient were found and the soil temperatures at 50 cm depth in this campaign were always within the range of local mean air temperatures. Soil CO2 flux values ranged from 1.3 to 59,000 g/m2/d and can be modelled with the overlapping of 3 or 4 flux populations. A possible biological background is estimated in 6.8±1.8 g/m2/d while the other populations are characterized by an anomalous average flux ranging from 180 to 33,000 g/m2/d. The CO2 total emission, estimated both with a statistical and geostatistical approach, provided similar values in the order of 50 t/d. This has to be considered as a minimum value because only areas with evident signs of alteration have been investigated. Nevertheless, the estimated output is quite high for an area unrelated with recent volcanism or geothermal activity. The chemical composition of soil gases shows: CO2 (96.6%), N2 (1.8%), H2S (0.6%) and CH4 (0.3%) as the main gases. The present composition is almost indistinguishable from previous analyses made in 1957 and 1977 [1] pointing to a stability of the system in last decades. The isotope compositions indicate for CO2 (δ13C -0.2 ‰) a pure carbonate rock origin, for CH4 (δ13C -34.4 ‰ and δ2H -166 ‰) a thermogenic origin and for He (R/RA 0.10) a pure crustal origin. The H2S released at Duvalo may be produced by either microbial or thermochemical sulphate reduction favoured by hydrocarbons whose presence can be inferred by the uprise of thermogenic methane. Partial oxidation of H2S during its upflow, producing sulphuric acid, may be responsible of the production of abundant CO2 through dissolution of carbonate rocks. Similar processes have been evidenced also in other parts of North Macedonia [2]. These gases rise up through the N–S trending normal faults bordering the seismically active Ohrid basin graben [3] being released to the atmosphere through the soils of Duvalo “volcano”.

Samples of efflorescences and encrustations of hydrothermal origin have been collected at three fumarolic areas in Greece. The three sites are Sousaki, Thiafi (Methana) and Kokkino Nero (Kos) and all belong to the South Aegean Active Volcanic Arc. Samples were analysed for their mineralogical (XRD and SEM-EDS) and chemical composition. Solutions obtained from both mineralization with HNO3 and leaching with distilled water, were analysed for major (ICP-OES), minor and trace metals (ICP-MS) and for sulfate contents (IC). Results show that their composition is mainly controlled by the petrological composition of the substrate (ultramafic rocks at Sousaki, felsic volcanic rocks at Methana and low-grade metamorphic rocks at Kos). The microenvironmental conditions (humidity, oxidizing or anoxic, exposed or sheltered from meteoric agents) as well as the rainfall regime of the area play also an important role. The presence of highly soluble sulfate minerals with elevated contents of many metals further underscores the significant influence of hydrothermal activity on elements’ mobility. The sometimes very high concentrations in toxic elements like Al, As, Co, Cr, Ni evidence also a potential environmental impact.

In the period from 2004 to 2017, more than 350 samples of free and dissolved gases were collected along the whole Hellenic area. Some literature data have also been taken into consideration (Rizzo et al., 2016). Samples have been analysed for their chemical and isotope composition. The concentrations range from 0.10 to 3370 μmol/mol for He, 600 to 995,000 μmol/mol for N2, 0.60 to 915,000 μmol/mol for CH4 and 17 to 1,002,000 μmol/mol for CO2, whereas the isotope values range from 0.01 to 7.10 for R/RA and -29.91 to +6.00 for δ13C-CO2. Considering the R/RA and 4He/20Ne ratios the atmospheric, mantle and crustal contributions for He have been calculated (Sano and Wakita, 1985). The highest mantle contribution (50 to 90%) is found in the South Aegean Active Volcanic Arc (SAAVA), whereas the lowest in continental Greece (0-20%). Atmospheric contribution is mostly negligible. Taking into consideration the geographical distribution of the gases, it is evident that the R/RA increases in areas characterized by: i) thin crust; ii) elevated heat flow values; iii) recent (Pleistocene-Quaternary) volcanic activity; and iv) deep routed extensional or transtensional regional faults. The highest values are therefore found along the SAAVA and the lowest in the western part of Greece. Furthermore, based on the CO2/3He and δ13C-CO2 values (Sano and Marty, 1995), the contribution of Sediment, Mantle and Limestone end-members for CO2 was determined. The majority of the collected samples present a prevailing limestone C component and only few samples have a prevailing mantle C component. However, with the present data, it is not possible to distinguish CO2 deriving from crustal and slab-related limestones. Additionally, due to the complex geodynamic history, the mantle C isotopic composition could be affected by subduction-related metasomatism and, similarly to the nearby Italian area (Martelli et al., 2008), the C isotope composition could be more positive. In this case, the mantle contribution is probably underestimated.

The Sperchios Basin is an actively spreading rift area with deeply rooted extensional faults and also a site of quaternary volcanic activity. Such geologic conditions favoured the formation of many hydrothermal systems, whose surface expressions are among the biggest thermal springs of the whole Greece. Degassing of deeply derived geogenic CO2 is highlighted by strong bubbling within the main pools of the springs. Flux measurements were made in the Thermopyles spring with the floating chamber method and results showed that bubbling gases in the spring release about 1 ton/day of CO2. The outgoing stream has a flow of more than 250 l/s of water rich in CO2 (about 16 mmol/l). Although no bubbling is visible along the stream, after 300 m, the CO2 content decreases to 2 mmol/l, indicating an intense CO2 degassing. This was quantified in more than 10 tons/day, suggesting that most of the degassing is not visible. Output estimations at the close by thermal springs of Psoroneria and Ypatis have not been made yet, but considering that the bubbling in their pools and the water outflow rates are similar, the CO2 emitted will be of the same order of magnitude. Further contributions from the Sperchios area may come from the Kamena Vourla springs and from diffuse soil degassing. To sum up, the best estimate of the total CO2 output of the studied area is in the order of many tens of tons/day. Such output is comparable to that of the single active volcanic systems along the South Aegean Volcanic Arc (Sousaki, Methana, Milos, Santorini, Kos and Nisyros) and it highlights the importance of hidden degassing along CO2-oversaturated streams.

