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  • 1
    Publication Date: 2024-05-09
    Description: This paper describes the chemical and isotope features of water and dissolved gases from lake Paterno (max. depth 54 m), a sinkhole located in the NE sector of the S. Vittorino plain (Rieti, Central Italy), where evidences of past and present hydrothermal activity exists. In winter (February 2011) lake Paterno waters were almost completely mixed, whereas in summer time (July 2011) thermal and chemical stratifications established. During the stratification period, water and dissolved gas chemistry along the vertical water column were mainly controlled by biological processes, such as methanogenesis, sulfate-reduction, calcite precipitation, denitrification, and NH4 and H2 production. Reducing conditions at the interface between the bottom sediments and the anoxic waters are responsible for the relatively high concentrations of dissolved iron (Fe) and manganese (Mn), likely present in their reduced oxidation state. Minerogenic and biogenic products were recognized at the lake bottom even during the winter sampling. At relatively shallow depth the distribution of CH4 and CO2 was controlled by methanotrophic bacteria and photosynthesis, respectively. The carbon isotope signature of CO2 indicates a significant contribution of deep-originated inorganic CO2 that is related to the hydrothermal system feeding the CO2-rich mineralized springs discharging in the surrounding areas of lake Paterno. The seasonal lake stratification likely controls the vertical and horizontal distribution of fish populations in the different periods of the year.
    Description: Published
    Description: 245-260
    Description: 4.4. Scenari e mitigazione del rischio ambientale
    Description: JCR Journal
    Description: open
    Keywords: monomictic lake ; dissolved gas chemistry ; sinkhole ; lake Paterno ; water lake chemistry ; 02. Cryosphere::02.04. Sea ice::02.04.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2024-05-09
    Description: In this paper, fluid source(s) and processes controlling the chemical composition of VOCs (Volatile Organic Compounds) in gas discharges from Mt. Etna and Vulcano Island (Sicily, Italy) were investigated. The main composition of the Etnean and Volcano gas emissions is produced by mixing, to various degrees, of “magmatic” and “hydrothermal” components. VOCs are dominated by alkanes, alkenes and aromatics, with minor, though significant, concentrations of O-, S- and Cl(F)-substituted compounds. The main mechanism for the production of alkanes is likely related to pyrolysis of organic matter-bearing sediments that interact with the ascending magmatic fluids. Alkanes are then converted to alkene and aromatic compounds via catalytic reactions (dehydrogenation and dehydroaromatization, respectively). Nevertheless, an abiogenic origin for the light hydrocarbons cannot be ruled out. Oxidative processes of hydrocarbons at relatively high temperatures and oxidizing conditions, typical of these volcanic-hydrothermal fluids, may explain the production of alcohols, esters, aldehydes, as well as O- and S-bearing heterocycles. By comparing the concentrations of hydrochlorofluorocarbons (HCFCs) in the fumarolic discharges with respect to those of background air, it is possible to highlight that they have a geogenic origin likely due to halogenation of both methane and alkenes. Finally, CFC (chlorofluorocarbon) abundances appear to be consistent with background air, although the strong air contamination that affects the Mt. Etna fumaroles may mask a possible geogenic contribution for these compounds. On the other hand, no CFCs were detected in the Vulcano gases, which are characterized by low air contribution. Nevertheless, a geogenic source for these compounds cannot be excluded on the basis of the present data.
    Description: Published
    Description: D17305
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: JCR Journal
    Description: open
    Keywords: etna, vulcano, VOC ; 03. Hydrosphere::03.04. Chemical and biological::03.04.05. Gases
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2024-05-09
    Description: Measurements of soil fluxes of hydrothermal gases, with special emphasis on C6H6, as well as chemical composition of mono-aromatic compounds in fumaroles and air, were carried out in April 2012 at the Solfatara crater (Campi Flegrei, Southern Italy) to investigate the distribution and behavior of these species as they migrate through the soil from their deep source to the atmosphere. Soil fluxes of CO2, CH4 and C6H6 exhibit good spatial correlation, suggesting that diffuse degassing is mainly controlled by local fractures. The calculated total output of diffuse C6H6 from Solfatara is 0.10 kg day 1, whereas fluxes of CO2 and CH4 are 79 103 and 1.04 kg day 1, respectively. A comparison between soil gas fluxes and fumarole composition reveals that within the crater soil CH4 is significantly affected by oxidation processes, which are more efficient for low gas fluxes, being dependent on the residence time of the uprising hydrothermal gases at shallow depth. Benzene degradation, mainly proceeding through oxidation via benzoate, seems to be strongly controlled by the presence of a shallow SO2 4 -rich aquifer located in the central and southwestern sectors of the crater, suggesting that the process is particularly efficient when SO2 4 acts as terminal electron acceptor (SO4 reduction). Relatively high C6H6/C7H8 ratios, typical of hydrothermal fluids, were measured in air close to the main fumarolic field of Solfatara crater. Here, C6H6 concentrations, whose detection limit is 0.1 lgm 3, are more than one order of magnitude higher than the limit value for ambient air (5 lgm 3). This suggests that hydrothermal fluids have a strong impact on air quality in the immediate surroundings of the fumarolic vents. Significant concentrations of endogenous mono-aromatics were also detected in air samples collected from the northern and western sides of the crater, where these gas compounds are mostly fed by diffuse degassing through the crater bottom soil.
