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Ricci, Andrea
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Ricci, Andrea
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- PublicationEmbargoExtremely deuterium depleted methane revealed in high-temperature volcanic gases(2024)
; ; ; ; ; ; ; ; ; ; ; Active volcanoes often discharge hot (T ≫ 100 °C) magmatic gases whose original composition has been modified through partial interaction with an externally fed hydrothermal system. The study of methane (CH4) in these volcanic discharges may provide useful information on the interplay between deep magmatic gases and shallow circulation of hydrothermal fluids. However, the origin of CH4 in high-temperature volcanic gases and the factors exerting control on its abundance and stable isotope composition are still largely unknown. Here, we present the abundances and stable isotopic composition of CH4 in hot (99–387 °C) volcanic gases from the La Fossa volcanic crater of Vulcano Island (Southern Italy). Our investigation revealed low (<1.5 μmol/mol) CH4 concentrations and an extraordinarily large variability in CH4 stable isotopic composition, with δ13C and δ2H values being positively correlated and varying from −35 to −9.2 ‰ and −670 to −102 ‰, respectively. Notably, CH4 isotopes measured at Vulcano almost encompasses the global-scale variability observed in natural fluids, with δ2H values ≤ −500 ‰ being the first ever reported in nature. Gases showing extremely negative δ13C-CH4 and δ2H-CH4 values systematically display higher CH4 abundances. We propose two possible scenarios in order to explain the observed huge variation in δ13C and δ2H: (1) mixing of 13C- and 2H-depleted CH4 with 13C- and 2H-enriched CH4 of thermogenic origin formed under hydrothermal conditions; (2) post-genetic removal and isotopic alteration of 13C- and 2H-depleted CH4 occurring during the ascent of volcanic gases. Comparing our dataset with available isotopic data from naturally occurring and artificially produced CH4, a thermogenic origin for the isotopically light CH4 seems unlikely. We postulate that the 13C- and 2H-depleted CH4 may have formed via kinetically-controlled abiotic synthesis through CO (or CO2) hydrogenation reactions in the hot ascending gas phase, possibly at temperatures intermediate between those typical of magmatic and hydrothermal conditions. Further investigations of methane in high-temperature volcanic gases are necessary to test this hypothesis.44 1 - PublicationOpen AccessDeep magma degassing and volatile fluxes through volcanic hydrothermal systems: Insights from the Askja and Kverkfjöll volcanoes, Iceland(2023-03-06)
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; Mantle volatiles are transported to Earth’s crust and surface by basaltic volcanism. During subaerial eruptions, vast amounts of carbon, sulfur and halogens can be released to the atmosphere during a short time-interval, with impacts ranging in scale from the local environment to the global climate. By contrast, passive volatile release at the surface originating from magmatic intrusions is characterized by much lower flux, yet may outsize eruptive volatile quantities over long timescales. Volcanic hydrothermal systems (VHSs) act as conduits for such volatile release from degassing intrusions and can be used to gauge the contribution of intrusive magmatism to global volatile cycles. Here, we present new compositional and isotopic (δD and δ18O-H2O, 3He/4He, δ13C-CO2, Δ33S- δ34S-H2S and SO4) data for thermal waters and fumarole gases from the Askja and Kverkfj¨oll volcanoes in central Iceland. We use the data together with magma degassing modelling and mass balance calculations to constrain the sources of volatiles in VHSs and to assess the role of intrusive magmatism to the volcanic volatile emission budgets in Iceland. The CO2/ΣS (10 30), 3He/4He (8.3–10.5 RA; 3He/4He relative to air), δ13C-CO2 ( 4.1 to 0.2 ‰) and Δ33S- δ34S-H2S ( 0.031 to 0.003 ‰ and 1.5 to +3.6‰) values in high-gas flux fumaroles (CO2 > 10 mmol/mol) are consistent with an intrusive magmatic origin for CO2 and S at Askja and Kverkfj¨oll. We demonstrate that deep (0.5–5 kbar, equivalent to ~2–18 km crustal depth) decompression degassing of basaltic intrusions in Iceland results in CO2 and S fluxes of 330–5060 and 6–210 kt/yr, respectively, which is sufficient to account for the estimated CO2 flux of Icelandic VHSs (3365–6730 kt/yr), but not the VHS S flux (220–440 kt/yr). Secondary, crystallization-driven degassing from maturing intrusions and leaching of crustal rocks are suggested as additional sources of S. Only a minor proportion of the mantle flux of Cl is channeled via VHSs whereas the H2O flux remains poorly constrained, because magmatic signals in Icelandic VHSs are masked by a dominant shallow groundwater component of meteoric water origin. These results suggest that the bulk of the mantle CO2 and S flux to the atmosphere in Iceland is supplied by intrusive, not eruptive magmatism, and is largely vented via hydrothermal fields.38 26 - PublicationOpen AccessA multi-instrumental geochemical approach to assess the environmental impact of CO2-rich gas emissions in a densely populated area: the case of Cava dei Selci (Latium, Italy)(2019)