Several gas samples have been collected from natural gas manifestations in the island of Milos. Most of them are located underwater along its coasts, whereas three anomalous degassing fumarolic areas (Kalamos, Paleochori and Adamas) were identified on land. Almost all the gases have CO2 as the prevailing gas species, with concentrations ranging from 88 to 99% for the samples taken underwater, while the on-land manifestations present a wider range (15-98%), being sometimes heavily contaminated by air. Methane reaches up to 1.0%, H2 up to 3.2% and H2S up to 3.5% indicating a hydrothermal origin of the gases. The isotope composition of He shows values ranging from 2.55 to 3.39 R/RA, highlighting a significant mantle contribution with the highest values measured at Adamas. C-isotope composition of CO2 is in the range from -1.9 to +1.3‰ vs. V-PDB, with most of the values found around -0.5‰ indicating a prevailing limestones origin. Isotope composition of CH4, ranging from -18.4 to-5.0‰ vs. V-PDB for C and from -295 to +7‰ vs. V-SMOW for H, points to a geothermal origin with sometimes evident secondary oxidation processes. CO2-flux measurements showed values up to 1100, 1500 and 8000 g/m2/day in the areas of Kalamos, Paleochori and Adamas respectively and up to about 23,000 g/m2/day in the marine area of Kanava. The south-western part of the island was covered with a lower density prospection, revealing only few anomalous CO2 flux values (up to 650 g/m2/day). Preliminary CO2 output estimations gave values of 1.1, 0.6 and 5.5 tons/day for the three fumarolic areas and of 1.1 tons/day for Kanava. The total output of the island (about 10 tons/day) is comparable to the other volcanic/geothermal systems of the south Aegean active volcanic arc (Nisyros, Kos, Nea Kameni, Methana and Sousaki).

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

Nisyros is the easternmost island of the South Aegean Active Volcanic arc in Greece. It is an active stratovolcano known for its intense hydrothermal activity. In this study we present the results of the mineralogical analyses of 20 soil samples collected in the caldera area. Samples were analysed through X-ray diffraction and the results allow us to divide them in two groups: Lakki Plain and Stefanos Crater. In their majority the soils of Lakki Plain have a main mineralogical assemblage that consists of quartz, feldspar and gismondine (Ca2Al4Si4O16·9H2O). Gismondine as well as stellerite (CaAl2Si7O18·7H2O), which is appearing in some samples, derive from hydrothermal alteration, whilst wollastonite (CaSiO3) is also found as a product of thermally metamorphosed siliceous carbonates. In the Stefanos Crater soils, due to the acid environment and the relatively high temperatures of the fumaroles (about 100°C), the main assemblages mostly comprises hydrothermal alteration minerals like quartz, sulfur, wollastonite, gypsum and gismondine. The lower amount of feldspars with respect to the Lakki Plain soils can be justified by the high percentage of gismondine, their alteration products. Voltaite (K2Fe(II)5Fe(III)3Al(SO4)12·18H2O) was also found in some of the samples as a product of hydrothermal alteration of Si deposits. Close to the fumaroles, the occurrence of alunogen (Al2(SO4)3·17H2O), a sulphide alteration mineral found in fumarolic environments, is also noticeable.

The geologic emissions of greenhouse gases (CO2 and CH4) give an important natural contribution to the global carbon budget. However, the contribution of these emissions to the global carbon cycle and their possible role on the climate change remain still poorly quantified (Guliyev and Feizullayev, 1997; Milkov, 2000; Etiope et al., 2015 and references therein). Methane, the most abundant organic compound in Earth's atmosphere, may be created either from existing organic matter or synthesized from inorganic molecules. Accordingly, it can be differentiated in two main classes: a) biotic (either microbial or thermogenic) and b) abiotic. For this study, 115 gas samples of fumarolic, thermal and cold discharges from all over the Hellenic territory were collected and both chemical (CO2, H2S, CH4, N2, O2, Ar, H2 and light hydrocarbons) and isotopic (13C-CO2, 13C-CH4, D-CH4) analyses were performed, in order to investigate the genetic processes that produced CH4 in fluids related with the complex geodynamic setting of Greece. On the basis of the spatial distribution of the gas discharges and their type of emission, the whole dataset was subdivided into 3 main “domains”, as follows: 1) Volcanic Arc (VA) - 34 samples; 2) External Hellenides (EH) - 23 samples of cold emissions and of hyperalkaline aqueous solutions; 3) Internal Hellenides (IH) - 62 samples of cold and geothermal emissions. Almost each group is characterized, as long as subdivided in 3 groups based on the type of emission (on-land free or dissolved gases and subaqueous gases) and a 4th group includes literature data.

The Greek territory belongs to the geodynamically active Alpine-Himalayan orogenic belt. As such, it shows intense seismic activity, active volcanic systems and areas of enhanced geothermal fluxes. One of these areas is the Sperchios basin and the northern part of Evia island in central Greece, which present widespread thermal manifestations [1]. Five of them with temperatures from 33 to 80°C present bubbling gases whose dominating species are either CO2 or N2. All gases contain from 27 to 4000 ppm of CH4. The isotopic composition of CH4 in these gases covers a wide range with δ13C values ranging from -21.7 to +16.9‰ and δ2H values ranging from -124 to +301‰. The hottest manifestation displays the lowest isotopic values within the typical range of volcanic and geothermal systems. All the remaining samples fit a methane oxidation trend reaching very positive values. If we consider the lowest values as the deep hydrothermal marker the obtained ΔH/ΔC values range between 5 and 13 which are close to those typical of microbially driven oxidation [2]. Although the outlet temperature of the hottest manifestations is at the upper limit for methanotrophic microrganisms [3], we can hypothesize that environmental conditions are not favorable for their survival at this site while they can thrive in the other strongly consuming methane and producing very positive isotopic values. [1] D’Alessandro et al. (2014), Mar. Petrol. Geol. 55, 295-308; [2] Kinnaman et al. (2007), Geochim. Cosmochim. Acta 71, 271-283; [3] Sharp et al. (2014), Environ. Microbiol. 16, 1867-1878

