Mercury concentration, speciation and budget in volcanic aquifers: Italy and Guadeloupe (Lesser Antilles)

Abstract Quantifying the contribution of volcanism to global mercury (Hg) emissions is important to understand the pathways and the mechanisms of Hg cycling through the Earth's geochemical reservoirs and to assess its environmental impacts. While previous studies have suggested that degassing volcanoes might contribute importantly to the atmospheric budget of mercury, little is known about the amount and behaviour of Hg in volcanic aquifers. Here we report on detailed investigations of both the content and the speciation of mercury in aquifers of active volcanoes in Italy and Guadeloupe Island (Lesser Antilles). In the studied groundwaters, total Hg (THg) concentrations range from 10 to 500…

Diffusive degassing of CO2 from soil and its relation whit different soil management

Sampling and analysis methodology of atmospheric deposition: a study case form Mount Etna

Geochemical characterization of surface waters and groundwater resources in the Managua area (Nicaragua, Central America)

This paper reports new geochemical data on dissolved major and minor constituents in surface waters and ground waters collected in the Managua region (Nicaragua), and provides a preliminary characterization of the hydrogeochemical processes governing the natural water evolution in this area. The peculiar geological features of the study site, an active tectonic region (Nicaragua Depression) characterized by active volcanism and thermalism, combined with significant anthropogenic pressure, contribute to a complex evolution of water chemistry, which results from the simultaneous action of several geochemical processes such as evaporation, rock leaching, mixing with saline brines of natural or…

DISPOSITIVO PER MISURARE UN GRADIENTE DI PRESSIONE NEL SUOLO, IN PARTICOLARE PER IL MONITORAGGIO DI SITI VULCANICI

Understanding volcanoes in the Vanuatu arc

We report the first helium isotope survey of volcanic gases, hot springs and some olivine phenocrysts along the Vanuatu island arc, from Tanna in the south to Vanua Lava in the north. Low CO2 content and low He-3/He-4 ratios in thermal fluids of Epi (4.0 +/- 0.1 R-a), Efate (4.5 +/- 0.1 R-a) and Pentecost (5.3 +/- 0.5 R-a) islands coherently indicate reduced mantle gas leakage and crustal contamination by radiogenic helium on these extinct volcanic systems of the former (Pliocene) arc. Instead, presently active Vanuatu volcanoes display He-3/He-4 and C/He-3 ratios typical of subduction-related volcanic arcs: He-3/He-4 ratios range from 6.4 +/- 0.5 Ra in southernmost Tanna and 7.23 +/- 0.09 …

Mercury gas emissions from La Soufrière Volcano, Guadeloupe Island (Lesser Antilles)

Abstract Quantifying mercury (Hg) emissions from active volcanoes is of particular interest for better constraining the global cycle and environmental impact of this highly toxic element. Here we report on the abundance of total gaseous (TGM = Hg 0 (g)  + Hg II (g) ) and particulate (Hg (p) ) mercury in the summit gas emissions of La Soufriere andesitic volcano (Guadeloupe island, Lesser Antilles), where enhanced degassing of mixed hydrothermal-magmatic volatiles has been occurring since 1992 from the Southern summit crater. We demonstrate that Hg in volcanic plume occurs predominantly as gaseous mercury, with a mean TGM/Hg (p) mass ratio of ~ 63. Combining the mean TGM/H 2 S mass ratio of …

Geochemistry and mineralogy of travertine deposits of the SW flank of Mt. Etna (Italy): Relationships with past volcanic and degassing activity

Abstract Travertine deposits outcropping in the lower SW flank of Mt. Etna were studied for their mapping, as well as for their chemical, mineralogical and isotopic compositions. These deposits are dated to about 24 to 5 ka in the Adrano area, located at the western limit of the study area. In this area travertines show high Mg contents and are composed mostly of dolomite, thus apparently ruling out any primary deposition in favour of a diagenetic origin. Travertines outcropping near Paterno, in the east part of the study area, should be younger than 18 ka. Those located to the SSW of Paterno (Paterno–Diga) show high Sr contents and aragonite as dominant mineralogical phase, thus suggesting…

Chemical and isotopic characterization of the gases of Mount Etna (Italy)

Abstract In the period 1990–1995, 43 samples of dissolved gases in groundwaters (wells, springs and drainage galleries) and 64 samples of free gases (fumaroles, bubbling and soil gases) from the Mount Etna area were collected and analysed. Isotopic analyses were also carried out of both the carbon of the CO 2 in free gases and dissolved inorganic carbon (DIC) in the waters. The chemical composition of the gases depends on the relative abundances of three interacting components. These are gases of (1) atmospheric origin enriched in O 2 and N 2 , present almost exclusively in dissolved gases, (2) deep origin enriched in CO 2 , prevalent in the majority of cases, and (3) more superficial origi…

Geochemical characterization of the Lake “Specchio di Venere”, Pantelleria island, Italy.

Differenziazione e quantificazione dei carbonati litogenici e pedogenici di Gypsisuoli forestali attraverso l'analisi isotopica

Gli autori riferiscono sui tipi e sui modelli di genesi dei carbonati dei suoli, attraverso l’uso degli isotopi del 13C. Lo studio è stato condotto in un’area dell’interno collinare argilloso siciliano, su suoli che evolvono sui depositi evaporitici della Serie Gessoso-Solfifera. Sono stati scelti cinque pedon su litotipi calcarei e non. I pedon sono stati descritti in campo e campionati secondo la sequenza degli orizzonti genetici; sui campioni di suolo sono state eseguite le seguenti analisi: tessitura, reazione, conducibilità elettrica, gesso, carbonio organico ed inorganico. Inoltre, parallelamente sono state eseguite le analisi isotopiche del carbonio organico ed inorganico. I risultat…

Methanotrophic activity and bacterial diversity in volcanic-geothermal soils at Pantelleria island (Italy)

Abstract. Volcanic and geothermal systems emit endogenous gases by widespread degassing from soils, including CH4, a greenhouse gas twenty-five times as potent as CO2. Recently, it has been demonstrated that volcanic/geothermal soils are source of methane, but also sites of methanotrophic activity. Methanotrophs are able to consume 10–40 Tg of CH4 a−1 and to trap more than 50% of the methane degassing through the soils. We report on methane microbial oxidation in the geothermally most active site of Pantelleria island (Italy), Favara Grande, whose total methane emission was previously estimated in about 2.5 t a−1. Laboratory incubation experiments with three top-soil samples from Favara Gra…

ENVIRONMENTAL IMPACT OF MT. ETNA’S VOLCANIC EMISSIONS: TRACE METAL BULK-DEPOSITION

CHEMICAL AND MINERALOGICAL CHARACTERIZATION OF ETNEAN VOLCANIC EMISSIONS USING ACTIVE BIOMONITORING TEC HNIQUE (MOSS-BAGS)

Quantification of methane output from mud volcanoes and mofettes south of Mt. Etna (Italy)

Rain-ash interaction during paroxysmal events as potential input of toxic trace element in the environment: example from Mt. Etna Volcano

The importance of methanotrophic activity in geothermal soils of Pantelleria island (Italy)

Methane is a major contributor to the greenhouse effect, its atmospheric concentration being more than doubled since the XIX century. Every year 22 Tg of methane are released to the atmosphere from several natural and anthropogenic sources. Natural sources include geothermal/volcanic areas but the estimation of the total methane emission from these areas is currently not well defined since the balance between emission through degassing and microbial oxidation within the soils is not well known. Microbial oxidation in soils contributes globally for about 3-9% to the removal of methane from the atmosphere and recent studies evidenced methanotrophic activity also in soils of volcanic/geotherma…

Magma and volatile supply to post-collapse volcanism and block resurgence in Siwi caldera (Tanna Island, Vanuatu arc)

