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  • 1
    Publication Date: 2020-12-18
    Description: Some 300–600 Tg of volatiles are globally vented each year by arc volcanism. Such arc gas emissions have contributed to past and present-day evolution of the Earth atmosphere and climate by recycling mineral-bound volatiles subducted along active slabs. Carbon dioxide (CO2) and total sulphur (ST) are, after water, the major components of volcanic arc gases. Understanding their relative abundances (e.g., the CO2/ST ratio) in arc volcanic gases is important to constrain origin and recycling efficiency of these volatiles along the subduction factory, and to better constrain the global arc volcanic CO2 flux.Here,we review currently available information on global variations of volcanic arc CO2/ST gas ratios. Weanalyse a dataset of N2000 published volcanic arc gasmeasurements that comprise (i) low-temperature hydrothermal gas emissions, in which ST is dominated by hydrothermal hydrogen sulphide (H2S), and (ii) high temperature “magmatic” gases rich in sulphur dioxide (SO2). We show that the global CO2/ST population of hydrothermal gases is mainly controlled by S loss to hydrothermal fluids/ rocks.Wethen select a subset of high-temperature (≥450 °C) arc gaseswhich, being less affected by S hydrothermal loss, can be used to infer the “deep” source of volatiles. Using a subset of time-averaged high-T gas compositions for 56 arc volcanoes, we identify sizeable along-arc and inter-arc variations in the “magmatic” arc gas CO2/ST ratio, which we ascribe to distinct volatile origins in the magma generation/storage zone. In the attempt to resolve the slab vs. crustal contributions to arc gas budgets, we explore the global association between volcanic gas CO2/ST ratios and non-volatile (trace elements) tracers in arc magmas. For the first time in a global study,we find evidence for higher carbon output (CO2/ST) in arcswhere carbonate sediment subducts on the seafloor. Indeed,most arc volcanoes exhibit gas vs. trace element relationships that are explained by addition of slabsediment melts±fluids to themantlewedge.We also identify a subset of CO2-rich arc volcanoeswith unusually high CO2/ST ratios (Etna, Stromboli, Vulcano Island, Popocatépetl, Soufriere of St Vincent, Bromo and Merapi), which we interpret as the product of magma-limestone interactions in the upper crust. Evidence for this process comes from carbonate xenoliths and/or carbonate basement that characterise these volcanic systems. Although the mean global CO2/ST ratio of arc gas (~2.5) reflects a predominant source from subducted sediment, limestone-assimilation-derived C may account for a substantial (~19–32%) fraction of the present-day global arc budget, and may have contributed to elevated atmospheric CO2 levels and warmer climate in Earth's past. Our global CO2/ST vs. trace element association paves the way to identifying the gas signature of volcanoes (or arc segments) for which gas information is currently missing, and so improve our current global volcanic arc CO2 flux inventory.
    Description: Published
    Description: 24-47
    Description: 3V. Proprietà dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2021-02-10
    Description: San Cristóbal volcano in northwest Nicaragua is one of the most active basaltic–andesitic stratovolcanoes of the Central American Volcanic Arc (CAVA). Here we provide novel constraints on the volcano's magmatic plumbing system, by presenting the first direct measurements of major volatile contents in mafic-to-intermediate glass inclusions from Holocene and historic-present volcanic activity. Olivine-hosted (forsterite [Fo] b80; Fob80) glass inclusions from Holocene tephra layers contain moderate amounts of H2O (0.1–3.3 wt%) and S and Cl up to 2500 μg/g, and define the mafic (basaltic) endmember component. Historic-present scoriae and tephra layers exhibit more-evolved olivines (Fo69–72) that contain distinctly lower volatile contents (0.1–2.2 wt% H2O, 760–1675 μg/g S, and 1021–1970 μg/g Cl), and represent a more-evolved basaltic–andesitic magma. All glass inclusions are relatively poor in CO2, with contents reaching 527 μg/g (as measured by nanoscale secondary ion mass spectrometry), suggesting pre- to postentrapment CO2 loss to a magmatic vapor. We use results of Raman spectroscopy obtained in a population of small (b50 μm) inclusions with CO2-bearing shrinkage bubbles (3–12 μm) to correct for postentrapment CO2 loss to bubbles, and to estimate the original minimumCO2 content in San Cristóbal parental melts at ~1889 μg/g, which is consistent with the less-CO2-degassed melt inclusions (MI) (N1500 μg/g) found in Nicaragua at Cerro Negro, Nejapa, and Granada. Models of H2O and CO2 solubilities constrain the degassing pathway of magmas up to 425 MPa (~16 km depth), which includes a deep CO2 degassing step (only partially preserved in the MI record), followed by coupled degassing of H2O and S plus crystal fractionation at magma volatile saturation pressures from ∼195 to b10 MPa. The variation in volatile contents from San Cristóbal MI is interpreted to reflect (1) Holocene eruptive cycles characterized by the rapid emplacement of basaltic magma batches, saturated in volatiles, at depths of 3.8–7.4 km, and (2) the ascent of more-differentiated and cogenetic volatile-poor basaltic andesites during historic-present eruptions, having longer residence times in the shallowest (b3.4 km) and hence coolest regions of the magmatic plumbing system. We also report the first measurements of the compositions of noble-gas isotopes (He, Ne, and Ar) in fluid inclusions in olivine and pyroxene crystals. While the measured 40Ar/36Ar ratios (300–304) and 4He/20Ne ratios (9–373) indicate some degree of air contamination, the 3He/4He ratios (7.01–7.20 Ra) support a common mantle source for Holocene basalts and historic-present basaltic andesites. The magmatic source is interpreted as generated by a primitive MORB-like mantle, that is influenced to variable extents by distinct slab fluid components for basalts (Ba/La ~ 76 and U/Th ~ 0.8) and basaltic andesites (Ba/La ~ 86 and U/Th ~ 1.0) in addition to effects of magma differentiation. These values for the geochemical markers are particularly high, and their correlation with strong plume CO2/S ratios from San Cristóbal is highly consistent with volatile recycling at the CAVA subduction zone, where sediment involvement in mantle fluids influences the typical relatively C-rich signature of volcanic gases in Nicaragua.
    Description: Published
    Description: 131-148
    Description: 1V. Storia eruttiva
    Description: JCR Journal
    Keywords: San Cristóbal, Volatiles, Melt inclusions, NanoSIMS, Multi-GAS, Noble gases ; Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2020-11-25
    Description: Over the past few decades, substantial progress has been made to overcome the technical difficulties of continuously measuring volcanic SO2 emissions. However, measurements of CO2 emissions still present many difficulties, partly due to the lack of instruments that can directly measure CO2 emissions and partly due to its strong atmospheric background. In order to overcome these difficulties, a commonly taken approach is to combine differential optical absorption spectroscopy (DOAS) by using NOVAC scan-DOAS instruments for continuous measurements of crateric SO2 emissions, and electrochemical/NDIR multi-component gas analyser system (multi-GAS) instruments for measuring CO2/SO2 ratios of excerpts of the volcanic plume. This study aims to quantify the representativeness of excerpts of CO2/SO2 ratios measured by Multi-GAS as a fraction of the whole plume composition, by comparison with simultaneously measured CO2/SO2 ratios using cross-crater Fourier transform infrared spectroscopy (FTIR). Two study cases are presented: Telica volcano (Nicaragua), with a homogenous plume, quiescent degassing from a deep source and ambient temperature, and Turrialba volcano (Costa Rica), which has a non-homogeneous plume from three main sources with different compositions and temperatures. Our comparison shows that in our “easier case” (Telica), FTIR and Multi-GAS CO2/SO2 ratios agree within a factor about 3 %. In our “complicated case” (Turrialba), Multi-GAS and FTIR yield CO2/SO2 ratios differing by approximately 13–25 % at most. These results suggest that a fair estimation of volcanic CO2 emissions can be provided by the combination of DOAS and Multi-GAS instruments for volcanoes with similar degassing conditions as Telica or Turrialba. Based on the results of this comparison, we report that by the time our measurements were made, Telica and Turrialba were emitting approximately 100 and 1,000 t day−1 of CO2, respectively.
