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Ludovico Sicardi was a chemist and a pharmacist, and a passionate researcher, enthusiastic about phenomena related to volcanic activity. Due to a field survey within a project of mining research committed by a private company, he has the opportunity to visit the island of Vulcano (Eolie - Sicily), from December 1921 to June 1922. He was completely fascinated by the wild island of Vulcano and its gas manifestations. During several successive field trips in Vulcano, he observed and described the fumarolic field on a systematic basis, measuring the temperatures and recording their variations over time. He was one of the first to perform chemical analysis of fluids emitted by fumaroles in Vulcano Island and Solfatara di Pozzuoli (Italy). Furthermore, he was the first to suppose the coexistence of SO2 and H2S in fumarolic fluids, which by that time was considered to be impossible. Also, he succeeded in measuring their ratio by developing an in situ method that chemically separate the gaseous S-species. As the pioneer of applied geochemistry in volcanic fluids, he developed a method based on the sampling of fumarolic fluids using a glass flask that contained a NH4OH-AgNO3 solution to absorb the soluble acid gases (CO2, SO2 and HCl) and precipitate H2S as an insoluble Ag2S. A series of fortuitous coincidences allowed us to tell this story. Thanks to Prof. Marcello Carapezza and Prof. Mariano Valenza of the University of Palermo, the “scientific treasure” of Sicardi was preserved and it is nowadays studied and cataloged. It consists of Sicardi’s sampling-equipment, copies of the scientific articles, several historical maps and photos of Vulcano and Solfatara, manuscript notes and three important unpublished researches about Vulcano, Vesuvio and Campi Flegrei. Based on the remarkable scientific production, Sicardi has to be considered a precursor of modern volcanic monitoring based on fluid geochemistry.

Mt. Etna, on the eastern coast of Sicily (Italy), is one of the most active volcanoes on the planet and it is widely recognized as a big source of volcanic gases (e.g., CO2 and SO2), halogens, and a lot of trace elements, to the atmosphere in the Mediterranean region. Especially during eruptive periods, Etna’s emissions can be dispersed over long distances and cover wide areas. A group of trace elements has been recently brought to attention for their possible environmental and human health impacts, the Technology-critical elements. The current knowledge about their geochemical cycles is still scarce, nevertheless, recent studies (Brugnone et al., 2020) evidenced a contribution from the volcanic activity for some of them (Te, Tl, and REE). In 2021, in the framework of the research project “Pianeta Dinamico”, by INGV, a network of 10 bulk collectors was implemented to collect, monthly, atmospheric deposition samples. Four of these collectors are located on the flanks of Mt. Etna, other two are in the urban area of Catania and three are in the industrial area of Priolo, all most of the time downwind of the main craters. The last one, close to Cesarò (Nebrodi Regional Park), represents the regional background. The research aims to produce a database on major ions and trace element compositions of the bulk deposition and here we report the values of the main physical-chemical parameters and the deposition fluxes of major ions and trace elements from the first year of research. The pH ranged from 3.1 to 7.7, with a mean value of 5.6, in samples from the Etna area, while it ranged between 5.2 and 7.6, with a mean value of 6.4, in samples from the other study areas. The EC showed values ranging from 5 to 1032 μS cm-1, with a mean value of 65 μS cm-1. The most abundant ions were Cl- and SO42- for anions, Na+ and Ca+ for cations, whose mean deposition fluxes, considering all sampling sites, were 16.6, 6.8, 8.4, and 6.0 mg m-2 d, respectively. The highest deposition fluxes of volcanic refractory elements, such as Al, Fe, and Ti, were measured in the Etna’s sites, with mean values of 948, 464, and 34.3 μg m-2 d-1, respectively, higher than those detected in the other sampling sites, further away from the volcanic source (26.2, 12.4, 0.5 μg m-2 d-1, respectively). The same trend was also observed for volatile elements of prevailing volcanic origin, such as Tl (0.49 μg m-2 d-1), Te (0.07 μg m-2 d-1), As (0.95 μg m-2 d-1), Se (1.92 μg m-2 d-1), and Cd (0.39 μg m-2 d-1). Our preliminary results show that, close to a volcanic area, volcanic emissions must be considered among the major contributors of ions and trace elements to the atmosphere. Their deposition may significantly impact the pedosphere, hydrosphere, and biosphere and directly or indirectly human health.

