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  • 1
    Publication Date: 2021-06-22
    Description: Rare Earth Elements (REE; lanthanides and yttrium) are elements with high economic interest because they are critical elements for modern technologies. This study mainly focuses on the geochemical behavior of REE in hyperacid sulphate brines in volcanic-hydrothermal systems, where the precipitation of sulphate minerals occurs. Kawah Ijen lake, a hyperacid brine hosted in the Ijen caldera (Indonesia), was used as natural laboratory. ∑REE concentration in the lake water is high, ranging from 5.86 to 6.52 mg kg-1. The REE pattern of lake waters normalized to the average local volcanic rock is flat, suggesting isochemical dissolution. Minerals spontaneously precipitated in laboratory at 25 °C from water samples of Kawah Ijen were identified by XRD as gypsum. Microprobe analyses and the chemical composition of major constituents allow to identify possible other minerals precipitated: jarosite, Al-sulphate and Sr, Ba-sulphate. ∑REE concentration in minerals precipitated (mainly gypsum) range from 59.53 to 78.64 mg kg-1. The REE patterns of minerals precipitated normalized to the average local magmatic rock show enrichment in LREE. The REE distribution coefficient (KD), obtained from a ratio of its concentration in the minerals precipitated (mainly gypsum) and the lake water, shows higher values for LREE than HREE. KD-LREE/KD-HREE increases in the studied samples when the concentrations of BaO, MgO, Fe2O3, Al2O3, Na2O and the sum of total oxides (except SO3 and CaO) decrease in the solid phase. The presence of secondary minerals different than gypsum can be the cause of the distribution coefficient variations. High concentrations of REE in Kawah Ijen volcanic lake have to enhance the interest on these environments as possible REE reservoir, stimulating future investigations. The comparison of the KD calculated for REE after mineral precipitation (mainly gypsum) from Kawah Ijen and Poás hyperacid volcanic lakes allow to generalize that the gypsum precipitation removes the LREE from water.
    Description: Published
    Description: 140133
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: 2IT. Laboratori analitici e sperimentali
    Description: JCR Journal
    Keywords: Gypsum precipitation ; Rare Earth Elements ; Hyperacid crater lake ; Kawah Ijen volcano ; Poás volcano ; REE fractionation ; Geochemistry ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2020-10-19
    Description: The chemical and isotopic features of the fluids (water and gases) in the Lucane thermal area (southern Italy) have been investigated in order to verify their origin, water temperature in the geothermal reservoir, and to recognize the main natural processes concerning the water composition during ascent towards the surface. The Lucane geothermal system is placed in the southern sector of the Apennines chains, a seismically active area, close to the southern base of the Mt. Alpi carbonate massif. Along the study area, two main sets of high-angle faults form an almost orthogonal fault system that, as suggested by local structural geology, acts as a preferential pathway for uprising deep fluids. Here, we recognized two different types of waters: (i) cold shallow waters having a meteoritic origin and interacting with carbonate rocks (dolomite and calcite), whose dissolved gases show a dominant atmospheric contribution and (ii) hypothermal waters (average temperature of 21 °C), having a meteoritic origin and interacting with both carbonate rocks and inter-bedded evaporitic deposit. Geochemical data allow estimating a geothermal reservoir temperature between 30 °C and 60 °C, according to silica and Ca/ Mg geothermometers, respectively. A heat discharge related to hypothermal groundwater flow between 7.75E +06 and 2.00E+07 J/s was computed. δ18O and δ2Η data allowed recognizing a meteoric origin for hypothermal (hereafter TL) waters, with mean recharge (infiltration) elevations between 1300 and 1700 m a.s.l. These waters are gas-rich (e.g., CO2 and He), which amounts are higher than those in air-saturated water (ASW). Carbon and helium isotope signature in the TL waters indicate their mainly crustal origin and involve a tectonic control on fluid migration through the crust. Furthermore, we observe that the He isotopic signature in gases dissolved in TL waters is stable over time and its monitoring could be a powerful tool to assess the seismogenetic processes since their preparatory phases.