Siwi caldera, in the Vanuatu arc (Tanna island), is a rare volcanic complex where both persistent eruptive activity (Yasur volcano) and rapid block resurgence (Yenkahe horst) can be investigated simultaneously during a post-caldera stage. Here we provide new constraints on the feeding system of this volcanic complex, based on a detailed study of the petrology, geochemistry and volatile content of Yasur-Siwi bulk-rocks and melt inclusions, combined with measurements of the chemical composition and mass fluxes of Yasur volcanic gases. Major and trace element analyses of Yasur-Siwi volcanic rocks, together with literature data for other volcanic centers, point to a single magmatic series and p…

Atmospheric Deposition around the Industrial Areas of Milazzo and Priolo Gargallo (Sicily–Italy)—Part A: Major Ions

The chemical composition of rainwater was studied in two highly-industrialised areas in Sicily (southern Italy), between June 2018 and July 2019. The study areas were characterised by large oil refining plants and other industrial hubs whose processes contribute to the release of large amounts of gaseous species that can affect the chemical composition of atmospheric deposition As in most of the Mediterranean area, rainwater acidity (ranging in the study area between 3.9 and 8.3) was buffered by the dissolution of abundant geogenic carbonate aerosol. In particular, calcium and magnesium cations showed the highest pH-neutralizing factor, with ~92% of the acidity brought by SO42− and NO…

A biomonitoring study using endemic plants for the evaluation of volcanogenic deposition on Mt. Etna (Italy)

8. A biomonitoring survey using leaves of tree (Betulla aethnensis, Pinus nigra and Populus tremula) and two endemic species (Senecio aethnensis and Rumex aethnensis) above treeline level, was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (800-3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analyzed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind se…

A coupled geophysical and geochemical approach to the study of buried degassing structures on mt. Etna

Geochemical survey of Levante Bay, Vulcano Island (Italy), a natural laboratory for the study of ocean acidification

Abstract Shallow submarine gas vents in Levante Bay, Vulcano Island (Italy), emit around 3.6t CO2 per day providing a natural laboratory for the study of biogeochemical processes related to seabed CO2 leaks and ocean acidification. The main physico-chemical parameters (T, pH and Eh) were measured at more than 70 stations with 40 seawater samples were collected for chemical analyses. The main gas vent area had high concentrations of dissolved hydrothermal gases, low pH and negative redox values all of which returned to normal seawater values at distances of about 400 m from the main vents. Much of the bay around the vents is corrosive to calcium carbonate; the north shore has a gradient in s…

Soil CO2 emissions from the lower SW flank of Mt. Etna: possible relations with hidden faults and preliminary output estimate

New evidences on mercury emissions from Earth volcanism

Degassing of gaseous (elemental and reactive) and particulate mercury from Mount Etna volcano (Southern Italy)

Abstract There is an urgent need to better constrain the global rates of mercury degassing from natural sources, including active volcanoes. Hitherto, estimates of volcanic fluxes have been limited by the poorly determined speciation of Hg in volcanic emissions. Here, we present a systematic characterisation of mercury partitioning between gaseous (Hg(g)) and particulate (Hg(p)) forms in the volcanic plume of Mount Etna, the largest open-vent passively degassing volcano on Earth. We demonstrate that mercury transport is predominantly in the gas phase, with a mean Hg(p)/Hg(g) ratio of ∼0.01 by mass. We also present the first simultaneous measurement of divalent gaseous mercury ( Hg ( g ) II …

Seawater Trace Metals in acidified condition: an accumulation study in the blue mussel Mytilus galloprovincialis off Vulcano Island submarine vents (Italy)

Chemistry of atmospheric depositions over two polluted industrial areas of Sicily (Italy)

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 p…

Fluorine adsorption by volcanic soils at Mt. Etna, Italy

Abstract Fluorine adsorption experiments were performed on 28 samples of the first 5 cm of topsoil collected on the flanks of Mt. Etna. The soil samples were equilibrated with F-rich rainwater (3.25 mg/L) at a soil/water weight ratio of 1/25. Aliquots of the supernatant were collected after 1, 7, 72, 720 and 5640 h and analysed for F content. The soil samples could be subdivided into three groups based on their F-adsorption behaviours after 1 h and at the end of the experiment: (1) negative adsorption (F released from the soil to the solution) after 1 h and negative or moderately positive adsorption at the end, (2) from negative after 1 h to strongly positive adsorption at the end, and (3) …

Degassing and Cycling of Mercury at Nisyros Volcano (Greece)

Nisyros Island (Greece) is an active volcano hosting a high-enthalpy geothermal system. During June 2013, an extensive survey on Hg concentrations in different matrices (fumarolic fluids, atmosphere, soils, and plants) was carried out at the Lakki Plain, an intracaldera area affected by widespread soil and fumarolic degassing. Concentrations of gaseous elemental mercury (GEM), together with H2S and CO2, were simultaneously measured in both the fumarolic emissions and the atmosphere around them. At the same time, 130 samples of top soils and 31 samples of plants (Cistus creticus and salvifolius and Erica arborea and manipuliflora) were collected for Hg analysis. Mercury concentrations in fum…

Nitrate, sulphate and chloride contents in public drinking water supplies in Sicily, Italy.

Water samples collected from public drinking water supplies in Sicily were analysed for electric conductivity and for their chloride, sulphate and nitrate contents. The samples were collected as uniformly as possible from throughout the Sicilian territory, with an average sampling density of about one sample for every 7,600 inhabitants. Chloride contents that ranged from 5.53 to 1,302 mg/l were correlated strongly with electric conductivity, a parameter used as a proxy for water salinity. The highest values are attributable to seawater contamination along the coasts of the island. High chloride and sulphate values attributable to evaporitic rock dissolution were found in the central part of…

Atmospheric Impacts of Volcanic Volatiles: Trace Elements in Bulk Deposition at Mount Etna (Italy)

Survey on fluoride, bromide and chloride contents in public5 drinking water supplies in Sicily (Italy)

FIRST APPLICATION OF ACTIVE BIOMONITORING TECHNIQUES (MOSS-BAGS) TO MAP THE DISPERSION OF VOLCANIC EMISSIONS

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 o…

Flussi di evasione marina del mercurio elementare gassoso (Hg0) nell’atmosfera della Rada di Augusta

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…

Magmatic gas leakage at Mount Etna (Sicily, Italy): Relationships with the volcano-tectonic structures, the hydrological pattern and the eruptive activity.

In this paper we provide a review of chemical and isotopic data gathered over the last three decades on Etna volcano's fluid emissions and we present a synthetic framework of their spatial and temporal relationships with the volcano-tectonic structures, groundwater circulation and eruptive activity. We show that the chemistry, intensity and spatial distribution of gas exhalations are strongly controlled by the main volcano-tectonic fault systems. The emission of mantle-derived magmatic volatiles, supplied by deep to shallow degassing of alkali-hawaiitic basalts, persistently occurs through the central conduits, producing a huge volcanic plume. The magmatic derivation of the hot gases is ver…

The use of moss-bags technique to volcanic aerosols investigation on Mt. Etna (Italy)

DEEP RESERVOIR TEMPERATURES OF LOW-ENTHALPY GEOTHERMAL SYSTEMS IN TUNISIA: NEW CONSTRAINTS FROM CHEMISTRY OF THERMAL WATERS

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 temper…

The contribution of volcanic emissions (Etna, Stromboli and Vulcano) to the atmospheric trace metals budget in the Mediterranean basin

Volcanic emissions represent one of the major natural source for several trace metals (Cd, Cu, As, Pb, Hg and Zn) into the atmosphere both as gaseous and aerosol forms. The Mediterranean Sea can be considered a large geochemical sink for these elements whose source are the huge amounts of aerosols of different origin. The industrialized areas located in the northern part of the basin represent a nearly constant source of the anthropogenic-dominated aerosol. By contrast, the arid and desert regions located at the southern and eastern parts of the Mediterranean, are the sources of frequent dust “pulses” perturbing the “steady-state” conditions of the local atmosphere through the input of seve…

Geochemical mapping of magmatic gas–water–rock interactions in the aquifer of Mount Etna volcano

Abstract Systematic analysis of major and minor elements in groundwaters from springs and wells on the slopes of Mt. Etna in 1995–1998 provides a detailed geochemical mapping of the aquifer of the volcano and of the interactions between magmatic gas, water bodies and their host rocks. Strong spatial correlations between the largest anomalies in pCO2 (pH and alkalinity) K, Rb, Mg, Ca and Sr suggest a dominating control by magmatic gas (CO2) and consequent basalt leaching by acidified waters of the shallow (meteoric) Etnean aquifer. Most groundwaters displaying this magmatic-type interaction discharge within active faulted zones on the S–SW and E lower flanks of the volcanic pile, but also in…

Biomonitoring of volcanogenic trace elements using two endemic species (Senecio aethnensis and Rumex aethnensis) on Mt. Etna.