    Description: Published
    Description: 142–153
    Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: 4.5. Studi sul degassamento naturale e sui gas petroliferi
    Description: JCR Journal
    Description: restricted
    Keywords: hydrothermal gases ; Solfatara crater ; 03. Hydrosphere::03.02. Hydrology::03.02.04. Measurements and monitoring ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
    Publication Date: 2024-05-09
    Description: The Principal Cordillera of Central Chile is characterized by two belts of different ages and lithologies: (i) an eastern Mesozoic belt, consisting of limestone- and gypsum-rich sedimentary rocks at the border between Central Chile and Argentina, where the active volcanic arc occurs; and (ii) a western belt of Cenozoic age containing basaltic to andesitic volcanic and volcanoclastic sequences. This distinctive geological setting controls water chemistry of cold and thermal springs in the region, which are fed by meteoric water that circulates through deep regional structures. In the western sector of Principal Cordillera, water–rock interaction processes produce lowTDS, slightly alkaline HCO3 − dominatedwaters, although dissolution of underlyingMesozoic evaporitic rocks occasionally causes SO4 2− and Cl− enrichments. In this area, few Na+–HCO3 − and Na+–SO4 2− waters occurred, being likely produced by a Ca2+–Na+ exchange during water–rock interactions. Differently, the chemical features of Ca2+–Cl−waterswas likely related to an albitization–chloritization process affecting basaltic to andesitic rocks outcropping in this area. Addition of Na+–Cl− brines uprising from the eastern sector through the westverging thrust faults cannot be excluded, as suggested by the occurrence of mantle He (~19%) in dissolved gases. In contrast, in the eastern sector of the study region, mainly characterized by the occurrence of evaporitic sequences and relatively high heat flow,mature Na+–Cl− waters were recognized, the latter being likely related to promising geothermal reservoirs, as supported by the chemical composition of the associated bubbling and fumarolic gases. Their relatively low3He/4He ratios (up to 3.9 Ra)measured in the fumaroles on this area evidenced a significant crustal contamination by radiogenic 4He. The latter was likely due to (i) degassing from 4He-rich magma batches residing in the crust, and/or (ii) addition of fluids interacting with sedimentary rocks. This interpretation is consistent with the measured δ13C-CO2 values (from−13.2 to−5.72‰vs. V-PDB) and the CO2/3He ratios (up to 14.6 × 1010), which suggest that CO2 mostly originates from the limestone-rich basement and recycling of subducted sediments,with an important addition of sedimentary (organic-derived) carbon,whereas mantle degassing contributes at a minor extent. According to geothermometric estimations based on the Na+, K+, Mg2+ and Ca2+ contents, the mature Na+–Cl− rich waters approached a chemical equilibrium with calcite, dolomite, anhydrite, fluorite, albite, K-feldspar and Ca- andMg-saponites at a broad range of temperatures (up to ~300 °C) In the associated gas phase, equilibria of chemical reactions characterized by slowkinetics (e.g. sabatier reaction) suggested significant contributions from hot and oxidizing magmatic gases. This hypothesis is consistent with the δ13C-CO2, Rc/Ra, CO2/3He values of the fumarolic gases. Accordingly, the isotopic signatures of the fumarolic steam is similar to that of fluids discharged from the summit craters of the two active volcanoes in the study area (Tupungatito and Planchón–Peteroa). These results encourage the development of further geochemical and geophysical surveys aimed to provide an exhaustive evaluation of the geothermal potential of these volcanic–hydrothermal systems.