    Description: Published
    Description: 106618
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: geochemistry ; tectonics ; geothermy ; earthquakes ; 04. Solid Earth
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2021-12-06
    Description: In this study, we analysed the Gioia Tauro Plain (Tyrrhenian coast, southern Italy) in terms of hydrostratigraphy and the physicochemical status of groundwater. We investigated the hydrostratigraphic framework of the area identifying a deep aquifer (made by late Miocene succession), an aquitard (consisting of Pliocene clayey and silty deposits) and a shallow aquifer (including Late Pleistocene and Holocene marine and alluvial sediments) using subsoil data (boreholes and geophysics). Our reconstruction showed that the structural geology controls the spatial pattern of the aquitard top and the shallow aquifer thickness. Furthermore, we evaluated the hydraulic conductivity for the shallow aquifer using an empirical method, calibrated by slug tests, obtaining values ranging from 10􀀀4 to 10􀀀5 m/s with a maximum of 10􀀀3 m/s located close to inland dune fields. The piezometric level of the shallow aquifer recorded a significant drop between the 1970s and 2021 (􀀀35 m as the worst value). It is the effect of climate and soil use changes, the latter being the increased water demand for kiwi cultivation. Despite the overexploitation of the shallow aquifer, shallow groundwater is fresh (736 S/cm as mean electrical conductivity) except for a narrow coastal area where the electrical conductivity is more than 1500 S/cm, which can be due to the seawater intrusion. What was more complex was the physicochemical status of the deep aquifer characterised by high temperature (up to 25.8 C) and electrical conductivity up to 10,520 S/cm along the northern and southern plain boundaries marked by tectonic structures. This issue suggested the dominant role of the local fault system that is likely affecting the deep groundwater flow and its chemical evolution.
    Description: Published
    Description: 3279
    Description: 7A. Geofisica per il monitoraggio ambientale
    Description: JCR Journal
    Keywords: Gioia Tauro Plain; groundwater; hydrostratigraphic framework; seawater intrusion; physicochemical status; warm waters ; Hydrostratigraphic Framework and Physicochemical Status of Groundwater in the Gioia Tauro Coastal Plain (Calabria—Southern Italy)
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
    Publication Date: 2023-05-04
    Description: This work pursues the hydro-geochemical and isotopic characterization of the complex groundwater system of the Gioia Tauro Plain, one of the most important industrialized and agricultural coastal areas of southern Italy. The anthropic pressure exposes the water resources at risk of depletion and quality degradation making the plain groundwater a system of high scientific and social interest. The plain is characterized by a shallow aquifer, mostly recharged by local rains and a deep aquifer apparently less influenced by local precipitation. Both aquifers are mainly Ca-HCO3 waters except for localized sectors where Na-HCO3, Na-Cl and Ca-SO4 waters are present. In deep aquifer, both prolonged interaction with sedimentary rocks, mainly deriving from the erosion of crystalline rocks, and direct cation exchange represent the primary factors controlling the formation of Na-HCO3 waters. Mixing processes between these waters and either connate brine and/or deep thermal waters contribute to the formation of isolated high salinity Na-Cl-rich waters. In shallow aquifer, inputs of N-rich sewage and agriculture-related contaminants, and SOx emissions in proximity of the harbor are responsible of the increasing nitrate and sulphate concentrations, respectively. The Cl/Br and NO3/Cl ratios highlight contamination mainly linked to agricultural activities and contribution of wastewater. Along the northern boundary, the warmest groundwater (Na-Cl[SO4]) were found close to a bend of the main strike-slip fault system, locally favouring the rising of B- and Li-rich deep waters, testifying the influence of geological-structural features on deep water circulation. Despite the high-water demand, a direct marine intrusion is localized in a very restricted area, where we observed an incipient groundwater-seawater mixing (seawater contribution ≤7 %). The qualitative and quantitative conditions of the shallow aquifer still have acceptable levels because of the relatively high recharge inflow. A reliable hydrogeochemical conceptual model, able to explain the compositional variability of the studied waters, is proposed.