The Aegean area, which is geodynamically very active, is characterised by intense seismic activity, presence of active volcanic systems and anomalous geothermal gradients. Like other regions of intense geodynamic activity it is also characterized by extensive geogenic degassing. Gas manifestations are not only widespread on land but are also very frequent underwater. Many of these, as for example those of Milos and Santorini, are known since long time and have been previously studied although the targets were generally the hot waters or the sediments affected by the emissions (Smith and Cronan 1978, Dando et al. 1995, Price et al. 2013, Megalovassilis 2014).The present study aims at producing the first catalogue of the shallow submarine gas manifestations of the Aegean Sea andto characterizegeochemically the emitted gases.

Greece is located on a convergent plate boundary comprising the subduction of the African Plate beneath the Eurasian, while the Arabian plate approaches the Eurasian in a northwestward motion. It is considered to be one of the most tectonically active regions of Earth with a complex geodynamic setting, deriving from a long and complicated geological history. Due to this specific geological background, conditions for the formation of many thermal springs are favoured. In the past years, almost all the already known sites of degassing (fumaroles, soil gases, mofettes, gas bubbling in cold and thermal waters) located in the Hellenic area were sampled at least one time. Collected samples were analysed for their chemical (He, Ne, Ar, O2, N2, H2, H2S, CO, CH4 and CO2) and isotopic composition (He, C and N). Some of these sites have been selected for systematic sampling. Four of them have records longer than 10 years with tens of samplings also considering some literature data. Two of the sites are located in active volcanic areas (Santorini and Nisyros) while the other two are close to actively spreading graben structures with intense seismic activity (Gulf of Korinth and Sperchios basin). Results allowed to define long term background values and also some interesting variation related to seismic or volcanic activity.

It has recently been hypothesized that life on Earth could have been originated in hyperalkaline waters related to serpentinization of ophiolitic rocks, despite their extreme conditions (high pH and very low levels of nutrients). Five hyperalkaline springs of the Kizildag ophiolite complex (Turkey) were characterized. The dominant gases are either H2, CH4 or N2 . Bacterial diversity, analysed by RISA (Ribosomal Intergenic Spacer Analysis) revealed different profles for each spring. Sequencing of excised DNA bands allowed to identify the presence of Bacillus, Ralstonia, Pseudoalteromonas., Ureibacillus, Alicycliphilus, Anaerococcus. 16S ribosomal DNA sequencing by Illumina is in progress. Three samples were also positive for the presence of pmoA (encoding the key enzyme of methane oxidation) confrming the presence of methanotrophs in accordance to gas analyses that showed clues of microbial methane oxidation in the isotopic ratio. The presence of methanotrophs in these hyperalkaline springs highlights the extraordinary capability of the methanotrophs to adapt to extreme conditions.

The large amount of trace elements emitted from volcanoes has a strong impact on the close surrounding areas. Nyiragongo Volcano (Democratic Republic of Congo) belongs to the Virunga volcanic chain and is one of the most active volcanoes in Africa. It is characterized by the presence of an active and permanent lava lake with a persistent degassing activity. During a field trip in October-November 2014, we investigated the impact of the volcanogenic deposition in the surrounding of the crater by using different sampling techniques. Rain-gauges were used to collect atmospheric bulk deposition. Active and passive biomonitoring techniques (moss-bags and leaves of endemic plants – Senecio spp. and Amarantus viridis) were applied in order to investigate the dispersion of volcanic gas and particle emissions. We collected daily rainfall events at various sites: seven samples at the crater rim (on the western and southern side, 3470 m a.s.l.), one sample at the village Kibati (south-eastern flank, 1955 m a.s.l.) located at the up-wind base of the volcano (representing the local background), and four samples in the city of Goma (southern flank of the volcano, 1500 m a.s.l.). In order to implement our dataset, several samples of rainwater, amaranth leaves, soils and atmospheric depositions (by moss-bags and filters exposition) were sampled after the field trip by the researchers of the Goma Volcano Observatory (GVO). Since, the prevalent wind direction was blowing the plume in westerly or southwesterly direction, we exposed the raingauges in the villages of Bulengo, Rusayo and Kingi in the southwestern side respect to the volcano, and Kibumba in the southesthern as a background site, at increasing distance from the rim. In the same sites, leaves of Amarantus viridis, which is one of the principal vegetables eaten by the local population, were collected. Rainwater, moss bags and plant samples were analyzed for major and trace elements by IC, ICP-OES and ICP-MS. The large amount of emitted volcanic gases and particles includes sulfur, halogens and trace elements, that strongly affect rainwater chemistry and have a widespread impact on the surrounding vegetation of the volcano. Indeed, rainwater samples collected at the rim of the crater have low pH values (_ 3), high concentration of F- and Cl- (up to 12.0 and 12.8 mg/l, respectively) and dissolved toxic elements (such as Al, As, Cd, Cu, Fe and Pb), whereas samples from the city of Goma have pH values above 5 and the same elements show orders of magnitude lower concentrations. The biomonitoring results highlight that bioaccumulation of trace elements is extremely high in the proximity of the crater rim and decreases with the distance from the active craters. The data will be compared to earlier measurements taken in December 2011 and the impact of a slightly decreasing gas emission on the vegetation will be discussed.

