Fausto Grassa

Hydrogeochemistry and stable isotopes of thermal springs: earthquake-related chemical changes along Belice Fault (Western Sicily)

Abstract Three geothermal systems, Montevago, Castellammare-Alcamo and Sciacca, are located along the main seismogenetic structures in Western Sicily. Concentrations of dissolved species including the gases CO 2 , N 2 , He and the results of stable isotope measurements δ 18 O, δ D and δ 13 C TDIC in water samples collected from six thermal springs and 28 cold discharges were used to characterise their feeder aquifers and to reveal the relationships between water chemistry and regional seismicity. The Sciacca thermal springs differ chemically and isotopically from those of Montevago and the Castellammare-Alcamo areas. The inferred deep end-members of the thermal waters of Montevago and Castellammare-Alcamo are almost similar, suggesting that both systems are fed by carbonate waters and selenite waters. A slight contribution (1–3%) of seawater, during groundwater ascent it is also present. The Sciacca thermal springs are fed by a deep reservoir comprising a mixture of 50% carbonate water and 50% seawater. During ascent towards the surface, these waters interact with NaCl-rich evaporite layers. By combination of published and present data significant temporal variations of temperature and some chemical parameters in the thermal waters of Western Sicily have been recorded. These variations were mostly between 1966 and 1969. Although the data are discontinuous it is still possible to reveal a direct link between physico–chemical changes in the Acqua Pia and Terme Selinuntine springs and the 1968 Belice Valley earthquake. Within the studied springs, two kinds of geochemical behaviour have been recognised. The chemistry of the Montevago thermal springs was permanently changed in response to changes in the groundwater system. Water temperature and dissolved SO 4 , Cl, Na, and TDS showed minimum values before the earthquake and maximum values after the event. Almost constant values substantially higher than before, were recorded after the seismic event. Conversely, the temporal variations observed in the waters of the Terme Selinuntine spring, from 1965 to 1991, exhibit a transient increase most probably caused by a temporary contribution of deep CO 2 -rich fluids caused by the strain release during the 1968 earthquake.

Geochemistry of rainfall at Stromboli volcano (Aeolian Islands): Isotopic composition and plume‐rain interaction

The chemical and isotopic compositions of the precipitation at Stromboli Island, Italy, were investigated between October 2003 and October 2005. We employed a rain gauge network designed to cover the range in exposures and elevations of the volcanic edifice. The hydrogen and oxygen isotopic ratios vary greatly on a seasonal basis and correlate with air temperature. Deuterium excess values show a positive correlation with altitude. No direct contribution of volcanogenic H or O is evident in the isotopic composition of the rainwater. The chemical composition of the rainwater is principally controlled by the sea aerosol contribution at the coastal sites, whereas it is significantly influenced by volcanic activity near the summit vents. Interaction with volcanic acid gases is indicated by the pH, which is usually 1–2 units lower near the craters than at the coastal sites. The S/Cl, Cl/F, and S/F molar ratios in rainwater 1.5 km from the craters are consistent with those measured in the volcanic plume using other methods (diffusive tubes and Fourier transform infrared spectroscopy). Rising of undegassed magmas changes these molar ratios because of the differential degassing of sulphur, chlorine, and fluorine from the magma. We therefore propose that the chemical composition of precipitation, within 1.5 km of the craters, provides additional information that is useful for monitoring volcanic activity at Stromboli Island. Moreover, this paper presents estimates of the fluxes of F, Cl, S, Na, K, Ca, and Mg to the soil that could be useful for geochemical studies on groundwater.

The 2014 effusive eruption at Stromboli volcano (Italy): Inferences from soil CO2 flux and 3He/4He ratio in thermal waters

A new eruption started at Stromboli on 6 August 2014, which had been preceded by 2 months of increased Strombolian activity and several lava overflows from the craters. The eruption was characterized by a lava effusion in Sciara del Fuoco from a fracture at 650 m above sea level that lasted until 13–17 November. Here we present the first geochemical observations of this eruption, based on the soil CO2 flux in the summit area and on 3He/4He ratios in the thermal waters near Stromboli village. We infer that this eruption was triggered by the gradual replenishment of the feeding system by a CO2- and 3He-rich magma at the end of 2013 and after June 2014, suggested by the increase in 3He/4He ratio before eruption, which reached its highest value since 2007. We thus infer that this eruption was unusual, and we finally speculate on the evolutionary scenario of posteruption.