    Description: Published
    Description: 97-113
    Description: 1V. Storia e struttura dei sistemi vulcanici
    Description: JCR Journal
    Description: restricted
    Keywords: Fluid geochemistry ; Central Chile ; Water–gas–rock interaction ; Hydrothermal reservoir ; Geothermal resource ; Volcanoes ; 03. Hydrosphere::03.02. Hydrology::03.02.03. Groundwater processes ; 03. Hydrosphere::03.04. Chemical and biological::03.04.03. Chemistry of waters ; 03. Hydrosphere::03.04. Chemical and biological::03.04.05. Gases ; 03. Hydrosphere::03.04. Chemical and biological::03.04.06. Hydrothermal systems ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 5
    Publication Date: 2024-05-09
    Description: The Vicano–Cimino Volcanic District (VCVD) is related to the post-orogenic magmatic activity of the peri- Tyrrhenian sector of Central Italy. The chemical and isotopic compositions of 333 water discharges and 25 gas emissions indicate the occurrence of two main sources: 1) cold Ca-HCO3 to Ca(Na, K)-HCO3 type waters from relatively shallow aquifers hosted in volcanic and sedimentary formations; and 2) thermal Ca-SO4(HCO3) type waters located in a deep CO2-pressurized reservoir, hosted in carbonate–evaporite rocks and separated from the shallow aquifers by thick sequences of low-permeability formations. Carbon dioxide is mainly produced by thermal metamorphic decarbonation within the deepest and hottest parts of the carbonate–evaporite reservoir (δ13C–CO2 from−3.1 to+2.2‰vs. VPDB), likely affected by a mantle-rooted CO2. ReleaseofCO2-rich gases from the deep aquifer into the overlying shallow aquifers produces high-CO2 springs and bubbling pools. The spatial distribution of thermal waters and CO2-rich cold discharges is strongly controlled by fractures and faults located in correspondencewith buried structural highs. Stable isotopes (δD and δ18O) suggest thatmeteoric water feeds both the shallowand deep reservoirs. The relatively lowR/Ra values (0.27–1.19) indicate that He ismainly deriving from a crustal source, with minor component from the mantle affected by crustal contamination related to the subduction of the Adriatic plate. Consistently, relatively high N2/Ar and N2/3He ratios and positive δ15N–N2 values (from0.91 to 5.7‰vs. air) characterize the VCVD gas discharges, suggesting the occurrence of a significant “excess” nitrogen. Isotopic compositions of CH4 (δ13C–CH4 and δD–CH4 values from−28.9 to−22.1‰vs. VPDB and from −176 to −138‰ vs. VSMOW, respectively), and composition of light alkanes are indicative of prevalent thermogenic CH4, although the occurrence of abiogenic CH4 production cannot be excluded. The δ34S–H2S values (from+9.3 to+11.4‰vs. VCDT) are consistentwith the hypothesis of H2S production fromthermogenic reduction of Triassic anhydrites. Gas geothermometry in the H2O–H2–Ar–H2S system suggests that the VCVD gases equilibrated in a liquid phase at redox conditions controlled by interactions of fluids with the local mineral assemblage at temperatures lower (b200 °C) than that andmeasured in deep (N2000 m) geothermalwells. This confirms that secondary processes, i.e. steam condensation, gas dissolution in shallow aquifers, re-equilibration at lower temperature, and microbial activity, significantly affect the chemistry of the uprising fluids. Thermal water chemistry supports the occurrence in this area of an anomalous heat flowthat, coupledwith the recent demographic growth, makes this site suitable for direct and indirect exploitation of the geothermal resource, in agreement with the preliminary surveys carried out in the 1970's–1990's for geothermal exploration purposes.