Volcanic/geothermal areas are sites of complex interactions between geosphere and biosphere. Pantelleria island (Southern Mediterranean Sea) hosts a high enthalpy geothermal system characterized by high CH4 and low H2S fluxes. Two sites, FAV1 and FAV2, located a few meters apart at the main exhalative area of the island (Favara Grande), recorded similar physical conditions (soil temperature 60°C, soil gas composition enriched in CH4, H2 and CO2). However, while high methanotrophic activity (59.2 nmol g-1 h-1) and high diversity of methanotrophs was detected at FAV2, FAV1 was not active and appeared deprived of methanotrophs (1). Our aim was to investigate the main factors influencing methanotrophy as a result of biotic and abiotic interactions in this geothermal site. To this aim, soil bacterial and archaeal communities of the two sites were analysed by 16S rDNA MiSeq Illumina sequencing and the results related to geochemical data. At phylum level, both FAV1 and FAV2 bacterial sequences were mainly assigned to four phyla (Proteobacteria, Firmicutes, Actinobacteria and Chloroflexi) being Chloroflexi much more represented at FAV1 and Actinobacteria at FAV2. High abundance of thermo-acidophilic chemolithotrophs was detected in site FAV1, while FAV2 was dominated by methanotrophs (40% of the reads). The most represented species at FAV1 was Acidithiobacillus ferrooxidans (25%), while methanotrophs at FAV2 were dominated by Methylocaldum (31%). Archaea were almost exclusively represented, at both sites, by the chemolithotrophic ammonia-oxidating candidate species Nitrososphaera gargensis (Thaumarchaeota). Our results suggest that methanotrophs are not hampered at FAV1 by harsher conditions but by a previously unrecognized competition between chemolithotrophy and methanotrophy due to energetic convenience for chemolithotrophic lifestyle derived from higher availability of electron donors (NH4+, H2). (1) Gagliano et al., 2014 Biogeosciences, 11, 5865–5875

Like other geodynamically active areas, Greece is affected by a large number of geogenic gas manifestations. These occur either in form of point sources (fumaroles, mofettes, bubbling gases) or as diffuse emanations. We produced a catalogue of the geogenic gas manifestations of Greece also considering few literature data. Collected samples were analysed for their chemical (He, Ne, Ar, O2, N2, H2, H2S, CO, CH4 and CO2) and isotopic composition (He, C and N). Geogenic gases, apart from having important influences on the global climate, could have strong impact on human health. Gas hazard is often disregarded because fatal episodes are often not correctly attributed. Geodynamic active areas release geogenic gases for million years over wide areas and the potential risks should not be disregarded. A preliminary estimation of the gas hazard has been made for the last 20 years considering the whole population of Greece. In this period at least 2 fatal episodes with a total of 3 victims could be certainly attributed to CO2. This would give a risk of 1.310-8 fatality per annum. Such value, probably underestimated, is much lower than most other natural or anthropogenic risks. Nevertheless this risk, being unevenly distributed along the whole territory, should not be overlooked and better constrained in areas with high density of gas manifestations and high soil gas fluxes.

Quantification of gaseous emissions in geological systems is an important branch because it is a major source of greenhouse gas to the atmospheric budget. Of geological environments, there are two different categories: the first category includes emissions of the predominant carbon dioxide (CO2), while the second includes emissions of the predominant methane (CH4). The Hellenic territory has a very complex geodynamic setting deriving from a long and complicated geological history. It is strongly characterized by intense seismic activity and enhanced geothermal gradient. This activity, with the contribution of an active volcanic arc, favours the existence of many cold and thermal gas manifestations. 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. Geochemical studies based on the isotopic composition of carbon and hydrogen, along with helium isotopic ratios have become a good indicator of the origin of the gas. The isotopic ratio 13C/12C of CO2 expressed in _ 13C (h, provides important information about the amount of CO2 released from the Earth’s crust or mantle. For methane, carbon and hydrogen isotopic compositions and C1/(C2+C3) hydrocarbon ratios can characterize the origin of methane: biogenic (thermogenic or microbial) or abiogenic. Helium isotopic ratios provide additional information about crustal or mantle origin of the gas. In the present work, a large set of chemical and isotopic data is presented aiming at the identification of areas with geogenic gas emissions and their characterization in terms of different gas composition and origin. The present catalogue should be the base for the estimation total nationwide geogenic CO2 and CH4 fluxes.

Volcanic emissions represent one of the most important natural sources of trace elements (e.g. As, Cd, Cu, Hg, Pb, Sb, Tl and Zn) into the atmosphere, sequentially influencing the hydrosphere, lithosphere and biosphere. The human health hazard during episodic volcanic eruptions generally follows from deposition of coarse and fine particles (2.5-10 and < 2.5 μm) that produces effects such as asthma and lung and respiratory disease. Regarding passive degassing volcanoes, the harmful effects of fluorine fumigation are known both for vegetation (foliar necrosis) and human/animals (fluorosis), but only a few studies have been focused on the effects of potentially toxic trace elements. From a review published work on the metal output from active worldwide volcanoes, 52 publications (the first dating back to the 70’s) were identified, 13 of which on Etna and the others from some of the world most active volcanoes: Mt. St. Helens, Stromboli, Vulcano, Erebus, Merapi, White Island, Kilauea, Popocatepetl, Galeras,Indonesian arc, Satasuma and Masaya. In general, the review shows that available information is scarce and incomplete. We compiled a database both for concentrations and fluxes of 59 chemical elements (major and trace), which allowed us to constrain the compositional and output range. In this study we also present unpublished results from Etna (Italy), Turrialba (Costa Rica), Nyiragongo (Democratic Republic of Congo), Mutnovsky and Gorely (Kamchatka), Aso Asama and Oyama (Japan). Concentrations of major and trace elements were obtained by direct sampling of volcanic gases and aerosols on filters. Sulfur and halogens were collected by using filter-packs methodology, and analyzed by ion chromatography. Untreated filters for particulate were acid digested and analyzed by ICP-OES and ICP-MS. Sulfur to trace element ratios were related to sulfur fluxes to indirectly estimate elemental fluxes. Etna confirms to be one of the greatest point sources in the world. Nyiragongo results to be an additional large source of metals to the atmosphere, especially considering its persistent state of degassing from the lava lake. Turrialba and Gorely also have high emission rates of trace metals considering the global range. Only Mutnovsky volcano show values which are sometimes lower than the range obtained from the review, consistent with its dormant (fumarolic) stage of activity. The accurate estimation of individual and global volcanic emissions of trace metals is still affected by a high level of uncertainty. The latter depends on the large variability in the emission of the different volcanoes, and on their changing stage of activity. Moreover, only few of the potential sources in the world have been directly measured. This preliminary work highlights the need to expand the current dataset including many other active volcanoes for better constraining the global volcanic trace metal fluxes.