Geochemical and hydrogeological characterization of thermal springs in Western Sicily, Italy

Abstract Thermal and cold waters from Castellammare–Alcamo (Western Sicily-Italy) were collected between May 1994 and May 1995 and studied for their chemical and isotopic composition. During the same period, mean monthly samples of meteoric water were also collected and measured for their isotopic composition. The main purpose of this study was the characterization of the acquifers and, if possible, of their recharge areas. According to the results obtained, the acquifers were divided into three main groups: (a) selenitic waters, (b) cold carbonatic waters, and (c) deep thermal waters resulting from the mixing of the other two types. Besides a mixing process between carbonatic and selenitic waters, contamination processes of thermal waters by seawater take place during their ascent. The water temperature of the acquifer feeding the thermal springs was estimated by means of various geothermometers to range between 60°C and 97°C. Isotope data on rainwater samples show a wide seasonal variation of both δ 18 O and δ D values. The fairly constant values of thermal waters through time and the lack of an apparent correlation with the isotopic values of rainwater suggest the existence of a deep circuit determining an almost complete homogenisation of the seasonal variations of the isotopic values.

Fluid Geochemistry of Stromboli

An accurate description of the geochemical system is presented here based on a review of scientific work performed during the past decade. The surface manifestations of the volcanic system of Stromboli have been investigated using several measuring techniques. Studying the chemical composition of the volcanic plume and of fumarolic emissions has provided information on magma degassing processes. The total fluxes of the emitted gases from both the plume and the soil were found to vary with changes in volcanic activity (from normal Strombolian activity to effusive and/or paroxysmal activity). Thermal water results from the interaction between volcanic gases, host rock, seawater, and meteoric water and temporal changes observed in the chemical and the isotopic composition of the gases dissolved into thermal waters highlighted the rising of new magma batches. Combining modeling of gas―water―rock interactions with an understanding of the volcanic system allowed identifying preferential sampling sites and parameters for the geochemical monitoring of volcanic activity at Stromboli Island.

Nitrogen isotopes determination in natural gas: analytical method and first results on magmatic, hydrothermal and soil gas samples †

A continuous-flow GC/IRMS technique has been developed to analyse δ15N values for molecular nitrogen in gas samples. This method provides reliable results with accuracy better than 0.15 ‰ and reproducibility (1σ) within±0.1 ‰ for volumes of N2 between 1.35 (about 56 nmol) and 48.9 μL (about 2 μmol). The method was tested on magmatic and hydrothermal gases as well as on natural gas samples collected from various sites. Since the analysis of nitrogen isotope composition may be prone to atmospheric contamination mainly in samples with low N2 concentration, we set the instrument to determine also N2 and 36Ar contents in a single run. In fact, based on the simultaneously determined N2/36Ar ratios and assuming that 36Ar content in crustal and mantle-derived fluids is negligible with respect to 36Ar concentration in the atmosphere, for each sample, the degree of atmospheric contamination can be accurately evaluated. Therefore, the measured δ15N values can be properly corrected for air contamination.

The carbon-isotope signature of ultramafic xenoliths from the Hyblean Plateau (southeast Sicily, Italy): Evidence of mantle heterogeneity

We investigated the carbon isotope composition of mantle source beneath the Hyblean Plateau (southeast Sicily, Italy) by studying CO2 in fluid inclusions from ultramafic xenoliths recovered in some Miocene diatremes. In order to constrain the processes influencing the isotopic marker of carbon we combined δ13CCO2 results with information about noble gases (He and Ar) obtained in a previous investigation of the same products. Although Ar/CO2 and He/Ar ratios provide evidence of Rayleigh-type fractional degassing, the isotopic geochemistry of carbon is poorly influenced by this process. Mixing related to metasomatic processes where MORB-type pyroxenitic melts permeate a peridotite mantle probably contaminated by crustal fluids inherited from a fossil subduction can explain the measured δ13C and CO2/3He variations, ranging from −4‰ to −2‰ and from 109 to 1010, respectively. Simple mass-balance calculations highlighted that the Hyblean peridotite source was mainly contaminated by the carbonate source, being carbonate and organic matter present at a ratio that varied within the range from 7:1 to 4:1.

The 5 April 2003 paroxysm at Stromboli: a review of geochemical observations

This paper reviews the published geochemical variations observed during the 2002―2003 eruption at Stromboli volcano. At the end of 2002, a new eruption began at Stromboli with a lava flow that lasted until the end of July 2003. In 5 April 2003, an explosive paroxysm occurred with the ejection of bombs that reached the village of Ginostra, about 4 km from the craters. During the eruption, specific variations in chemical composition of groundwaters and summit fumaroles were recorded before the explosion, most of them for the first time. The water pH decreased significantly (0.5 units), and the dissolved CO 2 increased in two thermal wells (Cusolito and Zurro) located near Stromboli harbor from March until 5 April. Peaks in the dissolved He were also observed at all the sampling sites. All of these changes in the thermal aquifer suggested a pressurization of the system due to the degassing of a volatile-rich magma at depth. In the summit area, the SO 2 /HCl and SO 2 /HF ratios in the plume increased suddenly between 1 and 3 April due to the degassing of an S-rich magma that was approaching the shallow levels of the plumbing system, and this was involved in the explosion that occurred a few days later. This eruption was the first at Stromboli to be analyzed using geochemical models. The variations observed in the basal aquifer and in the summit area occurred on very different timescales: a few weeks and a few days, respectively.