    Description: Published
    Description: 160694
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Calabria; Coastal aquifers; Conceptual hydrogeochemical model; Hydrogeochemistry; Southern Italy; Water isotopes
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 5
    Publication Date: 2023-09-11
    Description: This work aims to define the geothermal conceptual model of the Spezzano Albanese thermal system located in the northern sector of the Calabria Region, along the western edge of the Sibari Plain. The study confirms that the deep thermal reservoir of Spezzano Albanese is mainly hosted within the permeable levels of the evaporite deposits of the Messinian succession including siltstones with manganese mineralisation, halite, and gypsumarenites. The thermal waters show discharging temperature between 20.2 and 26.6 ◦C and a high compositional variability, from Na–Cl to Na–Ca–HCO3. The compositional evolution (from Na–Cl to Na–HCO3) is accompanied by a decrease in both salinity and the concentrations of most dissolved constituents, including Cl, Br, B, Li, Na, K, Mg, Ca, and Ba. These variations are due to mixing between the thermal endmember, rich in Cl and related components, and low-salinity, cold shallow waters (temperature between 17.5 and 22.7 ◦C). The study points out that the thermal endmember derives by halite dissolution and more complex water-rock interaction processes involving (1) the dissolution of other solid phases of the Messinian deposits, as also confirmed by δ34S values of dissolved sulphate and sulphide, and (2) the precipitation of secondary solid phases (e.g., barite). The geothermometric modelling suggests that the thermal groundwaters in the deep reservoir are probably in equilibrium with either (i) quartz, calcite, disordered dolomite, low-albite, and K-feldspar, as well as with pyrophyllite and poorly crystalline kaolinite (as proxies of clay minerals) at temperatures of 65.5 ± 4.5 ◦C or (ii) quartz, calcite, disordered dolomite, low-albite, disordered adularia, laumontite and saponites at temperatures of 56.1 ± 4.3 ◦C, based on the first and second geothermometric model, respectively. The δ18O and δ2H values of water confirm a meteoric origin for the thermal waters with average recharge altitudes between 745 and 857 m a.s.l. These elevations are compatible with the recharge from the western side of the Esaro valley where evaporite successions are found close to the surface. The isotopic value of the dissolved CO2 associated to the Spezzano Terme water highlights its likely microbial origin, as recognised for other thermal circuits hosted in sedimentary rocks of the southern Apennines. Furthermore, the thermal endmember shows a noteworthy enrichment in CH4 with respect to air due to the interaction of groundwater with sediments rich in organic matter. Although methane could have a biogenic origin, the presence of a minor component of thermogenic methane in the gas phase dissolved in the Spezzano Terme waters cannot be completely excluded. The data obtained in this study allow to assume that the recharge meteoric waters descend to a maximum depth of about 1.1–1.4 km below the main emergence area and then the regional NE-SW fault systems probably act as a preferential pathway for the ascent of the thermal waters towards the surface. These waters discharge at Spezzano Albanese, where the crystalline-metamorphic units cropping out immediately upstream of the emergence area act as cap-rock favouring the final ascent towards the surface of the thermal waters.
    Description: Published
    Description: 106407
    Description: 1TR. Georisorse
    Description: JCR Journal
    Keywords: Thermal waters ; Geothermometric model ; Sulphur isotopes ; δ18O and δ2H ; Spezzano albanese ; Calabria region ; 03.02. Hydrology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 6
    Publication Date: 2022-10-10
    Description: There are three classes of geothermometers and fCO2-indicators (collectively known as geoindicators): the traditional or classical ones, the theoretical activity-based geoindicators, and multicomponent chemical geothermometry. Most traditional geothermometers (e.g., SiO2, Nasingle bondK, Na-K-Ca, Ksingle bondMg) are linear functions linking the logarithm of the equilibrium constant of the controlling reaction to the absolute temperature reciprocal. Total concentrations are considered in most traditional geothermometers. Thanks to these two characteristics, the traditional geothermometers are simple to be used, which explains their widespread use. However, there are at least two issues which have been disregarded or not properly considered in the derivation of traditional geothermometers. One is that total concentrations of relevant solutes can deviate considerably from the activities of the aqueous species participating to the controlling mineral-solution reactions due to the formation of aqueous complexes. The other concerns the hydrothermal minerals, with some having variable composition and adularia being affected by Alsingle bondSi order-disorder on the tetrahedral sites. To overcome these two issues, theoretical activity-based geoindicators were recently proposed. To use these geoindicators is necessary to run a speciation program, but computed temperatures and CO2 fugacities are more reliable than those given by traditional geoindicators and additional information is obtained on the hydrothermal minerals present in the geothermal aquifer. Multicomponent chemical geothermometry consists in simulating the heating of the aqueous solution of interest from the P-T conditions present at the surface to those occurring in the geothermal aquifer. Both multicomponent chemical geothermometry and theoretical activity-based geoindicators call for the use of a suitable computer code and an internally consistent thermodynamic database. It would be desirable for the database to be shared, accepted and used by the entire scientific community.
    Description: Published
    Description: 107097
    Description: 1TR. Georisorse
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 7
    Publication Date: 2023-01-31
    Description: Carbon dioxide (CO2) is released from the Earth’s interior into the atmosphere through both volcanic and non-volcanic sources in a variety of tectonic settings. A quantitative understanding of CO2 outgassing fluxes in different geological settings is thus critical for decoding the link between the global carbon budget and different natural processes (e.g., volcanic eruption and earthquake nucleation) and the effects on the climate evolution over geological time. It has recently been proposed that CO2 degassing from non-volcanic areas is a major component of the natural CO2 emission budget, but available data are still sparse and incomplete. Here, we report the results of a geochemical survey aimed at quantifying CO2 emissions through cold and thermal springs of the tectonically active Pollino Massif and Calabrian arc (Southern Italy). The chemical ad isotopic (He and C) composition of fifty-five dissolved gas samples allows to identify two different domains: 1) a shallow system dominated by gas components of atmospheric signature (helium, hereafter He) and biogenic origin (C), and 2) a deeper system in which crustal/deep fluids (CO2 and He) are dominant. The measured He isotope ratios range from 0.03 to 1.1 Ra (where Ra is the He isotopic ratio in the atmosphere) revealing a variable atmospheric contamination. Furthermore, the He isotopic data indicate the presence of traces of mantle He contributions (2%–3%) in the thermal groundwater. The prevailing low R/Ra values reflect the addition of crustal radiogenic 4He during groundwater circulation. Using helium and carbon isotope data, we explore the possible sources of fluids and the secondary processes (dissolution/ precipitation) that act to modify the chemistry of pristine volatiles. For the thermal springs, we estimate a deep C output of 2.3 x 107 to 6.1 x 108 mol year−1. These values correspond to deep CO2 fluxes per square km comparable with those estimated in several active and inactive volcanic areas and in continental regions affected by metamorphic CO2 degassing (e.g., the southern margin of the Tibetan Plateau).