    Description: Published
    Description: 96-114
    Description: 5A. Energia e georisorse
    Description: JCR Journal
    Description: restricted
    Keywords: geothermal resources ; 03. Hydrosphere::03.04. Chemical and biological::03.04.03. Chemistry of waters ; 03. Hydrosphere::03.04. Chemical and biological::03.04.05. Gases ; 03. Hydrosphere::03.04. Chemical and biological::03.04.06. Hydrothermal systems
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 6
    Publication Date: 2024-05-09
    Description: We investigated the effect of microbial activity on the chemistry of hydrothermal fluids related to the Vicano–Cimino system, central Italy. The database included the composition and d13C CO2 and d13C CH4 values for soil gas from an area characterized by intense degassing of fluids having a deep origin. The d13C CH4 values along vertical profiles in the soil indicated that CH4 was controlled by microbial oxidation occurring at shallow (〈50 cm) depth, where free O2 was available. This was consistent with the vertical gradients of CH4, H2S and O2 concentrations. The d13C CO2 values in soil gas, characterized by a composition similar to that of the hydrothermal fluids, were not significantly influenced by biodegradation. On the contrary, gas strongly affected by air contamination showed a significant d13C CO2 fractionation. Microbial activity caused strong consumption of hydrothermal alkanes, alkenes, cyclics and hydrogenated halocarbons, whereas benzene was recalcitrant. Oxygenated compounds from hydrocarbon degradation consisted of alcohols, with minor aldehydes, ketones and carboxylic acids. A predominance of alcohols at a high rate of degassing flux, corresponding to a short residence time of hydrothermal gas within the soil, indicated incomplete oxidation. N-bearing compounds were likely produced by humic substances in the soil and/or related to contamination by pesticides, whereas a-pinene traced air entering the soil. The study demonstrates that microbial communities in the soil play an important role for mitigating the release to the atmosphere of C-bearing gases, especially CH4, through diffuse soil degassing, a mechanism that in central Italy significantly contributes to the discharge of CO2-rich gas from deep sources
    Description: Published
    Description: 81-93
    Description: 6A. Geochimica per l'ambiente
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 7
    Publication Date: 2024-05-09
    Description: This study reports a complete geochemical dataset of 215 water and 9 gas samples collected in 2015 from thermal and cold discharges located in the eastern sector of the Sabatini Volcanic District (SVD), Italy. Based on these data, two main aquifers were recognized, as follows: 1) a cold Ca-HCO3 to Ca(Na)-HCO3 aquifer related to a shallow circuit within Pliocene-Pleistocene volcanic and sedimentary formations and 2) a deep CO2-pressurized aquifer hosted in Mesozoic carbonate-evaporitic rocks characterized by a Ca- HCO3(SO4) to Na(Ca)-HCO3(Cl) composition. A thick sequence of low-permeability formations represents a physical barrier between the two reservoirs. Interaction of the CO2-rich gas phase with the shallow aquifer, locally producing high-TDS and low-pH cold waters, is controlled by fractures and faults related to buried horst-graben structures. The d18O-H2O and dD-H2O values indicate meteoric water as the main source for both the shallow and deep reservoirs. Carbon dioxide, which is characterized by d13C-CO2 values ranging from 4.7 to þ1.0‰ V-PDB, is mostly produced by thermo-metamorphic decarbonation involving Mesozoic rock formations, masking possible CO2 contribution from mantle degassing. The relatively low R/Ra values (0.07e1.04) indicate dominant crustal He, with a minor mantle He contribution. The CO2/3He ratios, up to 6 1012, support a dominant crustal source for these two gases. The d34SH2S values (from þ9.3 to þ11.3‰ V-CDT) suggests that H2S is mainly related to thermogenic reduction of Triassic anhydrites. The d13C-CH4 and dD-CH4 values (from 33.4 to 24.9‰ V-PDB and from 168 to 140‰ V-SMOW, respectively) and the relatively low C1/C2þ ratios (〈100) are indicative of a prevailing CH4 production through thermogenic degradation of organic matter. The low N2/Ar and high N2/ He ratios, as well as the 40Ar/36Ar ratios (〈305) close to atmospheric ratio, suggest that both N2 and Ar mostly derive from air. Notwithstanding, the positive d15N-N2 values (from þ0.91 to þ3.7‰ NBS air) point to a significant extra-atmospheric N2 contribution. Gas geothermometry in the CH4-CO2-H2 and H2S-CO2-H2 systems indicate equilibrium temperatures 〈200 C, i.e. lower than those measured in deep geothermal wells (~300 C), due to either an incomplete attainment of the chemical equilibria or secondary processes (dilution and/or scrubbing) affecting the chemistry of the uprising fluids. Although the highly saline Na-Cl fluids discharged from the explorative geothermal wells in the study area support the occurrence of a well-developed hydrothermal reservoir suitable for direct exploitation, the chemistry of the fluid discharges highlights that the uprising hydrothermal fluids are efficiently cooled and diluted by the meteoric water recharge from the nearby Apennine sedimentary belt. This explains the different chemical and isotopic features shown by the fluids from the eastern and western sectors of SVD, respectively, the latter being influenced by this process at a lesser extent. Direct uses may be considered a valid alternative for the exploitation of this resource.