Mt. Etna, on the eastern coast of Sicily (Italy), is one of the most active and most intensely monitored volcanoes on the Earth, widely recognized as a big source of volcanic gases, such as CO2, SO2, halogens, and many trace elements, including technological critical elements (TCEs), to the atmosphere on a regional and global scale. Mt. Etna emissions account for a significant percentage of the worldwide average volcanic budget and especially during eruptive periods, its products can be dispersed over great distances and they influence the chemical composition of the atmosphere of other continents too. The current knowledge about the geochemical cycle of TCEs is still scarce, nevertheless, recent studies [Brugnone et al., 2020], evidenced a contribution from the volcanic activity for some of them (Te, Tl, and REE). Here we report the arithmetic mean of the volume-weighted mean concentration values of each sampling site of both volcanic gas-derived anions SO42-, Cl-, and F-, and of some TCEs (i.e. Te and Tl). These were determined on bulk deposition samples collected, on monthly basis, during three different research projects: (1) SEW, from July 2017 to July 2018; (2) CISAS, from June 2018 to June 2019; (3) HEAVEN, which started in March 2021 and still ongoing. All the samples were analysed for major ion contents and many trace elements by IC, ICP-OES, and ICP-MS. During the first project, samples were acquired with 3 bulk collectors, located on the eastern slope of Etna, i.e., the slope toward which the volcanic emissions are usually dispersed by the prevalent regional winds. During this period, Etna showed ordinary outgassing activity and occasional ash emissions. Volume-weighted-mean (VWM) concentrations of 3.37, 6.87, and 0.48 mg L-1 were measured for SO42-, Cl-, and F- respectively (maxima up to 12.74, 44.80, and 2.55 mg L-1, respectively). High concentrations of Te and Tl were measured especially at the sampling sites closest to the central craters (VWM 0.012 µg L-1 and maximum 0.129 µg L-1 for Te; VWM 0.122 µg L-1 and maximum 0.978 µg L-1 for Tl). During the CISAS project, atmospheric bulk depositions were collected through a network of 11 bulk collectors, which were installed in the area of Siracusa, a town on the east coast of Sicily, about 80 km SSE of Mt. Etna, and in Milazzo, a town on the northern coast of Sicily, about 55 km NNE of Mt. Etna. Between 24-30 December 2018, a major eruption of Etna occurred, characterized by lava fountains and ash emissions. The samples collected in the study area of Siracusa during the period straddling the eruptive event were characterized by high concentrations of SO42- (up to 6.68 mg L-1), Cl- (up to 19.00 mg L-1), and F- (up to 0.88 mg L-1). In the same samples, the maximum concentrations were 0.025 µg L-1 and 0.164 µg L-1 for Te and Tl, respectively, showing values one order of magnitude higher than the median concentrations measured in the samples of the other monitoring campaigns carried out in the same study area. The study area of Milazzo, due to the prevailing winds from the North direction during the period of the eruption, has not been affected by the volcanic plume, and therefore the signature of the eruption was not visible in the samples collected in that area. From March 2021 atmospheric bulk deposition samples were collected through a network of 10 bulk collectors, which were installed on Mt. Etna, at various distances from the summit craters and on different slopes of the volcano, near the city of Catania, in the Siracusa area and near the village of Cesarò, in the Nebrodi Natural Regional Park. Mt Etna experienced two long sequences of 53 short-living lava fountain episodes between December 2020 and March 2021 and April to October 2021. Other episodes occurred more recently, between February and May 2022. Volcanic emissions associated with these paroxysmal events have been dispersed over great distances, even reaching other continents (e.g., Asia), and have been important contributors to the chemical composition of atmospheric deposition at all monitoring sites during the first year of the research. VWM concentrations of 3.26 mg L-1 (maximum 189.60 mg L-1), 5.78 mg L-1 (maximum 244.60 mg L-1), and 0.43 mg L-1 (maximum 40.66 mg L-1) were recorded for SO42-, Cl-, and F-, respectively. High concentrations of Te and Tl were also recorded, especially at sites closer to the central craters of Mt. Etna, with VWM concentrations of 0.018 µg L-1 and 0.121 µg L-1 and values up to 0.369 µg L-1 and 2.101 µg L-1, respectively. Based on our finding, we highlight that volcanic emissions must be considered among the major contributors to the chemistry of the atmospheric bulk deposition in sites close to active volcano emissions, but also at considerable distances from the vents during high-magnitude eruption events.

The source of chemical elements dissolved in rainwater can be both natural and anthropogenic. A group of trace elements has been recently brought to attention for their possible environmental impacts, the Technology-critical elements (TCEs). The current knowledge about the geochemical cycle of TCEs is still scarce, nevertheless recent studies [e.g. Brugnone et al., 2020] evidenced a contribution from the volcanic activity for some of them (Te, Tl, and REE). Our research aims to produce a geochemical database on major and trace element depositions in different areas of Sicily: a volcanic area (Etna), two urban areas (Palermo, Catania), two industrial areas (Milazzo, Priolo), and a rural monitoring site (Cesarò). The samples are collected monthly through a network of 15 bulk collectors. Here we report about the chemical composition of rainwater from the first five sampling campaigns. The pH was between 5.5 and 7.8, with an average value of 7.0. EC showed values ranging from 8 to 184 μS/cm, with an average of 72 μS/cm. The most abundant major elements were Cl- and SO42- for anions, Ca+ and Na+ for cations. Regarding trace elements, the highest volume-weighted mean (VWM) concentrations were generally measured in the areas affected by volcanic emissions, especially for TCEs, such as Te and Tl, which show VWM concentrations of 4.5 ng/L and 50.8 ng/L, respectively, higher than the VWM values detected in samples far from the volcanic source (0.8 ng/L and 2.5 ng/L, respectively). Exceptions are Zn and Br with the highest VWM concentration found in the Priolo area, Cr and Fe in Palermo. The contribution of the various sources, including the volcanic one, can therefore be well evidenced through the characterization of the chemical composition of the atmospheric deposition.

The Earth C-cycle is complex, where endogenic and exogenic sources are interconnected, operating in a multiple spatial and temporal scale (Lee et al., 2019). Non-volcanic CO2 degassing from active tectonic structures is one of the less defined components of this cycle (Frondini et al., 2019). Carbon mass-balance (Chiodini et al., 2000) is a useful tool to quantify the geogenic carbon output from regional karst hydrosystems. This approach has been demonstrated for central Italy and may be valid also for Greece, due to the similar geodynamic settings. Deep degassing in Greece has been ascertained mainly at hydrothermal and volcanic areas, but the impact of geogenic CO2 released by active tectonic areas has not yet been quantified. The main aim of this research is to investigate the possible deep degassing through the big karst aquifers of Greece. Since 2016, 156 karst springs were sampled along most of the Greek territory. To discriminate the sources of carbon, the analysis of the isotopic composition of carbon was carried out. δ13CTDIC values vary from -16.61 to -0.91‰ and can be subdivided into two groups characterized by (a) low δ13CTDIC, and (b) intermediate to high δ13CTDIC with a threshold value of -6.55‰. The composition of the first group can be related to the mixing of organic-derived CO2 and the dissolution of marine carbonates. Springs of the second group, mostly located close to Quaternary volcanic areas, are linked to possible carbon input from deep sources.

Mt. Etna, in eastern coast of Sicily (Italy), is one of the most active and most intensely monitored volcanoes of the planet. It is the biggest volcanic point source of volcanic gases and particles to the troposphere in the Mediterranean basin. On the morning of December 24th 2018, a new lateral eruption of the Mount Etna started. This eruption was related to an intrusion of a magmatic dike on the high eastern flank of the volcano, which a two kilometers long fracture in the NNW - SSE direction. At the same time, the summit craters also produced a continuous strombolian activity generating a very dense dark ash plume, dispersed by the wind into the southeastern direction. This volcanic event well record from the atmospheric precipitations. During the period from June 2018 to May 2019, atmospheric precipitations were collected in the area of Priolo, eighty kilometer far SSE from Mt. Etna. The sampling and analytical protocols were chosen following the guidelines published by the main international agency involved in the monitoring of atmospheric precipitation. The rain gauges were open during the entire exposure time, collecting both wet and dry deposition (bulk collectors). All the collected water samples were analysed for major ion contents and for a large number of trace elements. The atmospheric precipitation of the period straddling the eruptive event is characterized by high concentration of major ions, such as Fluoride (up to 0.88 mg/l), Chloride (up to 124 mg/l) and Sulphate (23.1 mg/l). These derive mainly from the emitted volcanic gases (HF, HCl and SO2). On the another hand, an enrichment of some trace elements is also presented, such as Aluminum (up to 152 μg/l), Thallium (0.16 μg/l), Tellurium (0.025 μg/l). While Tl and Te are highly volatile elements typically enriched in volcanic emissions, Al is a refractory element that is probably correlated to the dissolution of the emitted volcanic ashes.

