Description: I was lucky enough to meet Mariano Valenza in September 1995. I was hitchhiking on the highway that leads from Cefalù 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 Palermo. I will never forget the first introductive lesson of his course: “… we are going to study how the chemical elements have formed in the stars, and how these elements have spread out on our planet; we are going to study the chemicalphysical laws regulating their geochemical cycles and how they move in between the atmosphere, the hydrosphere and the lithosphere. We will also learn how the isotopes of these elements allow us to date the geological phenomena and the age of our own planet Earth; …let’s imagine that we are ourselves made of billions and billions and billions of atoms, and it is statically possible that one of Napoleon atom could be here, in this class room!”. I was truly fascinated and I discovered my passion for this interesting subject. In via Archirafi 36, in the historical building of the University of Palermo, once home of the Istituto di Mineralogia, I have graduated and got a Ph.D. in Geochemistry, and still nowadays I am working there. In these last 25 years I have learnt to know the stories of different personalities and their scientific researches, which have been hidden and looked after in the ancient building of the University for almost one century. With this article, we would like to remember Professor Mariano Valenza, by telling some stories about him and some others told by himself. Amongst these extraordinary stories we have focused on the one of a little-known scientist, Ludovico Sicardi (1895 - 1987), a modest man who followed his passion for volcanoes. In his field, he was a true innovator and the present research in the field of the geochemical surveillance of volcanos is deeply in debt to him. The “Scuola di Geochimica dei Fluidi”, born in the ‘70s at the University of Palermo, has the most debt of gratitude to him, but also the one which has treasured best his memory. This special paper is dedicated to Professor Valenza, who was one of the founders of this school and, before that, the teacher of most of this piece’s authors. He had preserved, beside the historical memory, also many documents, photos, and the scientific equipment used by Sicardi for his studies. Sergio Calabrese, Palermo, March 2020

Description: Published

Description: 413-435

Description: 4V. Processi pre-eruttivi

Description: 6TM. Poli Museali

Description: JCR Journal

Description: 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 the acidity has been recognised mainly due to the suspended alkaline dust particles, which have a buffering role in rainwater. A high load of Na+ and Cl- was observed at all sites, related to the closeness of the study areas to the coast, showing a high positive correlation (R2 = 0.989) along the line of Na+/Cl- ratio in seawater. During the eruption, the volcanic plume was carried by the winds for long distance (more than 300 km) affecting the area of Priolo but not that of Milazzo, which was upwind with respect to Mt. Etna. The impact of volcanic HF was clearly recognised in the samples collected after the eruption. Volcanic SO2 and HCl had a lower impact due to the overwhelming input of anthropogenic sulfate and marine chloride. On the contrary, the signature of the Mt. Etna eruption can be well recognised in the high concentrations of certain trace elements in the samples collected immediately after the eruption. The strongest contrast between affected and non-affected samples was recognised in Al, Cd, and especially in the volatile elements Tl and Te, which are typically enriched in volcanic emissions. The results showed that volcanic eruptions might have a relevant effect on the atmospheric chemistry and on the composition of rainwater up to distances of 80 km from the emission vents.

Description: Published

Description: 341-358

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

Description: 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 〈 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 (δ18O-H2O, δ2H-H2O) composition. They can be subdivided into alkaline (pH 〈11) of both Mg-Ca-HCO3 and Na-HCO3 composition and hyperalkaline (pH 〉 11 and Ca-OH composition). Trace elements generally showed very low concentrations and mostly inversely correlated with pH. Gases were analysed for their chemical (He, Ne, Ar, H2, O2, N2, CH4, C2H6, CO2 and H2S) and isotope (δ13C-CH4, δ2H-CH4, δ13C-CO2) composition. Samples from alkaline waters were mainly dominated by CH4 (from 128,000 to 915,000 μmol/mol), while hyperalkaline waters showed a N2-rich composition (from 727,000 to 977,000 μmol/mol). Methane had a wide range of isotope compositions (δ13C-CH4 from -74.5 to -14.5 ‰ and δ2H-CH4 from -343 to -62 ‰). Alkaline waters present the most negative isotope values for CH4, evidencing a biogenic (both thermogenic and microbial) origin. Many of the hyperalkaline waters had CH4 isotope values compatible with an abiogenic origin through serpentinization processes but occasionaly very negative values were recorded, indicating sometimes a clear biogenic contribution. Finally, few samples both from alkaline and hyperalkaline waters showed some evidence of secondary oxidation processes.

