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  • 1
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    Geochemistry of hydrothermal fluids from the eastern sector of the Sabatini Volcanic District (central Italy) (2017)
    Details
    Publication Date: 2021-02-17
    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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  • 2
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    Gas geochemistry of the magmatic-hydrothermal fluid reservoir in the Copahue–Caviahue Volcanic Complex (Argentina) (2014)
    Elsevier Science Limited
    Details
    Publication Date: 2020-12-15
    Description: Copahue volcano is part of the Caviahue–Copahue Volcanic Complex (CCVC),which is located in the southwestern sector of the Caviahue volcano-tectonic depression (Argentina–Chile). This depression is a pull-apart basin accommodating stresses between the southern Liquiñe–Ofqui strike slip and the northern Copahue–Antiñir compressive fault systems, in a back-arc setting with respect to the Southern Andean Volcanic Zone. In this study, we present chemical (inorganic and organic) and isotope compositions (δ13C-CO2, δ15N, 3He/4He, 40Ar/36Ar, δ13C-CH4, δD-CH4, and δD-H2O and δ18O-H2O) of fumaroles and bubbling gases of thermal springs located at the foot of Copahue volcano sampled in 2006, 2007 and 2012. Helium isotope ratios, the highest observed for a Southern American volcano (R/Ra up to 7.94), indicate a non-classic arc-like setting, but rather an extensional regime subdued to asthenospheric thinning. δ13C-CO2 values (from −8.8‰ to −6.8‰ vs. V-PDB), δ15N values (+5.3‰ to +5.5‰ vs. Air) and CO2/3He ratios (from 1.4 to 8.8 × 109) suggest that the magmatic source is significantly affected by contamination of subducted sediments. Gases discharged from the northern sector of the CCVC show contribution of 3He-poor fluids likely permeating through local fault systems. Despite the clear mantle isotope signature in the CCVC gases, the acidic gas species have suffered scrubbing processes by a hydrothermal system mainly recharged by meteoric water. Gas geothermometry in the H2O-CO2-CH4-CO-H2 system suggests that CO and H2 re-equilibrate in a separated vapor phase at 200°–220 °C. On the contrary, rock–fluid interactions controlling CO2, CH4 production from Sabatier reaction and C3H8 dehydrogenation seem to occur within the hydrothermal reservoir at temperatures ranging from 250° to 300 °C. Fumarole gases sampled in 2006–2007 show relatively low N2/He and N2/Ar ratios and high R/Ra values with respect to those measured in 2012. Such compositional and isotope variations were likely related to injection of mafic magma that likely triggered the 2000 eruption. Therefore, changes affecting the magmatic systemhad a delayed effect on the chemistry of the CCVC gases due to the presence of the hydrothermal reservoir. However, geochemical monitoring activities mainly focused on the behavior of inert gas compounds (N2 and He), should be increased to investigate the mechanism at the origin of the unrest started in 2011.
    Description: Published
    Description: 44–56
    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: Fluid geochemistry ; Copahue volcano ; Fumarolic fluid ; Hydrothermal reservoir ; Volcanic unrest ; 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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  • 3
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    Chemical and isotopic features of cold and thermal fluids discharged in the Southern Volcanic Zone between 32.5°S and 36°S: Insights into the physical and chemical processes controlling fluid geochemistry in geothermal systems of Central Chile (2016)
    Elsevier Science Limited
    Details
    Publication Date: 2020-12-07
    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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  • 4
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    Geochemical and isotopic changes in the fumarolic and submerged gas discharges during the 2011–2012 unrest at Santorini caldera (Greece) (2014)
    Springer Berlin Heidelberg
    Details
    Publication Date: 2021-06-08
    Description: Abstract A geochemical survey of fumarolic and submerged gases from fluid discharges located in the Nea Kameni and Palea Kameni islets (Santorini Island, Greece) was carried out before, during, and after the unrest related to the anomalously high seismic and ground deformation activity that affected this volcanic system since January 2011. Our data show that from May 2011 to February 2012, the Nea Kameni fumaroles showed a significant increase of H2 concentrations. After this period, an abrupt decrease in the H2 contents, accompanied by decreasing seismic events, was recorded. A similar temporal pattern was shown by the F−, Cl−, SO4 2−, and NH4 + concentrations in the fumarolic condensates. During the sharp increase of H2 concentrations, when values up to 158 mmol/ mol were measured, the δ13C–CO2 values, which prior to January 2011 were consistent with a dominant CO2 thermometamorphic source, have shown a significant decrease, suggesting an increase of mantle CO2 contribution. Light hydrocarbons, including CH4, which are controlled by chemical reactions kinetically slower than H2 production from H2O dissociation, displayed a sharp increase in March 2012, under enhanced reducing conditions caused by the high H2 concentrations of May 2011–February 2012. The general increase in light hydrocarbons continued up to July 2012, notwithstanding the contemporaneous H2 decrease. The temporal patterns of CO2 concentrations and N2/Ar ratios increased similarly to that of H2, possibly due to sealing processes in the fumarolic conduits that diminished the contamination related to the entrance of atmospheric gases in the fumarolic conduits. The compositional evolution of the Nea Kameni fumaroles can be explained by a convective heat pulse from depth associated with the seismic activation of the NE–SW-oriented Kameni tectonic lineament, possibly triggered by either injection of new magma below Nea Kameni island, as apparently suggested by the evolution of the seismic and ground deformation activity, or increased permeability of the volcanic plumbing system resulting from the tectonic movements affecting the area. The results of the present study demonstrate that the geophysical and geochemical signals at Santorini are interrelated and may be precursory signals of renewed volcanic activity and encourage the development of interdisciplinary monitoring program to mitigate the volcanic risk in the most tourist-visited island of the Mediterranean Sea.