Il mercurio (Ilg) è uno dei principali inquinanti emessi in atmosfera. La sua complessità geochimica, unitamente alla tossicità c agli effetti persistenti della sua presenza nell’ecosistema terrestre, lo hanno inserito nella lista delle priorità di un numero sempre crescente di accordi internazionali rivolti alla tutela ambientale e della stiline umana (The Arctic- Monitoring and Assessment Program, AMAR, United Nations - Economie Commission for Europe: Ileavy Metals Protocol, UN- ECE, The Helsinki Commission, IIELCOM, la convenzione OSPAR). I progressi raggiunti neH’ullimo decennio sullo studio del Hg come ‘global poi Intani '(Pirrone et al.. 2001; Hedgecock et al, 2000: Paeyna et al, 2006; Bullock and Jacgle, 2000; Dastoor e Davignon, 2009; Eriedli et al., 2(X)!); .Jaegle et al, 2009; Jung et al. 2009; Seigneur et al, 2009; Travnikov and Ilyin, 2009) hanno contribuito a fornire una valutazione aggiornata delle emissioni di Hg a scala globale provenienti sia da fonti antropogeniche che naturali. A oggi, le sorgenti antropiche sono responsabili di circa il 30% delle emissioni annue di mercurio in atmosfera. Un altro 10% proviene da fonti geologiche naturali, mentre il restante 60% dalla “ri-emissione” di mercurio precedentemente depositatosi nell’ecosistema terrestre (Kocman et al., 2013). E’stato stimato che circa 5207 t di Hg vengono emesse annualmente da parte dei processi naturali (emissioni primarie di mercurio + ri-emissioni). Nel complesso, di queste 5207 t anno1, circa 2429 t anno1 di Ilg vengono emessi dalle superfici terrest ri (47% del totale delle emissioni naturali di Hg), mentre l’evasione oceanica contribuisce con un flusso di - 2778 anno1 (Pirrone et al. 2010). Per mitigare il rischio associato a tali emissioni è necessario conoscere a fondo le dinamiche che regolano lo scambio di Hg tra la sorgente e il recettore. In che misura è possibile quindi prevedere la futura evoluzione del Ilg rilasciato in atmosfera?

Le interazioni del Hg con l'ambiente costituiscono il ciclo geochimico di questo elemento che si esplica per mezzo di complessi processi fisico-chimici differenti per ciascun comparto geochimico. Si stima che circa i due terzi del mercurio presente in ambiente sia stato prodotto durante il ventesimo secolo, e che il carico di mercurio immesso attualmente sia aumentato di circa 3 volte rispetto agli inizi del 1900 (Mason et al.. 1994). Il comparto ambientale certamente più coinvolto dalle emissioni di mercurio è quello atmosferico, da cui poi l’elemento si diffonde anche negli altri comparti, suolo e sedimenti compresi (Filzgerald & Clarkson, 1991). L’Atmosfera costituisce un importante reservoir temporaneo di mercurio. Infatti, i processi chimici che avvengono in atmosfera trasformano il mercurio dallo stato elementare allo stato bivalente, influenzandone cosi le modalità di trasporto e la velocità di deposizione di questo metallo sulla superficie terrestre. Il mercurio è rilasciato in atmosfera da una varietà di sorgenti naturali (Siegei e Siegei, 1983; Filzgerald, 1986; Xiao et al., 1991; Mason et al.. 1994; Lindberg et al., 1995) ed antropogeniche (Lindqvist et al., 1991; Ferrara et al., 1992; Pirrone et al., 2010; Carpi e Lindberg, 1997; Lacerda, 1997). Le sorgenti naturali includono i vulcani, i suoli, le foreste, i laghi, gli oceani apert i per un i nput totale di circa 2000 lon/anno (Mason et al., 1994); le sorgenti antropogeniche sono principalmente legate alla produzione energetica mediante l’utilizzo di carboni fossili, la combustione e l'incenerimento dei rifiuti, e ad alcuni processi industriali- metallurgici, determinando un flusso totale di circa 4000 lon/anno (Forcella et al., 1997). Il trend delle emissioni di mercurio antropogenico su scala globale è in crescila, soprattutto a causa delle emissioni dai Paesi in forte via di sviluppo (es., Cina, India).

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

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.

Since its last magmatic eruption in 1530 AD, La Soufrière andesitic volcano in Guadeloupe has displayed intense hydrothermal activity and six phreatic eruptive crises (the last of which, in 1976-1977, with 73000 evacuees). Here we report on the first direct quantification of gas plume emissions from La Soufrière summit vents, which gradually intensified during the past 20 years. Gas fluxes were determined in 2006 then 2012 [1] by measuring the horizontal and vertical distribution of volcanic gas concentrations in the air-diluted plume, the composition of the hot fumarolic fluid at exit (108°C), and scaling to the speed of plume transport (in situ measurements and FLIR imaging). We first demonstrate that all fumarolic vents of La Soufrière are fed by a common H2O-rich (97-98 mol %) fluid end-member, emitted almost unmodified at the most active South Crater while affected by secondary alterations (steam condensation, sulphur scrubbing) at other vents. Daily fluxes in 2012 (200 tons of H2O, 15 tons of CO2, ~4 tons of H2S and 1 ton of HCl) were augmented by a factor ~3 compared to 2006, in agreement with increasing activity. Summit fumarolic degassing contributes most of the bulk volatile and heat budget (8 MW) of the volcano. Isotopic evidences demonstrate that La Soufrière hydrothermal emissions are sustained by continuous heat and gas supply from an andesitic magma reservoir confined at 6-7 km depth. This magmatic supply mixes with abundant groundwater of tropical meteoric origin in the hydrothermal system. Based on petro-geochemical data for the erupted magma(s), we assess that the volcanic gas fluxes in 2012 can be accounted for by the release of free magmatic gas derived from about 1000 m3 per day of the basaltic melt replenishing the reservoir at depth. In terms of mass budget, the current degassing unrest is compatible with enhanced free gas release from that reservoir, without requiring any (actually undetected) magma intrusion. We recommend a regular survey of the fumarolic gas flux from La Soufrière in order to anticipate the evolution of the magma reservoir. [1] P. Allard et al., Chemical Geology 384, 76-93, 2014.

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 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.