A biomonitoring survey, above treeline level, using two endemic species (Senecio aethnensis and Rumex aethnensis) was performed on Mt. Etna, in order to evaluate the dispersion and the impact of volcanic emissions. Samples of leaves were collected in summer 2008 from 30 sites in the upper part of the volcano (1500-3000 m a.s.l). Acid digestion of samples was carried out with a microwave oven, and 44 elements were analysed by using plasma spectrometry (ICP-MS and ICP-OES). The highest concentrations of all investigated elements were found in the samples collected closest to the degassing craters, and in the downwind sector, confirming that the eastern flank of Mt. Etna is the most impacted b…

Trace element mobility during interaction between rain and volcanic ash on Mt. Etna

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, S…

High diversity of methanotrophic bacteria in a geothermal site: Pantelleria island

Trace elements mobility in soils from the active hydrothermal area of Nisyros (Greece)

Nisyros Island, Greece, is a stratovolcano known for its intense hydrothermal activity. On June 2013, during a multidisciplinary field campaign, soil samples were collected in the caldera area to determinate the main mineralogical paragenesis and to investigate the distribution of trace elements concentrations and the possible relationship to the contribution of deep originated fluids. Soil samples were analysed with XRD and for the chemical composition of their leachable (deionized water) and near total (microwave digestion) fraction both for major and trace elements. All data were compared to a local background soil. The results allow to divide the samples in 2 groups: Lakki Plain and Ste…

Geochemistry and mineralogy of travertine deposits of the SW flank of Mt. Etna (Italy): Relationships with past volcanic and degassing activity.

Environmental impact of Mt. Etna’s degassing: volcanogenic trace elements bioaccumulation in two endemic plant species (Senecio aethnensis and Rumex aethnensis)

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 mos…

Application of the moss bag biomonitoring technique in an active volcanic environment (Mt. Etna, Italy).

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.

CHEMICAL COMPOSITION OF ATMOSPHERIC BULK DEPOSITION AT THE INDUSTRIAL AREA OF GELA (SICILY, ITALY)

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…

Real-time simultaneous detection of volcanic Hg and SO2at La Fossa Crater, Vulcano (Aeolian Islands, Sicily)

Measuring Hg/SO2 ratios in volcanic emissions is essential for better apportioning the volcanic contribution to the global Hg atmospheric cycle. Here, we report the first real-time simultaneous measurement of Hg and SO2 in a volcanic plume, based on Lumex and MultiGAS techniques, respectively. We demonstrate that the use of these novel techniques allows the measurements of Hg/SO2 ratios with a far better time resolution than possible with more conventional methods. The Hg/SO2 ratio in the plume of FO fumarole on La Fossa Crater, Vulcano Island spanned an order of magnitude over a 30 minute monitoring period, but was on average in qualitative agreement with the Hg/SO2 ratio directly measured…

Helium isotope systematics of volcanic gases and thermal waters of Guadeloupe Island, Lesser Antilles

Abstract The island of Guadeloupe is located in the middle of the 850 km long Lesser Antilles island arc. Present-day volcanic and geothermal activity is concentrated in two systems both located in the southwestern part of the island (Basse Terre): the La Soufriere volcanic complex and the Bouillante hydrothermal system, some 20 km to the northwest of the volcano. We report here the largest isotopic data set for helium isotopes in hydrothermal gases and waters from both systems, acquired between 1980 and 2012. 3 He/ 4 He ratios in the fumarolic gases of La Soufriere volcano have been quite homogeneous and stable over the last thirty years. The average ratio of 8.2 ± 0.2 R a confirms that th…

Signature of the 24th December 2018 eruption of Mt. Etna on the chemical composition of bulk deposition in the Siracusa area (Italy)

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 Medi…

Geological development of a gypsum lake formed at the beginning of the 2oth century in central Sicily, Italy: Integration of historical data with modern survey techniques

A limnological investigation was carried out on the small, endorheic lake, called Lake Sfondato, located in central Sicily (Italy). All the aquatic environments in the central part of the island are rich in salt, with conductivity values above 5 mS cm−1, and are characterized by high alkalinity values and hard waters. In addition, due to intensive agriculture, many of these ecosystems have experienced a strong anthropogenic eutrophication over the last decades. In order to better understand the functioning of these peculiar environments, the morphology, hydrology, and geochemistry, as well as several selected physical and biological characteristics of Lake Sfondato, were studied in the year…

Preliminary estimates of volcanic gaseous and particulate-phase mercury emissions at Mt. Etna and Vulcano Island

Isotope geochemistry of Pantelleria volcanic fluids, Sicily Channel rift: a mantle volatile end-member for volcanism in southern Europe

Chemical and isotopic ratio (He, C, H and O) analysis of hydrothermal manifestations on Pantelleria island, the southernmost active volcano in Italy, provides us with the first data upon mantle degassing through the Sicily Channel rift zone, south of the African–European collision plate boundary. We find that Pantelleria fluids contain a CO2–He-rich gas component of mantle magmatic derivation which, at shallow depth, variably interacts with a main thermal (∼100°C) aquifer of mixed marine–meteoric water. The measured 3He/4He ratios and δ13C of both the free gases (4.5–7.3 Ra and −5.8 to −4.2‰, respectively) and dissolved helium and carbon in waters (1.0–6.3 Ra and −7.1 to −0.9‰), together wi…

Active Moss biomonitoring of mercury in the mine-polluted area of Mt. Amiata (Central Italy)

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.…

The use of moss-bags technique for volcanic aerosols investigation on Mt. Etna (Italy)

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 s…

Gas manifestations of Greece: Catalogue, geochemical characterization and gas hazard definition

Like other geodynamically active areas, Greece is affected by a large number of geogenic gas manifestations. These occur either in form of point sources (fumaroles, mofettes, bubbling gases) or as diffuse emanations. We produced a first catalogue of the geogenic gas manifestations of Greece also considering few literature data. Collected samples were analysed for their chemical (He, Ne, Ar, O2, N2, H2, H2S, CO, CH4 and CO2) and isotopic composition (He, C and N). Most of the sampled gas manifestation are found along the South Aegean active volcanic arc (32 sites) and in the majority they belong to the CO2 dominated group. Very few gas manifestations, N2- or CH4- dominated, are found along t…

Distribution and air-sea exchange of mercury (Hg) in polluted marine environments

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…

Prospezione geochimica sulle risorse idriche sotterranee e superficiali della Provincia di Palermo: costituenti inorganici maggiori, minori ed in traccia. Risultati preliminari.