In the winter 2013, mercury concentrations in air from the mine-polluted area of Mt. Amiata (1738 m a.s.l.), in southern Tuscany (Central Italy), were measured by active moss biomonitoring. This area is part of the geologic anomaly of Hg in the Mediterranean basin, which contains about 65 % of the world’s cinnabar (HgS). Mt. Amiata covers some 400 km2 and is drained by several rivers. Esploitation activity at Abbadia S. Salvatore, in the SE sector of the mountain, sprang up during the 19th century as one of the largest mercury mining and smelting plants in Europe, after those of Almaden Spain. In this area, Sphagnum moss bags were exposed for about two months, from October to December 2013. At each site (10 sites), one covered and one uncovered moss bag were deployed. Concentrations of mercury in air were also investigated in the same sites with a portable spectrophotometer (Lumex RA-915M). After exposure, mosses were oven-dried, grinded and each sample was divided in two aliquots: one was analyzed for mercury by using a Hydra C cold vapor atomic absorption analyzer (INGV-Palermo), following 7473 US EPA method; the second was microwave digested in acid solution (HNO3 + H2O2). Extraction solutions were analyzed by ICP-MS for total concentrations of a large suite of trace elements, including potentially toxic elements e.g. As, Cd, Cr, Cu, Mo, Sb, Se, V. Mercury air concentrations measured with the Lumex showed extremely high values in the mine district of Abbadia, with median values ranging from 2,000 to 4,000 ng/m3 and maximum values up to 20,000 ng/m3, in contrast with the lower values (median values from 20 to 200 ng/m3) measured in the distal sites few kilometres from the mine-district area. In agreement with these results, in the vicinity of the district uncovered bags were in the range of 10,000 – 100,000 ng/g of Hg, whereas in the distal sites they were in the range of 1,000 – 10,000 ng/g. The moss-blank (unexposed moss) was ~100 ng/g. Covered moss bags were not significantly enriched in Hg with respect to the concentrations recovered from the moss-blank, suggesting that the mercury trapped in the mosses was mainly in particulate form. The particles carried from the winds were probably associated with soils re-mobilization, as also confirmed by the associated enrichments of some lithophile elements (Li and lanthanides) and anthropogenic element (As, Cr, Cd, Fe, Se, V). These preliminary results confirm the intense contamination of the study area not only for mercury but also for other potentially toxic elements.

Volcanic and geothermal areas are important emitters of natural gas compounds into the atmosphere, which can be of concern when discharging close to densely, populated sites. Mercury has a strong environmental impact, its organic and inorganic complexes being toxic. The dominant form of Hg in the atmosphere is gaseous elemental mercury (GEM), which has high volatility and residence time of 1-2 years. Volcanic degassing accounts for a significant part of the natural mercury emissions. No mercury limits or target values in ambient air are present in the EU legislations, whereas US-EPA and ATSDR impose 300 and 200 ng/m3, respectively, as a limit for chronic exposure. WHO has proposed the annual average value of 1,000 ng/m3 as a guideline for Hg0 in ambient air. The determination of Hg0 concentrations is often performed via passive/diffusive samplers, which provide time-integrated gas concentrations, but not able to assess the highly variable distributions of GEM. Different weather factors and photochemical reactions indeed affect the Hg0 dispersion. In volcanic/geothermal sites, GEM measurements can be associated with H2S, an irritating and suffocating substance and detectable at very low concentrations (7 μg/m3, ~5 ppb) due to its typical rotten eggs odor. WHO recommends a guideline value of 150 μg/m3 (~107 ppb) with a 24h averaging time. In April 2014 real-time Hg0 and H2S measurements in air were conducted at the Solfatara Crater, which is nested in the town of Pozzuoli (Southern Italy). The main aims were to (1) test this new methodological approach and (2) investigate the Hg0 the H2S concentrations and their spatial distribution. GEM and H2S continuous measurements were determined with a portable Zeeman atomic absorption spectrometer with high frequency modulation of light polarization (Lumex RA-915M, DL: 2ng/m3) and a pulsed fluorescence gas analyzer (Thermo 450i, DL: 1 ppb), respectively. The GEM and H2S and meteorological data were acquired along previously planned pathways at an average speed