Description: Published

Description: 42-56

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

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

Description: Published

Description: Athens, Greece

Description: 6A. Geochimica per l'ambiente e geologia medica

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

Description: Published

Description: Athens, Greece

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: Greece is a region characterised by intense geodynamic activity that favours the circulation of hydrothermal fluids in the crust transporting volatiles from either the deep crust or the mantle to the surface. Elevated heat flow values are detectable at Sperchios Basin and North Euboea (central Greece), two areas defined by a system of deeply rooted extensional faults and Quaternary volcanic activity. This setting contributed to the formation of numerous hydrothermal systems, which are mostly expressed as CO2-rich thermal springs with intense bubbling. The CO2 output from six bubbling pools has been determined by flux measurements with the use of the floating chamber method. The highest bubbling CO2 output has been found at Thermopyles and Psoroneria (0.6 and 0.84 t/d, respectively), where the outgoing channels have an elevated flow (〉250 l/s) of gas-charged water (〉15 mmol/l of CO2). Although no bubbling is noticed along the stream, the CO2 content decreases by an order of magnitude after few hundreds of metres, indicating an intense degassing from the water. Taking into account the water flow and the amount of CO2 lost to the atmosphere, the CO2 output of the outgoing channels is quantified in 12.5 t/d for Thermopyles and 9.23 t/d for Psoroneria. Output estimation has also been made for the other springs of the area. The diffuse CO2 release from the outgoing channels has always been higher respect to that of the visible bubbling, suggesting that most of the degassing is “hidden”. Furthermore, the loss of CO2 from the water has determined a shift in dissolved carbonate species as demonstrated by the pH increase along the channel that led eventually to an oversaturation in carbonate minerals and therefore travertine deposition. The total CO2 output to the atmosphere of the study area is estimated at ~27 t/d, with the major contribution deriving from the degassing along the outflow channels of the thermal springs. Such output is comparable to that of the single active volcanic systems along the South Aegean Active Volcanic Arc and highlights the importance of “hidden” degassing along CO2-oversaturated streams.

Description: Published

Description: 104660

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

Description: Forty five gas samples have been collected from natural gas manifestations at the island of Kos, the majority of which is found underwater along the southern coast of the island. On land, two anomalous degassing areas have been recognized. These areas are mainly characterised by lack of vegetation and after long dry periods by the presence of sulfate salt efflorescences. Carbon dioxide is the prevailing gas species (ranging from 88 to 99 %), whilst minor amounts of N2 (up to 7.5 %) and CH4 (up to 2.1 %) are also present. Significant contents of H2 (up to 0.2 %) and H2S (up to 0.3 %) are found in the on-land manifestations. Only one of the underwater manifestations is generally rich in N2 (up to 98.9 %) with CH4 concentrations up to 11.7 % and occasionally extremely low CO2 amounts (down to 0.09 %). Isotope composition of He ranges from 0.85 to 6.71 R/RA, indicating a sometimes strong mantle contribution; the highest values measured are found in the two highly degassing areas of Paradise Beach and Volcania. C-isotope composition of CO2 ranges from -20.1 to 0.64 ‰ vs V-PDB, with the majority of the values being concentrated around -1 ‰ and therefore proposing a mixed mantle – limestones origin. Isotope composition of CH4 ranges from -21.5 to +2.8 ‰ vs V-PDB for C and from -143 to +36 ‰ vs V-SMOW for H, pointing to a geothermal origin with sometimes evident secondary oxidation processes. The dataset presented in this work consists of sites that were repeatedly sampled in the last few years, with some of which being also sampled just before and immediately after the magnitude 6.6 earthquake that occurred on the 20th of July 2017 about 15 km ENE of the island of Kos. Changes in the degassing areas along with significant variations in the geochemical parameters of the released gases were observed both before and after the seismic event, however no coherent model explaining those changes was obtained. CO2-flux measurements showed values up to about 104 g×m-2×d-1 in the areas of Volcania and Kokkinonero, 5×104 g×m-2×d-1 at Paradise beach and 8×105 g×m-2×d-1 at Therma spring. CO2 output estimations gave values of 24.6, 16.8, 12.7 and 20.6 t×d-1 respectively for the above four areas. The total output of the island is 74.7 t×d-1 and is comparable to the other active volcanic/geothermal systems of Greece (Nisyros, Nea Kameni, Milos, Methana and Sousaki).