Il Mercurio nel suolo e in ambiente terrestre

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 …

Geogenic carbon transport through karst hydrosystems of Greece

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 tecto…

A literature review and new data of trace metals fluxes from worldwide active volcanoes

Atmospheric sources and sinks of volcanogenic elements in a basaltic volcano (Etna, Italy)

Abstract This study reports on the first quantitative assessment of the geochemical cycling of volcanogenic elements, from their atmospheric release to their deposition back to the ground. Etna’s emissions and atmospheric depositions were characterised for more than 2 years, providing data on major and trace element abundance in both volcanic aerosols and bulk depositions. Volcanic aerosols were collected from 2004 to 2007, at the summit vents by conventional filtration techniques. Precipitation was collected, from 2006 to 2007, in five rain gauges, at various altitudes around the summit craters. Analytical results for volcanic aerosols showed that the dominant anions were S, Cl, and F, and…

New clues on the contribution of Earth's volcanism to the global mercury cycle

Helium-carbon isotopic composition of thermal waters from Tunisia

Mercury content and speciation in the Phlegrean Fields volcanic complex: evidence from hydrothermal system and fumaroles

Abstract Mercury is outstanding among the global environmental pollutants of continuing concern. Although degassing of active volcanic areas represents an important natural source of mercury into the atmosphere, still little is known about the amount and behaviour of Hg in volcanic aquifers, especially regarding its chemical speciation. In order to assess the importance of mercury emissions from active volcanoes, thermal waters were sampled in the area surrounding La Solfatara, Pozzuoli bay. This is the most active zone of the Phlegrean Fields complex (coastal area north–west of Naples), with intense hydrothermal activity at present day. Studied groundwaters show total Hg (THg) concentratio…

Magmatic gas leakage at Mt. Etna (Sicily,Italy): Relationships with the vocano-tectonic structures ,the hydrological pattern and the eruptive activity

Cropping system influente on soil carbon isotopic pedogenic carbonates

Bulk deposition at the industrial area of Gela (southern Sicily, Italy): preliminary results

Caratterizzazione Geochimica ed Isotopica e valutazione della qualità delle acque superficiali e sotterranee campionate nel foglio 549 MURAVERA.

Hydrologic and geochemical survey of the lake ‘‘Specchio di Venere’’ (Pantelleria island, Southern Italy)

Hydrological and geochemical studies performed on Lake Specchio di Venere on Pantelleria island (Italy) indicate that this endorheic basin has been formed through upwelling of the water table, and that it is continuously fed by the thermal springs situated on its shores. The lake is periodically stratified both thermally and in salinity, albeit this stratification is rather unstable over time, since meteorological events such as strong rain or wind can determine the mixing of its waters. Periodical analyses of the lake water chemistry show large variations of the salt content due to the yearly evaporation-rain dilution cycle. These processes are also responsible for the saline stratificatio…

Geochemistry and mineralogy of travertine deposits of the SW flanks of Mt. Etna: An indicator of past degassing activity

Fluid geochemistry of the San Vicente geothermal field (El Salvador)

The volcano Chichontepeque (San Vicente) is one of the nine recent volcanoes making up the El Salvador sector of the WNW-ESE-trending active Central American volcanic belt. Thermal activity is at present reduced to a few thermal springs and fumaroles. The most important manifestations (Agua Agria and Los Infernillos Ciegos) are boiling springs and fumaroles located on the northern slope of the volcano (850 m a.s.l.) along two radial faults. The chloride acid waters of the Los Infernillos area are partly fed by a deep hydrothermal aquifer (crossed at 1100–1300 m by a geothermal exploration well), which finds a preferential path to the surface through the radial fault system. C02 is the most …

So close, so different: geothermal flux shapes divergent soil microbial communities at neighbouring sites

This study is focused on the (micro)biogeochemical features of two close geothermal sites (FAV1 and FAV2), both selected at the main exhalative area of Pantelleria Island, Italy. A previous biogeochemical survey revealed high CH4 consumption and the presence of a diverse community of methanotrophs at FAV2 site, whereas the close site FAV1 was apparently devoid of methanotrophs and recorded no CH4 consumption. Next-Generation Sequencing (NGS) techniques were applied to describe the bacterial and archaeal communities which have been linked to the physicochemical conditions and the geothermal sources of energy available at the two sites. Both sites are dominated by Bacteria and host a negligib…

La riduzione delle emissioni e il ruolo degli ecosistemi terrestri

Interaction between the deep fluids and the shallow groundwaters on Vulcano island (Italy)

The aim of this work is to study the interactions processes between the fluids of deep origin and the shallow groundwaters of the Vulcano Porto area. During 1995, 13 well waters were sampled three times (May, July and November) and analysed for major and some minor elements (B, Br and NH4) and for dissolved gases. The close relationship of these waters with the deep magmatic source is highlighted by the composition of the dissolved gases. Furthermore, the areal distribution of dissolved species is controlled mainly by the gas fluxes from depth and by the presence of a deeper thermal aquifer. The distribution of major anomalies in the parameters measured in the groundwaters, in fact, overlap…

Continuous SO2 flux measurements for Vulcano Island, Italy

<p>The La Fossa cone of Vulcano Island (Aeolian Archipelago, Italy) is a closed conduit volcano. Today, Vulcano Island is characterized by sulfataric activity, with a large fumarolic field that is mainly located in the summit area. A scanning differential optical absorption spectroscopy instrument designed by the Optical Sensing Group of Chalmers University of Technology in Göteborg, Sweden, was installed in the framework of the European project "Network for Observation of Volcanic and Atmospheric Change", in March 2008. This study presents the first dataset of SO<sub>2</sub> plume fluxes recorded for a closed volcanic system. Between 2008 and 2010, the SO<sub>2</…

Soil gas prospection of He,222Rn and CO2: Vulcano Porto area, Aeolian Islands, Italy

Abstract In March 1994, soil gases were sampled in the area of Vulcano Porto, on the island of Vulcano, using a grid of about 200 points/km 2 . Analysed gases were CO 2 , He and 222 Rn and, over a smaller area, H 2 S. Some of the samples were also analysed for the isotope composition of CO 2 C. Three anomalous CO 2 degassing areas were identified: Grotta dei Palizzi, the area near the Telephone Exchange, and the area near the beach fumaroles. The behaviour of He and 222 Rn is different in these 3 areas. The concentration of He is much lower than that of atmospheric He (down to −3950 ppb) in the isthmus, and only in the area near Grotta dei Palizzi does it have values significantly higher th…

A christmas gift: Signature of the 24th December 2018 eruption of Mt. Etna on the chemical composition of bulk deposition in eastern sicily

The eruption of Mt. Etna which occurred on December 24th 2018 was characterized by strombolian activity and fire fountains, emitted by the New South-East Crater and along a fissure that propagated towards the SE. The influence of volcanic emissions on atmospheric deposition was clearly detectable at several kilometres from the source. Wet and dry (bulk) deposition samples were collected each month, through a network of eleven collectors, in the areas of Milazzo, and Priolo between June 2018 and June 2019. They were analysed for major ions and trace elements concentrations. The pH values range from 3.9 to 8.3, while the EC values range from 7 to 396 μS cm-1. An extensive neutralization of th…

Hydrothermal methane fluxes from the soil at Lakki plain (Nisyros Island, Greece)

Μετρήσεις φυσικής ροής μεθανίου και διοξειδίου του άνθρακα από το έδαφος πραγματοποιήθηκαν με τη μέθοδο συγκέντρωσης θαλάμου στην περιοχή Λακκί της Καλδέρας της Νισύρου, καλύπτοντας έκταση περίπου 0.06 km2 συμπεριλαμβάνοντας τις περιοχές Καμινάκια, Στέφανος και Αλέξανδρο όπου παρατηρείται έντονη ατμιδική δραστηριότητας. Οι τιμές ροής που μετρήθηκαν σε 77 σημεία κυμαίνονται από –3.4 μέχρι 1420 mg m-2 d-1 για το CH4 και από 0.1, μέχρι 383 g m-2 d-1 για το CO2. Στις τρεις ατμιδικές περιοχές παρουσιάζονται διαφορετικοί ρυθμοί διαφυγής μεθανίου, ιδίως στα Καμινάκια όπου προέκυψαν οι μεγαλύτερες τιμές ροής. Η εξερχόμενη ποσότητα μεθανίου εκτιμάται σε 0.01 t a-1 από μια έκταση περίπου 2500 m2 στον…

The sea–air exchange of mercury (Hg) in the marine boundary layer of the Augusta basin (southern Italy): Concentrations and evasion flux