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.

Tunisia is characterized by hot and warm groundwaters (temperature up to 75 °C) which represent the surface manifestation of geothermal systems hosted in carbonate-evaporite rock sequences. The T-conditions of Tunisia deep thermal reservoirs are here evaluated for the first time at the regional scale. The results here shown clearly highlight the limitations inherent in the application of common geothermometric methods in the estimation of equilibrium temperatures in sedimentary environments. The modeling approach proposed by Chiodini et alii (1995), which makes use of the ratios between dissolved HCO3, SO4 and F, provides the most reliable results, and allows us to derive equilibrium temperatures up to 200 °C for the Tunisian thermal reservoirs. Very high equilibrium pCO2 (100 bar) values are also estimated, likely indicative of the confined aquifer conditions.

Mercury (Hg) is emitted in the atmosphere by anthropogenic and natural sources, these last accounting for one third of the total emissions. Since the pre-industrial age, the atmospheric deposition of mercury have increased notably, while ocean emissions have doubled owing to the re-emission of anthropogenic mercury. Exchange between the atmosphere and ocean plays an important role in cycling and transport of mercury. We present the preliminary results from a study on the distribution and evasion flux of mercury at the atmosphere/sea interface in the Augusta basin (SE Sicily, southern Italy), a semi-enclosed marine area affected by a high degree of contamination (heavy metals and PHA) due to the oil refineries placed inside its commercial harbor. It seems that the intense industrial activity of the past have lead to an high Hg pollution in the bottom sediments of the basin, whose concentrations are far from the background mercury value found in most of the Sicily Strait sediments. The release of mercury into the harbor seawater and its dispersion by diffusion from sediments to the surface, make the Augusta basin a potential supplier of mercury both to the Mediterranean Sea and the atmosphere. Based on these considerations, mercury concentration and flux at the air-sea interface of the Bay have been estimated using a real-time atomic adsorption spectrometer (LUMEX-RA 915+) and an home-made accumulation chamber, respectively. Estimated Total Atmospheric Mercury ($TGM$) concentrations during the cruise on the bay were in the range of 1 - 3 ng∙m-3, with a mean value of about 1.4 ng∙m-3. This data well fit with the background Hgatm concentration values detected on the land (1-2 ng∙m-3, this work), and, more in general, with the background atmospheric TGM levels found in the North Hemisphere (1.5 – 1.7 ng∙m-3 ) [a]. Besides, our measurements are in the range of those reported for other important polluted marine areas. The mercury evasion flux at the air-sea interface measured during the first cruise ranges from 110 to 1500 ng m-2 day-1. This range is 1-2 order of magnitude higher than most of marine environments (Pacific Ocean, Mediterranean Sea, Artic Ocean) and some important polluted marine areas, such as the Tokyo Bay (19–259 ng m-2 day-1)[b] and the Yellow Sea (156–722 ng m-2 day-1)[c]. Further estimates on Hg atmospheric deposition flux (wet and dry) and biomonitoring are required for finally assessing a mass balance of Hg in Augusta basin.

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.

We report helium isotope data for 0.03–1Ma olivine-bearing basaltic hawaiites from three volcanoes of the southern Italy magmatic province (Ustica, Pantelleria, and Linosa Islands). Homogenous 3He/4He ratios (range: 7.3–7.6 Ra) for the three islands, and their similarity with the ratio of modern volcanic gases on Pantelleria, indicate a common magmatic end-member. In particular, Ustica (7.6 ± 0.2Ra) clearly differs from the nearby Aeolian Islands Arc volcanism, despite its location on the Tyrrhenian side of the plate boundary. Although limited in size, our data set complements the large existing database for helium isotope in southern Italy and adds further constraints upon the spatial extent of intraplate alkaline volcanism in southern Mediterranea. As already discussed by others, the He-Pb isotopic signature of this magmatic province indicates a derivation from a mantle diapir of a OIB-type that is partially diluted by the depleted upper mantle (MORB mantle) at its periphery.

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

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

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

Besides human activities, volcanoes also introduce significant quantities of potentially harmful chemical compounds into the environment, mainly in the forms of gases and particles. High-temperature emissions from persistently degassing volcanoes are a known source of trace metal emissions to the atmosphere which may have important environmental consequences. Among these metals, mercury (Hg) is of particular interest since it is a toxic volatile metal found at elevated concentrations in remote regions of the world. Many natural Hg pathways include a recycled component of anthropogenic material. The anthropogenic contribution to the global atmospheric Hg budget is now well constrained, with most recent estimates ranging from 1484 [AMAP/UNEP, 2008] to 1894 t yr-1 [2005/2006 inventory; Streets et al 2009]. Hg emissions from natural sources are, on the other hand, still poorly characterized, though being likely in the same range [estimates from 500 to 3000 t yr-1; Nriagu 1989] of those reported for anthropogenic release. The poorly constrained Hg speciation in volcanic emissions, and the limited number of studies so far, have hampered accurate estimation of the global Hg flux, with previous estimates ranging from as low as ~1 t yr-1 [Ferrara et al. 2000] to >800 t yr-1 [Varekamp and Buseck 1986]. Besides, historical archives such as ice-cores documented that large eruptions can release quantities of Hg similar to the present anthropogenic burden. The effects, or potential effects, of active volcanoes on the environment and on public health is an important issue, given the large number of communities and populated cities that exist and keep growing around and upon active and dormant volcanoes. Poisonous gases, and in the specific mercury, are also released continuously or semi-continuously into the environment by non-erupting volcanoes causing however regional environmental effects equally severe to the volcanic events of massive proportions. A major uncertainty regarding the impacts of volcanic Hg is the extent to which Hg emitted from a volcano is deposited locally or transported globally. Actually, volcanogenic mercury fluxes are poorly constrained and there is an almost complete absence of data on the factors (magma composition, eruptive temperature, or volcanic gas composition) that influence its degassing rates at different volcanoes. In order to better understand the role of volcanoes in the global mercury budget and to extend the currently limited dataset on volcanogenic Hg emissions, a number of field campaigns were carried out to evaluate Hg flux in volcanic gases by the simultaneously-determined Hg/SO2 ratios and SO2 flux. Measurements were made at the crater edge of a number of quiescently degassing volcanoes (Etna, Stromboli, Asama, Miyakejima, Montserrat, Ambrym, Yasur, Nyiragongo, Masaya). Emissions from open vents were investigated and concentrations of Hg elevated above usual background levels (rural areas far from emitting source, 1-2 ng m-3) were detected. We found that in volcanic plume mercury is mainly found as the relatively inert form of gaseous elemental mercury (GEM) with concentrations ranging from 18 to 373 ng Hg m-3. GEM has a long atmospheric lifetime estimated as 0.5-2 years due to its low solubility and gaseous nature, promoting long-range global transport [Nriagu 1989; Pyle and Mather, 2003]. High variability found in plume Hg concentrations depends on both volcanic (gas flux) and non-volcanic factors (extent of mixing and dilution in the vent; wind speed and direction), hence comparing the concentrations of Hg species between different volcanoes is not necessarily meaningful and it is more useful to compare Hg/SO2 ratios. Using our determined Hg/SO2 mass ratios in tandem with the simultaneously-determined SO2 emission rates, we estimated that the investigated volcanoes have Hg emission rates ranging from 0.2 to 18 t•yr-1 (corresponding to a total Hg flux of ~54 t•yr-1). Based on our dataset and previous works, we propose that a Hg/SO2 plume ratio ~10-5 is best-representative of gas emissions from quiescent degassing volcanoes. Using this ratio, we infer a global volcanic Hg flux from persistent degassing of ~95 t•yr-1. If representative of other volcanoes, these results suggest degassing of basaltic magma plays an important part of the global atmospheric Hg budget. According to both these data and recent observations [Bagnato et al., 2010], volcanism thus would contribute from as little as 12 to as much as 78% of the estimated global natural Hg budget. Volcanic Hg therefore has a greater potential for local and global environmental impact than Hg from the more prodigious but diffuse natural and anthropogenic sources. In particular, Hg released from Mt Etna degassing, the largest active volcano in Europe, represents approximately 5% of the total industrial Hg emissions in the Mediterranean area [~105 t•yr-1, Pirrone et al., 2009] and about 2% of the anthropogenic Hg supplies throughout Europe [~239 t•yr-1, EMEP 2002]. With these new estimates we critically revisit the idea that volcanic activity is a trivial contribution to the atmospheric Hg supply in the Mediterranean area. We shall re-examine the status of the global volcanic mercury emissions budget and its uncertainties, even when only considering quiescent phases of volcanic activity. Besides, large sectors of the planet (SW Pacific) are still un-explored, and thus our global Hg flux value estimated from passive degassing may constitutes a lower limit. However, Hg flux measurements in eruptive gases is a priority for future mercury research at volcanoes.