Description: Published

Description: ID 3041037

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

Description: Earthquakes and volcanic eruptions represent a hazard. However, the impact of gases released in geodynamically active areas should not be underestimated. It is commonly known that geogenic sources release great amounts of gases, which, apart from having an important influence on the global climate, can also have a strong impact on human health causing both acute and chronic effects. In particular, CO2 and sulphur gases (mainly H2S and SO2) are the main compounds responsible for acute mortality due to their asphyxiating and/or toxic properties. One of the most known and also worst episodes occurred, took place on the 21th of August 1986 at Lake Nyos, Cameroon, when about 1700 people were killed and 850 injured by a massive CO2 release (D’Alessandro, 2006). Like other geodynamically active areas, Greece is also affected by a large number of geogenic gas manifestations (Daskalopoulou et al., 2018a). These occur either in the form of point sources (fumaroles, mofettes, bubbling gases) or of diffuse soil gas emanations (Daskalopoulou et al., 2018b). D’Alessandro and Kyriakopoulos (2013) made a preliminary estimation of the risk related to geogenic gases in Greece for the time period of 1992-2011; the whole population of the country was considered. In that period, at least two fatal episodes with a total of three victims took place, likely caused to the exposure to geogenic gases (specifically CO2). This would give a risk of 1.310-8 fatality from geogenic gas manifestations per annum. This value, although probably underestimated, is much lower than many other natural or anthropogenic risks. Since deaths due to natural gases are often wrongly attributed, it cannot be excluded that some fatal episode has not been recognized and thus that the risk is somewhat higher than assessed. Although very low, this risk should not be neglected, not only because it is possibly underestimated, but also because simple countermeasures could be adopted for risk reduction. Dangerous areas could be easily identified and delimited by geochemical prospecting and their hazards properly highlighted. Apart from the sites where fatal episodes occurred, many other hazardous sites have been recognized in Greece. Here we present data collected at Loutra Ypatis (central Greece). Study area Sperchios Basin – Evoikos Gulf Graben is a 130 km long actively spreading graben in Central Greece (1 cm/a). The high geothermal gradient of the area is evident by the presence of many thermal springs with temperatures that vary from 24 to 82 °C. In the waters of these springs, discharging along the normal faults bordering the graben, an abundant gas phase is bubbling. Loutra Ypatis is one of the emerging springs and its waters (31 °C) are exploited by a spa. The water is currently drained by a gallery and therefore the water level is about 5 m below ground at the bottom of a funnel-like hole (Fig. 1 left). For safety reasons the hole was covered by a closed building (Fig. 1 left and center). The gas, which is vigorously bubbling in the spring, is mostly (〉 96%) composed of CO2 (D’Alessandro et al., 2014). The walls of the hole are covered of sulfur that derives from the partial oxidation of the H2S (2500 ppm) contained in the released gas (D’Alessandro et al., 2014).Methods In October 2015 atmospheric concentrations of CO2 were measured with a Licor LI820 NDIR spectrometer (range 0 to 20,000 ppm, accuracy of 2%), whilst in April 2016, the atmospheric concentrations of CO2 and H2S were measured with a Multi-GAS analyser manufactured by INGV-Palermo equipped with Licor LI-840 NDIR spectrometer (CO2 0-20,000 ppm) and an EZ3H electrochemical sensor by City Technology Ltd. (H2S 0–100 ppm). Simultaneous CO2, CH4 (both 0-100%), CO, H2S (both 0-500 ppm) and O2 (0 – 25%) concentrations within the building were measured with a portable gas analyser GA2000 (Geotechnical Instruments). Results and discussion Due to the fact that a building covers the thermal spring, the intense bubbling activity of its waters creates a strong gas accumulation inside. The main component of the released gases is CO2, which has a higher density with respect to atmospheric air, thus creating the conditions for gas accumulation. About 2 m above the water level, CO2 concentrations of 〉95% and non-detectable O2 concentrations were measured. At higher levels above the water, CO2 concentrations were decreased but never below 50%. Such concentrations within the building are lethal for both animals and human beings. Of course, access is forbidden, but as the building is not perfectly sealed, the gases permeate to the outside through fissures and cracks. Figure 2 shows the CO2 concentrations measured in the air on October 2015 at 1.5 m height while walking around the walls of the edifice at about 2 m distance. Leaking of CO2 from the edifice is made evident by concentrations reaching values of more than 6000 ppm. The highest values were measured close to the entrance of the edifice were fissures and cracks are concentrated. Due to the tendency of CO2 to accumulate at lower levels, in this place, close to the ground, CO2 levels lethal to small animal can be reached. This was made evident by a dead bird found in that occasion (Fig. 1). In April 2016, due to the much windier conditions, CO2 concentrations at the same places reached values never exceeding 1000 ppm while H2S was always below 1 ppm. These values sharply increased getting closer to the fissures around the main entrance of the building and reached saturation of the sensors (CO2 〉 20,000 ppm and H2S 〉 100 ppm) at a distance of few centimeters. The intense CO2 degassing observed at Loutra Ypatis may be responsible for elevated levels that can have an impact on human beings. It is worth noting that values measured in the atmosphere close to the building exceed the Occupational Recommended Exposure Limit of 5000 ppm (NIOSH, 2005). In closed spaces lethal levels can be easily reached. An older inhabitant of the close by village told us that in his childhood a playmate died by going inside the gallery that drains the thermal water out of the spa due to the high CO2 levels. Such episode underscores the need not to disregard the gas hazard created by intense natural gas manifestations like the thermal spring of Loutra Ypatis.