Abstract The first attempt to systematically investigate the atmospheric mercury (Hg) in the MBL of the Augusta basin (SE Sicily, Italy) has been undertaken. In the past the basin was the receptor for Hg from an intense industrial activity which contaminated the bottom sediments of the Bay, making this area a potential source of pollution for the surrounding Mediterranean. Three oceanographic cruises have been thus performed in the basin during the winter and summer 2011/2012, where we estimated averaged Hg atm concentrations of about 1.5 ± 0.4 (range 0.9–3.1) and 2.1 ± 0.98 (range 1.1–3.1) ng m −3 for the two seasons, respectively. These data are somewhat higher than the background Hg atm …

Passive degassing at Nyiragongo (D.R. Congo) and Etna (Italy) volcanoes

Volcanoes are well known as an impressive large natural source of trace elements into the troposphere. Etna (Italy) and Nyiragongo (D.R. Congo) are two stratovolcanoes located in different geological settings, both characterized by persistent passive degassing from their summit craters. Here, we present some results on trace element composition in volcanic plume emissions, atmospheric bulk deposition (rainwater) and their uptake by the surrounding vegetation, with the aim to compare and identify differences and similarities between these two volcanoes. Volcanic emissions were sampled by using active filter-packs for acid gases (sulfur and halogens) and specific teflon filters for particulat…

Geochemistry of gases and waters discharged by the mud volcanoes at Paternò, Mt. Etna (Italy)

Approximately 20 km south of Mt. Etna craters, at the contact between volcanic and sedimentary formations, three mud volcanoes discharge CO2-rich gases and Na–Cl brines. The compositions of gas and liquid phases indicate that they are fed by a hydrothermal system for which temperatures of 100–150 °C were estimated by means of both gas and solute geothermometry. The hydrothermal system may be associated with CO2-rich groundwaters over a large area extending from the central part of Etna to the mud volcanoes. Numerous data on the He, CH4, CO2 composition of the gases of the three manifestations, sampled over the past 5 years, indicate clearly that variations are due to separation processes of…

Impact of Volcanic Emissions on Trace Elements Contents Measured in Endemic Plants at Mt. Etna (Italy)

Passive degassing at Nyiragongo (D.R. Congo) and Etna (Italy) volcanoes: the chemical characterization of the emissions and assessment of their uptake of trace elements emissions on the local environment

Volcanic soils of Mt. Etna (Italy): Relationships between fluorine absorption and soil characteristics.

Exploring methanotrophic activity in geothermal soils from Pantelleria Island (Italy)

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 proteobacteria…

The impact of methanotrophic activity on methane emissions through the soils of geothermal areas

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 fe…

High diversity of methanotrophic bacteria in geothermal soils affected by high methane fluxes

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 know…

Mercury emissions from active volcanic areas of Italy

Environmental impact of magmatic fluorine emission in the Mt. Etna area

The sustained and uninterrupted plume degassing at Mount Etna volcano, Southern Italy, represents the troposphere's most prominent natural source of fluorine. Of the ∼ 200 Mg of fluorine (as HFg) emitted daily by the volcano, 1.6 ± 2.7 Mg are deposited by wet and dry deposition. Fluorine-deposition via volcanic ash, here characterised for the first time, can be quite significant during volcanic eruptions (i.e. 60 Mg of fluorine were deposited during the 2001 eruption through volcanic ash, corresponding to ∼ 85% of the total fluorine deposition). Despite the fact that these depositions are huge, the fate of the deposited fluorine and its impact on the environment are poorly understood. We he…

Mobility and fluxes of major, minor and trace metals during basalt weathering and groundwater transport at Mt. Etna volcano (Sicily)

Abstract The concentrations and fluxes of major, minor and trace metals were determined in 53 samples of groundwaters from around Mt Etna, in order to evaluate the conditions and extent of alkali basalt weathering by waters enriched in magma-derived CO 2 and the contribution of aqueous transport to the overall metal discharge of the volcano. We show that gaseous input of magmatic volatile metals into the Etnean aquifer is small or negligible, being limited by cooling of the rising fluids. Basalt leaching by weakly acidic, CO 2 -charged water is the overwhelming source of metals and appears to be more extensive in two sectors of the S-SW (Paterno) and E (Zafferana) volcano flanks, where out …

Fluorine speciation in topsoils of three active volcanoes of Sicily (Italy)

Fluorine is one of the many environmental harmful elements released by volcanic activity. The content of total oxalate-extractable and water-extractable fluorine was determined in 96 topsoils of three active volcanic systems of southern Italy (Mt Etna, Stromboli and Vulcano). Total fluorine (F) content (F TOT) ranges from 112 to 7,430 mg kg−1, F extracted with oxalate (F OX) ranges from 16 to 2,320 mg kg−1 (2–93% of F TOT) and F extracted with distilled water ( $$ F_{{{\text{H}}_{{\text{2}}} {\text{O}}}} $$ ) ranges from 1.7 to 159 mg kg−1 (0.2–40 % of F TOT). Fluorine in the sampled topsoils derives both from the weathering of volcanic rocks and ashes and from the enhanced deposition due t…

Mount Etna, the major point source of metals in the Mediterranean basin: impact on atmospheric precipitation

Regional variations in the chemical and helium–carbon isotope composition of geothermal fluids across Tunisia

Abstract Tunisia has numerous thermo-mineral springs. Previous studies have shown that their chemical composition and occurrence are strongly influenced by the regional geology. However little work has been done so far to study the isotopic composition of volatiles associated with these geothermal manifestations. Here, we report on the results of an extensive survey of both natural hot springs and production wells across Tunisia, aimed at investigating the spatial distribution of thermal fluids' geochemical characteristics and He–C isotopic composition. The chemistry of the analyzed samples highlights the heterogeneity of the water mineralization processes in Tunisia, as a consequence of th…

A landscape approach in the isotopic modeling of natural precipitations: two cases in Mediterranean mountain areas.

CO 2 output and δ 13 C(CO 2 ) from Mount Etna as indicators of degassing of shallow asthenosphere

An estimated average CO2 output from Etna's summit craters in the range of 13±3 Mt/a has recently been determined from the measured SO2 output and measured CO2/SO2 molar ratios. To this amount the CO2 output emitted diffusely from the soil (≈ 1 Mt/a) and the amount of CO2 dissolved in Etna's aquifers (≈ 0.25 Mt/a) must be added. Data on the solubility of CO2 in Etnean magmas at high temperature and pressure allow the volume of magma involved in the release of such an amount of this gas to be estimated. This volume of magma (≈ 0.7 km3/a) is approximately 20 times greater than the volume of magma erupted annually during the period 1971–1995. On the basis of C-isotopic data of CO2 collected in…

Pre- and syn-eruptive geochemistry of volcanic gases from Soufriere Hills of Montserrat, West Indies

International audience; Soufriere Hills fumaroles contained magmaderived volatiles before and during the eruption initiated in 1995 but also preserved a typical and quite steady hydrothermal coinposition. Chemical changes due to increased boiling and a greater input of oxidizing magmatic gas occurred only at Galway's Soufriere, the most active fumarolic field. Hydrothermal buffering of the fumaroles has been favoured by their remote location (!-2 km) froin the eruptive vents and by a preferential degassing of the uprising magma through intrusive conduits under the crater. High temperature (720øC) gas collected froin the extruding lava dome in Feb. 1996 was chemically and isotopically repres…

Methane efflux from the soil and methanotrophic activity in volcanic-geothermal areas: Examples from Italy and Greece

Soil CO2 emission from the lower flanks of Mt Etna: possible relations withj hidden faults and preliminary output estimate

Environmental impact of magmatic fluorine emission in the Mt. Etna area

-UniversitA degli Studi di Palermo, Italy -Istituto Nazionale di Geofisica e Vulcanologia, Sezione di Palermo - Unione Europea, Fondo Sociale Europeo