    Description: Published
    Description: 946707
    Description: 9T. Geochimica dei fluidi applicata allo studio e al monitoraggio di aree sismiche
    Description: JCR Journal
    Keywords: erath degassing ; carbon dioxide ; helium ; eartquakes
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 8
    Publication Date: 2023-02-28
    Description: Groundwater is the main water supply for agricultural and industrial needs in many coastal plains worldwide. Groundwater depletion often triggers land subsidence, which threatens manmade infrastructure and activities and aggravates other geohazards. We applied a multi-temporal interferometric synthetic aperture radar technique to Sentinel-1 datasets to detect ground motion in the Gioia Tauro plain (Calabria, Southern Italy) from 2018 to 2021. The InSAR data were analysed through the integrated use of groundwater head, stratigraphical and geomorphological data, and land use information to distinguish the potential subsidence divers. The results show that subsiding areas, with a mean rate of about 10 mm/yr, are in the middle of the plain, and their location is influenced by the spatial distribution of compressible sediments included in the shallow aquifer. Furthermore, the subsidence arrangement is spatially accordant with the main groundwater depression area, which can be ascribed to the ongoing and increasing water pumping for predominantly agricultural usage. We also observed that subsidence (up to 10 mm/yr) affects the western dock of the Gioia Tauro harbour, in front of which, in very shallow water, are two submarine canyon heads already affected by slides in the past.
    Description: Published
    Description: 2926
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: Gioia Tauro plain ; groundwater exploitation ; land use change ; InSAR
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 9
    Publication Date: 2024-03-20
    Description: Volcanic lakes are complex natural systems and their chemical composition is related to a myriad of processes. The chemical composition of major, minor, Rare Earth Elements (REE) and physico-chemical parameters at the hyperacid crater lake of Rincón de la Vieja volcano (Costa Rica) are here investigated during February 2013–August 2014. The study of the lake chemical composition allows to identify the main geochemical processes occurring in the lake and to track the changes in the volcanic activity, both important for active volcanoes monitoring. The total REE concentration ( REE) dissolved in the crater lake varies from 2.7 to 3.6 mg kg−1 during the period of observation. REE in the water lake samples normalized to the average volcanic local rock (REEN-local rock) are depleted in light REE (LREE). On the contrary REEN-local rock in the solids precipitated (mainly gypsum/anhydrite), from lake water samples in laboratory at 22°C, are enriched in LREE. The low variability of (La/Pr)N-local rock and (LREE/ HREE)N-local rock ratios (0.92–1.07 and 0.66–0.81, respectively) in crater lake waters is consistent with the low phreatic activity (less than 10 phreatic eruptions in 2 years) observed during the period of observation. This period of low activity precedes the unrest started in 2015, thus, it could be considered as a pre-unrest, characterized by infrequent phreatic eruptions. No clear changes in the REE chemistry are associated with the phreatic eruption occurred at mid- 2013. The results obtained investigating water-rock interaction processes at theRincón de la Vieja crater lake show that rock dissolution and mineral precipitation/ dissolution are the main processes that control the variability of cations composition over time. In particular, precipitation and dissolution of gypsum and alunite are responsible for the variations of REE in the waters. Despite the low variations of (La/Pr)N-local rock and (LREE/HREE)N-local rock ratios, this study allows to suggest that REE can be used, together with major elements, as practical tracers of water-rock interaction processes and mineral precipitation/ dissolution at active hyperacid crater lakes over time, also during periods of quiescence and low phreatic activity.
    Description: Published
    Description: 1197568
    Description: OSV3: Sviluppo di nuovi sistemi osservazionali e di analisi ad alta sensibilità
    Description: JCR Journal
    Keywords: Rare earth elements ; hyperacid crater lake ; geochemical monitoring ; sulfate minerals ; water-rock interaction
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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