    Description: This work was supported by the Swedish International Development Agency (SIDA), and the DECADE initiative in coordination with OVSICORI-UNA and INETER. The research leading to these results received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007/2013)/ERC grant agreement n1305377 (PI Aiuppa)
    Description: Published
    Description: 2335–2347
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: volcanic degassing ; Multi-GAS ; UV spectroscopy ; FTIR
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
    Publication Date: 2021-01-26
    Description: Hydrothermally-altered rocks collected at Solfatara volcano, Campi Flegrei caldera complex, Italy, are comparable to zones of steam-heated alterations found at low sulfidation epithermal deposits, and volcanic gases collected at Solfatara have temperatures and C-O-H isotopic compositions akin to those forming low sulfidation epithermal deposits. By contrast, hydrothermal alterations collected at La Fossa volcano, Vulcano island, Italy, are comparable to zones of residual vuggy silica formed in high sulfidation epithermal deposits, and volcanic gases collected at La Fossa have temperatures and C-O-H isotopic compositions comparable to those forming high sulfidation epithermal deposits. At Solfatara, amorphous and hydrous opal-A is responsible for shifts in δ7Li values, from +2.2‰ in fresher rocks, to −3.6‰ in most altered rocks, with increases in Au and Cu concentrations (up to 3 ppb and 96 ppm). The increase in Au and Cu concentrations in progressively-altered rocks resulted from the transport of Cu-Au in magmatic-hydrothermal fluids and their partitioning into pyrite, Fe oxides, phyllosilicates, sulfates, and/or opal-A. It is proposed that the combination of opal-A, decreases in δ7Li values, and increases in Cu and Au concentrations represent an exploration vector for low sulfidation epithermal veins. At La Fossa, α-cristobalite is responsible for shifts in δ7Li values, ranging from −0.9‰ in least-altered rocks, to +4.7‰ in most altered rocks, with decreases in Au-Cu concentrations. The decrease in Au and Cu concentrations in progressively-altered rocks may have resulted from the metasomatism of pyrite and Fe oxides, the dissolution of clinopyroxene and opal, and the invasion of the samples by α-cristobalite. The combination of α-cristobalite, increases in δ7Li values, and decreases in Cu and Au concentrations are proposed as proxies for potential high sulfidation epithermal disseminations. Alternating phases of high eruptive activity and quiescent degassing at volcanoes generally, and at Solfatara and La Fossa specifically, suggest that the physicochemical conditions of individual subvolcanic hydrothermal systems should also be alternating, between conditions that are characteristic of low- and high sulfidation epithermal ore-forming environments, and that the related zones of silicification should be alternating between low δ7Li and high Cu-Au values dominated by opal-A, and higher δ7Li and lower Cu-Au values dominated by α-cristobalite.
    Description: Published
    Description: 103934
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Keywords: Active ore-forming processes ; Opalization and cristobalization ; Lithium isotopes ; High and low sulfidation epithermal Au-Cu ore deposits ; La Fossa, Vulcano, Italy ; Solfatara, Campi Flegrei, Italy ; 04.08. Volcanology ; 05.04. Instrumentation and techniques of general interest ; Geochemistry
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 5
    Publication Date: 2021-06-16
    Description: New analytical results for the composition of shrinkage bubbles (0·9–7·0 vol. %) in olivine-hosted (Fo 〈80%) primary melt inclusions (MIs) have been incorporated into a novel geochemical model for San Cristóbal volcano, Nicaragua. The vapour, liquid, and mineral components found inside shrinkage bubbles may represent relics of early C–O–H–S fluids exsolved from a magmatic-hydrothermal system. This conclusion is supported by high-resolution Raman microspectroscopy revealing: (1) gaseous CO2 (d = 0·17–0·31 g/cm3 in 31 samples) coexisting with liquid H2O (in seven samples) at ambient temperature (〈22°C) inside the shrinkage bubbles of naturally quenched inclusions; (2) several mineral phases (i.e. Fe, Cu-sulfides, Ca-sulfates and Mg-carbonates) formed along the bubble–glass interface, as confirmed by electron backscattered/energy-dispersive spectroscopy. The presence of liquid water was revealed by applying a novel subtraction method to fitted Raman spectra that isolated an isosbestic liquid-water band at 3460 ± 60/cm-1 (mean ± SD). In MIs, the major oxide composition of glasses containing shrinkage bubbles were analysed by electron microprobe, whereas glass volatile contents were measured with nanoscale secondary-ion mass spectroscopy. According to the water content of the glass inclusions (≤ 3·3 wt %) and the presence of liquid water at the bubble–glass interface, only small amounts of water (0·3 wt %) appear to have migrated inside the bubbles. From pre-eruptive (up to 1200°C) to post-eruptive temperatures, aqueous fluids represent the principal agents for chemical reactions inside MI bubbles involving dissolved ionic species (e.g. SO42-, CO32-, and Cl-) and major and/or trace elements from the inclusion glass (e.g. Mg, Fe, Cu, Si, Al, Na, and K). After the initiation of nucleation (1009–1141°C), the volume of shrinkage bubbles expands and the surrounding glass contracts (at 〈530°C). The Fe–Mg–Cu-rich (vapour) shrinkage-bubble paragenetic mineral sequence formed during different cooling stages: (A) high-temperature sulfide precipitation at 500–700°C; (B) low-temperature magnesite precipitation at hydrothermal conditions 〈350°C; and finally (C) low-to-ambient temperature precipitation of carbonates and sulfates in liquid water at 〈150°C. Our findings indicate that the C–O–H–S fluids in shrinkage bubbles can represent an ideal preserved/closed magmatic-hydrothermal system evolving after the exsolution of magmatic fluids during cooling.
