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  • 1
    Publication Date: 2017-04-04
    Description: This paper discusses the abundance, speciation and mobility of As in groundwater systems from active volcanic areas in Italy. Using literature data and new additional determinations, the main geochemical processes controlling the fate of As during gas–water–rock interaction in these systems are examined. Arsenic concentrations in the fluids range from 0.1 to 6940 mg/l, with wide differences observed among the different volcanoes and within each area. The dependence of As content on water temperature, pH, redox potential and major ions is investigated. Results demonstrate that As concentrations are highest where active hydrothermal circulation takes place at shallow levels, i.e. at Vulcano Island and the Phlegrean Fields. In both areas the dissolution of As-bearing sulphides is likely to be the main source of As. Mature Cl-rich groundwaters, representative of the discharge from the deep thermal reservoirs, are typically enriched in As with respect to SO4-rich ‘‘steam heated groundwaters’’. In the HCO3 groundwaters recovered at Vesuvius and Etna, aqueous As cycling is limited by the absence of high-temperature interactions and by high-Fe content of the host rocks, resulting in oxidative As adsorption. Thermodynamic modelling suggests that reducing H2S-rich groundwaters are in equilibrium with realgar, whereas in oxidising environments over-saturation with respect to Fe oxyhydroxides is indicated. Under these oxidising conditions, As solubility decreases controlled by As co-precipitation with, or adsorption on, Fe oxy-hydroxides. Consistent with thermodynamic considerations, As mobility in the studied areas is enhanced in intermediate redox environments, where both sulphides and Fe hydroxides are unstable.
    Description: Published
    Description: 1283–1296
    Description: partially_open
    Keywords: Hydrogeochemistry ; Arsenic ; volcanic groundwaters ; speciation ; 03. Hydrosphere::03.01. General::03.01.01. Analytical and numerical modeling ; 03. Hydrosphere::03.02. Hydrology::03.02.02. Hydrological processes: interaction, transport, dynamics ; 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::03.04.06. Hydrothermal systems
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
    Format: 539 bytes
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  • 2
    Publication Date: 2017-04-04
    Description: This paper documents arsenic concentrations in 157 groundwater samples from the island of Ischia and the Phlegrean Fields, two of the most active volcano-hosted hydrothermal systems from the Campanian Volcanic Province (Southern Italy), in an attempt to identify the environmental conditions and mineral-solution reactions governing arsenic aqueous cycling. On Ischia and in the Phlegrean Fields, groundwaters range in composition from NaCl brines, which we interpret as the surface discharge of deep reservoir fluids, to shallow-depth circulating fluids, the latter ranging from acid-sulphate steam-heated to hypothermal, cold, bicarbonate groundwaters. Arsenic concentrations range from 1.6 to 6900 μg·l−1 and from 2.6 to 3800 μg·l−1 in the Phlegrean Fields and on Ischia, respectively. They increase with increasing water temperature and chlorine contents, and in the sequence bicarbonate groundwatersbsteam-heated groundwatersbNaCl brines. According to thermochemical modeling, we propose that high As concentrations in NaCl brines form after prolonged water–rock interactions at reservoir T, fO2 and fH2S conditions, and under the buffering action of an arsenopyrite+pyrite+pyrrhotite rock assemblage. On their ascent toward the surface, NaCl brines become diluted by As-depleted meteoric-derived bicarbonate groundwaters, giving rise to hybrid water types with intermediate to low As contents. Steam-heated groundwaters give their intermediate to high As concentrations to extensive rock leaching promoted by interaction with As-bearing hydrothermal steam.
    Description: Published
    Description: 313–330
    Description: reserved
    Keywords: Arsenic geochemistry ; Hydrothermal systems ; Water–rock interaction ; Hydrogeochemistry ; Arsenopyrite ; 03. Hydrosphere::03.04. Chemical and biological::03.04.06. Hydrothermal systems
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
    Publication Date: 2017-04-04
    Description: New geochemical data on dissolved major and minor constituents in 276 groundwater samples from Etna aquifers reveal the main processes responsible for their geochemical evolution and mineralisation. This topic is of particular interest in the light of the progressive depletion of water resources and groundwater quality in the area. Multivariate statistical analysis reveal 3 sources of solutes: (a) the leaching of the host basalt, driven by the dissolution of magmaderived CO2; (b) mixing processes with saline brines rising from the sedimentary basement below Etna; (c) contamination from agricultural and urban wastewaters. The last process, highlighted by increased concentrations of SO4,NO3, Ca, F and PO4, is more pronounced on the lower slopes of the volcanic edifice, associated with areas of high population and intensive agriculture. However, this study demonstrates that natural processes (a) and (b) are also very effective in producing highly mineralised waters, which in turn results in many constituents (B, V, Mg) exceeding maximum admissible concentrations for drinking water.
    Description: Published
    Description: 863–882
    Description: partially_open
    Keywords: Hydrogeochemistry ; water quality ; Mt. Etna ; 03. Hydrosphere::03.02. Hydrology::03.02.03. Groundwater processes ; 03. Hydrosphere::03.02. Hydrology::03.02.04. Measurements and monitoring ; 03. Hydrosphere::03.02. Hydrology::03.02.06. Water resources ; 03. Hydrosphere::03.04. Chemical and biological::03.04.03. Chemistry of waters
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
    Publication Date: 2017-04-04
    Description: Reaction path modelling, coupled with preparatory inverse modelling, was applied to test this model’s ability to reproduce the wide compositional range of ground waters circulating in a restricted area in Piedmont, Italy. This approach is based on the assumption that the chemistry of groundwater evolves through a series of partial equilibria with secondary minerals until it reaches its final composition. PHREEQC (Purkhurst and Appelo, 1999) and EQ3/6 (Wolery and Daveler, 1992) software packages were used to effect simulations. Reaction-path modelling was performed in time mode, taking into account the different rates of dissolution of each dissolving mineral. Data from literature regarding the kinetic parameters of dissolving minerals and the mineralogical composition of the host-rock were used. The results of the reaction-path modelling show that the composition of the analysed water samples was adequately reproduced, notwithstanding the hydrogeological complexity of the studied area. Modelling results provided very different water compositions as an effect of the chemical maturity, the physico-chemical parameters (fCO2, fO2, and temperature) and the variable amounts of gypsum among dissolving rock-forming minerals, which occur in Miocene levels of the sedimentary sequence. Further variability is related to the occasional contribution of brackish waters trapped in euxinic marly sediments, locally sealed by overlying clays, that have assumed an artesian character. The composition of some of the water samples can only be predicted by simulation runs performed at a temperature higher than that of the outlet (40°C). These warm waters probably circulate in a restricted area near the town of Nizza Monferrato. The same area has recently been affected by moderate seismicity, which has been accompanied by changes in either the temperature or chemistry, or both, of the ground waters. The changes recorded, interpreted as having been triggered by variations in the local/regional stress load and/or seismic activity, have to be ascribed to the vertical heterogeneity of the aquifers, where waters of different temperature, salinity and chemical composition circulate and occasionally mix.
    Description: In press
    Description: 2.4. TTC - Laboratori di geochimica dei fluidi
    Description: JCR Journal
    Description: open
    Keywords: reaction-path modelling ; EQ3/6 ; Inverse modelling ; Tertiary Piedmont Basin ; Monferrato ; Seismicity ; 03. Hydrosphere::03.01. General::03.01.01. Analytical and numerical modeling
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: manuscript
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