The soil CO2 degassing is a ected by processes of isotope exchange and fractionation during transport across the soil, which can deeply modify the pristine isotope composition. This has been observed in 10 the Solfatara volcano, upon a eld survey of 110 points, where the CO2 ux was measured, together with temperature, CO2 concentra- tion and oxygen and carbon isotopes within the soil. Furthermore, in some selected sites, the measurements were made at di erent depths, in order to analyze vertical gradients. Oxygen isotope composition 15 appears controlled by exchange with soil water (either meteoric or fumarolic condensate), due to the fast kinetic of the isotopic equilib- rium between CO2 and water. Carbon isotope composition is reliably controlled by transport-driven fractionation, due to the di erences in di usion coe cients between 13C16O2 and 12C16O2. We model the 20 processes a ecting CO2 transport across the soil in La Solfatara vol- cano by means of the Dusty Gas Model applied to a multicomponent system, to evaluate the reciprocal e ect on di usion of involved gases, i.e. 12C16O2, 13C16O2, N2 and O2 in our case. Both numerical and simpli ed analytical solutions of the equations based on the Dusty 25 Gas Model are given. The modeling results t well with the experimental data and put in evidence an isotope fractionation of carbon up to about +4:4h with respect to the source value in the soil gas. This fractionation is independent from the entity of the CO2 ux, and occurs as long as a concentration gradient exists within the soil. On 30 these grounds, the Dusty Gas Model can be applied to whichever dif- fusing gas mixture to evaluate the extent of chemical and/or isotopic fractionation that can a ect ascending gases upon di usion in any geothermal, volcanic or tectonic area.

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

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

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

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

Mt. Etna, in the eastern coast of Sicily (Italy), is one of the most active and most intensely monitored volcanoes of the planet. It is widely recognized as a big source of volcanic gases, such as CO2, SO2 and halogens, to the troposphere in the Mediterranean basin, and its gas emissions account for a significant percentage respect to the worldwide average volcanic budget. The SO2 flux from Mt. Etna’s plume has been routinely measured by the INGV since 1987. SO2 flux ranges between 600 to 25000 Mg/d; fluxes greater than 100000 Mg/d were prevalently measured during eruptive events. During eruptive periods, Etna’s emissions can be dispersed over long distances and cover wide areas of the Mediterranean region. Mt. Etna is also considered a huge source of many trace elements to the atmosphere on regional and global scale. On the morning of December 24th 2018, a moderate lateral eruption of the Mt. Etna started. This eruption was related to an intrusion of a magmatic dike on the high eastern flank of the volcano, through a 2 kilometres long fracture in the NNW SSE direction. At the same time, the summit craters produced a continuous strombolian activity generating a very dense ash plume, dispersed by the wind into the S/SE direction. From June 2018 to June 2019, atmospheric precipitations were collected in the area of Siracusa, a city on the east coast of Sicily, about 80 km SSE of Mt. Etna, and in the area of Milazzo, a city on the northern coast of Sicily. Atmospheric precipitations were monthly collected through a network of 12 pluviometers; the collectors were open during the entire exposure time, receiving both wet and dry deposition (bulk collectors). All the collected water samples were analysed for major ion contents and for a large number of trace elements by ICPOES and ICPMS. During the eruptive period (from 24th to 27th December 2018), the prevailing winds blew from the North direction and there were light rainfalls in the monitored sites (between 0.2 mm in Siracusa and Augusta, and 1.6 mm in Palazzolo Acreide). As a consequence, gases and particles of Etna’s plume were carried for long distance from the emission point, and they were deposited as dry and wet deposition also in the area of Siracusa. During the eruption event and in the following days, the plume reached distances of more than 300 km from the emission point (island of Malta). The samples collected in the study area of Siracusa during the period straddling the eruptive event are characterized by high concentrations of some major ions, such as Fluoride (up to 0.88 mg/l), Chloride (up to 124 mg/l) and Sulphate (23.1 mg/l). These ions derive mainly from the emitted volcanic gases (HF, HCl and SO2). The effect of the described eruption is also visible in the high concentrations of some trace elements, such as Aluminium, Thallium and Tellurium. The mean concentrations of the selected trace elements in the samples collected in the area of Siracusa, in the period before the eruptive event, are: 18.2 μg/l for Aluminium, 0.009 μg/l for Thallium, while Tellurium was always under the detection limit (0.004 μg/l); the concentrations of the same elements in the samples collected during the eruptive event reach 152 μg/l for Aluminium, 0.16 Âg/l for Thallium and 0.025 μg/l for Tellurium, therefore showing a strong enrichment. While Thallium and Tellurium are highly volatile elements typically enriched in volcanic emissions, Aluminium is a refractory element that was probably released by the dissolution of the related volcanic ashes. The study area of Milazzo, due to the prevailing winds from the North direction during the period of the eruption, has not been affected by the plume and therefore the signature of the eruption is not visible in the samples collected in that area, as shown by the mean values of the selected trace elements: 24.2 μg/l, 0.026 μg/l and < 0.004 μg/l for Aluminum, Thallium and Tellurium respectively. In conclusion, close to active volcanic areas, volcanic emissions have to be considered among the major contributors to the chemistry of rainwater, especially during eruptive periods.