Prodigious emission rates and magma degassing budget of major, trace and radioactive volatile species from Ambrym basaltic volcano, Vanuatu island Arc

Abstract Ambrym volcano, in the Vanuatu arc, is one of the most active volcanoes of the Southwest Pacific region, where persistent lava lake and/or Strombolian activity sustains voluminous gas plume emissions. Here we report on the first comprehensive budget for the discharge of major, minor, trace and radioactive volatile species from Ambrym volcano, as well as the first data for volatiles dissolved in its basaltic magma (olivine-hosted melt inclusions). In situ MultiGAS analysis of H 2 O, CO 2 , SO 2 and H 2 S in crater rim emissions, coupled with filter-pack determination of SO 2 , halogens, stable and radioactive metals demonstrates a common magmatic source for volcanic gases emitted by…

First combined flux chamber survey of mercury and CO2 emissions from soil diffuse degassing at Solfatara of Pozzuoli crater, Campi Flegrei (Italy): Mapping and quantification of gas release

Abstract There have been limited studies to date targeting gaseous elemental mercury (GEM) flux from soil emission in enriched volcanic substrates and its relation with CO 2 release and tectonic structures. In order to evaluate and understand the processes of soil–air exchanges involved at Solfatara of Pozzuoli volcano, the most active zone of Campi Flegrei caldera (Italy), an intensive field measurement survey has been achieved in September 2013 by using high-time resolution techniques. Soil–air exchange fluxes of GEM and CO 2 have been measured simultaneously at 116 points, widely distributed within the crater. Quantification of gas flux has been assessed by using field accumulation chamb…

Carbon degassing through karst hydrosystems of Greece

Estimation of CO2 degassing from active tectonic structures and regional hydrothermal systems is essential for the quantification of presentday Earth degassing [Frondini et al., 2019 and references therein]. Due to the high solubility of CO2 in water, great amounts of deep inorganic carbon can be dissolved, transported, and released from regional aquifers. By applying a massbalance approach [Chiodini et al., 2000], different sources of the dissolved CO2 can be discriminated. The main source of degassing in Greece is concentrated in hydrothermal and volcanic areas. However, deep CO2 from active tectonic areas has not yet been quantified. A key point of this research is to investigate the pos…

Full scale evaluation of atmospheric mercury budget from persistent volcanic degassing

In the recent years, there has been an increase in environmental concerns related to the pollution of many trace metals emitted from volcanic degassing because of their toxicity and long residence times in the earth’s ecosystems. Among volcanogenic trace elements, mercury (Hg) is one of the most environmentally-significant in light of its potential harmful effects on biological systems. At present, however, the global Hg flux from volcanic sources is still poorly known. We report on Hg levels in volcanic plumes and fumaroles that, in combination with sulphur analyses and SO2 flux data, lead to global Hg estimates. We found that mercury transport in the plume is mainly in the gas-phase, as H…

Volcanogenic particulates and gases from Etna volcano (Italy)

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 coll…

Mercury concentration and speciation in volcanic aquifers: measurements in Italy and Guadeloupe (Lesser Antilles)

Geochemical mapping of magmatic gas-water-rock interactions in the aquifer of Mount Etna volcano

Magma-derived gas influx and water-rock interactions in the volcanic aquifer of Mt. Vesuvius, Italy

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius.Vesuvius groundwaters are dilute (mean TDS ∼ 2800 mg/L) hypothermal fluids ( mean T = 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, l…

Metallic nanoparticle enrichment at low temperature, shallow CO2 seeps in Southern Italy

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shallow seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (<100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods. We provide analytical evidence for the pre…

The impact of volcanogenic emissions of major and trace elements at Mt. Etna, Sicily, on precipitation (rain and snow) chemistry

Microbiological evidences of methanotriphic activity in the soils of the geothermal area of Pantelleria island (Italy)

Methane plays an important role in the Earth’s atmospheric chemistry and radiative balance being the second most important greenhouse gas after carbon dioxide. Methane is released to the atmosphere by a wide number of sources, both natural and anthropogenic, with the latter being twice as large as the former. It has recently been established that significant amounts of geological methane, produced within the Earth’s crust, are currently released naturally into the atmosphere. Active or recent volcanic/geothermal areas represent one of these sources of geological methane. Microbial oxidation in soils contributes for about 3-9% to the total removal of CH4 from the atmosphere. Recent studies e…

Catalogue of the main gas manifestations in the Hellenic territory: a first step towards the estimation of the nationwide geogenic gas output

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 manifes…

Volcanogenic particulates and gases from Etna volcano (Italy)

Do Volcanic Eruptions Solve Global Atmospheric Mercury Pollution?

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 …

Geochemical comparison of natural and anthropogenic metal fluxes in extreme environments: Mt. Etna volcano (Italy) and Šalek Valley (Slovenia)

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.

Environmental impact of trace metals emission at Mt. Etna area (Italy): preliminary estimates of trace metals in bulk-deposition

Methanotrophic activity and diversity of methanotrophs in volcanic geothermal soils at Pantelleria (Italy)

Volcanic and geothermal systems emit endogenous gases by widespread degassing from soils, including CH4, a greenhouse gas twenty-five times as potent as CO2. Recently, it has been demonstrated that volcanic or geothermal soils are not only a source of methane, but are also sites of methanotrophic activity. Methanotrophs are able to consume 10–40 Tg of CH4 a−1 and to trap more than 50% of the methane degassing through the soils. We report on methane microbial oxidation in the geothermally most active site of Pantelleria (Italy), Favara Grande, whose total methane emission was previously estimated at about 2.5 Mg a−1 (t a−1). Laboratory incubation experiments with three top-soil samples from …

Evaluation of the environmental impact of volcanic emissions from the chemistry of rainwater: Mount Etna area (Sicily)

Abstract The S, halogen and NO 3 contents of rainwater samples from the Etnean area were studied in order to define the environmental impact of plume emissions on the local environment. Samples, collected on a network of 11 bulk rain gauges, show significant variability in anion content, which can be ascribed to different meteorological and environmental conditions at each sampling site and to a variable distance from the different source areas. Data analysis suggests that S, F, Cl and Br are mainly magma-derived, whereas NO 3 mainly originates from anthropogenic sources. Samples collected from sites close to craters display considerable temporal variability, with increased anion concentrat…

Focused and diffuse effluxes of CO2 from mud volcanoes and mofettes south of Mt. Etna (Italy).

Abstract Several sites with anomalous emissions of carbon dioxide were investigated in the region south of Mt. Etna volcano in order to assess the types of emission (focused and/or diffuse), their surface extension and the total output of CO 2 . Most of the studied emissions are located on the southwest boundary of Mt. Etna, near the town of Paterno. They consist of three mud volcanoes (known as Salinelle), one spring with bubbling gas (Acqua Grassa) and one area of diffuse degassing (Pescheria). Another site (Naftia Lake) with remarkable gas emissions (bubbling gas into a lake as well as adjacent areas of diffuse soil degassing) is located further southwest of Mt. Etna in an area of extinc…

The environmental impact of magmatic fluorine emissions in the Mt.Etna area.

le potenzialità dei suoli siciliani nel sequestro del carbonio

Hydrochemical mercury distribution and air-sea exchange over the submarine hydrothermal vents off-shore Panarea Island (Aeolian arc, Tyrrhenian Sea)

Abstract There is a growing concern about the mercury (Hg) vented from submarine hydrothermal fluids to the marine surrounding and exchange of dissolved gaseous mercury (DGM) between the sea surface and the atmosphere. A geochemical survey of thermal waters collected from submarine vents at Panarea Island (Aeolian Islands, southern Italy) was carried out in 2015 (15–17th June and 17–18th November), in order to investigate the concentration of Hg species in hydrothermal fluids and the vertical distribution in the overlying water column close to the submarine exhalative area. Specific sampling methods were employed by Scuba divers at five submarine vents located along the main regional tecton…

Magmatic gas leakage at Mt.Etna (Sicily,Italy):Relationships with the volcano-tectonic structures,the hydrological pattern and the eruptive activity