    Description: Published
    Description: 2093–2122
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 6
    Publication Date: 2017-09-11
    Description: Telica volcano, in north-west Nicaragua, is a young stratovolcano of intermediate magma composition producing frequent Vulcanian to phreatic explosive eruptions. The Telica stratigraphic record also includes examples of (pre)historic sub-Plinian activity. To refine our knowledge of this very active volcano, weanalyzedmajor element composition and volatile content of melt inclusions fromsomestratigraphically significant Telica tephra deposits. These include: (1) the Scoria Telica Superior (STS) deposit (2000 to 200 years Before Present; Volcanic Explosive Index, VEI, of 2–3) and (2) pyroclasts from the post-1970s eruptive cycle (1982; 2011). Based on measurements with nanoscale secondary ion mass spectrometry, olivine-hosted (forsterite [Fo] N 80) glass inclusions fall into 2 distinct clusters: a group of H2O-rich (1.8–5.2 wt%) inclusions, similar to those of nearby Cerro Negro volcano, and a second group of CO2-rich (360–1700 μg/g CO2) inclusions (Nejapa, Granada). Model calculations show that CO2 dominates the equilibrium magmatic vapor phase in the majority of the primitive inclusions (XCO2 N 0.62–0.95). CO2, sulfur (generally b2000 μg/g) and H2O are lost to the vapor phase during deep decompression (P N 400 MPa) and early crystallization of magmas. Chlorine exhibits a wide concentration range (400–2300 μg/g) in primitive olivine-entrapped melts (likely suggesting variable source heterogeneity) and is typically enriched in the most differentiated melts (1000–3000 μg/g). Primitive, volatile-rich olivine-hosted melt inclusions (entrapment pressures, 5–15 km depth) are exclusively found in the largest-scale Telica eruptions (exemplified by STS in our study). These eruptions are thus tentatively explained as due to injection of deep CO2-rich mafic magma into the shallow crustal plumbing system. More recent (post-1970), milder (VEI 1–2) eruptions, instead, do only exhibit evidence for low-pressure (P b 50–60 MPa), volatile-poor (H2O b 0.3–1.7 wt%; CO2 b 23–308 μg/g) magmatic conditions. These are manifested as andesitic magmas, recording multiple magma mixing events, in pyroxene inclusions.Wepropose that post-1970s eruptions are possibly related to the high viscosity of resident magma in shallow plumbing system (b2.4 km), due to crystallization and degassing
    Description: Published
    Description: 131-148
    Description: 1V. Storia eruttiva
    Description: JCR Journal
    Keywords: Telica, Nicaragua ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 7
    Publication Date: 2022-04-26
    Description: Constraining the magmatic 3He/4He signature of fluids degassed from a magmatic system is crucial for making inferences on its mantle source. This is especially important in arc volcanism, where variations in the composition of the wedge potentially induced by slab sediment fluids must be distinguished from the effects of magma differentiation, degassing, and crustal contamination. The study of fluid inclusions (FIs) trapped in minerals of volcanic rocks is becoming an increasingly used methodology in geochemical studies that integrates the classical study of volcanic and geothermal fluids. Here, we report on the first noble gas (He, Ne, Ar) concentrations and isotopic ratios of FI in olivine (Ol) and pyroxene (Px) crystals separated from eruptive products of the Telica and Baru volcanoes, belonging to the Nicaraguan and Panamanian arc-segments of Central America Volcanic arc (CAVA). FIs from Telica yield air corrected 3He/4He (Rc/Ra) of 7.2–7.4 Ra in Ol and 6.1–7.3 in Px, while those from Baru give 7.1–8.0 Ra in Ol and 4.2–5.8 Ra in Px. After a data quality check and a comparison with previous 3He/4He measurements carried out on the same volcanoes and along CAVA, we constrained a magmatic Rc/Ra signature of 7.5 Ra for Telica and of 8.0 Ra for Baru, both within the MORB range (8 1 Ra). These 3He/4He differences also reflect variations in the respective arc-segments, which cannot be explained by radiogenic 4He addition due to variable crust thickness, as the mantle beneath Nicaragua and Panama is at about 35 and 30 km, respectively. We instead highlight that the lowest 3He/4He signature observed in the Nicaraguan arc segment reflects a contamination of the underlying wedge by slab sediment fluids. Rc/Ra values up to 9.0 Ra are found at Pacaya volcano in Guatemala, where the crust is 45 km thick, while a 3He/4He signature of about 8.0 Ra was measured at Turrialba volcano in Costa Rica, which is similar to that of Baru, and reflects possible influence of slab melting, triggered by a change in subduction conditions and the contemporary subduction of the Galapagos hot-spot track below southern Costa Rica and western Panama.