From 25th of October to 5th of November 2014 field surveys were carried out at Nyiragongo and Nyamulagira volcanoes, DR Congo. These two volcanoes belong to the eight volcanoes in the Virunga volcanic chain. They have an altitude of about 3470 m.a.s.l. and 3060 m.a.s.l., respectively. The craters of the two volcanoes lie within a distance of less than 15 km and both have a diameter of about 1000 m and 2000 m, respectively showing a similar inner geometry containing several terraces inside. The lava lake of Nyamulagira is still under formation while Nyiragongo’s lava lake is known since more than 100 years with short interruptions after the eruptions in 1977 and 2002. However, also Nyamulagira had a long period of lava lake activity, at least from 1912 to 1938. Both volcanoes are characterized by low SiO2 content of their lava, but Nyiragongo being exceptionally low in SiO2 and with significantly higher alkali content than Nyamulagira. There is a clear distinction between both lavas; a basaltic to tephritic one in the case of Nyamulagira and an often foidite one in the case of Nyiragongo. Also their volcanic activity has differed significantly during the last decades from each other. While Nyiragongo is famous for its permanent lava lake, Nyamulagira is characterized by frequent eruptions, which sum up to more than 40 since 1865. During our field survey we investigated and compared the gas composition and fluxes of both volcanoes in autumn 2014. The ground - based remote sensing technique - Multi Axis Differential Optical Absorption spectroscopy (MAX-DOAS) using scattered sunlight, the in-situ Multi-GAS-instrument, as well as active alkaline and particle traps have been simultaneously applied at each crater of the two volcanoes during the field trip. Downwind installed DOAS instruments (appendant to NOVAC (Network of Observation of Volcanic and Atmospheric Change)) were used to determine SO2 emission fluxes. Among others, bromine monoxide/sulphur dioxide (BrO/SO2) and carbon dioxide/sulphur dioxide (CO2/SO2) ratios were calculated to differ between Nyamulagira and Nyiragongo by of about a factor 5 and 3, respectively. Fluxes of major compounds (CO2, H2O, SO2, HCl, HF, HBr) and trace elements (Cd, Cu, As, Pb, Zn, etc.) will be here presented, giving a very detailed view of similarities and differences between the plume of both volcanoes. The differences in the gas composition of these two plumes will be discussed and with a view on earlier petrological data some possible processes responsible for them will be proposed.

Volcanic and geothermal systems emit endogenous gases by widespread degassing from soils, including CH4, a greenhouse gas 25 times as potent as CO2. Recently, it has been demonstrated that volcanic/geothermal soils act as source, but also as biological filter for methane release to the atmosphere. For long time, volcanic/geothermal soils has been considered inhospitable for methanotrophic microorganisms, but new extremophile methanotrophs belonging to Verrucomicrobia were identified in three different areas (Pozzuoli, Italy; Hell’s Gate, New Zealand; Kamchatka, Russia), explaining anomalous behaviours in methane leakages of several geothermal/volcanic sites. Our aim was to increase the knowledge of the relationship between methane emissions from volcanic/geothermal areas and biological methane oxidation, by investigating a geothermal site of Pantelleria island (Italy). Pantelleria Island hosts a high enthalpy geothermal system characterized by high temperature, high CH4 and very low H2S fluxes. Such characteristics are reflected in potentially great supply of methane for methanotrophs and scarce presence of inhibitors of their activity (H2S and NH3) in the Pantelleria soils. Potential methanotrophic activity within these soils was already evidenced by the CH4/CO2 ratio of the flux measurements which was lower than that of the respective fumarolic manifestations indicating a loss of CH4 during the gas travel towards the earth’s surface. In this study laboratory incubation experiments using soils sampled at Favara Grande, the main hydrothermal area of Pantelleria, showed very high methane consumption rates (up to 9500 ng CH4 h1 g1). Furthermore, microbiological and culture-independent molecular analyses allowed to detect the presence of methanotrophs affiliated to Gamma- and Alpha-Proteobacteria and to the newly discovered acidothermophilic methanotrophs Verrucomicrobia. Culturable methanotrophic Alpha-proteobacteria of the genus Methylocystis were isolated by enrichment cultures. The isolates showed a wide range of tolerance to pH (3.5 – 8) and temperatures (18 – 45 C), and an average methane oxidation rate of 450 ppm/h. A larger diversity of proteobacterial and verrucomicrobial methanotrophs was detected by the amplification of the methane mono-oxygenase gene pmoA. This study demonstrates the coexistence of both the methanotrophic phyla Verrucomicrobia and Proteobacteria in the same geothermal site. The presence of proteobacterial methanotrophs was quite unexpected because they are generally considered not adapted to live in such harsh environments. Their presence at Favara Grande could be explained by not so low soil pH values (> 5) of this specific geothermal site and by the high methane availability. Such species could have found their niches in the shallowest part of the soils, were the temperatures are not so high, thriving on the abundant upraising methane. Understanding the ecology of methanotrophy in geothermal sites will increase our knowledge of their role in methane emissions to the atmosphere.

Explosive eruptions and volcanic passive degassing inject large quantities of gas and particles into the atmosphere that are ultimately deposited at the Earth’s surface through wet or dry deposition processes, affecting the atmosphere, the hydrosphere and the biosphere. Mount Etna (Italy) is one of the most prodigious and persistent sources of gases and particles to the troposphere. Volcanic emissions were studied at Etna volcano by using moss-bags technique. Mosses (Sphagnum species) were exposed around the volcano at different distances from the active vents to evaluate the impact of its emissions into the atmosphere and in the local surrounding. The results confirmed the huge amount of silicates, sulfates and halides compounds emitted into the atmosphere from Mount Etna. X-ray microanalysis showed that chemical composition of the particles is mostly defined by silicate (from pure silica to metal-rich silicate composition) and sulfate/halide compounds. The contents of major and trace elements in the Sphagnum moss-bags significantly increased after their exposure to volcanic emissions, confirming mosses as efficient accumulators. Metals uptake rate rapidly decreases with the distance from the volcanic emission vents. The elements that showed the greatest accumulation after exposition were S, Na, Fe, Al, Cu, V, As, Cd, Li, Se, Sc, Th, Bi and Tl. This study confirmed the marked environmental impact of volcanic emissions in the eastern sector of Etna, leading to an intense “geochemical anomaly” of volatile major and trace elements due to the fumigation by the volcanic plume, in agreement with passive biomonitoring studies reported by previous authors. Finally, moss-bags techniques provide a cheap and efficient method to investigate quantitatively in space and time the environmental impact of volcanogenic atmospheric deposition.