CO2 degassing at La Solfatara volcano (Phlegrean Fields): Processes affecting and of soil CO2

Abstract The soil CO2 degassing is affected 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 the Solfatara volcano, upon a field survey of 110 points, where the CO2 flux was measured, together with temperature, CO2 concentration and oxygen and carbon isotopes within the soil. Furthermore, in some selected sites, the measurements were made at different depths, in order to analyze vertical gradients. Oxygen isotope composition appears controlled by exchange with soil water (either meteoric or fumarolic condensate), due to the fast kinetic of the isotopic equilibrium between …

Helium isotope constraints on the mantle source of OIB-type Na-alkaline magmatism in Southern Mediterranea

Investigation of the methanotrophic activity in the soils of a geothermal site of Pantelleria Island (Italy)

Greenhouse gas as a nutrient: methanotrophic activity in soils of hydrothermal systems

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…

Steam and gas emission rates from La Soufrière of Guadeloupe (Antilles arc): implications for the magmatic supply degassing during unrest

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 dem…

Tellurium in active volcanic environments: Preliminary results

Pedogenic carbonates and carbon pools in gypsiferous soils of a semiarid Mediterranean environment in south Italy

Abstract Soil carbonates are key features in soils of arid and semiarid environment, playing an important role from pedogenetic, landscape history, paleoclimatic and environmental points of view. The objectives of this work were (i) to study pathways of pedogenic carbonate (PC) formation, (ii) to distinguish between lithogenic and pedogenic inorganic C by using the natural C isotope abundance, and (iii) to estimate the soil C pools in a gypsiferous semiarid Mediterranean environment (Sicily, Italy). Five soil pedons developed on calcareous and non-calcareous parent materials from Holocene (10,000 years BP) to Upper Tortonian (7.2–5.3 Ma BP) in age were surveyed. During field soil descriptio…

The cycle of major and trace elements in a volcanic environment

Another kind of “volcanic risk”: the acidification of sea-water. Vulcano Island (Italy) a natural laboratory for ocean acidification studies

Characterization of the Etna volcanic emissions through an active biomonitoring technique (moss-bags): Part 1 – Major and trace element composition

Active biomonitoring using moss-bags was applied to an active volcanic environment for the first time. Bioaccumulation originating from atmospheric deposition was evaluated by exposing mixtures of washed and air-dried mosses (Sphagnum species) at 24 sites on Mt. Etna volcano (Italy). Concentrations of major and a large suite of trace elements were analysed by inductively coupled mass and optical spectrometry (ICP-MS and ICP-OES) after total acid digestion. Of the 49 elements analysed those which closely reflect summit volcanic emissions were S, Tl, Bi, Se, Cd, As, Cu, B, Na, Fe, Al. Enrichment factors and cluster analysis allowed clear distinction between volcanogenic, geogenic and anthropo…

Geochemical characterisation of the alkaline and hyperalkaline groundwater in the Othrys Ophiolite Massif, central Greece

The complex geology of Greece includes two important parallel running ophiolitic belts. The Othrys Massif in central Greece belongs to the westernmost of them. In the current study, 33 water samples from cold hyperalkaline and hypothermal (T &lt; 40°C) alkaline springs and 30 gas samples (either dissolved or free) were collected at 17 different sites in and around this wide ophiolite outcrop, aiming to determine the origin of fluids and evidence gas-water-rock interaction processes taking place in the area. Water samples were analysed for their chemical (major ions and trace elements) and isotope (d18O-H2O, d2H-H2O) composition. They can be subdivided into alkaline (pH &lt;11) of both Mg-Ca…

Active biomonitoring (moss-bags) of volcanic emissions on Mt. Etna

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 Cycle of volcanogenic trace elements at Mt Etna (Italy): From volcanic emissions to atmospheric deposition

Quantification of deep CO2 fluxes from Central Italy. Examples of carbon balance for regional aquifers and of soil diffuse degassing.

Abstract In Central Italy non-volcanic CO 2 is discharged by focused degassing (strong diffuse emission and vents) and by high-CO 2 groundwater. 3 He / 4 He data and the carbon isotopic composition of CO 2 are compatible with derivation from mantle degassing and/or metamorphic decarbonation. The gases produced at depth accumulate in permeable reservoirs composed of Mesozoic carbonates. When total pressure (roughly corresponding to p CO 2 ) of the reservoir fluid exceeds hydrostatic pressure, a free gas phase forms gas reservoirs within the permeable host rocks from which gases may escape toward the surface. This process generates both the focused vents and the CO 2 -rich springs which chara…

The Fate of Volcanogenic Major and Trace Elements emitted from the plume of Mount Etna

Mercury’s Distribution in the Atmosphere, Soils and Plants of the Active Hydrothermal Area of Nisyros (Greece).

Geological development of a gypsum lake formed at the beginning of the 20th century in central Sicily, Italy: Integration of historical data with modern survey techniques

A limnological investigation was carried out on the small, endorheic lake, called Lake Sfondato, located in central Sicily (Italy). All the aquatic environments in the central part of the island are rich in salt, with conductivity values above 5 mS cm−1, and are characterized by high alkalinity values and hard waters. In addition, due to intensive agriculture, many of these ecosystems have experienced a strong anthropogenic eutrophication over the last decades. In order to better understand the functioning of these peculiar environments, the morphology, hydrology, and geochemistry, as well as several selected physical and biological characteristics of Lake Sfondato, were studied in the year…

GEOCHEMISTRY OF THE GAS MANIFESTATIONS OF GREECE: METHANE AND LIGHT HYDROCARBONS

Το σύνθετο γεωδυναμικό καθεστώς της Ελλάδας πηγάζει από την πολύπλοκη γεωλογική της ιστορία, η οποία χαρακτηρίζεται από έντονη σεισμική δραστηριότητα και ενισχυμένη γεωθερμική βαθμίδα. Αυτή η δραστηριότητα σε συνδυασμό με το ενεργό ηφαιστειακό τόξο, ευνοεί την ύπαρξη πολλών εκπομπών αερίων, με αποτέλεσμα την κατηγοριοποίηση σε CO2-, N2- και CH4-αέρια, ανάλογα με το επικρατών είδος. Η παρούσα εργασία επικεντρώνεται στο μεθάνιο και τους ελαφρούς υδρογονάνθρακες (C2-C6) με σκοπό τον προσδιορισμό της προέλευσή τους. Οι συγκεντρώσεις του CH4 (&lt;2 έως 915,200 μmol/mol) και η ισοτοπική του αναλογία (δ13C -79.8 έως +16.9 ‰, δD -298 έως +264‰) καλύπτουν ένα ευρύ φάσμα τιμών, που υποδεικνύει διαφορ…

The precious treasure of Mariano Valenza: The history of Ludovico Sicardi and the birth of geochemical volcano monitoring

I was lucky enough to meet Mariano Valenza in September 1995. I was hitchhiking on the highway that leads from Cefalu to Palermo to go back home. I had spent my summer holidays in the beautiful and wild Madonie mountains. An off-road vehicle (a Land Rover Defender) stopped and a refined gentleman with a curious and charismatic gaze offered me a ride. During our journey, we chatted pleasantly and he told he was originally from that area. When I told him, I was a Geology student, he smiled at me and said Then we will meet again soon, I am going to be your Teacher of Geochemistry!. After a few weeks the lessons began and I met again Professor Valenza in Via Archirafi 36, at the University of P…

First 13C/12C isotopic characterisation of volcanic plume CO2

We describe analytical details and uncertainty evaluation of a simple technique for the measurement of the carbon isotopic composition of CO2 in volcanic plumes. Data collected at Solfatara and Vulcano, where plumes are fed by fumaroles which are accessible for direct sampling, were first used to validate the technique. For both volcanoes, the plume-derived carbon isotopic compositions are in good agreement with the fumarolic compositions, thus providing confidence on the method, and allowing its application at volcanoes where the volcanic component is inaccessible to direct sampling. As a notable example, we applied the same method to Mount Etna where we derived a δ13C of volcanic CO2 betw…