    Description: Published
    Description: 2076-3417
    Description: 1V. Storia eruttiva
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: 3V. Proprietà chimico-fisiche dei magmi e dei prodotti vulcanici
    Description: JCR Journal
    Keywords: Telica volcano ; Baru volcano ; 3He/4He ; fluid inclusions ; CAVA ; slab fluids ; Isotope Geochemistry ; Noble gases ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 8
    Publication Date: 2021-11-25
    Description: This study combines new noble gas data from fluid inclusions in minerals from Sabancaya, Ubinas, and El Misti (CVZ, Peru) and Villarica (South Chile, SVZ) with a revised noble gas compilation in the Andes, to identify systematic along arc variations in helium isotope compositions. We find 3He/4He ratios varying from 8.8 RA (Colombia) to 7.4 RA (Ecuador) within the NVZ, and only as high as 6.4 RA in the CVZ (RA is the atmospheric 3He/4He ratio of 1.39 × 10–6). These distinct isotope compositions cannot be explained by variable radiogenic 4He production via slab fluid transport of U and Th in the mantle wedge, since both NVZ and CVZ share similar slab sediment inputs (Th/La ≈ 0.08–0.13). Instead, the progressively more radiogenic 3He/4He signatures in Ecuador and Peru reflect 4He addition upon magma ascent/storage in the crust, this being especially thick in Peru (〉70 km) and Ecuador (〉50 km) relative to Colombia (∼30–45 km). The intermediate compositions in the North (8.0 RA) and South (7.9 RA) Chile, both high sediment flux margins, mostly reflect a more efficient delivery of radiogenic He in the wedge from the subducted (U-Th-rich) terrigenous sediments. Our results bring strong evidence for the major role played by crustal processes in governing noble gas compositions along continental arcs.
    Description: Published
    Description: 45-49
    Description: 1V. Storia eruttiva
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: 4V. Processi pre-eruttivi
    Description: JCR Journal
    Keywords: Noble gases ; Fluid inclusions ; Andean volcanic Arc ; crustal contamination ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 9
    Publication Date: 2023-11-16
    Description: Lascar (5592 m a.s.l.) and Lastarria (5697 m a.s.l.) are Chilean active stratovolcanoes located in the Central Volcanic Zone (CVZ; 16°S to 28°S) that have developed on top of a 71 km thick continental crust. Independently of the similarities in their Plinian/Vulcanian eruptive styles, their complex magmatic feeding structures and the origins of their magmatic fluids still necessitate constraints in order to improve the reliability of geochemical monitoring. Here we investigate the petrography, bulk-rock chemistry, and mineral chemistry in products from the 1986–1993 explosive eruptive cycle at Lascar and from several Holocene eruptive sequences at Lastarria. These data are integratedwith measurements of the noble gas isotopes in fluid inclusions (FIs) of minerals fromthe same products as well as in fumarole gases. The geochemistry ofminerals and rocks shows that the studied products belong to high-K–calc-alkaline series typical of subduction-related settings, and provide evidence of differentiation,mixing, and crustal assimilation that are higher at Lastarria. The contribution of slab sediments and fluids to magma genesis in thewedge is limited, suggesting a homogeneous mantle beneath CVZ. The deepest crystallization processes occurred at variable levels of the plumbing systems according to the lithostatic equivalent depths estimated with mineral equilibrium geobarometers at Lascar (15–29 km) and Lastarria (~20–40 km). The 40Ar/36Ar and 4He/20Ne ratios in FIs and fumarole gases indicate the presence of some degree of air contamination in the fluids from both volcanoes. The 3He/4He values at Lascar (6.9–7.3 Ra) are relatively homogeneous and comparable to those of fumaroles, suggesting a main zone of magma crystallization and degassing. In contrast, the 3He/4He values at Lastarria (5.31–8.01 Ra) vary over a wide range, suggesting various magma storage levels and providing evidence of crustal contamination, as indicated by the rock chemistry.We argue thatmantle beneath the two volcanoes has a MORB-like signature of 3He/4He, while local crustal contamination explains the lower ratios measured at Lascar.
    Description: Published
    Description: 105615
    Description: 1V. Storia eruttiva
    Description: 2V. Struttura e sistema di alimentazione dei vulcani
    Description: JCR Journal
    Keywords: Lascar ; Lastarria ; noble gases ; Fluid inclusions ; Crustal contamination ; Mantle wedge ; 04.08. Volcanology ; 04.01. Earth Interior
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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