    Description: Published
    Description: 187-201
    Description: 6A. Geochimica per l'ambiente
    Description: 2IT. Laboratori sperimentali e analitici
    Description: 1VV. Altro
    Description: JCR Journal
    Keywords: Fluid geochemistry ; Central Italy ; Water-gas-rock interaction ; Geothermometry ; Sabatini Volcanic District ; 03.02. Hydrology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 8
    Publication Date: 2024-05-09
    Description: Real-time measurements of GEM and H2S discharged fromnatural and anthropogenic sources are a valuable tool to investigate the dispersion dynamics of these contaminants in air. In this study, a new approach to measure GEM and H2S concentrations in air, carried out by coupling a portable Zeeman atomic absorption spectrometer with high frequency modulation of light polarization (Lumex RA-915M) and a pulsed fluorescence gas analyzer (Thermo Scientific Model 450i), was applied to two distinct areas: (i) in the surroundings of Piancastagnaio (Siena, Central Italy), located in the eastern flanks ofMt. Amiata (a 200,000 years old volcano), where three geothermal plants are operating and whose exhaust gases are dispersed in the atmosphere after passing through the turbines and an abatement system to mitigate the environmental impact on air, and (ii) at Solfatara Crater (Campi Flegrei, Southern Italy), a volcanic apparatus characterized by intense hydrothermal activity. In 2014, seven GEMand H2S surveys were carried out in the two areas along pre-defined pathways performed by car at both the study sites. The lowest and highest recorded GEM and H2S concentrations at Piancastagnaio were up to 194 and 77 ng/m3, respectively, whilst at Solfatara Crater were up to 690 and 3392 μg/m3, respectively. Although the GEM concentrations at Piancastagnaio were lower than the limit value recommended by local regulations for outdoor environment (300 ng/m3), they were almost one order of magnitude higher than the GEM background both in Tuscany (~3.5 ng/m3) and Mt. Amiata (3–5 ng/m3), suggesting that the main source of GEM was likely related to the geothermal plants. At Solfatara Crater, the highest GEM values were recognized in proximity of the main fumarolic gas discharges. As far as the H2S concentrations are concerned, the guideline value of 150 μg/m3, recommended by WHO (2000), was frequently overcome in the study areas. Dot (in the surroundings of Piancastagnaio) and contour (at Solfatara Crater) maps for GEM and H2S concentrations built for each survey highlighted the important effects played by the meteorological parameters, the latter being measured by a Davis® Vantage Vue weather station. In particular, the GEM and H2S plumes were strongly affected by the wind speed and direction thatwere able to modify the dispersion of the two parameters in air in a matter of hours, indicating that the proposed analytical approach is able to produce a more realistic picture of the distribution of these air pollutants than that provided by using passive traps. Finally, the H2S/GEMratio, calculated by normalizing the measured GEM and H2S concentrations to their highest values (nH2S/GEM),was used as a good proxy for the chemical-physical processes that these two gas species can suffer once emitted in the air. In particular, H2S resulted to be more affected by secondary processes than GEM, possibly related to photochemical oxidation reactions.