3He/4He Ratio in Olivines from Linosa, Ustica, and Pantelleria Islands (Southern Italy)

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 exte…

Soil CO2 emissions from the lower SW flank of Mt. Etna: Estimate of organic and magmatic contributions to the total degassing

Mount Etna volcano (Italy) as a major “dust” point source in the Mediterranean area

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 local to global scale. They can also severely affect the atmospheric and terrestrial environment at timescales ranging from a few to millions of years. Mt. 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 is to characterize the chemical composition and the mineralogical features of the volcanogenic aerosol passively emitted from Mt. Etna. Twenty-five samples were c…

Helium isotopes distribution in groundwater and thermal waters of Tunisia: relationship to tectonics and geology

Selenium around Etna Volcano, Italy

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…

Oxygen isotope composition of natural waters in the Mt. Etna area

Oxygen isotopes of both rainwater and groundwater samples from Mt Etna were used to obtain information on recharge areas, flow paths, and the origin of wet air masses. Oxygen isotope composition was determined in rainwater samples collected for a period of 3 years (October 1997– October 2000), in 11 rain-gauges distributed along the flanks of Mt Etna from sea level to 2900 m of altitude. Values ranged from 213.8 to þ 1.9‰, the lowest values being measured at higher altitudes and/or during cooler periods. For rain-gauges located from sea level up to 1000 m altitude, volume weighted values defined an isotopic gradient of 22.7‰/km, which is in the range observed in the Mediterranean area. High…

THE IMPACT OF VOLCANIC EMISSIONS ON ETNA’S SNOW COVER

New results and review of major and trace element output from worldwide passive degassing volcanoes

Atmospheric Deposition around the Industrial Areas of Milazzo and Priolo Gargallo (Sicily–Italy)—Part B: Trace Elements

The concentrations of trace elements in atmospheric bulk depositions (wet plus dry) were investigated from two highly industrialised areas of Sicily (southern Italy) from June 2018 to July 2019, in order to recognise the main natural and anthropogenic sources. A side objective of this study was to improve the common sampling procedures and analytical methods used for monitoring trace elements in atmospheric deposition. The trace element VWM (Volume-Weighted Mean) concentrations ranged from less than 0.01 &mu;g L&minus;1 for trace elements such as Cs, Tl, and U, up to 24 &mu;g L&minus;1 for minor elements (Al, Zn, Sr), in the filtered aliquot, while they reached concentrations up to 144 &mu;…

CO2 degassing at La Solfatara volcano (Phlegrean Fields): Processes affecting d13C and d18O of soil CO2

Abstract 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 betw…

Volcanic health hazard: the acidification of seawater and trace metals accumulation study in Blue Mussels (Mytilus galloprovincialis). Vulcano Island (Italy)

Magmatic Volatile Emissions from Ambrym and Yasur Volcanoes (Vanuatu Arc)

Origin of methane and light hydrocarbons in natural fluids emissions: A study from Greece.

Abstract Greece, a country characterised by intense seismic and volcanic activity, has a complex geodynamic and geological setting that favours the occurrence of many gas manifestations. In this study, we address the origin of CH 4 and light hydrocarbons in cold and thermal emissions discharging along the Hellenic territory. Also, we investigate their possible relationship with the main geochemical composition of the gases and the different geological settings of the sampling sites. For this purpose we collected 101 new samples that were analysed for their chemical (O 2 , N 2 , CH 4 , CO 2 , He, Ne, Ar, H 2 , H 2 S and C 2 -C 6 hydrocarbons) and isotopic (R/R A , δ 13 C-CO 2 , δ 13 C-CH 4 a…

The contribution of volcanoes to the atmospheric trace metals budget in the Mediterranean basin

Volcanic emissions represent one of the major natural source for several trace metals (Cd, Cu, As, Pb, Hg and Zn) into the atmosphere both as gaseous and aerosol forms. The Mediterranean Sea can be considered a large geochemical sink for these elements whose source are the huge amounts of aerosols of different origin. The industrialised areas located in the northern part of the basin represent a nearly constant source of the anthropogenic-dominated aerosol. By contrast, the arid and desert regions located at the southern and eastern parts of the Mediterranean, are the sources of frequent dust “pulses” perturbing the “steady-state” conditions of the local atmosphere through the input of seve…

Origin and distribution of methane and C2-C6 hydrocarbons in hydrothermal and cold gaseous emissions in Greece

The Hellenic territory has a very complex geodynamic setting from a long and composite geological history, giving rise to an intense seismic activity deriving and favoring the occurrence of many cold and thermal gas manifestations. Geogenic sources release huge amounts of gases, which have a significant impact on the global balance of the subaerial Carbon Cycle. The study of the geochemistry of the natural gas emissions of the Greek territory is actually underway. In the present work, we focus on methane and light hydrocarbons (C2-C6) to define their origin. Concentrations of methane range from &lt; 2 to 915,200 mmol/mol and its isotopic ratios cover a wide range (d13C from -79.8‰ to +16.9‰…

Geochemical characterisation of the thermo-mineral waters of Greece

AbstractGeothermal areas of Greece are located in regions affected by recent volcanism and in continental basins characterised by elevated heat flow. Many of them are found along the coast, and thus, water is often saline due to marine intrusion. In the current study, we present about 300 unpublished and literature data from thermal and cold mineral waters collected along Greece. Samples were analysed for major ions, Li, SiO2 and isotopes in water. Measured temperatures range from 6.5 to 98 °C, pH from 1.96 to 11.98, while Total Dissolved Solutes (TDS) from 0.22 to 51 g/L. Waters were subdivided into four main groups: (1) thermal; (2) cold; (3) acidic (pH &lt; 5); and (4) hyperalkaline (pH …

Microbiology meets geochemistry: geothermal flux shapes different microbial communities at the same exhalative area

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 methan…

Preliminary results of trace elements mobility in soils and plants from the active hydrothermal area of Nisyros island (Greece)

Volcanic signature of volatile trace elements on atmospheric deposition at Mt. Etna, Italy

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, w…

Image analysis from TEM and AFM micrograph, Table S1, S2, S3, Figure S1, Figure S2

We report on metal enrichment along a natural pH gradient owing to increased CO2 degassing at cold, shal- low seeps of Vulcano Island in the Mediterranean Sea, off Sicily. We assessed composition of unfiltered and filtered seawater (b100 nm) along acidic zones ranging between ambient and pH 5, and showed that most seep derived elements are present as nanoclusters which then aggregate into larger colloids while mixing with ambient seawater along a pH gradient. Size and elemental composition of such naturally occurring nanoparticles assessed by modern characterisation methods were in good agreement with the results from conventional analytical methods.We provide analytical evidence for the pr…

Active volcanoes as emission point sources of atmospheric mercury

ercury emissions from active volcanoes are of interest for estimating the volcanogenic contribution of Hg to the atmosphere and for monitoring volcanic activity. The global Hg flux from natural sources is poorly known and considerable uncertainty still exists with respect to the complex physical and chemical reactions taking place in the atmosphere among the various Hg forms. The environmental hazard of Hg have been widely demonstrated for its high toxicity. Previous estimates from volcanic plumes are based on limited measurements and poorly determined speciation of Hg in volcanic emissions which is crucial for making reliable estimates of volcanic Hg source strengths and for predicting atm…

Chemical-physical parameters, major, minor and trace elements composition of thermo-mineral groundwaters of Greece

This dataset comprises samples of thermo-mineral waters collected by the same team over the period from October 2004 to March 2020 and analysed in the same laboratory. Samples were collected on the whole territory of Greece.

Chemical-physical parameters, major, minor and trace elements compositions of big karst springs of Greece

This database consists of samples of karst springs collected in Greece and selected on the base of their water flow (&gt; 50 L s-1), over the period from May 2016 to October 2022