Jean-Baptiste, Philippe

Recent geophysical evidence for large-scale regional crustal inflation and localized crustal magma intrusion has made Lastarria volcano (northern Chile) the target of numerous geological, geophysical, and geochemical studies. The chemical composition of volcanic gases sampled during discrete campaigns from Lastarria volcano indicated a well-developed hydrothermal system from direct fumarole samples in A.D. 2006, 2008, and 2009, and shallow magma degassing using measurements from in situ plume sampling techniques in 2012. It is unclear if the differences in measured gas compositions and resulting interpretations were due to artifacts of the different sampling methods employed, short-term excursions from baseline due to localized changes in stress, or a systematic change in Lastarria’s magmatic-hydrothermal system between 2009 and 2012. Integrated results from a two-day volcanic gas sampling and measurement campaign during the 2014 International Association of Volcanology and Chemistry of the Earth’s Interior (IAVCEI) Commission on the Chemistry of Volcanic Gases (CCVG) 12th Gas Workshop are used here to compare and evaluate current gas sampling and measurement techniques, refine the existing subsurface models for Lastarria volcano, and provide new constraints on its magmatic-hydrothermal system and total degassing budget. While compositional differences among sampling methods are present, distinct compositional changes are observed, which if representative of longterm trends, indicate a change in Lastarria’s overall magmatic-hydrothermal system. The composition of volcanic gases measured in 2014 contained high proportions of relatively magma- and water-soluble gases consistent with degassing of shallow magma, and in agreement with the 2012 gas composition. When compared with gas compositions measured in 2006–2009, higher relative H2O/CO2 ratios combined with lower relative CO2/St and H2O/St and stable HCl/St ratios (where St is total S [SO2 + H2S]) are observed in 2012 and 2014. These compositional changes suggest variations in the magmatic-hydrothermal system between 2009 and 2012, with possible scenarios to explain these trends including: (1) decompression-induced degassing due to magma ascent within the shallow crust; (2) crystallization-induced degassing of a stalled magma body; (3) depletion of the hydrothermal system due to heating, changes in local stress, and/or minimal precipitation; and/or (4) acidification of the hydrothermal system. These scenarios are evaluated and compared against the geophysical observations of continuous shallow inflation at ~8 km depth between 1997 and 2016, and near-surface (<1 km) inflation between 2000 and 2008, to further refine the existing subsurface models. Higher relative H2O/CO2 observed in 2012 and 2014 is not consistent with the depletion or acidification of a hydrothermal system, while all other observations are consistent with the four proposed models. Based on these observations, we find that scenarios 1 or 2 are the most likely to explain the geochemical and geophysical observations, and propose that targeted shallow interferometric synthetic-aperture radar (InSAR) studies could help discriminate between these two scenarios. Lastly, we use an average SO2 flux of 604 ± 296 t/d measured on 22 November 2014, along with the average gas composition and diffuse soil CO2 flux measurements, to estimate a total volatile flux from Lastarria volcano in 2014 of ~12,400 t/d, which is similar to previous estimates from 2012.

We report in this paper a systematic investigation of the chemical and isotopic composition of groundwaters flowing in the volcanic aquifer of Mt. Vesuvius during its current phase of dormancy, including the first data on dissolved helium isotope composition and tritium content. The relevant results on dissolved He and C presented in this paper reveal that an extensive interaction between rising magmatic volatiles and groundwaters currently takes place at Vesuvius. Vesuvius groundwaters are dilute (mean TDS 2800 mg/L) hypothermal fluids (mean T 17.7°C) with a prevalent alkaline-bicarbonate composition. Calcium-bicarbonate groundwaters normally occur on the surrounding Campanian Plain, likely recharged from the Apennines. D and 18O data evidence an essentially meteoric origin of Vesuvius groundwaters, the contribution from either Tyrrhenian seawater or 18O-enriched thermal water appearing to be small or negligible. However, the dissolution of CO2-rich gases at depth promotes acid alteration and isochemical leaching of the permeable volcanic rocks, which explains the generally low pH and high total carbon content of waters. Attainment of chemical equilibrium between the rock and the weathering solutions is prevented by commonly low temperature (10 to 28°C) and acid-reducing conditions. The chemical and isotope (C and He) composition of dissolved gases highlights the magmatic origin of the gas phase feeding the aquifer. We show that although the pristine magmatic composition may vary upon gas ascent because of either dilution by a soil-atmospheric component or fractionation processes during interaction with the aquifer, both 13C/12C and 3He/4He measurements indicate the contribution of a magmatic component with a 13C 0‰ and R/Ra of 2.7, which is consistent with data from Vesuvius fumaroles and phenocryst melt inclusions in olivine phenocrysts. A main control of tectonics on gas ascent is revealed by data presented in this paper. For example, two areas of high CO2 release and enhanced rock leaching are recognized on the western (Torre del Greco) and southwestern (Torre Annunziata–Pompeii) flanks of Vesuvius, where important NE-SW and NW-SE tectonic structures are recognized. In contrast, waters flowing through the northern sector of the volcano are generally colder, less saline, and CO2 depleted, despite in some cases containing significant concentrations of magmaderived helium. The remarkable differences among the various sectors of the volcano are reconciled in a geochemical interpretative model, which is consistent with recent structural and geophysical evidences on the structure of Somma-Vesuvius volcanic complex.