Bulk deposition has been collected at six sampling sites in area of Gela plain (Italy) in the period from February 2008 to May 2009. Samples collected each two weeks were analysed for the major ion and trace elements content. Preliminary results allow identifying three different sources that control the abundance of the elements in atmospheric deposition: (1) sea spray, (2)geogenic dust, and (3) anthropogenic pollution. Due to the closeness of the coast, clear evidence of sea spray input is detectable for most of the samples. The high excess of non sea-salt sulphate(50 - 90% of the total) is prevailingly ascribable to the abundant SO2 emissions of the refinery.The pH values of the collected samples range from 4.2 to 8.6, with 80% of them above pH 6.5,indicating an extensive neutralization. This is due to NH3 coming from widespread agricultural activities in the plain of Gela, and geogenic CaCO3 either from local or from regional (desert dust) sources. Elevated levels of trace metals (Zn, V, Sb, Ni, Cr, Ni and Cu) can be observed in the samples collected close to the industrial area. All these elements can be identified as “anthropogenic” and attributed to the human activities, mainly to the industrial emissions, but a contribution could also derive from the intensive vehicular traffic.

The studied area is a 130 km 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 2004e2012, 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.

Quantification of gaseous emissions in geological systems is an important branch because it is a major source of greenhouse gas to the atmospheric budget. Of geological environments, there are two different categories: the first category includes emissions of the predominant carbon dioxide (CO 2), while the second includes emissions of the predominant methane (CH4). The Hellenic territory has a very complex geodynamic setting deriving from a long and complicated geological history. It is strongly characterized by intense seismic activity and enhanced geothermal gradient. This activity, with the contribution of an active volcanic arc, favours the existence of many cold and thermal gas manifestations. 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. Geochemical studies based on the isotopic composition of carbon and hydrogen, along with helium isotopic ratios have become a good indicator of the origin of the gas. The isotopic ratio 13C/12C of CO 2 expressed in δ 13C (provides important information about the amount of CO 2 released from the Earth's crust or mantle. For methane, carbon and hydrogen isotopic compositions and C1/(C2+C3) hydrocarbon ratios can characterize the origin of methane: biogenic (thermogenic or microbial) or abiogenic. Helium isotopic ratios provide additional information about crustal or mantle origin of the gas. In the present work, a large set of chemical and isotopic data is presented aiming at the identification of areas with geogenic gas emissions and their characterization in terms of different gas composition and origin. The present catalogue should be the base for the estimation total nationwide geogenic CO 2 and CH4 fluxes.

Volcanic emissions represent one of the most relevant natural sources of trace elements to the troposphere. Due to their potential toxicity they may have important environmental impacts from the local to the global scale and they can severely affect the atmospheric and terrestrial environment also at timescales ranging from a few to million years. Etna volcano is known as one of the largest global contributors of magmatic gases (CO2, SO2, and halogens) and particulate matter, including some toxic trace elements. The aim of this study was to characterize the chemical composition and the mineralogical features of the volcanogenic aerosol passively emitted from Mt. Etna. Nine samples were collected by using the filtration technique at different sites on summer 2010 and 2011. Chemical and mineralogical analyses allowed to discriminate two main constituents: the first is mainly referable to the silicate component in the volcanic plume, like lithic and juvenile fragments, crystals (e.g., plagioclases, pyroxenes, oxides) and shards of volcanic glass; the second one is linked to the soluble components like sulfosalts or halide minerals (sulfates, chlorides and fluorides). These investigations are especially important in the study area because the summit of Mt. Etna is yearly visited by nearly one hundred thousand tourists that are exposed to potentially harmful compounds.

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 2 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. References: Cardellini C., Chiodini G., Frondini F., Granieri D., Lewicki J., Peruzzi L., 2003. Accumulation chamber measurements of methane fluxes: application to volcanic–geothermal areas and landfills. Appl. Geochem. 18, 45–54. Castaldi S., Tedesco D., 2005. Methane production and consumption in an active volcanic environment of Southern Italy. Chemosphere 58, 131–139. Chiodini G., Granieri D., Avino R., Caliro S., Costa A., 2005. Carbon dioxide diffuse degassing and estimation of heat release from volcanic and hydrothermal systems. J. Geophys. Res. 110, B08204. D’Alessandro W., Bellomo S., Brusca L., Fiebig J., Longo M., Martelli M., Pecoraino G., Salerno F., 2009. Hydrothermal methane fluxes from the soil at Pantelleria island (Italy). J. Volcanol. Geotherm. Res. 187, 147–157. D’Alessandro W., Brusca L., Kyriakopoulos K., Martelli M., Michas G., Papadakis G., Salerno F., 2011. Diffuse hydrothermal methane output and evidence of methanotrophic activity within the soils at Sousaki (Greece). Geofluids 11, 97–107 D’Alessandro W., Gagliano A.L., Kyriakopoulos K., Parello F., 2013. Hydrothermal methane fluxes from the soil at Lakki plain (Nisyros island, Greece). Bull. Geol. Soc. Greece, vol. XLVII Proc. of the 13th International Congress, Chania, Sept. 2013 Dunfield P.F., Yuryev A., Senin P., Smirnova A.V., Stott M.B., Hou S., Ly B., Saw J.H., Zhou Z., Ren Y, Wang J., Mountain B.W., Crowe M.A., Weatherby T.M., Bodelier P.L.E., Liesack W., Feng L., Wang L., Alam M., 2007. Methane oxidation by an extremely acidophilic bacterium of the phylum Verrucomicrobia. Nature, 450, 879–882. Etiope G., Fridriksson T., Italiano F., Winiwarter W., Theloke J., 2007. Natural emissions of methane from geothermal and volcanic sources in Europe. J. Volcanol. Geotherm. Res. 165, 76–86. Etiope G., Lassey K.R., Klusman R.W., Boschi E., 2008. Reappraisal of the fossil methane budget and related emission from geologic sources. Geophys. Res. Lett. 35, L09307. Islam T., Jensen S., Reigstad L.J., Larsen Ø., Birkeland N.K., 2008. Methane oxidation at 55°C and pH 2 by a thermoacidophilic bacterium belonging to the Verrucomicrobia phylum. Proc. Natl. Acad. Sci. 105, 300–304. Kizilova A.K., Dvoryanchikova E.N., Sukhacheva M.V., Kravchenko I.K., Gal’chenko V.F., 2012. Investigation of the communities of the Hot Springs of the Uzon Caldera, Kamchatka, by Molecular Ecological Techniques. Microbiology, 81, 606-613. Pol A., Heijmans K., Harhangi H.R., Tedesco D., Jetten M.S.M., Op den Camp H.J.M., 2007. Methanotrophy below pH 1 by a new Verrucomicrobia species. Nature, 450, 874–878.