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;; ; ; ; ;; ; The Colli Albani volcanic complex (Lazio, Italy) hosts areas characterized by anomalously high emissions of CO2-rich gases (e.g. Tivoli, Cava dei Selci, Tor Caldara, Solforata). The source of these gases is a regional aquifer within the Mesozoic carbonate rock sequences. These degassing zones release significant concentrations of H2S and other toxic gases (e.g. GEM: Gaseous Elemental Mercury, and Rn) and represent a serious hazard for local inhabitants, especially for those living at Cava dei Selci (near Rome, Italy), where the emitting areas are nested inside residential neighborhoods. In April 2016, a comprehensive geochemical survey was carried out in an abandoned stone quarry nearby the urban settlement aimed to: (i) investigate the gas composition from both punctual discharges and anomalously high diffuse soil degassing sites, and (ii) evaluate their environmental impact on the local air quality. The spatial distribution of the soil CO2 fluxes was mainly dependent on the local geostructural setting, whereas shallow secondary processes (e.g. oxidation and gas-water interaction) likely represent the main controlling factor on reactive and/or water-soluble gas species, such as CH4 and H2S. The total output of CO2 from the abandoned stone quarry accounted for 0.53% of total CO2 discharged from the whole Colli Albani volcanic district. The naturally emitted toxic gases (e.g. CO2, H2S, CH4, GEM) largely affect the air quality and pose a serious threat for the health of the local residents. A mobile multi-instrumental station able to continuously and simultaneously acquire CO2, H2S, SO2, CH4, GEM and CO was deployed to verify the concentrations of both the main deep-originated gas compounds and potential secondary gaseous contaminants (i.e. SO2) around and inside the urban settlement most exposed to the lethal gases. Hydrogen sulfide was found to be the most impacting gas, occasionally exceeding the 24-h air quality guideline for ambient air and causing odor annoyance at a distance up to more than 250 m downwind from the emitting area. In poorly ventilated basements, toxic gas accumulations up to hazardous levels were measured, producing anomalous outdoor air concentrations at the street level in front of the descending vehicular access to private garages and relatively far from the main emitting area. The geochemical survey, carried out via mobile station and soil gas measurements, resulted to be particularly efficient for evaluating the potential effects caused by gas emissions in inhabited areas. The multi-measurement approach adopted in the present study is of paramount importance for managing future urban development plans.1081 104 - PublicationOpen AccessSources and migration pathways of methane and light hydrocarbons in the subsurface of the Southern Po River Basin (Northern Italy)(2023)
; ; ; ; ; ; ; ; ; ; ; ; ; ; ;; ; ; ;This paper presents new chemical and isotopic data on gases from deep oil and gas fields, bubbling gases, dissolved gases in groundwaters and dry seeps of the Southern Po River Basin (Emilia-Romagna, Italy), aiming to (i) characterize and differentiate the various types of deep natural gases; (ii) identify the source(s) of methane and light hydrocarbons in shallow aquifers and surface gas-rich emissions; (iii) propose a conceptual model of natural fluid migration pathways in the sedimentary prism of the Southern Po River Basin. Based on the isotopic composition of CH4 and C2–C4 n-alkanes, CH4/(C2H6+C3H8) ratio, relative proportion of the C7 hydrocarbons and relative concentration of cyclic compounds with respect to the total cyclic abundance, three main deep reservoirs of hydrocarbons are identified in the subsurface of the Southern Po River Basin: (1) microbial gas hosted in Pliocene-Pleistocene marine sediments, (2) thermogenic gas hosted in Miocene deposits and (3) thermogenic gas produced in Triassic carbonates. Helium isotopes of these deep fluids indicate an almost pure crustal origin (Rc/Ra values = 0.014–0.04), with negligible contributions from mantle-derived helium. A variable contribution of atmosphere-derived fluids is highlighted by low 4He/20Ne (down to 5.42) and 40Ar/36Ar (≤319.5) values. Comparison of chemical and isotopic signatures of deep and surficial hydrocarbon occurrences suggests that methane in shallow groundwaters or gas seeps is sourced by microbial gas migrating upward from deep Plio-Pleistocene reservoirs, with no detectable contributions of Triassic or Miocene thermogenic hydrocarbons. At shallow depths (roughly around 20–50 m.b.g.l.), Plio-Pleistocene microbial methane appears to be mainly stored in anoxic aquifers. However, where CH4 further migrates upwards and reaches aerobic environments (e.g., aquifers or soils), it readily undergoes a process of exothermic microbial oxidation mediated by methanotrophic bacteria. Where the structural architecture of the sedimentary sequence favors the migration of fluids, the methanotrophic biofilter is bypassed and CH4 is discharged through soil diffuse degassing or gas bubbling at water wells. We argue that microbial consumption might be able to bio-sequester significant amounts of Plio-Pleistocene deep-sourced methane in the form of CO2 and biomass. Such process might be widespread in the subsurface of the Southern Po River Basin and, possibly, in other foreland basins worldwide.465 86 - PublicationOpen AccessFractionation processes affecting the stable carbon isotope signature of thermal waters from hydrothermal/volcanic systems: The examples of Campi Flegrei and Vulcano Island (southern Italy)(2017)
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 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.393 95