    Description: Published
    Description: 48-58
    Description: 4V. Vulcani e ambiente
    Description: JCR Journal
    Description: restricted
    Keywords: Real-time measurements ; gaseous elemental mercury ; Hydrogen sulphide ; Gaseous contaminants ; Solfatara crater ; Mt. Amiata ; 01. Atmosphere::01.01. Atmosphere::01.01.03. Pollution ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 9
    Publication Date: 2024-05-09
    Description: In this study, hydrogen sulfide (H2S) measurements in air carried out using (a) passive/diffusive samplers (Radiello® traps) and (b) a high-frequency (60 s) real-time analyzer (Thermo® 450i) were compared in order to evaluate advantages and limitations of the two techniques. Four different sites in urban environments (Florence, Italy) and two volcanic areas characterized by intense degassing of H2S-rich fluids (Campi Flegrei and Vulcano Island, Italy) were selected for such measurements. The concentrations of H2S generally varied over 5 orders of magnitude (from 10 1e103 mg/m3), the H2S values measured with the Radiello® traps (H2SR) being significantly higher than the average values measured by the Thermo® 450i during the trap exposure (H2STa), especially when H2S was 〈30 mg/m3. To test the reproducibility of the Radiello® traps, 8 passive/diffusive samplers were contemporaneously deployed within an 0.2 m2 area in an H2S-contaminated site at Mt. Amiata (Tuscany, Italy), revealing that the precision of the H2SR values was ±49%. This large uncertainty, whose cause was not recognizable, is to be added to that related to the environmental conditions (wind speed and direction, humidity, temperature), which are known to strongly affect passive measurements. The Thermo® 450i analyzer measurements highlighted the occurrence of short-term temporal variations of the H2S concentrations, with peak values (up to 5732 mg/m3) potentially harmful to the human health. The Radiello® traps were not able to detect such temporal variability due to their large exposure time. The disagreement between the H2SR and H2STa values poses severe concerns for the selection of an appropriate methodological approach aimed to provide an accurate measurement of this highly toxic air pollutant in compliance with the WHO air quality guidelines. Although passive samplers may offer the opportunity to carry out low-cost preliminary surveys, the use of the high-frequency H2S analyzer is preferred when an accurate assessment of air quality is required. In fact, the latter provides precise real-time measurements for a reliable estimation of the effective exposure to hazardous H2S concentrations, giving insights into the mechanisms regulating the dispersion of this air pollutant in relation to the meteorological parameters.
    Description: Published
    Description: 51-58
    Description: 4V. Vulcani e ambiente
    Description: JCR Journal
    Description: restricted
    Keywords: active analysers ; Passive/diffusive samplers ; Gaseous contaminants ; Air quality monitoring ; Hydrogen sulphide ; 01. Atmosphere::01.01. Atmosphere::01.01.03. Pollution ; 01. Atmosphere::01.01. Atmosphere::01.01.07. Volcanic effects ; 01. Atmosphere::01.01. Atmosphere::01.01.08. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 10
    Publication Date: 2024-05-09
    Description: The carbon isotopic composition of dissolved C-bearing species is a powerful tool to discriminate the origin of carbon in thermal waters from volcanic and hydrothermal systems. However, the δ13C values of dissolved CO2 and TDIC (Total Dissolved Inorganic Carbon) are often different with respect to the isotopic signature that characterizes the potential carbon primary sources, i.e. deep hydrothermal reservoirs, magmatic gases and organic activity. The most commonly invoked explanation for such isotopic values is related to mixing processes between deep and shallow end-members. Nevertheless, experimental and empirical investigations demonstrated that isotopic fractionation due to secondary processes acting on the uprising fluids from the hydrothermal reservoirs is able to reproduce the measured isotopic values. In this paper,we investigated the chemistry of thermalwaters, collected at Campi Flegrei and Vulcano Island (southern Italy),whose origin is related to interaction processesamongmagmatic gases, meteoric water, seawater and hosting rocks. A special focus was dedicated to the δ13C values of dissolved CO2 (δ13CCO2(aq)) and total dissolved inorganic carbon (δ13CTDIC). The δ13CCO2(aq) and δ13CTDIC values in the water samples fromboth these systems ranged from(i) those measured in fumarolic gases, likely directly related to the deep hydrothermal-magmatic reservoir, and (ii) those typically characterizing biogenic CO2, i.e. produced by microbially-driven degradation of organic matter. A simple mixingmodel of the two end-members, apparently explaining these intermediate carbon isotopic values, contrastswith the chemical composition of the dissolved gases. On the contrary, isotopic fractionation due to secondary processes, such as calcite precipitation, affecting hydrothermal fluids during their underground circulation, seems to exhaustively justify both the chemical and isotopic data. If not recognized, these processes, which frequently occur in volcanic and hydrothermal systems, may lead to an erroneous interpretation of the carbon source, causing an underestimation of the contribution of the hydrothermal/magmatic fluids to the dissolved carbon species. These results pose extreme caution in the interpretation of intermediate δ13CCO2(aq) and δ13CTDIC values for the assessment of the carbon budget of hydrothermal- volcanic systems.
    Description: Published
    Description: 46–57
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: 4V. Dinamica dei processi pre-eruttivi
    Description: JCR Journal
    Keywords: Thermal waters ; Carbon isotopes ; Dissolved CO2 ; TDIC ; Volcanic-hydrothermal systems ; Secondary fractionation processes ; 04.08. Volcanology ; 03.02. Hydrology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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