Tunisia has numerous thermo-mineral springs. Previous studies have shown that their chemical composition and occurrence are strongly influenced by the regional geology. However little work has been done so far to study the isotopic composition of volatiles associated with these geothermal manifestations. Here, we report on the results of an extensive survey of both natural hot springs and production wells across Tunisia, aimed at investigating the spatial distribution of thermal fluids' geochemical characteristics and He–C isotopic composition. The chemistry of the analyzed samples highlights the heterogeneity of the water mineralization processes in Tunisia, as a consequence of the complex geological and tectonic setting of the country. In terms of chemical composition, we are able to conclude, however, that dissolution of halite and gypsum plays a key control on groundwater chemistry. Helium and carbon isotope systematics confirm the prevalently crustal origin of the volatiles interacting with the aquifer systems, consistent with the absence of any recent magmatism. Most samples are characterized by crustal-type helium (3He/4He in the range 0.02 Ra–0.4 Ra) associated with a CO2 predominantly metamorphic in origin (with the exception of the Saharan platform where the carbon content is low and mostly organically-derived). In Eastern Tunisia, however, a few samples have He–C isotope compositions which suggest (at least partial) mantle derivation of the dissolved gas phase : the 3He/4He ratio reaches 2.4 Ra (corresponding to 30% of mantle-derived helium) at the Ain Garci site, a CO2 rich mineral spring located some 30 km south of the city of Zaghouan. This mantle signature is consistent with the fact that the Pelagian Block, to which Eastern Tunisia belongs, has been deeply affected by extensional and transtensional tectonics since the opening of the Tethys, a process which is still ongoing in the Sicily channel (Pantelleria Rift). As a whole however, our results show that the Italian mantle gas anomaly only marginally extends to Northwestern Africa.

We present the first helium isotope data for thermal waters and gas emissions on the islands of Terceira, Graciosa, Faial, Pico and Flores, as well as new data for Sao Miguel. The results allow us to track current mantle degassing associated with the Azores hot spot, to delineate its spatial distribution and to discuss its possible origin. As a general rule, we find that free gases tend to display somewhat higher 3He/4He ratio than groundwaters.We argue that this difference is likely due to radiogenic helium inputs to aquifers duringwater– rock interactions and, therefore, that gas phases are the fluid carriers with the most representative of mantle source signature. The measured 3He/4He ratios (normalized to the air ratio, Ra) range from lower-than-MORB values (5.23–6.07 Ra) on central Sao Miguel, to MORB values on Faial (8.53 Ra) and Flores (8.04 Ra) – located on either side of the Mid-Atlantic Ridge – and to plume-type values on Graciosa (11.2 Ra) and Terceira (13.5 Ra) where free gases also display ten times higher-than-MORB CO2/3He ratios (1.8–2.6×1010). Such a wide He isotopic range and its spatial distribution corroborate with available data for volcanic rocks, indicating that plume's head presently underlies the central part of the archipelago. The plume-type 3He/4He ratios on Terceira and Graciosa agree with geochemical and seismic evidence of a deep-rooted mantle plume feeding the Azores hot spot. Our finding that high 3He/4He ratios correspond to low 3He concentrations and high (arctype) CO2/3He values exclude a simple plume supply of 3He-rich primitive mantle. Instead, the simultaneity of both elevated CO2/3He and 3He/4He ratios is best explained by a 3He-rich contribution from the lower mantle diluted in a CO2-rich feeding plume that contains a recycled altered oceanic plate component. The alternative possibility of an enhanced time-integrated 3He/(U+Th) ratio in the Azores plume due to a greater compatibility of helium relative to U and Th during melting events is difficult to reconcile with the enriched pattern of volcanic rocks from the central islands. In any case, the Azores plume should derive from a mantle reservoir that could escape convective homogenization for a very long period of time, in agreement with subchondritic osmium isotopic ratios in volcanic rocks from the central islands of the archipelago.