Dry and wet depositions provide the pathways through which particles and gases emitted into the atmosphere return to the Earth’s surface. Bulk deposition is defined as the sum of dry and wet deposition, which is characterized by water-soluble and insoluble chemical species. Recent studies (e.g. Castillo et al., 2017) showed that most of the atmospheric deposition in Europe occurs in the wet form, but in southern European regions the role of dry contribution can be as significant as that of wet deposition. In the framework of the multidisciplinary project “CISAS” (Centro Internazionale di Studi Avanzati su Ambiente, ecosistema e Salute umana), bulk depositions were monthly sampled over two polluted industrial areas of Sicily (Milazzo and Priolo), through a network of 12 bulk collectors, from June 2018 to July 2019. In that period, 137 samples were collected and subdivided into 4 aliquots for different analytical determinations: (i) unfiltered aliquots for the total alkalinity; (ii) filtered aliquots (0.45 µm filters) for major anions by ionic chromatography (IC); (iii) filtered and acidified (with Ultrapure HNO3) for the analysis of major cations and a large suite of trace elements, respectively by ICP-OES and ICP-MS; (iv) unfiltered and acidified aliquots for the same suite of trace elements, to evaluate the contribution of less-soluble species. The filtration of the rain samples allows the separation of the water-soluble fraction from the particulate fraction (> 0.45 µm), which is retained by the filter. The comparison between filtered and unfiltered aliquots allowed to highlight the different geochemical mobility of the trace elements, and their distribution among the two fractions. The unfiltered aliquots, therefore, represent the less-soluble species found in the particulate under typical rainwater pH values (4 – 8), that becomes soluble due to the acidification of the samples (pH < 1). Results showed that the less-soluble fraction represents a significant part of the bulk deposition for several trace metals, especially during dry-dominated periods which are characterized by a long-range transport of geogenic particles (e.g. desert dust). In particular, Al, B, Ba, Fe, Li, Sr, and Ti showed significant enrichment if the less-soluble fraction is included. Similar enrichments are noteworthy also for As, Cr, Co, Cu, Ni, Pb, Se Tl, Te and V which can be attributed to the local industrial atmospheric pollution, as well as to Mt. Etna that is a permanent source of several volcanogenic elements (Brugnone et al., 2020).