Volcanic emissions represent one of the most relevant natural sources of trace elements to the troposphere, both during and between eruptions. Due to their potential toxicity they may have important environmental impacts from the local to the global scale. Atmospheric precipitation was collected approximately every two weeks, 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 Etna volcano. The collected samples were analysed for major (Ca, Mg, K, Na, F, SO4, Cl, NO3) and a large suite of trace elements (Ag, Al, As, Au, B, Ba, Be, Bi, Cd, Co, Cr, Cs, Cu, Fe, Hg, La, Li, Mn, Mo, Ni, Pb, Rb, Si, Sb, Sc, Se, Sr, Th, Ti, Tl, U, V, Zn) by using different techniques (IC and ICP-MS ). The raingauges occasionally collected also fresh volcanic ashes emitted by the volcano during paroxysmal events. The ashes were retained by the filter-system used to block the coarse material. More than twenty events of ashfall were collected, but only half of these samples were suitable for a complete chemical analysis, due to the small amount of sample. In order to obtain elemental chemical composition of ashes, powdered samples were analysed by a combination of methods, including XRF, total digestion ICP-MS, INAA, and IR. The chemistry of rainwater reveals that most of the investigated elements (both major and trace elements) have higher concentrations close to the emission vent of the volcano, confirming the prevailing volcanic contribution. Rainwater composition clearly reflects the volcanic plume input. Ash-normalised rainwater composition indicates a contrasting behaviour between volatile elements, which are highly-enriched in rainwater, and refractory elements, which have low rainwater/ash concentration ratios. The degree of interaction between collected ash and rainwater was variable, depending on several factors: (i) the length of the period in which tephra was present in the sampler (the ash fall may have occurred any day from the first to the last day of the rain collecting period); (ii) the amount of rainwater fallen on the collectors after the ash-fall event, and its acidity; (iii) the granulometry of the ash samples that was widely variable (from few centimetres to micrometric particles) with increasing interaction due to the decreasing dimensions of the tephra grains; (iv) the distance of collector with respect to the craters. All these factors govern the efficiency of the dissolution processes of the volcanic ash, and the amount of elemental leaching from their surface. The results suggest that sulphate and halide salt aerosols are adsorbed onto ash particles, and their rate of dissolution in rainwater depends on solubility. Moreover, rapid chemical weathering of the silicate glass by the corrosive volcanic acid (SO2, HCl and HF) can also explain the enrichment of several refractory elements (Na, K, Ca, Mg, Si, Al, Fe, Ti, Sc).

Methane is released to the atmosphere by a wide number of natural (geological and biological) and anthropogenic sources, and is the second most important greenhouse gas after CO2. Microbial oxidation in soils by methanotrophic bacteria contributes to the removal of CH4 from the atmosphere and methanotrophic activity was also detected in volcanic/geothermal areas where degassing of endogenous gases occurs. Our aim is to describe the methanotrophs at the main exhalative area of Le Favare site at Pantelleria Island, where high CH4 consumption (up to 950 ng/g/ per h) was measured. Total soil bacterial diversity was analysed by TTGE of amplified 16S rRNA genes and the diversity of proteobacterial methanotrophs was investigated by creating a clone library of the amplified methane mono-oxygenase encoding genes, pmmoA. Enrichment cultures on a mineral medium in a CH4-enriched atmosphere led to the isolation of different strains that were identified as Methylocistis spp. Understanding the ecology of methanotrophy in geothermal sites will increase our knowledge of the role of such soils in methane emissions.

Methane is the most abundant hydrocarbon in the atmosphere and a significant contributor to the radiative forcing with a global warming potential about 21 times that of CO2. 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. Significant amounts of geological methane, produced within the Earth’s crust (e.g. volcanic/geothermal areas), are currently released into the atmosphere (48 Tg CH4/y). Microbial oxidation in soils by methanotrophic bacteria contributes to the removal of CH4 from the atmosphere for about 3-9%. Methanotrophs belong to the Gamma- and Alpha-proteobacteria and to the recently discovered acidophilic Verrucomicrobia. Evidence of methanotrophic activity also in soils of volcanic/geothermal areas has been recently revealed, notwithstanding their harsh environmental conditions (high temperatures, low pH, high concentrations of H2S and NH3). The purpose of our study was to verify the methanotrophic potential and the bacterial diversity of the soils of the main geothermal area of Pantelleria island (Italy). Close to the fumarolic area (Le Favare) the mean detected temperature is about 90 °C at 30 cm of depth and the mean measured pH of the soil is about 4.8. Laboratory incubation experiments with soil samples collected at the main exhalative area showed methane consumption values of up to 9500 ng/g of dry soil per hour while soils collected outside the geothermal area consumed less than 6 ng/g/h. Geothermal soils showed their maximum methane consumption in the shallowest part of the soil profile (0-3 cm). Furthermore they showed the maximum consumption at about 37°C, showing a still recognizable consumption (>20 ng/g/h) at 80°C. These results can be considered a clear evidence of the presence of methanotrophs. In order to evaluate the bacterial diversity, soil metagenomic DNA was extracted from Le Favare and analysed using a Temporal Temperature Gradient Electrophoresis (TTGE) analysis of the amplified Bacterial 16S rRNA gene. The amplification of metagenomic DNA with primers targeting Proteobacterial and Verrucomicrobial MMO (methane monooxygenase) genes is in progress. Enrichment cultures on a mineral medium in a CH4-enriched (25%) atmosphere led to the isolation of different strains that are under characterization.

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.

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.