Description: Published

Description: Athens, Greece

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: Duvalo “volcano” is a site of anomalous geogenic degassing close to Ohrid (North Macedonia) not related to volcanic activity, despite its name. CO2 flux measurements made with the accumulation chamber (321 sites over ∼50,000 m2) showed fluxes up to nearly 60,000 g m−2 d−1, sustaining a total output of ∼67 t d−1. Soil gas samples were taken at 50 cm depth from sites with high CO2 fluxes and analyzed for their chemical and isotope composition. The gas is mainly composed by CO2 (〉90%) with significant concentrations of H2S (up to 0.55%) and CH4 (up to 0.32%). The isotope compositions of He (R/RA 0.10) and of CO2 (δ13C ∼ 0‰) exclude significant mantle contribution, while δ13C-CH4 (∼−35‰) and δ2H-CH4 (∼−170‰) suggest a thermogenic origin for CH4. The area is characterized by intense seismic activity and Duvalo corresponds to an active tectonic structure bordering the Ohrid graben. The production of H2S within the stratigraphic sequence may be explained by thermochemical reduction of sulfate. The uprising H2S is partially oxidized to sulfuric acid that, reacting with carbonate rocks, releases CO2. The tectonic structure of the area favors fluid circulation, sustaining H2S production and oxidation, CO2 production and allowing the escape of the gases to the atmosphere. In the end, Duvalo represents a tectonic-related CO2 degassing area whose gases originate mostly, if not exclusively, in the shallowest part of the crust (〈10 km). This finding highlights that even systems with trivial mantle contribution may sustain intense CO2 degassing (〉1,000 t km−2 d−1).

Description: Published

Description: e2021GC010198

Description: 6A. Geochimica per l'ambiente e geologia medica

Description: JCR Journal

Description: We report on the results of an extensive geochemical survey of fluids released in the Vardar zone (central-western Serbia), a mega-suture zone at the boundary between Eurasia and Africa plates. Thirty-one bubbling gas samples are investigated for their chemical and isotopic compositions (He, C, Ar) and cluster into three distinct groups (CO2-dominated, N2-dominated, and CH4-dominated) based on the dominant gas species. The measured He isotope ratios range from 0.08 to 1.19 Ra (where Ra is the atmospheric ratio), and reveal for the first time the presence of a minor (〈20%) but detectable regional mantle-derived component in Serbia. δ13C values range from −20.2‰ to −0.1‰ (versus PDB), with the more negative compositions observed in N2-dominated samples. The carbon-helium relationship indicates that these negative δ13C compositions could be due to isotopic fractionation processes during CO2 dissolution into groundwater. In contrast, CO2-rich samples reflect mixing between crustal and mantle-derived CO2. Our estimated mantle-derived He flux (9.0 × 109 atoms m−2 s−1) is up to 2 orders of magnitude higher than the typical fluxes in stable continental areas, suggesting a structural/tectonic setting favoring the migration of deep-mantle fluids through the crust.

Description: Published

Description: e2021GC010017

Description: 9T. Geochimica dei fluidi applicata allo studio e al monitoraggio di aree sismiche

Description: JCR Journal