Sin dagli anni ’70, la ricerca scientifica ha evidenziato una forte relazione tra il degassamento di carbonio profondo e le aree tettonicamente attive, sottolineando l’elevata importanza del contributo di queste emissioni nella quantificazione del carbonio globale. La Penisola Balcanica presenta grandi aree caratterizzate da degassamento di carbonio di origine mantellica, da attività vulcaniche Quaternarie, da un’elevata sismicità e da strutture tettoniche a scala regionale. Purtroppo, la stima del degassamento di anidride carbonica profonda in quest’area è ancora poco studiata. La ricerca di questa tesi di dottorato si è focalizzata sulla (i) stima dell’output di carbonio profondo dalle grandi sorgenti carsiche della Grecia, e sulla (ii) caratterizzazione della composizione chimica e isotopica delle principali manifestazioni gassose della Macedonia del Nord. Inoltre, è stato condotto anche uno studio sull’impatto dei processi geogenici ed antropogenici sulla qualità delle acque dei grandi sistemi carsici della Grecia. Negli acquiferi carsici delle Grecia sono state riconosciute tre principali composizioni chimiche dell’acqua: (i) bicarbonato-calcica per le sorgenti continentali; (ii) cloruro-sodica per le sorgenti in area di costa, (iii) solfato-calcica dovuta a processi di dissoluzione di gesso all’interno dell’acquifero. I risultati, in termini di specie maggiori ed elementi in traccia, sono stati comparati con i limiti sulle acque potabili imposte dalle Direttive della Comunità Europea, CE/98/83 e CE/2020/2184, i quali raramente vengono superati tranne per quei parametri che risentono della influenza dell’intrusione marina (Conduttività Elettrica, Na, Cl, B). In queste sorgenti, sono stati rivelati elevati valori di nitrato, sebbene sempre al di sotto del limite di potabilità. Per quanto riguarda la composizione chimica dei gas disciolti e liberi, l’azoto risulta essere il gas dominante, con concentrazioni fino a 985,300 µmol mol-1. Il δ13CTDIC varia tra -16.6 ‰ e -0.10 ‰ (vs. V-PDB), mentre il δ13CCO2, misurato nel gas libero, varia da -29.9 ‰ a -7.41 ‰ (vs. V-PDB). La composizione isotopica dell’elio è stata misurata solo in pochi campioni (R/RA = 0.20 - 0.33), con valori che indicano una sorgente principalmente crostale. Applicando il bilancio di massa del carbonio, è stata fatta una stima del carbonio endogenico (1.43 × 109 mol a-1), la quale sorgente potrebbe essere associata a diverse sorgenti, tra cui termo-metamorfismo di carbonati indotto dall’intrusione di corpi magmatici di età Quaternaria e/o strutture tettoniche regionali. La ricerca condotta in Macedonia del Nord rappresenta un primo catalogo delle principali manifestazioni gassose presenti nell’area, sebbene ancora incompleto. Le manifestazioni gassose campionate, comprendenti sia sistemi caldi sia sistemi freddi, sono stati suddivisi in tre gruppi: (i) dominati in N2; (ii) dominati in CO2; (iii) ricchi in H2S. Queste categorie sono ben separate geograficamente, associate, soprattutto, al regime tettonico estensionale e, spesso, associati alle aree di confine tra le principali unità geotettoniche. Il δ13CCO2 varia tra -15.7 ‰ e +1.0 ‰, mentre i valori di R/RA variano da 0.1 a 1.8, suggerendo un’origine perlopiù crostale con un contributo mantellico fino al 20%. La composizione isotopica del metano presenta valori di δ13CCH4 tra -57.8 ‰ e -7.2 ‰ e valori di δ2HCH4 tra -303 ‰ e -80 ‰. Inoltre, misure di flusso di CO2 al suolo sono state condotte a Duvalo Kosel, Petkoniva e Botun. Per quanto riguardo Duvalo Kosel, un’area studiata in dettaglio, si è stimato una emissione di CO2 di 66.9 t × d-1. A Petkoniva and Botun sono state condotte delle misure preliminari, limitate ad aree caratterizzate da forte alterazione del suolo e mancanza di vegetazione, rivelando un flusso di CO2 di 0.20 t × d-1 a Petkoniva e di 0.59 t × d-1 a Botun. Since the 1970s, scientific research evidenced the close relationship between deeply-derived carbon degassing and active tectonic zones, highlighting the utmost importance of tectonic degassing contribution within the global carbon cycle. Large-scale degassing of mantle-derived carbon, Quaternary volcanic activity, seismic activity, and regional active fault systems are widespread in the Balkan Peninsula. However, the estimation of geogenic CO2 release from this area is currently still poorly quantified. This PhD research is focused on (i) the estimation of endogenous carbon release from the main karst hydro-systems of Greece and on (ii) the chemical and isotopic characterization of the main gas manifestation in North Macedonia. Moreover, a study about the geogenic and anthropogenic processes affecting the water quality of Hellenic karst aquifers was carried out. Three main water types were recognized in the Hellenic karst aquifers: (i) calcium-bicarbonate for hinterland springs; (ii) sodium-chloride for coastal springs; (iii) calcium-sulfate derived from gypsum dissolution. Results in terms of major ions and trace elements were compared with the drinking water limits set by the Directive 98/83/EC and the Directive 2020/2184/EC, which are rarely exceeded except for parameters related to marine intrusion along the coastal areas (EC, Na, Cl, B). In these springs, the highest nitrate levels are also found, though always below the drinking water limit. Regarding the chemical composition of the dissolved and free gases collected in the above-mentioned springs, the nitrogen is the dominant gas (up to 985,300 µmol mol-1). The δ13CTDIC varies between -16.6 ‰ and -0.10 ‰ (vs. V-PDB), whereas the δ13CCO2 in free gases ranged from -29.9 ‰ to -7.41 ‰ (vs. V-PDB). The isotopic composition of helium was measured in few samples (R/RA = 0.20 - 0.33), with values indicating a mainly crustal source. An estimation of the endogenous carbon (1.43 × 109 mol a-1) released from these systems was carried out, applying the isotope-carbon mass balance. The geogenic source of carbon may be associated to multiple sources, such as thermo-metamorphism of buried carbonates associated to intrusions of Quaternary magmatic bodies and/or regional tectonic structures. The research about the gas manifestations in North Macedonia represented a first catalogue, although still incomplete. The collected gas manifestations, comprising both thermal and cold systems, were subdivided in three groups: (i) N2-dominated group; (ii) CO2-dominated group; (iii) H2S-rich group. These categories are geographically well separated, mainly, related to the extensional tectonic regime of the area and, sometimes, associated with boundaries between the major geotectonic units. The δ13CCO2 varies between -15.7 ‰ and +1.0 ‰, whereas the R/RA values vary from 0.1 to 1.8, suggesting a prevailing crustal source with a mantle contribution up to 20%. On the other hand, the isotope composition of methane showed δ13CCH4 values ranging between -57.8 ‰ and -7.2 ‰ and δ2HCH4 varying from -303 ‰ to -80 ‰. Furthermore, soil CO2 flux measurements were carried out at Duvalo Kosel, Petkoniva and Botun. Regarding the former, a detailed investigation was carried out, estimanting a total CO2 output of 66.9 t × d-1. A preliminary investigation was done at Petkoniva and Botun, limited only to patches with heavy soil alteration and devoid of vegetation, revealing a CO2 output of 0.20 t × d-1 at Petkoniva and of 0.59 t × d-1 at Botun.