    Description: Published
    Description: 711
    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: Santorini Island . ; Fluid geochemistry ; Geochemical monitoring ; Seismic crisis ; 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)
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  • 5
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    Preliminary conceptual model of the Cerro Blanco caldera-hosted geothermal system (Southern Puna, Argentina): Inferences from geochemical investigations (2020)
    Details
    Publication Date: 2020-12-21
    Description: The Cerro Blanco Caldera (CBC) is the youngest collapse caldera system in the Southern Central Andes (Southern Puna, Argentina). The CBC is subsiding with at an average velocity of 0.87 cm/year and hosts an active geothermal system. A geochemical characterization of emitted fluids was carried out based on the chemical and isotopic compositions of fumaroles, and thermal and cold springs discharged in this volcanic area with the aim of constructing the first hydrogeochemical conceptual model and preliminary estimate the geothermal potential. The main hydrothermal reservoir, likely hosted within the pre-caldera basement rocks, has a Na+-Clˉ(HCO3)ˉ composition with estimated temperatures ≥135 °C. The unconsolidated, fine-grained Cerro Blanco ignimbrite likely acts as the cap-rock of the hydrothermal system. The presence of phreatic eruption breccias in the surrounding area of the geothermal fumaroles supports the effectiveness of the pyroclastic deposit as sealing rocks. The isotopic data of water (δ18O and δD) indicate a meteoric recharge of the hydrothermal reservoir, suggesting as recharge areas the sectors surrounding the CBC, mainly towards the W and NW where large outcrops of the pre-caldera basement exist. A fault-controlled hydraulic connection between the hot springs and the hydrothermal reservoir is proposed for the Los Hornitos area. The fumaroles show the typical compositional features of hydrothermal fluids, being dominated by water vapor with significant concentrations of H2S, CH4 and H2. Considering the high geothermal gradient of this area (∼104 °C/km) and the relatively high fraction of mantle He (∼39%) calculated on the basis of the measured R/Ra values, the hydrothermal aquifer likely receives inputs of magmatic fluids from the degassing magma chamber. The preliminary geothermal potential at CBC was evaluated with the Volume Method, calculating up to E = 11.4*1018 J. Both the scarce presence of superficial thermal manifestations and the occurrence of an efficient cap-rock likely contribute to minimize the loss of thermal energy from the reservoir. The results here presented constitute the necessary base of knowledge for further accurate assessment of the geothermal potential and ultimately the implementation of the geothermal resource as a viable energy alternative for small localities or mining facilities isolated from the National Interconnected System due to their remote localization.
    Description: Published
    Description: 102213
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Hydrothermal system ; Fluid geochemistry ; Geothermal prospection ; Quaternary caldera ; Northwestern Argentina ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
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    Geochemical modeling of CO2 storage in deep reservoirs: The Weyburn Project (Canada) case study (2010)
    Details
    Publication Date: 2017-04-04
    Description: Geological storage is presently one of the most promising options for reducing anthropogenic emissions of CO2. Among the several projects investigating the fate of CO2 stored at depth, the EnCana's CO2 injection EOR (Enhancing Oil Recovery) project at Weyburn (Saskatchewan, Canada) is the most important oil production development that hosts an international monitoring project. In the Weyburn EOR Project CO2 is used to increase recovery of heavy oil from the Midale Beds, a Mississippian reservoir consisting of shallow marine carbonate, where about 3 billions standard m3 of supercritical CO2 have been injected since 2000 with an injection rate of 5000 ton/day. In this work the available dataset (bulk mineralogy of the reservoir, gas-cap composition and selected preand post-CO2 injection water samples) provided by the International Energy Agency Weyburn CO2 Monitoring & Storage Project has been used in order to: i) reconstruct the pre-injection reservoir chemical composition (including pH and the boundary conditions at 62 °C and 15 MPa); ii) assess the evolution of the reservoir subjected to CO2 injection and predict dissolution/precipitation processes of the Weyburn brines over 100 years after injection; iii) validate the short-term (September 2000–2003) evolution of the in situ reservoir fluids due to the CO2 injection, by comparing the surface analytical data with the composition of the computed depressurized brines. To achieve these goals the PRHEEQC (V2.14) Software Package was used with both modified thermodynamic database and correction for supercritical CO2 fugacity. The oil–gas–water interaction and the non-ideality of the gas phase (with exception of CO2) were not considered in the numerical simulations. Despite intrinsic limitations and uncertainties of geochemical modeling, the main results can be summarized, as follows: 1) the calculated pre-injection chemical composition of the Midale Beds brine is consistent with the analytical data of the waters collected in 2000 (baseline survey), 2) the main reservoir reactions (CO2 and carbonate dissolution) take place within the first year of simulation, 3) the temporal evolution of the chemical features of the fluids in the Weyburn reservoir suggests that CO2 can safely be stored by solubility (as CO2(aq)) and mineral trapping (via dawsonite precipitation). The short-term validation performed by calculating chemical composition of the reservoir fluids (corrected for surface conditions) after the simulation of 3 years of CO2 injection is consistent (error ≤5%) with the analytical data of the wellhead water samples collected in 2003, with the exception of Ca and Mg (error N90%), likely due to complexation effect of carboxilic acid.
    Description: Published
    Description: 181-197
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: partially_open
    Keywords: CO2 ; Geochemical modeling ; geological storage ; Fluid geochemistry ; EOR Weyburn Oil Field Brines ; 04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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