Κατά την περίοδο 2004 με 2017, συλλέχθηκαν περισσότερα από 350 δείγματα ελεύθερων και διαλελυμένων αερίων στην Ελλάδα. Μαζί με αυτά συνυπολογίστηκαν και βιβλιογραφικά δεδομένα. Για καλύτερη κατανόηση της μελέτης, η χώρα διαιρέθηκε σε τέσσερις γεωλογικές ενότητες (Εξωτερικές [EH] και Εσωτερικές [IH] Ελληνίδες, Ελληνική Ενδοχώρα [HH] και ενεργό ηφαιστειακό τόξο [VA]) και με βάση τον συγκεκριμένο διαχωρισμό ερευνήθηκε η πιθανή σχέση της κύριας γεωχημικής σύστασης των αερίων με τα διάφορα γεωλογικά και γεωδυναμικά καθεστώτα των περιοχών δειγματοληψίας. Τα δείγματα αναλύθηκαν για την χημική (O2, N2, CH4, CO2, He, Ne, Ar, H2, H2S και C2-C6 υδρογονάνθρακες) και ισοτοπική τους (R/RA, δ13C-CO2, δ13C-CH4 and δ2H-CH4) σύσταση. Οι συγκεντρώσεις κυμαίνονταν από 0.10 έως 3370 μmol/mol για το He, 600 έως 995,000 μmol/mol για το N2, 0.60 έως 915,000 μmol/mol για το CH4 και 17 έως 1,000,000 μmol/mol για το CO2, ενώ οι ισοτοπικές τους τιμές από 0.01 έως 7.10 R/RA, -29.91 έως +6.00 vs. V-PDB για το δ13C-CO2, -79.8 έως +45.0‰ vs. V-PDB για το δ13C-CH4 και -311 έως +301‰ vs. V-SMOW για το δ2H-CH4. Λαμβάνοντας υπ’όψιν τις τιμές των R/RA και 4He/20Ne, υπολογίστηκε η συνεισφορά της ατμόσφαιρας, του μανδύα και του φλοιού για το He. Η μεγαλύτερη μανδυακή συνεισφορά (έως και 90%) βρέθηκε στο VA, ενώ η χαμηλότερη (0-20%) στο EH. Η συνεισφορά της ατμόσφαιρας ήταν σχετικά αμελητέα. Σύμφωνα με την γεωγραφική κατανομή των αερίων, είναι εμφανές πως το R/RA αυξάνεται σε περιοχές που χαρακτηρίζονται από: i) λεπτό φλοιό; ii) αυξημένες τιμές ροής θερμότητας; iii) πρόσφατη (Πλειστόκενο-Τεταρτογενής) ηφαιστειακή δραστηριότητα; και iv) τοπικά εκτατικά ή διασταλτικά ρήγματα. Οι υψηλότερες τιμές βρέθηκαν κατά μήκος του VA και οι χαμηλότερες στις EH. Επιπλέον, με βάση τις τιμές των CO2/3He και δ13C-CO2, υπολογίστηκε η συνεισφορά των Ιζηματογενών, Μανδυακών και Ασβεστολιθικών end-members του CO2. Οι πλειοψηφία των δειγμάτων παρουσίασε μία κυρίως ασβεστολιθική σύσταση για τον C, ενώ μόνο λίγα δείγματα έδειξαν μανδυακή σύσταση. Παρ’όλα αυτά, με τα υπάρχοντα δεδομένα, είναι αδύνατος ο διαχωρισμός του CO2 που προέρχεται από τους ασβεστολίθους του φλοιού και από εκείνους της υπό βύθισης πλάκας. Επί προσθέτως, λόγω της σύνθετης γεωδυναμικής ιστορίας, η ισοτοπική σύσταση του μανδυακού C θα μπορούσε να είναι επηρεασμένη από μετασωμάτωση συσχετιζόμενη με την βύθιση της πλάκας, όπως συμβαίνει και στην γειτνιακή περιοχή της Ιταλίας, κάνοντας την ισοτοπική του σύσταση πιο θετική. Σε τέτοια περίπτωση, η συνεισφορά του μανδύα θεωρείται ότι έχει υποτιμηθεί. Κάποια δείγματα παραθέτουν πολύ χαμηλες τιμές CO2/3He και δ13CO2 λόγω απώλειας του CO2, η οποία έχει προκληθεί είτε από διάλυση του CO2 σε υπόγεια νερά μικρού βάθους είτε από την καθίζηση του ασβεστίτη που λαμβάνει μέρος στε ορισμένες θερμές πηγές. Από την άλλη μεριά, οι τιμές του CH4/(C2H6+C3H8) (από 1.5 έως 93,200) σε συνδιασμό με τα ισοτοπικά χαρακτηριστικά του CH4, συνιστούν πως οι ελαφριές αλκάνες προέρχονται από διαφορετική αρχική πηγή και αρκετές φορές επηρεάζονται από δευτερογενή διαδικασίες. Στα αέρια των EH παρατηρείται μια σχετικά αποκλειστική βιοτική, κυρίως μικροβιακή, προέλευση για το CH4. Τα αέρια των ψυχρών πηγών των IH έχουν κυρίως θερμογενή προέλευση, αν και κάποια από αυτά συνδέονται με ηπειρωτικές σερπεντινιώσεις και μοιάζει να έχουν αβιοτική προέλευση. Το CH4 στις θερμές πηγές των IH, HH and VA και στα φουμαρολικά αέρια του VA φαίνεται να είναι κυρίως αβιοτικό, αν και τα χημικά και ισοτοπικά χαρακτηριστικά του μοιάζει να έχουν επηρεαστεί από δευτερογενή οξείδωση του CH4 θερμογενούς προέλευσης. Τέλος, κάποια από τα δείγματα παρουσιάζουν αρκετά θετικές ισοτοπικές τιμές (δ13C-CH4 έως +45.0‰ vs. V-PDB και δ2H-CH4 έως +301‰ vs. V-SMOW) πιθανότατα λόγω οξείδωσής τους από μικρόβια. 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. For a better comprehension of this study, Greece was subdivided in four geologic units (External [EH], Internal [IH] Hellenides, Hellenic Hinterland [HH] and active Volcanic Arc [VA]) and based on that division, I investigate the possible relationship of the main geochemical composition of the gases with the different geological and geodynamical settings of the sampling sites. Samples have been analysed for their chemical (O2, N2, CH4, CO2, He, Ne, Ar, H2, H2S and C2-C6 hydrocarbons) and isotope (R/RA, δ13C-CO2, δ13C-CH4 and δ2H-CH4) 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 1,000,000 μmol/mol for CO2, whereas the isotope values range from 0.01 to 7.10 for R/RA, -29.91 to +6.00 vs. V-PDB for δ13C-CO2, -79.8 to +45.0‰ vs. V-PDB for δ13C-CH4 and -311 to +301‰ vs. V-SMOW for δ2H-CH4. Considering the R/RA and 4 He/20Ne ratios the atmospheric, mantle and crustal contributions for He have been calculated. The highest mantle contribution (up to 90%) is found in the VA, 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 characterised by: i) thin crust; ii) elevated heat flow values; iii) recent (PleistoceneQuaternary) volcanic activity; and iv) deep routed extensional or transtensional regional faults. The highest values are therefore found along VA and the lowest in EH. Furthermore, based on the CO2/3He and δ13C-CO2 values, the contribution of Sediment, Mantle and Limestone endmembers 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 isotope composition could be affected by subduction-related metasomatism and, similarly to the nearby Italian area, the C isotope composition could be more positive. In this case, the mantle contribution is probably underestimated. Some samples display very low CO2/3He and δ13CO2 values due to the CO2 loss caused either by dissolution of CO2 in shallow groundwater or by the calcite precipitation that is taking place in most of the thermal springs. On the other hand, the CH4/(C2H6+C3H8) ratios (from 1.5 to 93,200) coupled with CH4 isotopic features, suggest the light alkanes derive from a different primary source and are sometimes affected by secondary processes. An almost exclusive biotic, mainly microbial, origin of CH4 can be attributed to EH gases. Cold gases at IH have mainly a thermogenic origin, although some gases connected to continental serpentinization may have an abiogenic origin. Methane in gases bubbling in thermal waters of IH, HH and VA and fumarolic gases of the VA seem to have a prevailing abiogenic origin, although their chemical and isotopic characteristics may have been produced by secondary oxidation of thermogenic CH4. Finally, in some of the sampled gases, the isotopic values are extremely positive (δ13C-CH4 up to +45.0‰ vs. V-PDB and δ2H-CH4 up to +301‰ vs. V-SMOW) most probably caused by microbial oxidation.